NCD980602163_19990126_Warren County PCB Landfill_SERB C_BCD Patent and License-OCR

;'{"f)plica!n of the base catalyzed ... with US Navy vessels. Final nhttp://www.doe.gov:80/cgi-bin/gpog ... zed+Detoxification&byte_count=2594
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REPORT RECORD
See Bottom of Page for Report Location Information
Application of the base catalyzed decomposition process to treatment of PCB-contaminated
insulation and other materials associated with US Navy vessels. Final report . Schmidt, A.J .;
Zacher, A.H.; Gano, S.R .. Pacific Northwest National Lab., Richland, WA (United States). Sep 1996 .
170p. DOE Co ntract AC0676RL0 18 30. Sup.Doc.Num. E l.99:DE97050891. NTTS Order Number
DE97050891 . Source: OSTI (DOE and DOE contractors only); NTIS (Public Sales); GPO Dep.
(Depository Libraries)
The BCD process was applied to dechlorination of two types of PCB-contaminated materials ge nerated
from Navy vessel decommissioning activities at Puget Sound Naval Shipyard: insul ation of wool felt
impregnated with PCB, and PCB-containing paint chips/debri s from removal of paint from metal
surfaces. The BCD process is a two-stage, low-temperature chemical dehalogenation process. In Stage 1,
the materials are mixed with sodium bicarbonate and heated to 350 C. The vo latilized halogenated
contaminants ( eg, PCBs, dioxins, furans ), which are collected in a small volume of particulates and
granular acti vated carbon, are decomposed by the liquid-phase reaction (Stage 2) in a stirred-tank
reactor, using a high-boiling-point hydrocarbon oil as the reaction medium, with addition of a hydrogen
donor, a base (NaOH), and a catalyst. The tests showed that treating wool felt insul ati on and paint chip
wastes with Stage 2 on a large scale is feasible, but compared with current disposal costs for PCB-
contaminated materials, using Stage 2 would not be economical at this time. For paint chips generated
fro m shot/sand blasting, the solid-phase BCD process (Stage 1) should be considered, if paint removal
activiti es are accelerated in the future.
KEYWORDS:
SHIPS/decommissioning;MILIT ARY EQUIPMENT /decommissioning; POL YCHLORINA TED
BIPHENYLS/decomposition;PROGRESS REPORT;SHIPS;DECOMMISSIONING ;
DECOMPOSITION;REMEDIAL ACTION;WASTES;PAINTS;REMOVAL
GPO SUBJECT CATEGORIES TEXT:
ENV-SOCIAL ASPECTS OF ENERGY TECH
GPO SUBJECT CATEGORY NUMBERS:
0430-M-32
GPO SUBJECT CATEGORY NUMBERS -PACKED:
0430M32
DOE/EDB SUBJECT CATEGORY TEXT:
ENERGY PLANNING AND POLICY
DOE/EDB SUBJECT CATEGORY NUMBERS:
290300 . Primary Report Number: PNNL--11332
PACKED PRIMARY REPORT NUMBER:
PNNLl 1332
DATE OF PUBLICATION:
09 /01 /1 996
LANGUAGE TEXT:
19960900
COUNTRY OF PUBLICATION: us
TYPE OF ITEM:
REPORT
SERIAL NUMBER:
97001721250
WAIS ENTRY DATE:
03/10/1997
1/26/99 2:45 PM
f
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SHIPMENT NUMBER:
1997:23DM
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Government Printing Office, Washington, D.C. 20402; phone [phone] or fax [phone]
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REPORT RECORD
See Bottom of Page for Report Location Information
Demonstration of base catalyzed decomposition process, Navy Public Works Center, Guam,
Mariana Islands . Schmidt, A.J.; Freeman, H.D.;Brown, M.D.; Zacher, A.H.;Neuenschwander, G.N.;
Wilcox, W.A.; Gano, S.R. [Pacific Northwest National Lab., Richland, WA (United States)]; Kirn,
B.C.;Gavaskar, A.R. [Battelle Columbus Div., OH (United States)] . Pacific Northwest Nati onal Lab.,
Richland , WA (United States). Feb 1996. 21 lp. DOE Contract AC0676RL01830 . Sup.Doc.Num. E
l .99:DE96010695. NTIS Order Number DE96010695. Primary Report Number: PNNL--10972.
Source: OSTl (DOE and DOE contractors only); NTIS (Public Sales); GPO Dep. (Depository Librari es)
Base Catalyzed Decomposition (BCD) is a chemical dehalogenation process designed for treating soils
and other substrate contaminated with polychlorinated biphenyls (PCB), pesticides, dioxins, furans, and
other hazardous organic substances. PCBs are heavy organic liquids once widely used in industry as
lubricants, heat transfer oi ls, and transformer dielectric fluid s. In 1976, production was banned when
PCBs were recognized as carcinogenic substances. It was estimated that significant quantities ( one
billion tons) of U.S. soils, including areas on U.S. military bases outside the country, were contaminated
by PCB le aks and spills, and cleanup activities began. The BCD technology was developed in response
to these activities. This report details the evolution of the process, from in ception to deployment in
Guam, and describes the process and system components provided to the Navy to meet the remediation
requirements. The report is divided into several sections to cover the range of development and
demonstration activiti es. Section 2.0 gives an overview of the proj ect history. Section 3 .0 describes the
process chemistry and remediation steps involved. Section 4.0 provides a detailed description of each
component and specific development activities. Section 5.0 details the testing and deployment
operations and provides the results of the individual demonstration campaigns. Secti on 6.0 gives an
economic assessment of the process. Section 7.0 presents the conclusions and recommendations form
this proj ec t. The appendices contain equipment and instrument li sts, equipment drawings, and detailed
run and analytical data
KEYWORDS:
POL YCHLORINATED BIPHENYLS/decompos ition;REMEDIAL ACTION/demonstration
programs;S OTLS/contami nation;TOXlC MA TERIALS/decomposition;MTLIT ARY
F AC ILITTES/waste processing;PROGRESS
REPORT;DECOMPOSITION;SOILS;CONTAMINATION; GUAM;CHEMICAL
REACTORS;SODIUM CARBONATES;CATAL YSTS;BENCH-SCALE EXPERIMENTS;
TECHNOLOGY ASSESSMENT;TEST FACILITIES; WASTE MANAGEME
GPO SUBJECT CATEGORIES TEXT:
NUCLEAR FUELS
GPO SUBJECT CATEGORY NUMBERS:
0430-M-05
GPO SUBJECT CATEGORY NUMBERS -PACKED:
0430M05
DOE/EDB SUBJECT CATEGORY TEXT:
NUCLEAR FUELS
DOE/EDB SUBJECT CATEGORY NUMBERS:
054000;052000
PACKED PRIMARY REPORT NUMBER:
PNNL10972
DATE OF PUBLICATION:
02/01 /1996
LANGUAGE TEXT:
English
1/26/99 243 PM
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COUNTRY OF PUBLICATION: us
TYPE OF ITEM:
REPORT
SERIAL NUMBER:
96001593581
WAIS ENTRY DA TE:
07/26/1996
SHIPMENT NUMBER:
1996:43DM
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United ~"tates Patent: 5,064,526 http:l/164.195.100.11/netacgi/nph-... rs.INZZ.&OS=IN/Rogers&RS=IN/Rogers
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United States Patent
Rogers, et al.
[USPTO]
( 17 of 103)
5,064,526
November 12, 1991
Method for the base-catalyzed decomposition of halogenated and non-halogenated
organic compounds in a contaminated medium
Abstract
A method for the decomposition of halogenated and non-halogenated organic contaminant compounds
contained in a contaminated medium comprises adding an alkali or alkaline earth metal carbonate,
bicarbonate or hydroxide to the contaminated medium in an aqueous solution or in a solvent having a
boiling point of at least 200.degree. C., or in the form of a solid dispersion or suspension. The medium
includes a hydrogen donor compound. The hydrogen donor compound may be originally contained in
the medium or may be added to the medium. The medium further includes a catalytic source of carbon,
for example, a carabohydrate, which will cause formation of a free radical hydrogen ion from the
hydrogen donor compound. The medium is heated to dehydrate the medium and then is further heated at
a temperature between about 200.degree. and 400.degree. C. to cause formation of the free radical
hydrogen ion and effect reductive decomposition of the halogenated and non-halogenated organic
contaminant compounds. An acid is then added to the medium in an amount sufficient to neutralize the
same.
Inventors: Rogers; Charles J. (Cincinnati, OH); Kornel; Alfred (Cincinnati, OH); Sparks; Harold
L. (Fayetteville, OH)
Assignee: The United _States of America as represented by the Administrator of the
(W ashingtori, DC)
Appl. No.: 620127
Filed: November 30, 1990
U.S. Class: 208/262.5; 208/262.1; 208/13; 210/909; 134/10; 134/26;
Intern'I Class:
Field of Search:
134/27; 134/28; 134/42; 423/659; 423/DIG.20; 502/25;
502/27; 502/515
Cl0G 017/00
134/26,27,28,42 208/262.1,262.5 210/909 502/515,25,27
423/659,DIG. 20
References Cited [Referenced By]
U.S. Patent Documents
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4246255 Dec., 1981 Grantham.
4327027 Apr., 1982 Howard 260/340.
4337368 Jun., 1982 Pytlewski et al. 568/730.
4349380 Sep., 1982 Pytlewski et al. 75/117.
4351718 Sep., 1982 Brunelle 208/262.
4353793 Oct., 1982 Brunelle 208/262.
4400552 Aug., 1983 Pytlewski 568/715.
4417977 Nov., 1983 Pytlewski et al. 208/262.
4430208 Feb., 1984 Pytlewski et al. 208/262.
4447541 May., 1984 Peterson 435/170.
4460797 Jul., 1984 Pytlewski et al. 568/715.
4471143 Sep., 1984 Pytlewski et al. 568/715.
4483716 Oct., 1984 Heller 137/7.
4523043 Jan., 1985 Pytlewski et al. 568/910.
4574013 Mar., 1986 Peterson 134/2.
4602994 Jun., 1986 Pytlewski et al. 208/262.
4631183 Dec., 1986 Lalancette et al..
4663027 May., 1987 Mendiratta 208/262.
4675464 Jun., 1987 Rogers et al. 585/538.
4685220 Aug., 1987 Meenan 34/10.
4761221 Aug., 1988 Rossi 208/262.
4792407 Dec., 1988 Zeff et al. 210/148.
4793937 Dec., 1988 Meenan 310/171.
4801384 Jan., 1989 Steiner 134/42.
4841998 Jun., 1989 Bruya 210/909.
4869825 Sep., 1989 Steiner.
Foreign Patent Documents
118858 Sep., 1984 EP.
Other References
Chemical Abstracts, vol. 82, No. 139620p (1975).
Kernel et al., Journal of Hazardous Materials, 12 (1985), pp. 161-176.
Primary Examiner: Myers; Helane E.
Parent Case Text
RELATED APPLICATIONS
This application is a continuation-in-part of the Rogers et al copending application Ser. No. 07/515,892
filed Apr. 27, 1990.
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Claims
1. A method for the reductive decomposition of halogenated or non-halogenated organic contaminant
compounds contained in a contaminated medium, comprising
(a) adding an alkali or alkaline earth metal carbonate, bicarbonate or hydroxide to a contaminated
medium containing halogenated or non-halogenated organic contaminant compounds, said alkali or
alkaline earth metal carbonate, bicarbonate or hydroxide being added as an aqueous solution or as a
suspension in a solvent having a boiling point of at least 200.degree. C., or in the form of a solid
suspension, said contaminated medium further containing a hydrogen donor compound and a catalytic
form of carbon which will form a free radical hydrogen ion;
(b) heating the contaminated medium at a temperature and for a time sufficient to dehydrate the medium;
( c) further heating the medium at a temperature between about 200.degree. and 400.degree. C. for a time
sufficient to cause formation of a free radical hydrogen ion therein and effect reductive decomposition of
the halogenated or non-halogenated organic contaminant compounds; and
( d) adding an acid to the medium in an amount sufficient to provide the medium with a pH of from
about 7 to about 9.
2. A method as defined in claim 1, wherein the alkali or alkaline earth metal compound is added in an
aqueous solution.
3. A method as defined in claim 2, wherein the aqueous solution further contains a hydrocarbon solvent
having a boiling point of at least 200.degree. C.
4. A method as defined in claim 1, wherein the alkali or alkaline earth metal compound is added as a
suspension in a solvent having a boiling point of at least 200.degree. C.
5. A method as defined in claim 4, wherein the solvent comprises a hydrocarbon compound.
6. A method as defined in claim 1, wherein the alkali or alkaline earth metal compound is added as a
solid suspension.
7. A method as defined in claim 1, wherein the alkali or alkaline earth metal compound is added in an
amount of from about 1 to about 20 weight percent based on the weight of the contaminated medium.
8. A method as defined by claim 7, wherein the alkali or alkaline earth metal compound is added in an
amount of from about 2 to about 12 weight percent based on the weight of the contaminated medium.
9. A method as defined by claim 1, wherein the catalytic form of carbon comprises a carbohydrate which
decomposes to form a free radical hydrogen ion from the hydrogen donor compound.
10. A method as defined by claim 9, wherein the carbohydrate comprises sucrose.
11. A method as defined by claim 1, wherein the contaminated medium is heated under vacuum to
dehydrate the medium.
12. A method as defined by claim 1, wherein in step (c) the medium is further heated at a temperature
between about 280.degree. and 400.degree. C. to effect reductive decomposition of the organic
contaminant compounds.
13 . A method as defined by claim 1, wherein the acid which is added to the medium to provide a pH of
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from 7 to about 9 is selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric
acid and nitric acid.
14. A method as defined by claim 1, wherein the contaminated medium comprises soil.
15. A method as defined by claim 1, wherein the contaminated medium comprises sludge.
16. A method as defined by claim 1, wherein the contaminated medium comprises sediment.
17. A method as defined by claim 1, wherein the contaminated medium includes an absorbent
comprising spent activated carbon.
18. A method as defined by claim 1, wherein the contaminated medium comprises a liquid.
19. A method as defined by claim 1, wherein the contaminated medium contains up to 100,000 ppm of
halogenated organic compounds.
20. A method as defined by claim 1, wherein the contaminated medium comprises a pure halogenated
material.
21. A method as defined by claim 1, wherein the medium which results from the acid addition step is
returned to its original environment.
22. A method as defined by claim 1, wherein the contaminated medium originally contains the hydrogen
donor compound.
23. A method as defined by claim 1, wherein the hydrogen donor compound is added to the
contaminated medium.
Description
FIELD OF THE INVENTION
The present invention relates to a method for the base-catalyzed decomposition of halogenated and
non-halogenated organic contaminant compounds contained in a contaminated medium. More
particularly, the invention relates to a method for both the decomposition and removal of halogenated
and non-halogenated organic compounds contained in a contaminated medium by use of an alkali or
alkaline earth metal carbonate, bicarbonate or hydroxide, and an organic hydrogen donor compound in
the presence of a carbohydrate.
BACKGROUND OF THE INVENTION
The hazards to public health and the environment which are posed by a variety of synthetic halogenated
organic compounds are well known. Compounds such as polychlorinated biphenyls (PCB's),
dibenzodioxins, dibenzofurans, dichlorodiphenyl trichloroethane (DDT), dieldrin, lindane and
chlordane, as well as other halogenated pesticides, have been found to be persistent, environmentally
toxic materials which require safe and efficient means of disposal. PCB's pose a particularly serious
disposal problem. Once widely used as dielectric fluid additives in electrical equipment such as
transformers and capacitors because of their excellent insulating properties, the use of PCB's in many
applications has been banned by the U.S. Environmental Protection Agency owing to the cumulative
storage of PCB's in the human body and the extremely high toxicity of PCB's. Thus, methods for the
removal and/or destruction of halogenated organic compounds such as PCB's are required.
Various methods for the destruction or decomposition of halogenated organic compounds are known in
the art. For example, the Peterson U.S. Pat. Nos. 4,447,541 and 4,574,013 disclose methods for
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decontaminating soil which is contaminated with halogenated organic compounds. The Peterson U.S .
Pat. No. 4,447,541 discloses a process in which a reagent mixture of an alkaline constituent and a
sulfoxide catalyst (DMSO) are intimately mixed with soil contaminated with PCB's. The reagent
mixture affects a desorption of the halogenated contaminants from the soil and subsequently
dehalogenates the contaminants. However, this process is disadvantageous in that the kinetics are
relatively slow and therefore reduction of the PCB concentration to an acceptable level requires
extended time periods ranging from weeks to months, the soil must be completely dry for the destruction
to take place, large quantities of the reagent are required, and the sulfoxide catalyst may potentially
transport contaminants prior to their destruction. The Peterson U.S. Pat. No. 4,574,013 discloses a
process wherein a heated slurry of contaminated soil is treated with a mixture of an alkaline constituent
and a sulfoxide catalyst. However, this process is similarly disadvantageous in that the sulfoxide catalyst
may transport contaminants into living systems, and the sulfoxide catalyst produces odorous compounds
when heated to high temperatures and decomposes into combustible byproducts under elevated
temperature conditions. This process is also disadvantageous in that it requires large amounts of
reagents.
The Rogers et al U.S. Pat. No. 4,675,464 discloses a method for the chemical destruction of halogenated
aliphatic hydrocarbons, and more particularly a method for the chemical destruction of ethylene
dibromide. An alkali metal hydroxide is dissolved in an ethylene glycol and the resulting product is
reacted with the halogenated hydrocarbon. Rogers et al further disclose that the reaction temperature
should be maintained at 30.degree. C. or less to maintain the reaction products in solution.
The Rogers et al copending application Ser. No. 07/350,425 discloses a method for the destruction of
halogenated organic compounds in a contaminated medium wherein an aqueous solution containing
from about 0.1 to about 20 weight percent polyethylene glycol is added to a contaminated medium. An
alkali metal hydroxide is also added to the contaminated medium, and the contaminated medium is
heated at a temperature and for a time sufficient to dehydrate the medium. The medium is further heated
at a temperature of between about 100.degree. and 350.degree. C. for a time sufficient to effect
destruction of the halogenated organic compounds, and an acid is added to the medium in an amount
sufficient to provide the medium with a pH of from about 7 to about 9.
The Rogers et al copending application Ser. No. 07/515,892 discloses a method for the decomposition of
halogenated organic compounds contained in a contaminated medium wherein an aqueous solution of an
alkali metal carbonate or bicarbonate is added to the contaminated medium, and the medium is heated to
a temperature between about 250.degree. and 400.degree. C.
The Pytlewski et al U.S. Pat. No. 4,400,552 discloses a method for the decomposition of halogenated
organic compounds which employs a reagent comprising the product of the reaction of an alkali metal
hydroxide with a polyglycol or a polyglycol monoalkyl ether, and oxygen. The Pytlewski et al U.S. Pat.
Nos. 4,337,368 and 4,602,994 disclose similar methods of decomposing halogenated organic
compounds. Additionally, the Pytlewski et al U.S. Pat. Nos. 4,430,208, 4,417,977, 4,460,797 and
4,471,143 also disclose methods for separation and/or decomposition of halogenated organic
compounds. However, these methods are disadvantageous in that excess amounts of the alkali metal
hydroxide and polyglycol reagents are required in order to obtain a homogeneous distribution
throughout the contaminated material, for example soil, sediment, sludge or the like, which is treated.
The Pytlewski et al U.S. Pat. Nos. 4,349,380 and 4,523 ,043 disclose the use ofreagents made from an
alkali metal or alkali metal hydroxide and a polyglycol or a polyglycol monoalkyl ether for removing
metals from metal-containing materials and for decomposing organo sulfur compounds, respectively.
Similarly, the Brunelle U.S. Pat. Nos. 4,351,718 and 4,353,793 disclose methods for removing
polyhalogenated hydrocarbons from nonpolar organic solvent solutions by treating the contaminated
solutions with a mixture of polyethylene glycol and an alkali metal hydroxide. These methods are
similarly disadvantageous in that excess amounts of reagent are required.
Additional methods for removing and/or destructing halogenated organic compounds contained in
contaminated materials are disclosed in the Howard et al U.S. Pat. No. 4,327,027, the Heller U.S . Pat.
No. 4,483,716, the Mendiratta et al U.S. Pat. No. 4,663,027, the Meenan et al U.S. Pat. Nos. 4,685,220
and 4,793,937, the Rossi et al U.S. Pat. No. 4,761,221, the Zeff et al U.S. Pat. No. 4,792,407, European
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Patent Application No. 118,858, Chemical Abstracts, Vol. 82, No. 39620P (1975) and Kornel et al,
Journal ofHazardous Materials, 12 (1985), pages 161-176. However, many ofthese and additional
processes known in the art for the removal and/or destruction of halogenated organic compounds in
contaminated materials are inadequate in view of the time required for acceptable levels ofremoval
and/or destruction, the use of excessive amounts of various reagents, the use of expensive reagents, the
production of toxic and/or combustible byproducts, and/or the failure to obtain desired removal and/or
destruction levels. Thus, a need exists for improved, cost effective methods for the removal, reduction
and stripping of non-halogenated compounds from and the dehalogenation of halogenated organic
compounds in contaminated materials, which methods overcome the disadvantages of the prior art.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide new methods for the reductive
decomposition and removal of halogenated and non-halogenated organic compounds contained in a
contaminated medium. It is an additional object of the invention to provide methods for the reductive
decomposition and removal of halogenated and non-halogenated organic compounds contained in a
contaminated medium, which methods employ at least one hydrogen donor compound. It is a further
object of the invention to provide methods for the decomposition and removal of halogenated and
non-halogenated organic compounds contained in a contaminated medium which employ significantly
less amounts of reagent and which employ lower costing reagents, as compared with prior art methods.
It is a further object of the invention to provide such methods wherein environmentally acceptable levels
of halogenated and non-halogenated organic contaminant compounds are achieved in the treated
materials. It is a related object of the invention to provide such methods wherein the environmentally
acceptable levels of contaminants in the materials are obtainable within a short period of time.
These and additional objects are achieved by the present invention which relates to methods for the
base-catalyzed decomposition of halogenated and non-halogenated organic compounds contained in a
contaminated medium. The methods of the invention comprise the steps of adding an alkali metal or
alkaline earth metal carbonate, bicarbonate or hydroxide to a contaminated medium containing the
halogenated or non-halogenated organic contaminant compounds. The alkali or alkaline earth metal
carbonate, bicarbonate or hydroxide may be in an aqueous solution which distributes the metal
compound throughout the medium and acts as a wetting agent, or in a solvent, or may be added as a
solid dispersion or suspension. The contaminated medium further contains a hydrogen donor compound
and a catalytic form of carbon which will cause formation of a free radical hydrogen ion from the
organic hydrogen donor compound. For example, the organic hydrogen donor compound may comprise
a high boiling point aliphatic solvent and the catalytic form of carbon may comprise a carbohydrate.
Upon heating of the contaminated medium, the carbohydrate decomposes and causes formation of a free
radical hydrogen ion from the hydrogen donor compound. The free radical hydrogen ion is thereby
generated in situ, i.e. in the medium to be treated, and acts as the reducing agent for the halogenated and
non-halogenated contaminant compounds. Accordingly, according to the methods of the present
invention, the contaminated medium is then heated at a temperature and for a time sufficient to
dehydrate the medium. Although the water is removed, the alkali or alkaline earth metal compound and
the hydrogen donor compound are well distributed throughout the medium and are concentrated to a
very reactive state. After dehydration, the medium is then further heated at a temperature between about
200.degree. and 400.degree. C. for a time sufficient to effect hydrogen transfer from the donor
compound to the contaminants, both halogenated and non-halogenated. The reduced contaminants
decompose to simple hydrocarbon structures. Decomposition of the halogenated and non-halogenated
compounds in the contaminated medium is more dependent on the ease of hydrogen donation by the
donor compound (which is catalyzed by the decomposed carbohydrate) as the temperature increases
within the aforementioned range. Finally, an acid is added to the medium in an amount sufficient to
neutralize the medium so that it may be returned to its original environment. Because the aqueous
solution or solvent is employed, the amount of alkali or alkaline earth metal compound which is required
for the present methods is significantly reduced as compared with prior art methods. Additionally,
because the metal compound is well distributed throughout the medium by the aqueous solution, a
uniform destruction or reduction of the halogenated and non-halogenated organic compounds is
achieved. Moreover, because lower amounts of metal compounds are employed, recycling of excess
reagents is not required. Finally, the present methods employing an alkali metal carbonate or bicarbonate
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are advantageous in that these compounds are less corrosive than the alkali metal hydroxides and require
less acid for neutralization.
These and additional objects and advantages will become more fully understood in view of the following
detailed description.
DETAILED DESCRIPTION
The present invention comprises methods for the decomposition and removal of halogenated and
non-halogenated organic compounds contained in a contaminated medium. The contaminated medium
may comprise soil, sludge, sediment or a liquid. The present methods are particularly adapted for use
with soils, sludges and sediments. The methods are suitable for use with mediums which contain up to
100,000 ppm of halogenated organic compounds, aliphatic or aromatic, for example PCB's, or even
higher levels of the halogenated organic compounds, and for use with mediums which contain up to
100,000 ppm of non-halogenated organic contaminants. The contaminated mediums which are suitable
for use in the invention may also include an absorbent or adsorbent, for example spent activated carbon
or the like. Additionally, the methods of the invention may be used for the treatment of pure halogenated
materials, for example, aldrin, dieldrin and other halogenated pesticides.
Generally, the methods of the invention comprise adding an alkali or alkaline earth metal carbonate,
bicarbonate or hydroxide, or a mixture thereof, to the contaminated medium containing one or more
halogenated or non-halogenated organic contaminant compounds. The alkali or alkaline earth metal
carbonate, bicarbonate or hydroxide may be added to the contaminated medium in an aqueous solution
or in a high boiling solvent. Alternatively, the alkali or alkaline earth metal carbonate, bicarbonate or
hydroxide may be added in the form of a solid dispersion or suspension. When the alkali or alkaline
earth metal carbonate, bicarbonate or hydroxide is added in an aqueous solution, the water from the
aqueous solution assists in distributing the metal compound homogeneously throughout the
contaminated medium. Alternatively, if the metal carbonate, bicarbonate or hydroxide is added with a
high boiling solvent, suitable solvents have a boiling point of at least 200.degree. C., and preferably
from about 200.degree. to about 500.degree. C. Preferred solvents include hydrocarbon compounds. In
an additional embodiment, the alkali or alkaline earth metal carbonate, bicarbonate or hydroxide
compound may be added to the contaminated medium in an aqueous solution, wherein the aqueous
solution further contains a high boiling solvent.
The alkali or alkaline earth metal carbonate, bicarbonate or hydroxide is added to the contaminated
medium in an amount of from about 1 to about 20 weight percent, based on the weight of the
contaminated medium. The specific amount of metal compound which is required is dependent on the
level of halogenated or non-halogenated organic contaminant compounds contained in the contaminated
medium. In a preferred embodiment, the metal compound is added in an amount of from about 2 to
about 12 weight percent based on the weight of the contaminated medium. The metal which forms the
carbonate, bicarbonate or hydroxide reagent may be any of the alkali and alkaline earth metals, or
mixtures thereof. Preferred alkali metals include lithium, sodium and potassium with sodium and
potassium being particularly preferred.
The alkali and alkaline earth metal carbonates and bicarbonates are preferred for use in certain systems
owing to their lower corrosive effects as compared with alkali and alkaline earth metal hydroxides.
However, the hydroxide compounds are preferred for use in systems where the contaminated medium is
acidic in nature or comprises a hydrocarbon material.
In accordance with an important feature of the invention, the contaminated medium further contains a
hydrogen donor compound. The hydrogen donor compound provides hydrogen atoms for reaction with
the halogenated and non-halogenated contaminants. The resulting reduced reaction products decompose
to simple hydrocarbon structures. The hydrogen donor compound comprises an organic compound and
may be originally contained in the contaminated medium together with the halogenated or
non-halogenated contaminant. If the contaminated medium does not already contain a hydrogen donor
compound, the hydrogen donor compound may be added to the contaminated medium together with the
alkali or alkaline earth metal carbonate, bicarbonate or hydroxide. In one embodiment, the hydrogen
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donor compound may comprise the high boiling solvent in which the alkali or alkaline earth metal
compound is added to the contaminated medium. Suitable hydrogen donor compounds include fatty
acids, aliphatic alcohols or hydrocarbons, amines and the like. In order to activate these compounds to
produce free radical hydrogen, a source of carbon must be added either in solution or suspension. An
inexpensive carbon source which is water soluable and suitable for use in the invention comprises a
carbohydrate, for example sucrose.
After addition of the alkali or alkaline earth metal compound, the contaminated medium containing the
hydrogen donor compound is heated at a temperature and for a time sufficient to totally dehydrate the
medium, i.e., to remove 100 weight percent of the water contained therein. This heating step may be
performed at atmospheric pressure or at reduced or elevated pressures if so desired. As noted above, the
water which is included in the aqueous solution allows homogeneous distribution of the alkali or
alkaline earth metal compound throughout the medium and acts as a wetting agent and a penetrant.
Moreover, when the water is removed from the medium during the dehydration step, the metal
compound is then concentrated to a very reactive state yet is well distributed throughout the
contaminated medium. As will be apparent, when the contaminated medium is a liquid, addition of the
metal compound in solution is not required for even distribution of the compound throughout the
medium.
After dehydration, the medium is further heated at a temperature between about 200.degree. and
400.degree. C. for a time sufficient to effect reductive decomposition of the halogenated and
non-halogenated organic contaminant compounds. More preferably, the medium is heated at a
temperature between about 280.degree. and 350.degree. C. to effect reductive decomposition of the
halogenated and non-halogenated organic compounds. This step may be conducted at atmospheric
pressure or at reduced or elevated pressures. The time required for decomposition of the halogenated
organic compounds similarly depends upon the level of such compounds in the contaminated material.
Generally however, a time period of from about 0.5 to about 2 hours is sufficient.
When the contaminated medium is heated at a temperature of from 200.degree. to 400.degree. C., the
carbon source (i.e., a carbohydrate such as sucrose) acts as a catalyst for the formation of a reactive
hydrogen ion from the hydrogen donor compound. This catalyzed reaction is represented by the
following reaction formula: ##STRl## wherein R is the hydrogen donor compound, Mis the metal
compound, Carbon* is the source of carbon, for example a carbohydrate, and H is the free radical
hydrogen. The reactive free radical hydrogen ion then reacts with the halogenated organic contaminant
compounds contained in the contaminated medium according to the following reaction: ##STR2##
wherein R-X is the halogenated organic contaminant, X being the halogen atom, and R-H is the reduced
form of the contaminant compound.
Thus, the alkali or alkaline earth metal carbonate, bicarbonate or hydroxide catalyzes the dehalogenation
and reduction of both the halogenated and non-halogenated contaminants.
Finally, the medium is treated with an acid for neutralization. Preferably, the acid is added in amount
sufficient to provide the medium with a pH value of from about 7 to about 9. Suitable acids for use in
the invention comprise sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid. With the
exception of hydrochloric acid, these acids not only neutralize the medium but also provide valuable soil
fertilizers, for example Na.sub.2 SO.sub.4 or sodium sulfate from use of sulfuric acid, NaH.sub.2
PO.sub.4, Na.sub.2 HPO.sub.4, Na.sub.3 PO.sub.4 or sodium phosphates from the use of phosphoric
acid, and NaNO.sub.3 or sodium nitrate from the use of nitric acid, given that sodium is employed as the
alkali metal. If potassium is used, then the potassium salts are produced. The resulting medium may then
be safely returned to its original environment if desired.
In an alternate embodiment of the methods of the present invention, halogenated and non-halogenated
contaminants which may be stripped from contaminated mediums are collected in a condensate and
extracted in high boiling point oil. The contaminants may then be destroyed by use of the present
methods wherein an alkali or alkaline earth metal carbonate, bicarbonate or hydroxide, a hydrogen donor
compound and a carbon source are added to the contaminant and the resulting mixture is heated at a
temperature of 200.degree. to 400.degree. C.
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Generally, oxygen is not a detriment to the methods of the present invention and therefore air need not
be excluded. When applied to the decontamination of hydrocarbon fluids, either aliphatic or aromatic, it
may be desirable to exclude air in order to prevent ignition of the hydrocarbon. Thus, the present
methods may be performed either in the presence or the absence of an oxygen-containing atmosphere.
Because the present methods employ relatively small amounts of alkali or alkaline earth metal
compounds, and solvent if used, there is no need to recover excess reagents for reuse. Moreover, because
the present invention employs water to wet the contaminated medium and to distribute the alkali or
alkaline earth metal compounds therein, the present methods are significantly less costly than prior art
methods which employ polyethylene glycol to wet the contaminated medium. The present methods may
be performed in either a continuous or a batch system, and, if desired, all steps may be performed in a
single reactor. As will be demonstrated in the Examples, the methods of the invention decompose the
halogenated organic compounds, particularly haloaromatic, and cyclic aliphatic compounds, to
nondetectable levels. Additionally, the products of the present methods are non-mutagenic,
non-teratogenic and non-toxic to life forms.
Moreover, the base-catalyzed decomposition methods according to the present invention are
advantageous in that decomposition of both halogenated and non-halogenated contaminant compounds
is achieved to higher degrees in less time as compared with the prior art methods employing reagents
derived from the reaction of alkali metal hydroxides and polyethylene glycol. The methods according to
the present invention are also advantageous over such prior art methods in that the prior art methods
could not be employed to effectively decompose or remove non-halogenated organic contaminants from
contaminated mediums.
The methods of the present invention are demonstrated in the following Examples:
EXAMPLE 1
This example demonstrates the application of the methods according to the present invention to a
contaminated liquid material. Fifty ml of a contaminated high boiling aliphatic solvent material
containing 10% aldrin was mixed with an aqueous solution formed from 10 grams of sodium
bicarbonate and 10 ml of water containing 1 gram of sucrose. The solvent material served as the
hydrogen donor compound. The mixture was agitated by stirring and was heated to 290.degree. to
320.degree. C. for approximately one to two hours. The aldrin concentration rapidly fell to below
detectable limits, thus resulting in an aldrin-free solvent.
EXAMPLE2
This example demonstrates the application of the methods according to the present invention to
treatment of contaminated soil. One hundred grams of contaminated soil containing 2,200 ppm Aroclor
1260, 1,000 ppm Aroclor 1242, 1,000 ppm ofpentachlorophenol, 1,000 ppm of dieldrine, 1,000 ppm of
lindane and 500 ppm of the non-halogenated compound 2-phenylnaphthalene were supplied to a
chemical reactor system. Approximately 5 grams of sodium bicarbonate (5 weight percent of the
contaminated medium) and one ml of a high boiling point aliphatic hydrocarbon solvent were added to
the soil in a solution of 20 ml of water containing 1 gram of sucrose. The solvent served as the hydrogen
donor compound. The resulting mixture was slurried and heated such that the water contained in the
system was distilled off. The reaction system was then further heated to a temperature of approximately
290.degree. to 340.degree. C. for a period of from 0.25 to 1.5 hours. At about 0.25 hours and a
temperature of 340.degree. C., residuals in the soil were less than one ppm for all pollutants. The
2-phenylnaphthalene was reduced to a cyclic hydrocarbon which distilled out of the reaction flask.
EXAMPLE3
This example further demonstrates the reducing power of the present methods applied to a
polychlorinated biphenyl mixture. To a 50 ml portion of a high boiling aliphatic solvent (Boiling Point
• Range 340.degree.-390.degree. C.) was added 1.0 gram of neet Aroclor 1260. This material was placed
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in a 200 ml round bottom flask equipped with stirrer, and 5 grams of sodium hydroxide and 2 grams of
sucrose were added. The flask was also equipped with a fractionating column and condenser with
receiver. The contents of the flask were heated to 350.degree. C. for 2 hours, after which the contents of
the flask were cooled and sampled for residual PCB's. No polychlorinated biphenyls were detected in
this residual oil. A trace of bi phenyl was detected.
The condensate from this reaction which consisted of approximately 1.2 ml of water and 2 ml of an oily
material were also tested for PCB's. The major compound in the condensate was biphenyl with some
minor trace quantities of mono-and di-chlorobiphenyls. Further, the condensate contained low boiling
(100.degree.-200.degree. C.) aliphatic materials which were generated from the high boiling point
aliphatic solvent.
Thus, the methods of the present invention are advantageous for both destruction and removal of
halogenated and non-halogenated organic compounds from a contaminated medium. The methods of the
present invention employ relatively inexpensive compounds, namely, the alkali or alkaline earth metal
carbonates, bicarbonates and hydroxides, optionally high boiling hydrocarbon solvents, and a catalytic
form of carbon obtained from a carbohydrate. The reagents are employed in relatively small amounts as
compared with methods of the prior art. Additionally, the alkali or alkaline earth metal carbonates and
bicarbonates employed in the methods of the present invention are less corrosive than the alkali and
alkaline earth metal hydroxides, although as noted above, the hydroxides may be required in some
instances. Thus, the methods of the present invention provide an improved process for destroying or
reducing halogenated and non-halogenated compounds to non-detectable levels. The products produced
by the present methods are simple lower molecular weight materials, for example, hydrocarbons,
alkanes, alcohols and the like, which are non-mutagenic, non-teratogenic and non-toxic to life forms.
The preceding examples are set forth to illustrate specific embodiments of the invention, and are not
intended to limit the scope of the methods of the present invention. Additional embodiments and
advantages within the scope of the claimed invention will be apparent to one of ordinary skill in the art.
:NI■
1■r,,1,,J■
* * * * *
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United States Patent (19J
Rogers et al.
[54) METHOD FOR THE BASE-CATALYZED
DECOMPOSITION OF HALOGENATED
AND NON-HALOGENATED ORGANIC
COMPOUNDS IN A CONTAMINATED
MEDIUM
(75] Inventors: Charles J. Rogers; Alfred Kornel,
both of Cincinnati; Harold L. Sparks,
Fayetteville, all of Ohio
(73] Assignee: The United States of America as
represented by the Administrator of
the Environmental Protection
Agency, Washington, D.C.
(21]
[22]
[63]
(51)
(52]
[58)
[56]
Appl. No.: 620,127
Filed: Nov. 30, 1990
Related U.S. Application Data
Continuation-in-part of Ser. No. 515,892, Apr. 27,
1990.
Int. CJ.5 .............................................. CIOG 17/00
U.S. 0. .............................. 208/262.5; 208/262.1;
208/13; 210/909; 134/10; 134/26; 134/27;
134/28; 134/42; 423 /659; 423/DIG. 20;
502/25; 502/27; 502/5 I 5
Field of Search ....................... 134/26, 27, 28, 42;
208/262.1, 262.5; 210/909; 502/515, 25, 27;
423/659, DIG. 20
References Cited
U.S. PA TENT DOCUMENTS
4,246,255 12/1981 Grantham .
4.327.027 4/1982 Howard .............................. 260/340
4.337,368 6/1982 Pytlewski et al. .................. 568/730
4,349.380 9/1982 Pytlewski et al. .................... 75/117
4,351,718 9/1982 Brunelle .............................. 208/262
4,353,793 10/1982 Brunelle .............................. 208/262
4,400,552 8/1983 Pytlewski ............................ 568/715
4,417,977 11 /1983 Pytlewski et al. .................. 208/262
4,430.208 2/1984 Pytlewski et al. .................. 208/262
4,447,541 5/1984 Peterson .............................. 435/170
4.460, 797 7 / 1984 Pytlewski et al. .. ................ 568/715
4.471,143 9/1984 Pytlewski et al. .................. 568/715
4,483,7 16 10/1984 Heller ...................................... 137/7
4.523,043 1/1985 Pytlewski et al. .................. 568/910
4,574,013 3/1986 Peterson .................................. 134/2
[1 I] Patent Number:
[45] Date of Patent:
5,064,526
Nov. 12, 1991
4,602.994 6/1986 Pytlewski et al. .................. 208/262
4,631.1 83 12/1986 Lalancette et al. .
4,663 ,027 5/ 1987 Mendiratta .......................... 208/262
4,675,464 6/1987 Rogers et al. ....................... 585/538
4,685,220 8/1987 Meenan ................................... 34/10
4,761.221 8/1988 Rossi ................................... 208/262
4,792,407 12/1988 Zeff et al. ............................ 210/748
4,793 ,937 12/1988 Meenan ............................... 310/171
4,801,384 1/1989 Steiner .................................. 134/42
4,841,998 6/1989 Bruya .................................. 210/909
4,869,825 9/1989 Steiner .
FOREIGN PATENT DOCUMENTS
11 8858 9/1984 European Pat. Off.
OTHER PUBLICATIONS
Chemical Abstracts. vol. 82, No. I 39620p (1975).
Kornel et al., Journal of Hazardous Materials, 12 ( 1985),
pp. 161-176.
Primary Examiner-Helane E. Myers
(57) ABSTRACT
A method for the decomposition of halogenated and
non-halogenated organic contaminant compounds con-
tained in a contaminated medium comprises adding an
alkali or alkaline earth metal carbonate, bicarbonate or
hydroxide to the contaminated medium in an aqueous
solution or in a solvent having a boiling point of at least
200° C., or in the form of a solid dispersion or suspen-
sion. The medium includes a hydrogen donor com-
pound. The hydrogen donor compound may be origi-
nally contained in the medium or may be added to the
medium. The medium further includes a catalytic
source of carbon, for example, a carabohydrate, which
will cause formation of a free radical hydrogen ion from
the hydrogen donor compound. The medium is heated
to dehydrate the medium and then is further heated at a
temperature between about 200° and 400' C. to cause
formation of the free radical hydrogen ion and effect
reductive decomposition of the halogenated and non-
halogenated organic contaminant compounds. An acid
is then added to the medium in an amourit sufficient to
neutralize the same.
23 Claims, No Drawings
Copy provided by PTCS from the PTO A.PS lmaite Data Baw on 03/05/1999
5,064,526
1 2
sulfoxide catalyst produces odorous compounds when
heated to high temperatures and decomposes into com-
bustible byproducts under elevated temperature condi-
tions. This process is also disadvantageous in that it
METHOD FOR THE BASE-CATALYZED
DECOMPOSffiON OF HALOGENATED AND
NON-HALOGEN A TED ORGANIC COMPOUNDS
IN A CONTAMINATED MEDIUM 5 requires large amounts of reagents.
RELATED APPLICATIONS
This application is a continuation-in-part of the Ro-
gers et al copending application Ser. No. 07/515,892
filed Apr. 27, 1990. 10
FIELD OF THE INVENTION
The Rogers et al U.S. Pat. No. 4,675,464 discloses a
method for the chemical destruction of halogenated
aliphatic hydrocarbons, and more particularly a method
for the chemical destruction of ethylene dibromide. An
alkali metal hydroxide is dissolved in an ethylene glycol
and the resulting product is reacted with the haloge-
The present invention relates to a method for the
base-catalyzed decomposition of halogenated and non-
halogenated organic contaminant compounds contained
in a contaminated medium. More particularly, the in-
vention relates to a method for both the decomposition
and removal of halogenated and non-halogenated or-
ganic compounds contained in a contaminated medium
by use of an alkali or alkaline earth metal carbonate,
bicarbonate or hydroxide, and an organic hydrogen
donor compound in the presence of a carbohydrate.
nated hydrocarbon. Rogers et al further disclose that
the reaction temperature should be maintained at 30' C.
or less to maintain the reaction products in solution. 15 The Rogers et al copending application Ser. No.
BACKGROUND OF THE INVENTION
07 /350,425 discloses a method for the destruction of
halogenated organic compounds in a contaminated me-
dium wherein an aqueous solution containing from
about 0.1 to about 20 weight percent polyethylene gly-20 col is added to a contaminated medium. An alkali metal
hydroxide is also added to the contaminated medium,
and the contaminated medium is heated at a tempera-
ture and for a time sufficient to dehydrate the medium.
The hazards to public health and the environment 25
which are posed by a variety of synthetic halogenated
organic compounds are well known. Compounds such
as polychlorinated biphenyls (PCB's), dibenzodioxins,
dibenzofurans, dichlorodiphenyl trichloroethane
(DDT), dieldrin, lindane and chlordane, as well as other 30
halogenated pesticides, have been found to be persis-
tent, environmentally toxic materials which require safe
and efficient means of disposal. PCB's pose a particu-
larly serious disposal problem. Once widely used as
dielectric fluid additives in electrical equipment such as 35
transformers and capacitors because of their excellent
insulating properties, the use of PCB's in many applica-
tions has been banned by the U.S. Environmental Pro-
tection Agency owing to the cumulative storage of
PCB's in the human body and the extremely high toxic-40
ity of PCB's. Thus, methods for the removal and/or
destruction of halogenated organic compounds such as
PCB's are required.
Various methods for the destruction or decomposi-
tion of halogenated organic compounds are known in 45
the art. For example, the Peterson U.S. Pat. Nos.
4,447,541 and 4,574,013 disclose methods for decontam-
inating soil which is contaminated with halogenated
organic compounds. The Peterson U.S. Pat. No.
4,447,541 discloses a process in which a reagent mixture 50
of an alkaline constituent and a sulfoxide catalyst
(DMSO) are intimately mixed with soil contaminated
with PCB's. The reagent mixture affects a desorption of
the halogenated contaminants from the soil and subse-
quently dehalogenates the contaminants. However, this 55
process is disadvantageous in that the kinetics are rela-
tive! y slow and therefore reduction of the PCB concen-
tration to an acceptable level requires extended time
periods ranging from weeks to months, the soil must be
completely dry for the destruction to take place, large 60
quantities of the reagent are required, and the sulfoxide
catalyst may potentially transport contaminants prior to
their destruction. The Peterson U.S. Pat. No. 4,574,013
discloses a process wherein a heated slurry of contami-
nated soil is treated with a mixture of an alkaline constit-65
uent and a sulfoxide catalyst. However, this process is
similarly disadvantageous in that the sulfoxide catalyst
may transport contaminants into living systems, and the
The medium is further heated at a temperature of be-
tween about 100' and 350' C. for a time sufficient to
effect destruction of the halogenated organic com-
pounds, and an acid is added to the medium in an
amount sufficient to provide the medium with a pH of
from about 7 to about 9.
The Rogers et al copending application Ser. No.
07 /515,892 discloses a method for the decomposition of
halogenated organic compounds contained in a contam-
inated medium wherein an aqueous solution of an alkali
metal carbonate or bicarbonate is added to the contami-
nated medium, and the medium is heated to a tempera-
ture between about 250' and 400' C.
The Pytlewski et al U.S. Pat. No. 4,400,552 discloses
a method for the decomposition of halogenated organic
compounds which employs a reagent comprising the
product of the reaction of an alkali metal hydroxide
with a polyglycol or a polyglycol monoalkyl ether, and
oxygen. The Pytlewski et al U.S. Pat. Nos. 4,337,368
and 4,602,994 disclose similar methods of decomposing
halogenated organic compounds. Additionally, the Pyt-
lewski . et al U.S. Pat. Nos. 4,430,208, 4,417,977,
4,460,797 and 4,471,143 also disclose methods for sepa-
ration and/or decomposition of halogenated organic
compounds. However, these methods are disadvanta-
geous in that excess amounts of the alkali metal hydrox-
ide and polyglycol reagents are required in order to
obtain a homogeneous distribution throughout the con-
taminated material, for example soil, sediment, sludge
or the like, which is treated. The Pytlewski et al U.S.
Pat. Nos. 4,349,380 and 4,523,043 disclose the use of
reagents made from an alkali metal or alkali metal hy-
droxide and a polyglycol or a polyglycol monoalkyl
ether for removing metals from metal-containing mate-
rials and for decomposing organo sulfur compounds,
respectively. Similarly, the Brunelle U.S. Pat. Nos.
4,351,718 and 4,353,793 disclose methods for removing
polyhalogenated hydrocarbons from nonpolar organic
solvent solutions by treating the contaminated solutions
with a mixture of polyethylene glycol and an alkali
metal hydroxide. These methods are similarly disadvan-
tageous in that excess amounts of reagent are required.
Additional methods for removing and/or destructing
halogenated organic compounds contained in contami-
Copy provided by PTCS from the PTO APS IJnaxe Data Baw on 03/05/1999
,.. 5,064,526
3
nated materials are disclosed in the Howard et al U.S .
Pat. No. 4,327,027, the Heller U.S. Pat. No. 4,483,716,
the Mendiratta et al U.S. Pat. No. 4,663,027, the Mee-
nan et al U.S. Pat. Nos. 4,685,220 and 4,793,937, the
Rossi et al U.S. Pat. No. 4,761,221, the Zeff et al U.S. 5
Pat. No. 4,792,407, European Patent Application No.
118,858, Chemical Abstracts, Vol. 82, No. 39620P (1975)
and Kamel et al, Journal of Hazardous Materials, 12
( 1985), pages 161-176. However, many of these and
additional processes known in the art for the removal 10
and/or destruction of halogenated organic compounds
in contaminated materials are inadequate in view of the
time required for acceptable levels of removal and/or
destruction, the use of excessive amounts of various
reagents, the use of expensive reagents,. the production IS
of toxic and/or combustible byproducts, and/or the
failure to obtain desired removal and/or destruction
levels. Thus, a need exists for improved, cost effective
methods for the removal, reduction and stripping of
non-halogenated compounds from and the dehalogena-20
tion of halogenated organic compounds in contami-
nated materials, which methods overcome the disad-
vantages of the prior art.
4
carbon may comprise a carbohydrate. Upon heating of
the contaminated medium," the carbohydrate decom-
poses and causes formation of a free radical hydrogen
ion from the hydrogen donor compound. The free radi-
cal hydrogen ion is thereby generated in situ, i.e. in the
medium to be treated, and acts as the reducing agent for
the halogenated and non-halogenated contaminant
compounds. Accordingly, according to the methods of
the present invention, the contaminated medium is then
heated at a temperature and for a time sufficient to
dehydrate the medium. Although the water is removed,
the alkali or alkaline earth metal compound and the
hydrogen donor -compound are well distributed
throughout the medium and are concentrated to a very
reactive state. After dehydration, the medium is then
further heated at a temperature between about 200° and
400° C. for a time sufficient to effect hydrogen transfer
from the donor compQund to the contaminants, both
halogenated and non-halogenated. The reduced con-
taminants decompose to simple hydrocarbon structures.
Decomposition of the halogenated and non-
halogenated compounds in the contaminated medium is
more dependent on the ease of hydrogen donation by
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention
25 the donor compound (which is catalyzed by the decom-
posed carbohydrate) as the temperature increases
within the aforementioned range. Finally, an acid is
added to the medium in an amount sufficient to neutral-
ize the medium so that it may be returned to its original
to provide new methods for the reductive decomposi-
tion and removal of halogenated and non-halogenated
organic compounds contained in a contaminated me-
dium. It is an additional object of the invention to pro-30
vide methods for the reductive decomposition and re-
moval of halogenated and non-halogenated organic
compounds contained in a contaminated medium,
which methods employ at least one hydrogen donor
compound. It is a further object of the invention to 35
provide methods for the decomposition and removal of
halogenated and non-halogenated organic compounds
contained in a contaminated medium which employ
significantly less amounts of reagent and which employ
lower costing reagents, as compared with prior art 40
methods. It is a further object of the invention to pro-
vide such methods wherein environmentally acceptable
levels of halogenated and non-halogenated organic con-
taminant compounds are achieved in the treated materi-
als. It is a related object of the invention to provide such 45
methods wherein the environmentally acceptable levels
of contaminants in the materials are obtainable within a
short period of time.
These and additional objects are achieved by the
present invention which relates to methods for the base-50
catalyzed decomposition of halogenated and non-
halogenated organic compounds contained in a contam-
inated medium. The methods of the invention comprise
the steps of adding an alkali metal or alkaline earth
metal carbonate, bicarbonate or hydroxide to a contam-55
inated medium containing the halogenated or non-
halogenated organic contaminant compounds. The al-
kali or alkaline earth metal carbonate, bicarbonate or
hydroxide may be in an aqueous solution which distrib-
utes the metal compound throughout the medium and 60
acts as a wetting agent, or in a solvent, or may be added
as a solid dispersion or suspension. The contaminated
medium further contains a hydrogen donor compound
and a catalytic form of carbon which will cause forma-
tion of a free radical hydrogen ion from the organic 65
hydrogen donor compound. For example, the organic
hydrogen donor compound may comprise a high boil-
ing point aliphatic solvent and the catalytic form of
environment. Because the aqueous solution or solvent is
employed, the amount of alkali or alkaline earth metal
compound which is required for the present methods is
significantly reduced as compared with prior art meth-
ods. Additionally, because the metal compound is well
distributed throughout the medium by the aqueous solu-
tion, a uniform destruction or reduction of the haloge-
nated and non-halogenated organic compounds is
achieved. Moreover, because lower amounts of metal
compounds are employed, recycling of excess reagents
is not required. Finally, the present methods employing
an alkali metal carbonate or bicarbonate are advanta-
geous in that these compounds are less corrosive than
the alkali metal hydroxides and require Jess acid for
neutralization.
These and additional objects and advantages will
become more fully understood in view of the following
detailed description.
DETAILED DESCRIPTION
The present invention comprises methods for the
decomposition and removal of halogenated and non-
halogenated organic compounds contained in a contam-
inated medium. The contaminated medium may com-
prise soil, sludge, sediment or a liquid. The present
methods are particularly adapted for use with soils,
sludges and sediments. The methods are suitable for use
with mediums which contain up to 100,000 ppm of
halogenated organic compounds, aliphatic or aromatic,
for example PCB's, or even higher levels of the haloge-
nated organic compounds, and for use with mediums
which contain up to 100,000 ppm of non-halogenated
organic contaminants. The contaminated mediums
which are suitable for use in the invention may also
include an absorbent or adsorbent, for example spent
activated carbon or the like. Additionally, the methods
of the invention may be used for the treatment of pure
halogenated materials, for example, aldrin, dieldrin and
other halogenated pesticides. •
Copy provided. by PTCS from the PTO APS lma&e Data Bmie on 03/05/1999
5,064,526
5
Generally, the methods of the invention comprise
adding an alkali or alkaline earth metal carbonate, bicar-
bonate or hydroxide, or a mixture thereof, to the con-
taminated medium containing one or more halogenated
6
the like. In order to activate these compounds to pro-
duce free radical hydrogen, a source of carbon must be
added either in solution or suspension. An inexpensive
carbon source which is water soluable and suitable for
or non-halogenated organic contaminant compounds.
The alkali or alkaline earth metal carbonate, bicarbon-
5 use in the invention comprises a carbohydrate, for ex-
ample sucrose.
ate or hydroxide may be added to the contaminated
medium in an aqueous solution or in a high boiling
solvent. Alternatively, the alkali or alkaline earth metal
carbonate, bicarbonate or hydroxide may be added in JO
the form of a solid dispersion or suspension. When the
alkali or alkaline earth metal carbonate, bicarbonate or
hydroxide is added in an aqueous solution, the water
from the aqueous solution assists in distributing the
metal compound homogeneously throughout the con-15
taminated medium. Alternatively, if the metal carbon-
ate, bicarbonate or hydroxide is added with a high boil-
ing solvent, suitable solvents have a boiling point of at
least 200° C., and preferably from about 200° to about
500° C. Preferred solvents include hydrocarbon com-20
pounds. In an additional embodiment, the alkali or alka-
line earth metal carbonate, bicarbonate or hydroxide
compound may be added to the contaminated medium
in an aqueous solution, wherein the aqueous solution
further contains a high boiling solvent. 25
The alkali or alkaline earth metal carbonate, bicar-
bonate or hydroxide is added to the contaminated me-
dium in an amount of from about I to about 20 weight
percent, based on the weight of the contaminated me-
dium. The specific amount of metal compound which is 30
required is dependent on the level of halogenated or
non-halogenated organic contaminant compounds con-
tained in the contaminated medium. In a preferred em-
bodiment, the metal compound is added in an amount of
from about 2 to about 12 weight percent based on the 35
weight of the contaminated medium. The metal which
forms the carbonate, bicarbonate or hydroxide reagent
may be any of the alkali and alkaline earth metals, or
mixtures thereof. Preferred alkali metals include lith-
ium, sodium and potassium with sodium and potassium 40
being particularly preferred.
After addition of the alkali or alkaline earth metal
compound, the contaminated medium containing the
hydrogen donor compound is heated at a temperature
and for a time sufficient to totally dehydrate the me-
dium, i.e., to remove 100 weight percent of the water
contained therein. This heating step may be performed
at atmospheric pressure or at reduced or elevated pres-
sures if so desired. As noted above, the water which is
included in the aqueous solution allows homogeneous
distribution of the alkali or alkaline earth metal com-
pound throughout the medium and acts as a wetting
agent and a penetrant. Moreover, when the water is
removed from the medium during the dehydration step,
the metal compound is then concentrated to a very
reactive state yet is well distributed throughout the
contaminated medium. As will be apparent, when the
contaminated medium is a liquid, addition of the metal
compound in solution is not required for even distribu-
tion of the compound throughout the medium.
After dehydration, the medium is further heated at a
temperature between about 200° and 400° C. for a time
sufficient to effect reductive decomposition of the halo-
genated and non-halogenated organic contaminant
compounds. More preferably, the medium is heated at a
temperature between about 280° and 350° C. to effect
reductive decomposition of the halogenated and non-
halogenated organic compounds. This step may be con-
ducted at atmospheric pressure or at reduced or ele-
vated pressures. The time required for decomposition of
the halogenated organic compounds similarly depends
upon the level of such compounds in the contaminated
material. Generally however, a time period of from
about 0.5 to about 2 hours is sufficient.
When the contaminated medium is heated at a tem-
perature of from 200° to 400° C., the carbon source (i.e.,
a carbohydrate such as sucrose) acts as a catalyst for the
formation of a reactive hydrogen ion from the hydro-
The alkali and alkaline earth metal carbonates and
bicarbonates are preferred for use in certain systems
owing to their lower corrosive effects as compared with
alkali and alkaline earth metal hydroxides. However,
the hydroxide compounds are preferred for use in sys-
tems where the contaminated medium is acidic in nature
45 gen donor compound. This catalyzed reaction is repre-
sented by the following reaction formula:
or comprises a hydrocarbon material.
In accordance with an important feature of the inven-
tion, the contaminated medium further contains a hy-50
drogen donor compound. The hydrogen donor com-
pound provides hydrogen atoms for reaction with the
halogenated and non-halogenated contaminants. The
resulting reduced reaction products decompose to sim-
ple hydrocarbon structures. The hydrogen donor corn-55
pound comprises an organic compound and may be
originally contained in the contaminated medium to-
gether with the halogenated or non-halogenated con-
taminant. If the contaminated medium does not already
contain a hydrogen donor compound, the hydrogen 60
donor compound may be added to the contaminated
medium together with the alkali or alkaline earth metal
carbonate, bicarbonate or hydroxide. In one embodi-
ment, the hydrogen donor compound may comprise the
high boiling solvent in which the alkali or alkaline earth 65
metal compound is added to the contaminated medium.
Suitable hydrogen donor compounds include fatty
acids, aliphatic alcohols or hydrocarbons, amines and
R M 200-400" C. > R" H M+ + Carbon• + + ·
wherein R is the hydrogen donor compound, M is the
metal compound, Carbon• is the source of carbon, for
example a carbohydrate, and H is the free radical
hydrogen. The reactive free radical hydrogen ion then
reacts with the halogenated organic contaminant com-
pounds contained in the contaminated medium accord-
ing to the following reaction:
H + R-X + M + 200-400" C. > R-H + MX
wherein R-X is the halogenated organic contaminant, X
being the halogen atom, and R-H is the reduced form of
the contaminant compound.
Thus, the alkali or alkaline earth metal carbonate,
bicarbonate or hydroxide catalyzes the dehalogenation
and reduction of both the halogenated and non-
halogenated contaminants.
Copy provided by PTCS from the PTO APS lmaite Data B-on 03/05/1999
5,064,526
7
Finally, the medium is treated with an acid for neu-
tralization. Preferably, the acid is added in amount suffi-
cient to provide the medium with a pH value of from
about 7 to about 9. Suitable acids for use in the invention
comprise sulfuric acid, phosphoric acid, hydrochloric 5
acid and nitric acid. With the exception of hydrochloric
acid, these acids not only neutralize the medium but also
provide valuable soil fertilizers, for example Na2SO4 or
sodium sulfate from use of sulfuric acid, NaH2PO4,
Na2HPO4, Na3PO4 or sodium phosphates from the use 10
of phosphoric acid, and NaNO3 or sodium nitrate from
the use of nitric acid, given that sodium is employed as
the alkali metal. If potassium is used, then the potassium
salts are produced. The resulting medium may then be 15 safely returned to its original environment if desired.
8
EXAMPLE I
This example demonstrates the application of the
methods according to the present invention to a con-
taminated liquid material. Fifty ml of a contaminated
high boiling aliphatic solvent material containing 10%
aldrin was mixed with an aqueous solution formed from
10 grams of sodium bicarbonate and 10 ml of water
containing 1 gram of sucrose. The solvent material
served as the hydrogen donor compound. The mixture
was agitated by stirring and was heated to 290" to 320'
C. for approximately one to two hours. The aldrin con-
centration rapidly fell to below detectable limits, thus
resulting in an aldrin-free solvent.
EXAMPLE 2
This example demonstrates the application of the
methods according to the present invention to treat-
ment of contaminated soii. One hundred grams of con-
In an alternate embodiment of the methods of the
present invention, halogenated and non-halogenated
contaminants which may be stripped from contami-
nated mediums are collected in a condensate and ex-
tracted in high boiling point oil. The contaminants may
then be destroyed by use of the present methods
wherein an alkali or alkaline earth metal carbonate,
bicarbonate or hydroxide, a hydrogen donor compound
and a carbon source are added to the contaminant and
the resulting mixture is heated at a temperature of 200°
to 400° C.
20 taminated soil containing 2,200 ppm Aroclor 1260,
1,000 ppm Aroclor 1242, 1,000 ppm of pentachlorophe-
nol; l,000 ppm of dieldrine, 1,000 ppm of lindane and
500 ppm of the non-halogenated compound 2-phenyl-
naphthalene were supplied to a chemical reactor sys-
Generally, oxygen is not a detriment to the methods
of the present invention and therefore air need not be
excluded. When applied to the decontamination of hy-
drocarbon fluids, either aliphatic or aromatic, it may be
desirable to exclude air in order to prevent ignition of
25 tern. Approximately 5 grams of sodium bicarbonate (5
weight percent of the contaminated medium) and one
ml of a high boiling point aliphatic hydrocarbon solvent
were added to the soil in a solution of 20 ml of water
containing I gram of sucrose. The solvent served as the
the hydrocarbon. Thus, the present methods may be
performed either in the presence or the absence of an
oxygen-containing atmosphere.
30 hydrogen donor compound. The resulting mixture was
slurried and heated such that the water contained in the
system was distilled off The reaction system was then
further heated to a temperature of approximately 290'
to 340° C. for a period of from 0.25 to 1.5 hours. At
35 about 0.25 hours and a temperature of 340' C., residuals
in the soil were less than one ppm for all pollutants. The
2-phenylnaphthalene was reduced to a cyclic hydrocar-
bon which distilled out of the reaction flask.
Because the present methods employ relatively small
amounts of alkali or alkaline earth metal compounds,
and solvent if used, there is no need to recover excess
reagents for reuse. Moreover, because the present in-
vention employs water to wet the contaminated me-40
dium and to distribute the alkali or alkaline earth metal
compounds therein, the present methods are signifi-
cantly less costly than prior art methods which employ
polyethylene glycol to wet the contaminated medium.
The present methods may be performed in either a 45
continuous or a batch system, and, if desired, all steps
may be performed in a single reactor. As will be demon-
strated in the Examples, the methods of the invention
decompose the halogenated organic compounds, partic-50 ularly haloaromatic, and cyclic aliphatic compounds, to
nondetectable levels. Additionally, the products of the
present methods are non-mutagenic, non-teratogenic
and non-toxic to life forms.
Moreover, the base-catalyzed decomposition meth-55 ods according to the present invention are advanta-
geous in that decomposition of both halogenated and
non-halogenated contaminant compounds is achieved
EXAMPLE 3
This example further demonstrates the reducing
power of the present methods applied to a poly-
chlorinated biphenyl mixture. To a 50 ml portion of a
high boiling aliphatic solvent (Boiling Point Range
340° -390' C.) was added 1.0 gram of neet Aroclor 1260.
This material was placed in a 200 ml round bottom flask
equipped with stirrer, and 5 grams of sodium hydroxide
and 2 grams of sucrose were added. The flask was also
equipped with a fractionating column and condenser
with receiver. The contents of the flask were heated to
350° C. for 2 hours, after which the contents of the flask
were cooled and sampled for. residual PCB's. No poly-
chlorinated biphenyls were detected in this residual oil.
A trace of biphenyl was detected. •
The condensate from this reaction which consisted of
approximately 1.2 ml of water and 2 ml of an oily mate-
rial were also tested for PCB's. The major compound in
the condensate was biphenyl with some minor trace
quantities of mono-and di-chlorobiphenyls. Further, to higher degrees in less time as compared with the
prior art methods employing reagents derived from the
reaction of alkali metal hydroxides and polyethylene
glycol. The methods according to the present invention
are also advantageous over such prior art methods in
that the prior art methods could not be employed to
efTectively decompose or remove non-halogenated or-
ganic contaminants from contaminated mediums.
60 the condensate contained low boiling (100°-200° C.)
aliphatic materials which were generated from the high
boiling point aliphatic solvent.
The methods of the present invention are demon-
strated in the following Examples:
Thus, the methods of the present invention are advan-
tageous for both destruction and removal of haloge-
65 nated and non-halogenated organic compounds from a
contaminated medium. The methods of the present
invention employ relatively inexpensive compounds,
namely, the alkali or alkaline earth metal carbonates,
Copy provided by PTCS from the PTO APS ~e Data Bmie on 03/05/1999
5,064,526
9
bicarbonates and hydroxides, optionally high boiling
hydrocarbon solvents, and a catalytic form of carbon
obtained from a carbohydrate. The reagents are em-
ployed in relatively small amounts as compared with
methods of the prior art. Additionally, the alkali or 5
alkaline earth metal carbonates and bicarbonates em-
ployed in the methods of the present invention are less
corrosive than .the alkali and alkaline earth metal hy-
droxides, although as noted above, the hydroxides may 10 be required in some instances. Thus, the methods of the
present invention provide an improved process for de-
stroying or reducing halogenated and non-halogenated
compounds to non-detectable levels. The products pro-
duced by the present methods are simple lower molecu-15
lar weight materials, for example, hydrocarbons, al-
kanes, alcohols and the like, which are non-mutagenic,
non-teratogenic and non-toxic to life forms.
10
4. A method as defined in claim 1. wherein the alkali
or alkaline earth metal compound is added as a suspen-
sion in a solvent having a boiling point of at least 200' C.
5. A method as defined in claim 4, wherein the sol-
vent comprises a hydrocarbon compound.
6. A method as defined in claim 1, wherein the alkali
or alkaline earth metal compound is added as a solid
suspension.
7. A method as defined in claim 1, wherein the alkali
or alkaline earth metal compound is added in an amount
of from about I to about 20 weight percent based on the
weight of the contaminated medium.
8. A method as defined by claim 7, wherein the alkali
or alkaline earth metal compound is added in an amount
of from about 2 to about 12 weight percent based on the
weight of the contaminated medium.
9. A method as defined by claim 1, wherein the cata-
lytic form of carbon comprises a carbohydrate which
decomposes to form a free radical hydrogen ion from
the hydrogen donor compound.
10. A method as defined by claim 9, wherein the
carbohydrate comprises sucrose.
The preceding examples are set forth to illustrate
specific embodiments of the invention, and are not in-20
tended to limit the scope of the methods of the present
invention. Additional embodiments and advantages
within the scope of the claimed invention will be appar-11. A method as defined by claim 1, wherein the
contaminated medium is heated under vacuum to dehy-
25 drate the medium.
ent to one of ordinary skill in the art.
What is claimed is:
1. A method for the reductive decomposition of halo-
genated or non-halogenated organic contaminant com-
pounds contained in a contaminated medium, compris-
ing 30
(a) adding an alkali or alkaline earth metal carbonate,
bicarbonate or hydroxide to a contaminated me-
dium containing halogenated or non-halogenated
organic contaminant compounds, said alkali or
alkaline earth metal carbonate, bicarbonate or hy-35 droxide being added as an aqueous solution or as a
suspension in a solvent having a boiling point of at
least 200' C., or in the form of a solid suspension,
said contaminated medium further containing a
hydrogen donor compound and a catalytic form of 40
carbon which will form a free radical hydrogen
ion;
12. A method as defined by claim 1. wherein in step
(c) the medium is further heated at a temperature be-
tween about 280" and 400' C. to effect reductive decom-
position of the organic contaminant compounds.
13. A method as defined by claim 1, wherein the acid
which is added to the medium to provide a pH of from
7 to about 9 is selected from the group consisting of
sulfuric acid, phosphoric acid, hydrochloric acid and
nitric acid.
14. A method as defined by claim 1, wherein the
contaminated medium comprises soil.
15. A method as defined by claim 1, wherein the
contaminated medium comprises sludge.
16. A method as defined by claim 1, wherein the
contaminated medium comprises sediment.
17. A method as defined by claim 1, wherein the
contaminated medium includes an absorbent compris0
ing spent activated carbon. (b) heating the contaminated medium at a tempera-
ture and for a time sufficient to dehydrate the me-
dium;
18. A method as defined by claim 1, wherein the
45 contaminated medium comprises a liquid.
(c) further heating the medium at a temperature be-
tween about 200' and 400° C. for a time sufficient
to cause formation of a free radical hydrogen ion
therein and effect reductive decomposition of the
halogenated or non-halogenated organic contami-
nant compounds; and
(d) adding an acid to the medium in an amount suffi-
cient to provide the medium with a pH of from
about 7 to about 9.
2. A method as defined in claim 1, wherein the alkali
or alkaline earth metal compound is added in an aque-
ous solution.
3. A method as defined in claim 2, wherein the aque-
ous solution further contains a hydrocarbon solvent
having a boiling point of at least 200° C.
19. A method as defined by claim 1, wherein the
contaminated medium contains up to 100,000 ppm of
halogenated organic compounds.
20. A method as defined by claim .1, wherein the
50 contaminated medium comprises a pure halogenated
material.
55
21. A method as defined by claim 1, wherein the
medium which results from the acid addition step is
returned to its original environment.
22. A method as defined by claim 1, wherein the
contaminated medium originally contains the hydrogen
donor compound.
23. A method as defined by claim 1, wherein the
hydrogen donor compound is added to the contami-
60 nated medium. • • • • •
65
Copy provided by PTCS from the PTO APS lmaJte Data Base on 03/05/1999
•
Un ited States Patent
Rogers , et al.
5,039,350
August 13, 1991
Method for the decomposition of halogenated organic compounds in a
contaminated medium
Abstract
A method for the decomposition of halogenated organic compounds contained in a
contaminated medium comprises adding an alkali metal carbonate or bicarbonate to the
contaminated medium in an aqueous solution or in a solvent having a boiling point of at
least 200.degree. C., or in the form of a solid dispersion or suspension. The medium is
heated to dehydrate the medium and then is further heated at a temperahire between about
250.degree. and 400.degree. C. to effect decomposition of the halogenated organic
co mpounds. An acid is then added to the medium in an amount sufficient to neutralize the
same.
Inventors: Rogers; Charles J. (Cincinnati, OH); Kornel; Alfred (Cincinnati, OH);
Sparks; Harold L. (Fayetteville, OH)
Ass ignee: The United States of America as represented by the Administrator of the
(Washington, DC)
Appl. No.: 515892
Filed: April 27, 1990
Current U.S. Class:
Intern'! Class:
Field of Search:
4246255
432 7027
433 73 68
4349380
435 17 18
4353793
134/27; 134/10; 134/26; 134/28; 134/42; 208/13;
208/262.1 ; 208/262.5; 210/909; 423/659; 502/25;
502/27; 502/515
B08B 003 /08
134/26,27,28,42 208/262.1,262.5,909 502/515,25,27
423/650,DIG. 20
References Cited !Referenced Bvl
U.S. Patent Documents
Jan., 1981 Grantham 2 10/909.
Apr., 1982 Howard et al. 208/262.
Nov., 1982 Pytlewski 568/730.
Aug., 1982 Pytlewski 75/11 7.
Sep., 1982 Brunelle 208/262.
Oct., 1982 Brunelle 208/262.
,,
4400557 Sep., 1983 Pytlewski 568/715 .
44 16767 Nov., 1983 Jordan 208/262.
44 17977 Oct., 1983 Pytlewski 208/262.
4430208 .Jul., 1984 Pytlewski 208/262.
4447541. May., 1984 Peterson 208/262.
4460797 Sep., 1984 Pytlewski 568/715 .
4471143 Oct., 1984 Pytlewski 568/715.
1.l4837 I 6 Nov., 1984 Heller 137/7.
1+5? 3043 Jun., 1985 Pytlewski 568/910.
45740 13 Apr., 1986 Peterson 134/2.
4602994 Jan., 1986 Pytlewski 208/262.
4()3 l l 83 Dec ., 1986 Lalancette et al. 210/904.
4635220 Aug., 1937 Meenan 34/10.
4662948 May., 1987 Weitzman 134/42.
4663027 May., 1987 Mendiratta 208/262.
4675464 Nov., 1987 Rogers 585/538.
476 1221 Aug., 1988 Rossi et al. 210/904.
4792407 Dec., 1988 Zeff et al. 210/748.
4793937 Dec., 1988 Meenan 210/771.
480 l 384 Jan., 1989 Steiner 134/42.
4841998 .Jun., 1984 Bruya 210/909.
4869825 Sep., 1989 Steiner l 34/26.
Foreign Patent Documents
0118858 Sep., 1984 EP.
Other References
Chemical Abstracts, vol. 82, No. 139620P (1975).
K.ornel et al., .Journal of Hazardous Materials, 12 (1985), pp. 161-176.
Primarv Exam.iner: Myers; Helane E.
Claims
What is claimed is:
..
I . A method for the decomposition of halogenated organic compounds contained in a
contaminated medium, comprising
(,1) adding an alkali metal carbonate or bicarbonate to a contaminated medium containing
halogenated organic compounds, said alkali metal carbonate or bicarbonate being added
as an aqueous solution or in a solvent having a boiling point of at least 200.degree. C., or
in the form of a solid suspension;
( b) heating the contaminated medium at a temperature and for a time sufficient to
substantially dehydrate the medium;
(c) 1·urther heating the medium at a temperature between about 250.degree. and
400.degree. C. for a time sufficient to effect decomposition of the halogenated organic
compounds; and
(d) adding an acid to the medium in an amount sufficient to provide the medium with a
pH of from about 7 to about 9.
2. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is
added in an aqueous solution.
3. A method as defined in claim 2, wherein the aqueous solution further contains a
hydrocarbon solvent having a boiling point of at least 200.degree. C.
4. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is
added in a solvent having a boiling point of at least 200.degree. C.
5. A method as defined in claim 4, wherein the solvent comprises a hydrocarbon
compound.
6. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is
added as a so lid suspension.
7. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is
added in an amount of from about 1 to about 20 weight percent based on the weight of
the contaminated medium.
8. A method as defined by claim 7, wherein the alkali metal carbonate or bicarbonate is
added in an amount of from about 2 to about 12 weight percent based on the weight of
the contaminated medium.
l). A method as defined in claim 1, wherein the alkali metal comprises sodium.
I 0. A method as defined in claim 1, wherein the alkali metal comprises potass ium.
I I . A method as defined in claim 1, wherein the alkali metal comprises lithium.
12 . A method as defined by claim 1, wherein the contaminated medium is heated under
vacuum to dehydrate the medium.
I 3. A method as defined by claim 1, wherein in step ( c) the medium is further heated at a
temperature between about 250.degree. C. and 350.degree. C. to effect destruction of the
halogenated organic compounds.
14. A method as defined by claim 1, wherein the acid which is added to the medium to
provide a pH of from 7 to about 9 is selected from the group consisting of sulfuric acid,
phosphoric acid, hydrochloric acid and nitric acid.
I 5. A method as defined by claim 1, wherein the contaminated medium comprises soil.
16. A method as defined by claim 1, wherein the contaminated medium comprises
sludge.
I 7. A method as defined by claim l , wherein the contaminated medium comprises
sediment.
18. A method as defined by claim 1, wherein the contaminated medium includes an
absorbent comprising spent activated carbon.
I 9. A method as defined by claim 1, wherein the contaminated medium comprises a
liquid.
20. A method as defined by claim l , wherein the contaminated medium contains up to
I 00,000 ppm of halogenated organic compounds.
2 I . A method as defined by claim 1, wherein the contaminated medium comprises a pure
halogenated material.
22 . A method as defined by claim 1, wherein the medium which results from the acid
addition step is returned to its original environment.
Description
FIELD OF THE INVENTION
The present invention relates to a method for the decomposition of halogenated organic
compounds contained in a contaminated medium. More patiicularly, the invention relates
to a method for the decomposition and removal of halogenated organic compounds
con rained in a contaminated medium by use of an alkali metal carbonate or bicarbonate.
BACKGROUND OF THE INVENTION
The hazards to public health and the environment which are posed by a variety of
synthetic halogenated organic compounds are well lmown. Compounds such as
polychlorinated biphenyls (PCB's), dibenzodioxins, dibenzofurans, d1chlorodiphenyl
tr ich loroethane (DDT), dieldrin, lindane and chlordane, as well as other halogenated
pesticides, have been found to be persistent, environmentally toxic materials which
require safe and efficient means of disposal. PCB's pose a particularly serious di sposa l
problem. Onc e widely used as dielectric fluid additives in electrical equipment such as
transformers ai1d capacitors because of their excellent insulating properties, the use of
PCB's in many applications has been banned by the U.S. Environmental Protection
Agency owing to the cumulative storage of PCB's in the human body and the extremely
high toxicity of PCB's. Thus, methods for the removal and/or destruction of halogenated
organic compounds such as PCB's are required.
Va rious methods for the removal and/or the destruction or decomposition of halogenated
orgamc compounds are lmown in the art. For example, the Peterson U.S. Pat. Nos.
4,447,541 and 4,574,013 disclose methods for decontaminating soil which is
contaminated with halogenated organic compounds. The Peterson U.S. Pat. No.
4,447,541 discloses a process in which a reagent mixture of an alkaline constituent and a
sulfox ide catalyst (DMSO) are intimately mixed with soil contaminated with PCB's. The
reagent mixture affects a desorption of the halogenated contaminants from the soil and
subsequently dehalogenates the contaminants. However, this process is disadvantageous
in that the kinetics are relatively slow and therefore reduction of the PCB concentration to
an acceptable level requires extended time periods ranging from weeks to months, the
soil must be completely dry for the destruction to take place, large quantities of the
reagent are required, and the sulfoxide catalyst may potentially transport contaminants
prior to their destruction. The Peterson U.S. Pat. No. 4,574,013 discloses a process
wherein a heated slu1Ty of contaminated soil is treated with a mixture of an alkaline
constituent and a sulfoxide catalyst. However, this process is similarly disadvantageous
in that the sulfoxide catalyst may transpo1i contaminants into living systems, and the
sulfoxide catalyst produces odorous compounds when heated to high temperatures and
decomposes into combustible byproducts under elevated temperature conditions. This
process is also disadvantageous in that it requires large amounts of reagents.
The Rogers et al U.S. Pat. No. 4,675,464 discloses a method for the chemical destruction
of halogenated aliphatic hydrocarbons, and more particularly a method for the chemical
destruction of ethylene dibromide. An alkali metal hydroxide is dissolved in an ethylene
glycol and th e resulting product is reacted with the halogenated hydrocarbon. Rogers et al
further disclose that the reaction temperature should be maintained at 30.degree. C. or
less to maintain the reaction products in solution.
The Rogers et al copending application Ser. No. 07/350,425 discloses a method for the
destruction of halogenated organic compounds in a contaminated medium wherein an
,1queous solution containing from about 0.1 to about 20 weight percent polyethylene
glycol is addeq to a contaminated medium. An alkali metal hydroxide is also added to the
contaminated medium, and the contaminated medium is heated at a temperature and for a
ti me sufficient to dehydrate the medium. The medium is further heated at a temperature
of between about J 00.degree. and 350.degree. C. for a time sufficient to effect destruction
of the halogenated organic compounds, and an acid is added to the medium in an amount
sufficient to provide the medium with a pH of from about 7 to about 9.
The Pytl ewski et al U.S. Pat. No. 4,400,552 discloses a method for the decomposition of
halogenated organic compounds which employs a reagent comprising the product of the
reaction of an alkali metal hydroxide with a polyglycol or a polyglycol monoalkyl ether,
and oxygen. The Pytlewski et al U.S. Pat. Nos. 4,337,368 and 4,602,994 di sclose similar
methods of decomposing halogenated organic compounds. Additionally, the Pytlewski et
al U.S. Pat. Nos. 4,430,208, 4,417,977, 4,460,797 and 4,471,143 also disclose methods
for separation and/or decomposition of halogenated organic compounds. However, these
methods are disadvantageous in that excess amounts of the alkali metal hydroxide and
polyglycol reagents are required in order to obtain a homogeneous distribution
throughout the contaminated material, for example soil, sediment, sludge or the like,
whi ch is treated. The Pytlewski et al U.S. Pat. Nos. 4,349,380 and 4,523,043 disclose the
use of reagents made from an alkali metal or alkali metal hydroxide and a polyglycol or a
polyglycol monoalkyl ether for removing metals from metal-containing materials and for
decomposing organo sulfur compounds, respectively. Similarly, the Brunelle U.S . Pat.
Nos . 4,351,718 and 4,353,793 disclose methods for removing polyhalogenated
hydrocarbons from nonpolar organic solvent solutions by treating the contaminated
solutions with a mixture of polyethylene glycol and an alkali metal hydroxide. These
methods are similarly disadvantageous in that excess amounts of reagent are required.
Additional methods for removing and/or destructing halogenated organic compounds
contained in contaminated materials are disclosed in the Howard et al U.S. Pat. No.
4,327,027, the Heller U.S. Pat. No. 4,483,716, the Mendiratta et al U.S . Pat. No .
4,663,027, the Meenan et al U.S. Pat. Nos. 4,685,220 and 4,793 ,937, the Rossi et al U.S.
Pat. No. 4,761,221 , the Zeff et al U.S. Pat. No. 4,792,407, European Patent Application
No. 118,8 58, Chemical Abstracts, Vol. 82, No. 139620P (1975) and Komel et al, .Journal
of Ha zardous Materials, 12 (1985), pages 161-176. However, these and additional
processes known in the art for the removal and/or destruction of halogenated organic
compounds in contaminated materials are inadequate in view of the time required for
acceptable levels of removal and/or destruction, the use of excessive amounts of various
reagents, the use of expensive reagents, the production of toxic and/or combustible
byproducts, and/or the failure to obtain desired removal and/or destruction levels. Thus, a
need exists for additional methods for the removal and/or destruction of halogenated
organic compounds in contaminated materials, which methods overcome the
di sadvantages of the prior art.
SUMMARY OF THE INVENTION
Accordingl y, it is an object of the present invention to provide a new method for the
decomposition and removal of halogenated organic compounds contained in a
contaminated medium. It is a further object of the invention to provide a method for the
t
decomposition and removal of halogenated organic compounds contained in a
contaminated medium which employs significantly Jess amounts of reagent and which
employs lower costing reagents, as compared with prior art methods. lt is a further object
of the invention to provide such a method wherein environmentally acceptable levels of
halogenated organic compounds are achieved in the treated materials. lt is a related object
of the invention to provide such a method wherein the environmentally acceptable levels
of contaminants in the materials are obtainable within a short period of time.
These and additional objects are achieved by the present invention which relates to
methods for the decomposition of halogenated organic compounds contained in a
contaminated medium. The methods of the invention comprise the steps of adding an
alkali metal carbonate or bicarbonate to a contaminated medium containing the
halogenated 01:ganic compounds. The alkali metal carbonate or bicarbonate may be in an
aqueous solution which distributes the alkali metal compound throughout the medium
and acts as a wetting agent, or in a solvent, or may be added as a solid dispersion or
suspension . The contaminated medium is then heated at a temperature and for a time
sufficient to dehydrate the medium. Although the water is removed, the alkali metal
compound is well distributed throughout the medium and is concentrated to a very
reactive state. The medium is then further heated at a temperature between about
250 .degree. and 400.degree. C. for a time sufficient to effect decomposition of the
halogenated organic compounds. Decomposition of the halogenated compounds in the
contaminated medium is more dependent on the presence of the alkali metal compound
as the temperature increases within this range. Finally, an acid is added to the medium in
an amount sufficient to neutralize the medium so that it may be returned to its original
environment. Because the aqueous solution or solvent is employed, the amount of alkali
metal compound which is required for the present methods is significantly reduced as
compared with prior art methods. Additionally, because the reagent is well distributed
throughout the medium by the aqueous solution, a uniform destruction of the halogenated
organic compounds is achieved. Moreover, because lower amounts of reagent are
employed, recycling of excess reagents is not required. Finally, the present methods are
advantageous in the use of the alkali metal carbonate or bicarbonate in that these
compounds are less corrosive than the alkali metal hydroxides employed in prior art
methods and ryquire less acid for neutralization.
These and additional objects and advantages will become more fully understood in view
of the following detailed description.
DETAILED DESCRIPTION
The present invention comprises methods for the decomposition and removal of
halogenated organic compounds contained in a contaminated medium. The contaminated
medium may comprise soil, sludge, sediment or a liquid. The present methods are
particularly adapted for use with soils, sludges and sediments. The methods are suitable
for use with mediums which contain up to 100,000 ppm of halogenated organic
compounds, aliphatic or aromatic, for example PCB's, or even higher levels of the
halogenated organic compounds. The contaminated mediums which are suitable for use
in the invention may also include an absorbent or adsorbent, for example spent activated
carbon or the like. Additionally, the methods of the invention may be used for the
treatment of pure halogenated materials, for example, aldrin, dieldrin and other
halogenated pesticides.
Generally, the methods of the in vention comprise adding an alkali metal carbonate or
bicarbonate, or a mixture thereof, to the contaminated medium containing one or more
halogenated organic compounds. The alkali metal carbonate or bicarbonate may be added
lo the contaminated medium in an aqueous solution or in a high boiling solvent.
Alternatively, the alkali metal carbonate or bicarbonate may be added in the form of a
so lid dispersion or suspension. When the alkali metal carbonate or bicarbonate is added
in an aqueous solution, the water from the aqueous solution assists in distributing the
alkali metal compound homogeneously throughout the contaminated medium.
A I ternati vely, when the alkali metal carbonate or bicarbonate is added with a high boiling
solve nt, the solvent component serves to extract the contaminates and to raise their
bo iling points whereby the volatility of the pollutants is reduced and the pollutants are
retained in the reaction system for decomposition. The high boiling solvent also serves as
a hydrogen donor to produce decomposition fragments of the toxic and hazardous
pollutant compounds. Suitable solvents have a boiling point of at least 200.degree. C.,
,md preferably from about 200.degree. C. to about 500.degree. C. PrefetTed solvents
include hydrocarbon compounds. In an additional embodiment, the alkali meta] carbonate
or bicarbonate compounds may be added to the contaminated medium in an aqueous
solution, wherein the aqueous solution further contains a high boiling solvent.
The alkali metal carbonate or bicarbonate is added to the contaminated medium in an
amount of from about l to about 20 weight percent, based on the weight of the
contaminated medium. The specific amount of alkali metal compound which is required
is dependent on the level of halogenated organic compounds contained in the
contaminated medium. In a prefetTed embodiment, the alkali metal reagent is added in an
amount of from about 2 to about 12 weight percent based on the weight of the
contaminated medium. The metal which fonns the carbonate or bicarbonate reagent may
be any of the alkali metals, or mixtures thereof. PrefetTed alkali metals include lithium,
sodium and potassium with sodium and potassium being particularly preferred.
After addition of the alkali metal compound, the contaminated medium is heated at a
temperature and for a time sufficient to totally dehydrate the medium, i.e., to remove 100
weight percent of the water contained therein. This heating step may be performed at
atmospheric pressure or at reduced or elevated pressures if so desired. As noted above,
the water which is included in the aqueous solution allows homogeneous distribution of
the alkali metal compounds throughout the medium and acts as a wetting agent and a
penetrant. Moreover, when the water is removed from the medium during the dehydration
step, the reagent is then concentrated to a very reactive state yet is well distributed
throughout the contaminated medium.
After dehydration, the medium is further heated at a temperature between about
25 0.degree. and 400.degree. C. fo r a time sufficient to effect decomposition of the
I
halogenated organic compounds. More preferably, the medium is heated at a temperature
betwee n about 250.degree. C. and 350.degree. C. to effect decomposition of the
halogenated organic compounds. This step may be conducted at atmospheric pressure or
at reduced or elevated pressures. The time required for decomposition of the halogenated
organi c compounds similarly depends upon the level of such compounds in the
contaminated material. Generally however, a time period of from about 0.25 to about 4
hours is sufficient.
1 n the methods of the present invention, the alkali metal carbonate or bicarbonate reacts
with th e halogenated organic compounds, for example aromatics such PCB's, to initially
for111 an alkali metal halide and a partially dehalogenated PCB structure. Upon further
heatin g at temperatures above 250.degree. C., a base catalyzed removal of the halogens
occurs together with reduction and decomposition of the remaining organic compounds.
Finally, the medium is treated with an acid for neutralization. Preferably, the acid is
added in amount sufficient to provide the medium with a pH value of from about 7 to
about 9. Suitable acids for use in the invention comprise sulfuric acid, phosphoric acid,
hydrochloric acid and nitric acid. With the exception of hydrochloric acid, these acids not
onl y neutralize the medium but also provide valuable soil fertilizers, for example
Na.s ub.2 SO.sub.4 or sodium sulfate from use of sulfuric acid, NaH.sub.2 PO.sub.4,
Na.sub.2 HPO.sub.4, Na.sub.3 PO.sub.4 or sodium phosphates from the use of
phosphoric acid, and NaNO.sub.3 or sodium nitrate from the use of nitric acid, given that
sodium is employed as the alkali metal. If potassium is used, then the potassium salts are
produced. The resulting medium may then be safely returned to its original environment
if desired .
Generally, oxygen is not a detriment to the methods of the present invention and
th erefore air need not be excluded. When applied to the decontamination of hydrocarbon
fluids, either aliphatic or aromatic, it may be desirable to exclude air in order to prevent
ignition of the hydrocarbon. Thus, the present methods may be performed either in the
presence or the absence of an oxygen-containing atmosphere.
Because the present methods employ relatively small amounts of alkali metal reagents,
and solvent if used, there is no need to recover excess reagents for reuse. Moreover,
because the pnesent invention employs water to wet the contaminated medium and to
di stribute the alkali metal reagents therein, the present methods are significantly less
costly than prior art methods which employ polyethylerie glycol to wet the contaminated
111edium. The present methods may be performed in either a continuous or a batch
system, and, if desired, all steps may be perfonned in a single reactor. As will be
demonstrated in the Examples, the methods of the invention decompose the halogenated
organic compounds, particularly haloaromatic and cyclic aliphatic compounds, to
nondetectable levels. Additionally, the products of the present methods are non-
rnutagen ic , non-teratogenic and non-toxic to life forms.
The methods of the present invention are demonstrated in the following Examples:
EXAMPLE l
This example demonstrates the application of the methods according to the present
in vention to a contaminated liquid material. Fifty ml of a contaminated solvent material
containing 10% aldrin was mixed with an aqueous solution formed from 10 grams of
sodium bicarbonate and 10 ml of water. The mixture was agitated by stirring and was
hea ted to 290.degree. to 320.degree. C. for approximately one to two hours. The aldrin
concentration rapidly fell to below detectable limits, thus resulting in an aldrin-free
sol ve nt.
l:::XAMPLE 2
This example demonstrates the application of the methods according to the present
in vention to treatment of contaminated soil. One hundred grams of contaminated soil
co ntaining 2,200 ppm Aroclor 1260, 1,000 ppm Aroclor 1242, 1,000 ppm of
pentachlorophenol, 1,000 ppm of dieldrine and 1,000 ppm of lindane were supplied to a
chemi cal reactor system. Approximately 5 grams of sodium bicarbonate (5 weight
percent of the contaminated medium) and one ml of a high boiling point hydrocarbon
solvent were added to the soil in a solution of 20 ml of water. The resulting mixture was
slurried and heated such that the water contained in the system was distilled off The
reaction system was then further heated to a temperature of approximately 290.degree. to
340.degree. C. for a period of from 0.25 to 1.5 hours. At about 0.25 hours and a
temperature of 340.degree. C., residuals in the soil were less than one ppm for all
pollutants.
Thus, the metl1ods of the present invention are advantageous for removing halogenated
organic compounds from a contaminated medium. The methods of the present invention
employ relatively inexpensive reagents, namely, the alkali metal carbonates and
bicarbonates, and optionally high boiling solvents. The reagents are employed in
relatively small amounts as compared with methods of the prior art. Additionally, the
alkali metal carbonates and bicarbonates employed in the methods of the present
invention are less corrosive than the alkali metal hydroxides employed in many prior art
methods. Thus, the methods of the present invention provide an improved process for
destroying haloaromatic and aliphatic compounds to non-detectable levels. The products
produced by the present methods are simple lower molecular weight materials, for
example, hydrocarbons, alkanes, alcohols and the like, which are non-mutagenic, non-
teratogenic and non-toxic to life forms.
The preceding examples are set forth to illustrate specific embodiments of the invention,
and are not intended to limit the scope of the methods of the present invention. Additional
embodiments and advantages within the scope of the claimed invention will be apparent
to an ordinary skill in the art.
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United States Patent
Rogers , et al.
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5,039,350
August 13, 1991
Method for the decomposition of halogenated organic compounds in a contaminated
medium
Abstract
A method for the decomposition of halogenated organic compounds contained in a contaminated
medium comprises adding an alkali metal carbonate or bicarbonate to the contaminated medium in an
aqueous solution or in a solvent having a boiling point of at least 200.degree. C., or in the fmm of a
solid dispersion or suspension. The medium is heated to dehydrate the medium and then is fmiher
heated at a temperature between about 250.degree. and 400.degree. C. to effect decomposition of the
halogenated organic compounds. An acid is then added to the medium in an amount sufficient to
neutralize the same.
Inventors: Rogers; Charles J. (Cincinnati, OH); Kornel; Alfred (Cincinnati, OH); Sparks; Harold
L. (Fayetteville, OH)
Assignee: The United States of America as represented by the Administrator of the
(Washington, DC)
Appl. No.: 515892
Filed: April 27, 1990
Current U.S. Class:
Intern'} Class:
Field of Search:
134/27; 134/10; 134/26; 134/28; 134/42; 208/13 ; 208/262.1;
208 /262.5; 210/909; 423/659; 502/25; 502/27; 502/515
B08B 003/08
134/26,27,28,42 208/262.1,262.5,909 502/515,25,27
423/650,DIG. 20
References Cited !Referenced By!
U.S. Patent Documents
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4246255
4327027
4337368
4349380
4351718
4353793
4400552
4416767
4417977
4430208
4447541
4460797
4471143
4483716
4523043
4574013
4602994
4631183
4635220
4662948
4663027
4675464
4761221
4792407
4793937
4801384
4841998
4869825
Jan., 1981
Apr., 1982
Nov., 1982
Aug., 1982
Sep., 1982
Oct., 1982
Sep., 1983
Nov., 1983
Oct., 1983
Jul., 1984
May., 1984
Sep., 1984
Oct., 1984
Nov., 1984
Jun., 1985
Apr., 1986
Jan., 1986
Dec., 1986
Aug., 1937
May., 1987
May., 1987
Nov., 1987
Aug., 1988
Dec., 1988
Dec., 1988
Jan., 1989
Jun., 1984
Sep., 1989
Grantham
Howard et al.
Pytlewski
Pytlewski
Brunelle
Brunelle
Pytlewski
Jordan
Pytlewski
Pytlewski
Peterson
Pytlewski
Pytlewski
Heller
Pytlewski
Peterson
Pytlewski
Lalancette et al.
Meenan
Weitzman
Mendiratta
Rogers
Rossi et al.
Zeff et al.
Meenan
Steiner
Bruya
Steiner
Foreign Patent Documents
0118858 Sep., 1984 EP.
Other References
Chemical Abstracts, vol. 82, No. 139620P (1975).
Kamel et al., Journal of Hazardous Materials, 12 (1985), pp. 161-176.
Primary Examiner: Myers; Helane E.
Claims
What is claimed is:
210/909.
208/262.
568/730.
75/117.
208/262.
208/262.
568/715.
208/262.
208/262.
208/262.
208/262.
568/715.
568/715.
137/7.
568/910.
134/2.
208/262.
210/904.
34/10.
134/42.
208/262.
585/538 .
210/904.
210/748.
210/771.
134/42.
210/909.
134/26.
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1. A method for the decomposition of halogenated organic compounds contained in a contaminated
medium, comprising
(a) adding an alkali metal carbonate or bicarbonate to a contaminated medium containing halogenated
organic compounds, said alkali metal carbonate or bicarbonate being added as an aqueous solution or in
a solvent having a boiling point of at least 200 .degree. C., or in the form of a solid suspension;
(b) heating the contaminated medium at a temperature and for a time sufficient to substantially
dehydrate the medium;
(c) further heating the medium at a temperature between about 250.degree. and 400.degree. C. for a
time sufficient to effect decomposition of the halogenated organic compounds; and
( d) adding an acid to the medium in an amount sufficient to provide the medium with a pH of from
about 7 to about 9.
2. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is added in an
aqueous solution.
3. A method as defined in claim 2, wherein the aqueous solution further contains a hydrocarbon solvent
having a boiling point of at least 200.degree. C.
4. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is added in a
solvent having a boiling point of at least 200.degree. C.
5. A method as defined in claim 4, wherein the solvent comprises a hydrocarbon compound.
6. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is added as a solid
suspens10n.
7. A method as defined in claim 1, wherein the alkali metal carbonate or bicarbonate is added in an
amount of from about 1 to about 20 weight percent based on the weight of the contaminated medium.
8. A method as defined by claim 7, wherein the alkali metal carbonate or bicarbonate is added in an
amount of from about 2 to about 12 weight percent based on the weight of the contaminated medium.
9. A method as defined in claim 1, wherein the alkali metal comprises sodium.
10. A method as defined in claim 1, wherein the alkali metal comprises potassium.
11 . A method as defined in claim 1, wherein the alkali metal comprises lithium.
12. A method as defined by claim 1, wherein the contaminated medium is heated under vacuum to
dehydrate the medium.
13 . A method as defined by claim 1, wherein in step (c) the medium is further heated at a temperature
between about 250.degree. C. and 350.degree. C. to effect destruction of the halogenated organic
compounds.
14. A method as defined by claim 1, wherein the acid which is added to the medium to provide a pH of
from 7 to about 9 is selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric
acid and nitric acid.
15. A method as defined by claim 1, wherein the contaminated medium comprises soil.
16. A method as defined by claim 1, wherein the contaminated medium comprises sludge.
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17. A method as defined by claim 1, wherein the contaminated medium comprises sediment.
18. A method as defined by claim 1, wherein the contaminated medium includes an absorbent
comprising spent activated carbon.
19. A method as defined by claim 1, wherein the contaminated medium comprises a liquid.
20. A method as defined by claim 1, wherein the contaminated medium contains up to 100,000 ppm of
halogenated organic compounds.
21 . A method as defined by claim 1, wherein the contaminated medium comprises a pure halogenated
material.
22 . A method as defined by claim 1, wherein the medium which results from the acid addition step is
returned to its original environment.
Description
FIELD OF THE INVENTION
The present invention relates to a method for the decomposition of halogenated organic compounds
contained in a contaminated medium. More particularly, the invention relates to a method for the
decomposition and removal of halogenated organic compounds contained in a contaminated medium by
use of an alkali metal carbonate or bicarbonate.
BACKGROUND OF THE INVENTION
The hazards to public health and the environment which are posed by a variety of synthetic halogenated
organic compounds are well known. Compounds such as polychlorinated biphenyls (PCB's),
dibenzodioxins, dibenzofurans, dichlorodiphenyl trichloroethane (DDT), dieldrin, lindane and
chlordane, as well as other halogenated pesticides, have been found to be persistent, environmentally
toxic materials which require safe and efficient means of disposal. PCB's pose a particularly serious
disposal problem. Once widely used as dielectric fluid additives in electrical equipment such as
transformers and capacitors because of their excellent insulating properties, the use of PCB's in many
applications has been banned by the U.S. Environmental Protection Agency owing to the cumulative
storage of PCB's in the human body and the extremely high toxicity of PCB's. Thus, methods for the
removal and/or destruction of halogenated organic compounds such as PCB's are required.
Various methods for the removal and/or the destruction or decomposition of halogenated organic
compounds are known in the art. For example, the Peterson U.S. Pat. Nos. 4,447,541 and 4,574,013 ,
disclose methods for decontaminating soil which is contaminated with halogenated organic compounds.
The Peterson U.S . Pat. No. 4,447,541 discloses a process in which a reagent mixture of an alkaline
constituent and a sulfoxide catalyst (DMSO) are intimately mixed with soil contaminated with PCB's .
The reagent mixture affects a desorption of the halogenated contaminants from the soil and
subsequently dehalogenates the contaminants. However, this process is disadvantageous in that the
kinetics are relatively slow and therefore reduction of the PCB concentration to an acceptable level
requires extended time periods ranging from weeks to months, the soil must be completely d1y for the
destruction to take place, large quantities of the reagent are required, and the sulfoxide catalyst may
potentially transport contaminants prior to their destruction. The Peterson U.S. Pat. No. 4,574,013
discloses a process wherein a heated slurry of contaminated soil is treated with a mixture of an alkaline
constituent and a sulfoxide catalyst. However, this process is similarly disadvantageous in that the
sulfoxide catalyst may transport contaminants into living systems, and the sulfoxide catalyst produces
odorous compounds when heated to high temperatures and decomposes into combustible byproducts
under elevated temperature conditions. This process is also disadvantageous in that it requires large
amounts of reagents.
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The Rogers et al U.S. Pat. No. 4,675,464 discloses a method for the chemical destruction of halogenated
aliphatic hydrocarbons, and more particularly a method for the chemical destruction of ethylene
dibromide. An alkali metal hydroxide is dissolved in an ethylene glycol and the resulting product is
reacted with the halogenated hydrocarbon. Rogers et al further disclose that the reaction temperature
should be maintained at 30.degree. C. or less to maintain the reaction products in solution.
The Rogers et al copending application Ser. No. 07/350,425 discloses a method for the destruction of
halogenated organic compounds in a contaminated medium wherein an aqueous solution containing
from about 0.1 to about 20 weight percent polyethylene glycol is added to a contaminated medium. An
alkali metal hydroxide is also added to the contaminated medium, and the contaminated medium is
heated at a temperature and for a time sufficient to dehydrate the medium. The medium is fmther heated
at a temperature of between about 100.degree. and 350.degree. C. for a time sufficient to effect
destruction of the halogenated organic compounds, and an acid is added to the medium in an amount
sufficient to provide the medium with a pH of from about 7 to about 9.
The Pytlewski et al U.S. Pat. No. 4,400,552 discloses a method for the decomposition of halogenated
organic compounds which employs a reagent comprising the product of the reaction of an alkali metal
hydroxide with a polyglycol or a polyglycol monoalkyl ether, and oxygen. The Pytlewski et al U.S. Pat.
Nos. 4,337,368 and 4,602,994 disclose similar methods of decomposing halogenated organic
compounds. Additionally, the Pytlewski et al U.S. Pat. Nos. 4,430,208, 4,417,977, 4,460,797 and
4,471,143 also disclose methods for separation and/or decomposition of halogenated organic
compounds. However, these methods are disadvantageous in that excess amounts of the alkali metal
hydroxide and polyglycol reagents are required in order to obtain a homogeneous distribution
throughout the contaminated material, for example soil, sediment, sludge or the like, which is treated.
The Pytlewski et al U.S. Pat. Nos. 4,349,380 and 4,523,043 disclose the use ofreagents made from an
alkali metal or alkali metal hydroxide and a polyglycol or a polyglycol monoalkyl ether for removing
metals from metal-containing materials and for decomposing organo sulfur compounds, respectively.
Similarly, the Bmnelle U.S . Pat. Nos. 4,351,718 and 4,353,793 disclose methods for removing
polyhalogenated hydrocarbons from nonpolar organic solvent solutions by treating the contaminated
solutions with a mixture of polyethylene glycol and an alkali metal hydroxide. These methods are
similarly disadvantageous in that excess amounts of reagent are required. Additional methods for
removing and/or destructing halogenated organic compounds contained in contaminated mate1ials are
disclosed in the Howard et al U.S. Pat. No. 4,327,027, the Heller U.S . Pat. No. 4,483,716, the
Mendiratta et al U.S. Pat. No. 4,663,027, the Meenan et al U.S. Pat. Nos. 4,685,220 and 4,793,937, the
Rossi et al U.S . Pat. No. 4,761,221, the Zeff et al U.S . Pat. No. 4,792,407, European Patent Application
No. 118,858, Chemical Abstracts, Vol. 82, No. 139620P (1975) and Komel et al, Journal of Hazardous
Materials, 12 (1985), pages 161-176. However, these and additional processes known in the art for the
removal and/or destruction of halogenated organic compounds in contaminated materials are inadequate
in view of the time required for acceptable levels of removal and/ or destruction, the use of excessive
amounts of various reagents, the use of expensive reagents, the production of toxic and/or combustible
byproducts, and/or the failure to obtain desired removal and/or destruction levels . Thus, a need exists
for additional methods for the removal and/or destrnction of halogenated organic compounds in
contaminated materials, which methods overcome the disadvantages of the prior art.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a new method for the decomposition and
removal of halogenated organic compounds contained in a contaminated medium. It is a further object
of the invention to provide a method for the decomposition and removal of halogenated organic
compounds contained in a contaminated medium which employs significantly less amounts of reagent
and which employs lower costing reagents, as compared with prior art methods. It is a fmther object of
the invention to provide such a method wherein environmentally acceptable levels of halogenated
organic compounds are achieved in the treated materials. It is a related object of the invention to provide
such a method wherein the environmentally acceptable levels of contaminants in the materials are
obtainable within a shmt period of time.
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These and additional objects are achieved by the present invention which relates to methods for the
decomposition of halogenated organic compounds contained in a contaminated medium. The methods
of the invention comprise the steps of adding an alkali metal carbonate or bicarbonate to a contaminated
medium containing the halogenated organic compounds. The alkali metal carbonate or bicarbonate may
be in an aqueous solution which distributes the alkali metal compound throughout the medium and acts
as a wetting agent, or in a solvent, or may be added as a solid dispersion or suspension. The
contaminated medium is then heated at a temperature and for a time sufficient to dehydrate the medium.
Although the water is removed, the alkali metal compound is well distributed throughout the medium
and is concentrated to a very reactive state. The medium is then further heated at a temperature between
about 250.degree. and 400.degree. C. for a time sufficient to effect decomposition of the halogenated
organic compounds. Decomposition of the halogenated compounds in the contaminated medium is more
dependent on the presence of the alkali metal compound as the temperature increases within this range.
Finally, an acid is added to the medium in an amount sufficient to neutralize the medium so that it may
be returned to its original environment. Because the aqueous solution or solvent is employed, the
amount of alkali metal compound which is required for the present methods is significantly reduced as
compared with prior art methods. Additionally, because the reagent is well distributed throughout the
medium by the aqueous solution, a uniform destruction of the halogenated organic compounds is
achieved. Moreover, because lower amounts of reagent are employed, recycling of excess reagents is
not required. Finally, the present methods are advantageous in the use of the alkali metal carbonate or
bicarbonate in that these compounds are less corrosive than the alkali metal hydroxides employed in
prior art methods and require less acid for neutralization.
These and additional objects and advantages will become more fully understood in view of the
following detailed description.
DETAILED DESCRIPTION
The present invention comprises methods for the decomposition and removal of halogenated organic
compounds contained in a contaminated medium. The contaminated medium may comprise soil, sludge,
sediment or a liquid. The present methods are particularly adapted for use with soils, sludges and
sediments. The methods are suitable for use with mediums which contain up to 100,000 ppm of
halogenated organic compounds, aliphatic or aromatic, for example PCB's, or even higher levels of the
halogenated organic compounds. The contaminated mediums which are suitable for use in the invention
may also include an absorbent or adsorbent, for example spent activated carbon or the like.
Additionally, the methods of the invention may be used for the treatment of pure halogenated materials,
for example, aldrin, dieldrin and other halogenated pesticides.
Generally, the methods of the invention comprise adding an alkali metal carbonate or bicarbonate, or a
mixture thereof, to the contaminated medium containing one or more halogenated organic compounds.
The alkali metal carbonate or bicarbonate may be added to the contaminated medium in an aqueous
solution or in a high boiling solvent. Alternatively, the alkali metal carbonate or bicarbonate may be
added in the form of a solid dispersion or suspension. When the alkali metal carbonate or bicarbonate is
added in an aqueous solution, the water from the aqueous solution assists in distributing the alkali metal
compound homogeneously throughout the contaminated medium. Alternatively, when the alkali metal
carbonate or bicarbonate is added with a high boiling solvent, the solvent component serves to extract
the contaminates and to raise their boiling points whereby the volatility of the pollutants is reduced and
the pollutants are retained in the reaction system for decomposition. The high boiling solvent also serves
as a hydrogen donor to produce decomposition fragments of the toxic and hazardous pollutant
compounds. Suitable solvents have a boiling point of at least 200.degree. C., and preferably from about
200.degree. C. to about 500.degree. C. Preferred solvents include hydrocarbon compounds. In an
additional embodiment, the alkali metal carbonate or bicarbonate compounds may be added to the
contaminated medium in an aqueous solution, wherein the aqueous solution further contains a high
boiling solvent.
The alkali metal carbonate or bicarbonate is added to the contaminated medium in an amount of from
about 1 to about 20 weight percent, based on the weight of the contaminated medium. The specific
amount of alkali metal compound which is required is dependent on the level of halogenated organic
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compounds contained in the contaminated medium. In a preferred embodiment, the alkali metal reagent
is added in an amount of from about 2 to about 12 weight percent based on the weight of the
contaminated medium. The metal which fmms the carbonate or bicarbonate reagent may be any of the
alkali metals, or mixtures thereof. Preferred alkali metals include lithium, sodium and potassium with
sodium and potassium being particularly preferred.
After addition of the alkali metal compound, the contaminated medium is heated at a temperature and
for a time sufficient to totally dehydrate the medium, i.e., to remove 100 weight percent of the water
contained therein. This heating step may be perfmmed at atmospheric pressure or at reduced or elevated
pressures if so desired. As noted above, the water which is included in the aqueous solution allows
homogeneous distribution of the alkali metal compounds throughout the medium and acts as a wetting
agent and a penetrant. Moreover, when the water is removed from the medium during the dehydration
step, the reagent is then concentrated to a very reactive state yet is well distributed throughout the
contaminated medium.
After dehydration, the medium is further heated at a temperature between about 250.degree. and
400.degree. C. for a time sufficient to effect decomposition of the halogenated organic compounds .
More preferably, the medium is heated at a temperature between about 250.degree. C. and 350.degree.
C. to effect decomposition of the halogenated organic compounds. This step may be conducted at
atmospheric pressure or at reduced or elevated pressures. The time required for decomposition of the
halogenated organic compounds similarly depends upon the level of such compounds in the
contaminated mate1ial. Generally however, a time period of from about 0.25 to about 4 hours is
sufficient.
In the methods of the present invention, the alkali metal carbonate or bicarbonate reacts with the
halogenated organic compounds, for example aromatics such PCB's, to initially fmm an alkali metal
halide and a partially dehalogenated PCB structure. Upon further heating at temperatures above
250.degree. C., a base catalyzed removal of the halogens occurs together with reduction and
decomposition of the remaining organic compounds.
Finally, the medium is treated with an acid for neutralization. Preferably, the acid is added in amount
sufficient to provide the medium with a pH value of from about 7 to about 9. Suitable acids for use in
the invention comprise sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid. With the
exception of hydrochloric acid, these acids not only neutralize the medium but also provide valuable soil
fe1tilizers, for example Na.sub.2 SO .sub.4 or sodium sulfate from use of sulfuric acid, NaH.sub.2
PO .sub.4, Na.sub.2 HPO.sub.4, Na.sub.3 PO .sub.4 or sodium phosphates from the use of phosphoric
acid, and NaNO.sub.3 or sodium nitrate from the use of nitric acid, given that sodium is employed as
the alkali metal. If potassium is used, then the potassium salts are produced. The resulting medium may
then be safely returned to its original environment if desired.
Generally, oxygen is not a detriment to the methods of the present invention and therefore air need not
be excluded. When applied to the decontamination of hydrocarbon fluids, either aliphatic or aromatic, it
may be desirable to exclude air in order to prevent ignition of the hydrocarbon. Thus, the present
methods may be perf01med either in the presence or the absence of an oxygen-containing atmosphere.
Because the present methods employ relatively small amounts of alkali metal reagents, and solvent if
used, there is no need to recover excess reagents for reuse. Moreover, because the present invention
employs water to wet the contaminated medium and to distribute the alkali metal reagents therein, the
present methods are significantly less costly than prior rut methods which employ polyethylene glycol to
wet the contaminated medium. The present methods may be performed in either a continuous or a batch
system, and, if desired, all steps may be performed in a single reactor. As will be demonstrated in the
Examples, the methods of the invention decompose the halogenated organic compounds, pruticularly
haloaromatic and cyclic aliphatic compounds, to nondetectable levels. Additionally, the products of the
present methods are non-mutagenic, non-teratogenic and non-toxic to life forms .
The methods of the present invention are demonstrated in the following Examples:
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EXAMPLE 1
This example demonstrates the application of the methods according to the present invention to a
contaminated liquid material. Fifty ml of a contaminated solvent material containing 10% aldrin was
mixed with an aqueous solution formed from 10 grams of sodium bicarbonate and 10 ml of water. The
mixture was agitated by stitring and was heated to 290.degree. to 320.degree. C. for approximately one
to two hours. The aldrin concentration rapidly fell to below detectable limits, thus resulting in an
aldrin-free solvent.
EXAMPLE2
This example demonstrates the application of the methods according to the present invention to
treatment of contaminated soil. One hundred grams of contaminated soil containing 2,200 ppm Aroclor
1260, 1,000 ppm Aroclor 1242, 1,000 ppm of pentachlorophenol, 1,000 ppm of dieldrine and 1,000
ppm of lindane were supplied to a chemical reactor system. Approximately 5 grams of sodium
bicarbonate ( 5 weight percent of the contaminated medium) and one ml of a high boiling point
hydrocarbon solvent were added to the soil in a solution of 20 ml of water. The resulting mixture was
slutried and heated such that the water contained in the system was distilled off The reaction system
was then further heated to a temperature of approximately 290.degree. to 340.degree. C. for a period of
from 0.25 to 1.5 hours. At about 0.25 hours and a temperature of 340.degree. C., residuals in the soil
were less than one ppm for all pollutants.
Thus, the methods of the present invention are advantageous for removing halogenated organic
compounds from a contaminated medium. The methods of the present invention employ relatively
inexpensive reagents, namely, the alkali metal carbonates and bicarbonates, and optionally high boiling
solvents. The reagents are employed in relatively small amounts as compared with methods of the prior
art. Additionally, the alkali metal carbonates and bicarbonates employed in the methods of the present
invention are less con-osive than the alkali metal hydroxides employed in many prior art methods. Thus,
the methods of the present invention provide an improved process for destroying haloaromatic and
aliphatic compounds to non-detectable levels. The products produced by the present methods are simple
lower molecular weight materials, for example, hydrocarbons, alkanes, alcohols and the like, which are
non-mutagenic, non-teratogenic and non-toxic to life forms .
The preceding examples are set forth to illustrate specific embodiments of the invention, and are not
intended to limit the scope of the methods of the present invention. Additional embodiments and
advantages within the scope of the claimed invention will be apparent to an ordinary skill in the art.
* * * * *
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11/01/2000 3:27 PM
LICENSE FOR DEVELOPMENT AND USE
This LICENS·E AGREEMENT is made and entered by and between the
Director of the [LABORATORY NAME] US ------4,...:====~~!.2!:~-"--------, . .
Environmental Protection Agency, __ ___.[_,,C""'I~T,,_,Y:...].&.-.. __ ,
the representative of the United States of America (hereafter
LICENSOR), acting under the authority of 15 u.s.c. § 3710a(a) (2),
which was delegated to said Director by EPA Delegation 1200TN193 of
December 15, 1988, and --~[..:cN:..:..AM=E::_..;;O:.:P'---'C::.;O::..O::..P=-=E=-=RA=T~O~RuJ'--_, a
INCORPORATION] corporation having principal offices at
POST OFFICE ADDRESS] (hereafter LICENSEE).
WITNESS ETH:
[STATE OF
[COMPLETE
WHEREAS, The United States of America is the owner by assignment
of the entire right, title and interest to U.S. Patent No. 5,019,175
entitled "Method for the Destruction of Halogenated Organic Compounds
in a Contaminated Medium"; U.S. Patent No. 5,039,350 entitled "Method
for the Decomposition of Halogenated Organic Compounds in a
Contaminated Medium"; and U.S. Patent No. 5,064,526 entitled "Method
for the Base-catalyzed Decomposition of Halogenated and Non-
halogenated Organic Compounds in a contaminated Medium.
WHEREAS, LICENSOR desires the methods claimed and described in
U.S. Patent No(s). 5,019,175, 5,039,350 and 5,064,526 be made
available to the public in the shortest possible time, thereby serving
the public interest by providing improved products and processes tor
remediation of hazardous wastes containing chlorinated organic
materials;
2
WHEREAS, under the authority of Title 35 United States Code
§ 207, and 37 Code of Federal Regulations Part 404, LICENSOR has the
right to issue licenses under patents and patent applications assigned
to the United States of America;
WHEREAS, LICENSEE desires a non-exclusive license in the
LICENSOR'S Base Catalyzed Decomposition technology;
NOW, THEREFORE, in consideration of the promises, as well as the
obligations herein made and undertaken, the parties hereto, intending
to be legally bound, agree as follows:
ARTICLE I
DEFINITIONS
1.01 Terms in this LICENSE AGREEMENT (other than names of
parties and Article headings) which are set forth in upper case
letters have the meanings established for such terms in the succeeding
ARTICLES of this ARTICLE I.
1.02 LICENSE AGREEMENT means this non-exclusive License for
Development and Use, including any exhibits attached hereto.
1.03 LICENSE means the license granted pursuant to paragraph
2.01 of this LICENSE AGREEMENT.
3
1.04 LICENSED PATENTS means U.S. Patent No(s). 5,019,175,
5,039,350 and 5,064,526.
1.05 LICENSED TECHNICAL INFORMATION means technical information
including, but not limited to, data, know-how, trade secrets,
calculations, writings and drawings, whether or not patented, relating
to the licensed patents and disclosed and claimed in the licensed
patents.
1.06 LICENSED TECHNOLOGY means LICENSED TECHNICAL INFORMATION
and any products, methods, processes or uses which are disclosed and
claimed in the LICENSED PATENTS.
1.07 LICENSED AREA means United States of America.
1.08 LICENSOR'S REPRESENTATIVE means the Director of the Risk
·Reduction Engineering Laboratory of the U.S. Environmental Protection
Agency, Cincinnati, OH.
ARTICLE II
LICENSE GRANT
2.01 Upon the terms and conditions set forth herein and subject
to the payment of fees as set forth herein, LICENSOR grants to
LICENSEE a non-exclusive license to make, have made, use and sell the
LICENSED TECHNOLOGY throughout the LICENSED AREA for the term set
4
forth in paragraph 9.02 of this LICENSE AGREEMENT. The non-exclusive
LICENSE shall be for both solid and liquid applications.
ARTICLE III
ROYALTIES AND PAYMENTS
3.01 LICENSEE shall pay LICENSOR a licensing fee as follows:
a. LICENSEE shall pay to the LICENSOR a licensing fee of
$75,000 for the first year following the Effective Date of
this LICENSE AGREEMENT as described in paragraph 9.01.
b. LICENSEE shall pay the licensing fee payment of paragraph
3.01 (a) by quarterly payments of $18,750/quarter paid
thirty (30) days after the end of each fiscal quarter.
c. From the second year following the Effective Date of this
LICENSE AGREEMENT and thereafter, LICENSEE will pay LICENSOR
a licensing fee of $50,000 per year.
d. LICENSEE shall pay the licensing fee payment of paragraph
3. 01 (c) by quarterly paym.ents of $12, 500/quarter paid
thirty (30) days after the end of each fiscal quarter.
5
e. Any payments due under paragraphs 3.01 (b) and (d) not
received by LICENSOR by the due date shall be subject to
interest charges computed at ten percent (10%) per annum.
f. LICENSEE shall pay LICENSOR fifty percent (50%) of all fees
and royalties paid to LICENSEE by a sublicensee of LICENSEE,
payment to be made within ninety (90) days of receipt by
LICENSEE. Such payments shall be in addition to payments
under paragraph 3.01 (a), (b), (c) and (d) above.
3.02 Payments shall be made in United States dollars, by check
made payable to U.S. Environmental Protection Agency and mailed to:
U.S. Environmental Protection Agency
Headquarters Accounting and Operations Branch
Patent Royalties
P.O. Box 360227M, Pittsburgh
Pennsylvania 15251.
The check shall be accompanied by copies of the first page and
signature page of this Agreement.
ARTICLE IV
REPORTS AND RECORDS
4.01 LICENSEE shall provide LICENSOR'S REPRESENTATIVE with
written annual progress reports within ninety (90) days of the end of
each twelve (12) month period following the Effective Date of this
6
LICENSE AGREEMENT describing its efforts, and the efforts of any
sublicensee, to apply the methods licensed under this LICENSE
AGREEMENT. This report should specify amounts of waste treated,
dechlorination results in terms of feed and final product
concentrations, and important operating parameters applied such as
temperatures and reactor residence times.
4.02 LICENSEE agrees to keep records showing all sublicensing
fees or royalties collected from LICENSEE's sublicensees under the
LICENSE granted in this LICENSE AGREEMENT. These records shall be
retained for three years beyond the date of distribution or sale and
shall be in sufficient detail to enable the fees payable hereunder by
LICENSEE to be determined. These records may be examined from time to
time to the extent necessary to verify the claims made by the LICENSEE
in determining the fees to be paid as described in ARTICLE III, such
examination to be made at the expense of the LICENSOR by any auditor
appointed by LICENSOR who shall be acceptable to LICENSEE, or, at the
option and expense of LICENSEE, by a certified public accountant
appointed by LICENSOR.
4.03 The reports required under this ARTICLE IV shall also be made
within sixty (60) days of termination of this LICENSE AGREEMENT.
7
ARTICLE V
SUBLICENSING
5.01 LICENSEE shall have the right to grant sublicenses to
others under this LICENSE so long as a fee is paid by each sublicensee
to LICENSEE at a rate equal to or greater than fee paid by LICENSEE to
LICENSOR as set forth in paragraph 3.01 of this LICENSE AGREEMENT and
so long as the sublicenses are subject to the provisions of this
LICENSE AGREEMENT. Any sublicense shall make reference to this
LICENSE AGREEMENT including those rights retained by LICENSOR. A copy
of any sublicense shall be furnished to LICENSOR'S REPRESENTATIVE
within fifteen (15) days after its execution.
5.02 In the event of termination of this LICENSE AGREEMENT
sublicensees may exercise their option to convert their sublicenses to
licenses directly from LICENSOR. Any sublicense granted by LICENSEE
shall contain provisions corresponding to those of this ARTICLE
respecting termination.
ARTICLE VI
LICENSEE PERFORMANCE
6.01 LICENSEE shall expend reasonable efforts and resources to
carry out the development and marketing of the LICENSED TECHNOLOGY and
to bring the LICENSED TECHNOLOGY to THE POINT OF PRACTICAL
APPLICATION.
8
THE POINT OF PRACTICAL APPLICATION means the condition such that
the LICENSED TECHNOLOGY is being utilized and the benefits of the
LICENSED TECHNOLOGY are, to the extent permitted by law, being made
available to the public on reasonable terms on or before September 30,
1994, in accordance with the plan for development and marketing the
LICENSED TECHNOLOGY attached as Exhibit A.
6.02 After bringing the LICENSED TECHNOLOGY to THE POINT OF
PRACTICAL APPLICATION in the LICENSE AREA, LICENSEE agrees to make the
LICENSED TECHNOLOGY available to the public on reasonable terms during
the term of this LICENSE AGREEMENT. LICENSEE shall promptly report
discontinuance of its making the benefits of the methods reasonably
accessible to the public.
6.03 Failure to comply with the terms of this ARTICLE shall be
cause for modification or termination of this LICENSE AGREEMENT in
accordance with the provisions of ARTICLE IX below. No other rights
or remedies accrue to LICENSOR or any third parties by reason of such
failure.
ARTICLE VII
PATENT ENFORCEMENT
7.01 LICENSOR and LICENSEE shall notify each other promptly in
writing of any infringement of patents granted from the LICENSED
PATENT APPLICATION{S) which becomes known to either of them.
9
7.02 LICENSEE agrees to furnish technical and other necessary
assistance to assist LICENSOR in conducting any litigation necessary
to enforce the LICENSED PATENTS. LICENSOR agrees to furnish technical
and other necessary assistance to assist LICENSEE in defending any
litigation for patent infringement arising from LICENSEE's practice of
the LICENSED PATENTS. Expenses for such assistance will be paid by
the party requesting such assistance.
ARTICLE VIII
RESERVATION OF RIGHTS
8.01 The LICENSE granted in ARTICLE II of this LICENSE AGREEMENT
shall be subject to the irrevocable, royalty-free right of the
Government of the United States to practice and have practiced on
behalf of the United States, and on behalf of any foreign government
or international organization pursuant to any existing or future
treaty or agreement with the United States, the LICENSED TECHNOLOGY,
including the methods described and claimed in the LICENSED PATENTS.
The right reserved hereby will be exercised only to the extent
required by law and/or contracting policy and regulation of the United
States of America.
10
ARTICLE IX
TERM AND TERMINATION
9.01 The Effective Date of this LICENSE AGREEMENT is the date of
the last signature to this LICENSE AGREEMENT.
9.02 The term of this LICENSE AGREEMENT begins on its Effective
Date as set forth in paragraph 9.01. Unless sooner terminated or
otherwise modified as provided for in this ARTICLE IX, this LICENSE
AGREEMENT shall remain in full force and effect for an initial term of
five (5) years from the Effective Date. LICENSEE shall have the right
to renew this LICENSE AGREEMENT for successive periods up to five (5)
years upon written notice mailed to LICENSOR'S REPRESENTATIVE at least
sixty (60) days prior to the expiration of the initial term and each
subsequent renewal term, provided, however, that LICENSEE shall have
no right to renew this LICENSE AGREEMENT in the event that either
party hereto has exercised a right of termination under this ARTICLE
IX or in the event that LICENSEE in not making good faith efforts to
bring the LICENSED TECHNOLOGY to THE POINT OF PRACTICAL APPLICATION.
9.03 The LICENSOR may modify or terminate this non-exclusive
license, in whole or in part, if:
a. LICENSEE fails to meet the obligations set forth in ARTICLE
VI above;
11
b. The LICENSOR determines that such action is necessary to
meet requirements for public use specified by Federal
regulations issued after the date of this LICENSE AGREEMENT
and such requirements are not reasonably satisfied by the
LICENSEE;
c. The LICENSEE has willfully made a false statement or
willfully omitted a material fact in its license application
or in any report required by this LICENSE AGREEMENT;
d. The LICENSEE commits a substantial breach of a covenant or
agreement contained in this LICENSE AGREEMENT;
e. The LICENSEE defaults in making any payment or report
required by this LICENSE AGREEMENT;
•
f. The LICENSEE is adjudged a bankrupt or has its assets placed
in the hands of a receiver or makes any assignment or other
accommodation for the benefit of creditors; or
g. The LICENSEE or any of its sublicensees misuses the LICENSED
PATENTS.
9.04 Prior to any modification or termination of this LICENSE
AGREEMENT by LICENSOR, LICENSOR shall furnish LICENSEE and any
sublicensee of record a written notice of LICENSOR's intention to
modify or terminate, and the LICENSEE and any notified sublicensee
shall be allowed sixty (60) days after the date of such notice to
remedy any breach or default of any covenant or agreement of this
12
LICENSE AGREEMENT or to show cause why this LICENSE AGREEMENT should
not be modified or terminated.
9.05 LICENSEE may terminate this LICENSE AGREEMENT at any time by
giving LICENSOR'S REPRESENTATIVE prior written notice not less than
sixty (60) days before the date of such termination.
9.06 The word "termination" and cognate words, such as "term" and
"terminate," used in this ARTICLE IX and elsewhere in this LICENSE
AGREEMENT are to read, except where the contrary is specifically
indicated, as omitting from their effect the following rights and
obligations, all of which survive any termination to the degree
necessary to permit their complete fulfillment or discharge:
a. LICENSEE's obligation to supply a terminal report as
specified in ARTICLE IV of this LICENSE AGREEMENT;
b. LICENSEE'S right to use LICENSED TECHNOLOGY or to carry out
work for which LICENSEE has an outstanding order;
c. LICENSOR's right to receive or recover and LICENSEE's
obligation to pay fees accrued for payment at the time of any
termination, including fees for sales pursuant to 9.06(b);
d. LICENSEE'S obligation to maintain records and LICENSOR's
right to conduct a final audit as provided in ARTICLE IV of
this LICENSE AGREEMENT;
13
e. Any cause of action or claim of LICENSOR accrued or to
accrue, because of any breach or default by LICENSEE.
9.07 In the event of termination of this LICENSE AGREEMENT, any
affected sublicense of record granted pursuant to this LICENSE
AGREEMENT may be converted to a license with the LICENSOR in accordance
with the provisions of ARTICLE V herein.
9.08 LICENSOR and LICENSEE shall pay their own termination costs
out of their own funds. In no event shall LICENSOR or LICENSEE be
liable for the direct termination costs of the other party or the other
party's expenses caused by or related to the termination.
ARTICLE X
REPRESENTATIONS AND WARRANTIES
10.01 LICENSOR represents and warrants as follows:
a. The Risk Reduction Engineering Laboratory, U.S. Environmental
Protection Agency, Cincinnati, OH is a Federal laboratory of the EPA,
wholly owned by the U.S. Government, whose substantial purpose is the
performance of research, development or engineering by employees of
said Government;
b. The performance of the activities specified by this LICENSE
AGREEMENT are consistent with the mission of the Risk Reduction
14
Engineering Laboratory, U.S. Environmental Protection Agency,
Cincinnati, OH.;
c. All prior reviews and approvals required by regulations or law
have been obtained by the LICENSOR prior to the execution of this
LICENSE AGREEMENT. The Laboratory official executing this LICENSE
AGREEMENT on behalf of LICENSOR has the requisite authority to do so;
d. LICENSOR is the lawful owner of the LICENSED PATENTS and the
LICENSED TECHNOLOGY. LICENSOR has the right to license the LICENSED
TECHNOLOGY including the LICENSED PATENTS and LICENSOR has not executed
and is not aware of any assignment, license or other agreement
conflicting with any of the grants, assignments and transfers contained
in this LICENSE AGREEMENT;
e. No claim, whether or not embodied in an action past or
present, of infringement by the LICENSED TECHNOLOGY has been made or is
pending against LICENSOR.
10.02 LICENSEE represents and warrants as follows:
a. LICENSEE is a corporation duly organized, validly existing and
in good standing under the laws of the State of . I
b. LICENSEE has the requisite power and authority to enter into
this LICENSE AGREEMENT and to perform according to the terms thereof;
15
c. The Board of Directors and shareholders of LICENSEE .have taken
all actions, if any, required to be taken by law, LICENSEE's Articles
of Incorporation, its bylaws or otherwise, to authorize the execution
and delivery of this LICENSE AGREEMENT;
d. The execution and delivery of this LICENSE AGREEMENT does not
contravene any material provision of, or constitute a material default
under, any material agreement binding on LICENSEE or any valid order of
any court, or any regulatory agency or other body having authority to
which LICENSEE is subject, nor, to the best of its knowledge, is
LICENSEE the subject of any adversarial proceeding by any regulatory
governmental agency.
ARTICLE XI
GENERAL
11.01 This LICENSE AGREEMENT shall extend to any reissued patent
which may be derived from any of the LICENSED PATENTS, provided that
LICENSOR has custody of the right thereto and is able to grant a
license without incurring liability to third parties.
11.02 This LICENSE AGREEMENT shall not be transferred or assigned
by LICENSEE to any party other than to a successor or assignee of the
business interest of LICENSEE relating to the LICENSED TECHNOLOGY
without the approval of LICENSOR'S REPRESENTATIVE.
16
11.03 This LICENSE AGREEMENT does not confer any immunity from or
defenses under the antitrust laws, the export laws, the laws and
regulations of the United States pertaining to or administered by the
Environmental Protection Agency or the Food and Drug Administration,
nor does it confer immunity from a charge of patent misuse.
Furthermore, LICENSEE'S or sublicensee's acquisition and exercise of
rights hereunder are not immunized from the operation of any state or
Federal law by reason of the source of the grant. This LICENSE
AGREEMENT does not constitute an endorsement by LICENSOR of the
LICENSED TECHNOLOGY and LICENSEE shall not state or imply in any medium
that such endorsement exists as the result of this LICENSE AGREEMENT.
11.04 LICENSOR makes no warranty, express or implied, regarding
the validity of any LICENSED PATENTS and makes no representations
whatsoever with regard to the scope of such patents or that such
patents may be exploited without infringing other patents.
11.05 LICENSOR assumes no liability resulting from LICENSEE'S
exercise of its rights under this LICENSE AGREEMENT or from LICENSOR'S
.
exercise of its rights under this LICENSE AGREEMENT, including
modification or termination thereof.
11.06 In performing work under this LICENSE AGREEMENT in the
LICENSED AREA, LICENSEE agrees to apply its best efforts to use, sell
or otherwise distribute LICENSED TECHNOLOGY manufactured substantially
in the United States.
17
11.07 The decision of LICENSOR'S REPRESENTATIVE on any
requirement, dispute, interpretation, modification, or termination of
this LICENSE AGREEMENT shall be reduced to writing and a copy mailed or
otherwise furnished to LICENSEE. Such decision shall be final,
provided that LICENSEE may, within thirty (30) days of receiving notice
of such decision, submit a written appeal through LICENSOR'S
REPRESENTATIVE to the Associate General Counsel, General and
Information Law Division, Office of General Counsel, U.S. Environmental
Protection Agency, which appeal shall set forth in detail the decision
being appealed and the basis of the appeal and may include appropriate
supporting materials. Implementation of such decision shall be stayed
pending a final resolution of such appeal. Pending such final
resolution, LICENSEE shall proceed diligently with the performance of
its obligations under this LICENSE AGREEMENT.
11.08 The parties shall notify each other of any changes in name,
address, or business status, and any notice, payment or report required
to be given under the provisions of this LICENSE AGREEMENT shall be
considered duly given if mailed by first class mail, postage prepaid,
and addressed as follows:
a. If to LICENSOR: Mr. E. Timothy Oppelt, Director
b. If to LICENSEE:
Risk Reduction Engineering Laboratory
26 w. Martin Luther King Drive
Cincinnati, OH 45268
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11.09 The interpretation and application of the provisions of
this LICENSE AGREEMENT shall be governed by the laws of the United
States as interpreted and applied by the Federal courts in the District
of Columbia, United States of America.
11.10 This LICENSE AGREEMENT constitutes the entire understanding
between the parties and neither party shall be obligated by any
condition or representation other than those expressly stated herein or
as may be subsequently agreed to by the parties hereto in writing.
11.11 Titles and headings of the Articles and paragraphs of this
LICENSE AGREEMENT are for the convenience of reference only and do not
form a part of this _LICENSE AGREEMENT and shall in no way affect the
interpretation thereof.
11.12 None of the provisions of this LICENSE AGREEMENT shall be
considered waived by any party hereto unless such waiver is given in
writing to all other parties. The failure of any party to insist upon
strict performance of any of the terms and conditions hereof, or
failure or delay to exercise any rights provided herein or by law,
shall not be deemed a waiver of any rights of any party hereto.
19
11.13 The illegality or invalidity of any provisions of this
LICENSE AGREEMENT shall not impair, affect or invalidate the other
provisions of this LICENSE AGREEMENT.
11.14 If LICENSOR or LICENSEE desires a modification in this
LICENSE AGREEMENT, the parties shall, upon reasonable notice of the
proposed modification by the party desiring the change, confer in good
faith to determine the desirability of such modification. Such
modification shall not be effective until a written amendment is signed
by the representatives of LICENSOR and LICENSEE duly authorized to
execute such amendment.
11.15. The relationship of the LICENSOR and LICENSEE is that of
independent parties and not as agents of each other or as joint
venturers or partners. LICENSOR shall maintain sole and exclusive
control over its personnel and operations. LICENSEE shall maintain
sole and exclusive control over its personnel and operations.
20
IN WITNESS WHEREOF, each of the parties hereto has caused this
LICENSE AGREEMENT to be executed in duplicate originals by its duly
authorized officers or representatives.
FOR LICENSOR: FOR LICENSEE;
Name: Name:
Director Title:
[LABORATORY NAME AND ADDRESS) [COOPERATOR NAME AND ADDRESS]
Date: Date: --------------------------