NZ251522A - Reductive decomposition of chemical contaminants by reaction with at least one compound of an alkaline earth metal or alkali metal, h-donor compound, catalyst and heat - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £51 5££ New Zealand No. 251522 International No. PCT/US93/02220 TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates: International filing date: 11131<=»3 Classification:iPc(o-. Co7£3i/ocs CLlOGH-S/ai^ /oo Publication^: 2 5 JUL ^ Journal No.: | L\_ o NO DHJCTGS NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of invention: Method for the reductive decomposition oi chemical contaminants Name, address and nationality of applicant(s) as in international application form: ROGERS, Charles and KORNEL, Alfred respectively of 4191 Miami Trail Lane, Cincinnati, Ohio 45252, U.S.A.; and 3640 Erie Avenue, Cincinnati, Ohio 45208, U.S.A; bohy US c/f/X«v j. (folliveif (ay pays. IA) 0 R 1 R 9 METHOD FOR THE REDUCTIVE DECOMPOSITION OF CHEMICAL CONTAMINANTS FIELD OF THE INVENTION The present invention relates to methods for the base-catalyzed reductive decomposition of chemical contaminants. Mors particularly, the invention relates 5 to methods for the reductive decomposition of organic and/or inorganic compounds by use of an alkali and/or alkaline earth metal compound, and a hydrogen donor compound in the presence of a catalyst which causes formation of free radical hydrogen ions.

BACKGROUND OF THE INVENTION The hazards to public health and the environment which are posed by a variety of synthetic halogenated organic compounds and various inorganic compounds are well known. Compounds such as polychlorinated biphenyls 15 (PCB's), dibenzodioxins, dibenzofurans, dichlorodiphenyl trichloromethane (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 20 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.

WO 94/20591 PCT/US93/02220 «-;-3 j •* ' h i : • y Y US93/02220 " •" Environmental Protection Agency owing to the cumulative storage of PCB's in the human body and the extremely high toxicity of PCB' b . Thus, methods for the removal and/or destruction of halogenated organic compounds such 5 as PCB's are reguired.

Various non-halogenated organic compounds and inorganic compounds are also known to be environmentally toxic materials requiring safe and efficient means of disposal. Such compounds include 10 nitrogen bearing compounds, phosphorus bearing compounds, oxygenated compounds, and sulfur bearing compounds, both organic and inorganic, and the like.

Various methods for the destruction or decomposition of halogenated organic compounds are known 15 in the art. For example, the Peterson U.S. Patents Nos. 4,447,541 and 4,574,013 disclose methods for decontaminating soil which is contaminated with halogenated organic compounds. The Peterson U.S. Patent No. 4,447,541 discloses a process in which a reagent 20 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. 25 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 30 place, large quantities of the reagent are required, and the sulfoxide catalyst may potentially transport contaminants prior to their destruction. The Peterson U.S. Patent No. 4,574,013 discloses a process wherein a heated slurry of contaminated soil is treated with a 94/20591 ,5 1 5 2 .T/US93/02220 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 5 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. 10 The Rogers et al U.S. Patent 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 15 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 °C or less to maintain the reaction products in solution. 20 The Rogers et al U.S. Patent No. 5,019,175 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 25 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 and 30 350°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.

CO i oZZ WO 94/20591 PCT/US93/02220 The Rogers et al U.S. Patent No. 5,039 ,350 discloses a method for the decomposition of halogenated organic compounds contained in a contaminated medium wherein an aqueous solution of an alkali metal carbonate 5 or bicarbonate is added to the contaminated medium, and the medium is heated to a temperature between about 250 and 400°C.

The Rogers et al U.S. Patent No. 5,064 ,526 discloses a method for the decomposition of halogenated 10 or non-halogenated organic contaminants in a contaminated material. The method comprises adding an alkali or alkaline earth metal carbonate, bicarbonate or hydroxide to the contaminated material which further contains a hydrogen donor compound and a carbon 15 compound as a catalyst. The material is heated to dehydrate the material and then further heated to 200°C to 400°C to cause formation of a free radical hydrogen ion to effect the decomposition. An acid is then added to the material to provide a pH of 7-9. 20 The Pytlewski et al U.S. Patent 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 25 oxygen. The Pytlewski et al U.S. Patents Nos. 4,337,368 and 4,602,994 disclose similar methods of decomposing halogenated organic compounds. Additionally, the Pytlewski et al U.S. Patents Nos. 4,430,208, 4,417,977, 4,460,797 and 4,471,143 also disclose methods for 30 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 *.0? 52 material, for example soil, sediment, sludge or the like, which is treated. The Pytlewski et al U .S. Patents Nos. 4,349,380 and 4,523,043 disclose the use of reagents made from an alkali metal or alkali metal 5 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. Patents Nos. 4,351,718 and 4,353,793 disclose methods for removing 10 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 15 required, they do not achieve complete dechlorination and/or excessive time is required to achieve even partial dechlorination.

Additional methods for removing and/or destructing halogenated organic compounds contained in contaminated 20 materials are disclosed in the Howard et al U.S. Patent No. 4,327,027, the Heller U.S. Patent No. 4,483,716, the Mendiratta et al U.S. Patent No. 4,663,027, the Meenan et al U.S. Patents Nos. 4,685,220 and 4,793,937, the Rossi et al U.S. Patent No. 4,761,221, the Zeff et 25 al U.S. Patent No. 4,792,407, European Patent Application No. 118,858, Chemical Abstracts. Vol. 82, No. 139620P (1975) and Kornel et al, Journal of Hazardous Materials. 12 (1985), pages 161-176. However, many of these and additional processes known in the art 30 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 6 PCT/US93/02^20W 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 5 methods for the reduction of chemical contaminants, which methods overcome the disadvantages of the prior art.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present 10 invention to provide new methods for the reductive decomposition of chemical contaminants comprising organic compounds and/or inorganic compounds, alone in pure form or when contained in a contaminated medium. It is an additional object of the invention to provide 15 methods for the reductive decomposition of chemical contaminants, which methods employ at least one hydrogen donor compound. It is a further object of the invention to provide methods for the decomposition of chemical contaminants which employ significantly less amounts of 20 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 chemical contaminant compounds are achieved. It is a related 25 object of the invention to provide such methods wherein the environmentally acceptable levels of contaminants 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-30 catalyzed decomposition of halogenated and/or non- halogenated organic compounds and/or inorganic compounds, alone in pure form or when contained in a contaminated medium. The methods of the invention 3 li a 94/20591 PCT/US93/02220 comprise the steps of combining at least one alkali or alkaline earth metal compound and the chemical contaminant to form a reaction mixture, wherein the reaction mixture further contains a hydrogen donor 5 compound and a catalyst which will cause the formation of a free radical hydrogen ion. The methods further comprise heating the reaction mixture at a temperature in a predetermined range for a time sufficient to cause formation of a free radical hydrogen ion therein and 10 effect reductive decomposition of the chemical contaminant. Additionally, (i) when the chemical contaminant is an organic compound and an alkali metal compound or an alkaline earth metal compound is combined with the chemical contaminant, the predetermined 15 temperature range is from about 50°C to less than 200°C, (ii) when the chemical contaminant is an organic compound and both an alkali metal compound and an alkaline earth metal compound are combined with the chemical contaminant, the predetermined temperature 20 range is from about 50°C to 400°C, and (iii) when the chemical contaminant is an inorganic compound, the predetermined temperature range is from about 50°C to 400°C.

Upon heating of the contaminated reaction mixture, 25 the catalyst causes formation of a free radical hydrogen ion from the hydrogen donor compound. The free radical hydrogen is thereby generated in situ, i.e. in the same reaction mixture to be treated, and acts as the reducing agent for the chemical contaminant. The reduced organic 30 contaminants decompose to simple hydrocarbon structures.

Decomposition of the halogenated and non-halogenated organic chemical contaminant is more dependent on the ease of hydrogen donation by the donor compound (which is promoted by the catalyst) as the temperature /US93/0: u? 8 increases within the predetermined range. The inorganic chemical compounds undergo reduction to yield reduced forms of the metals contained therein, and/or hydrides or the like.

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 10 reductive decomposition of chemical contaminant compounds, alone in pure form or when 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 15 soils, sludges and sediments. The methods are suitable for use with mediums which contain up to 100,000 ppm of chemical contaminants such as halogenated organic compounds, aliphatic or aromatic, for example PCB's, or even higher levels of the halogenated organic compounds, 20 and for use with mediums which contain up to 100,000 ppm of non-halogenated organic contaminants or inorganic contaminants. Concentrations of contaminants greater than 100,000 ppm can be treated according to the present methods by regulating the addition of the alkali or 25 alkaline earth metal compound to prevent an excess increase in temperature and the potential release of pollutants during the process. The contaminated mediums which are suitable for use in the invention may also include an absorbent or adsorbent, for example spent 30 activated carbon or the like.

The chemical contaminant which is treated according to the present methods may comprise an organic chemical compound or an inorganic chemical compound. Organic 9 251522 chemical contaminants which may be treated according to the present invention include halogenated aromatic compounds and halogenated nonaromatic compounds, including, but not limited to PCB's, PCP, 5 ch1 orofluorocarbons, aliphatics, cyclic and heterocyclic compounds. Additional organic chemical contaminants may comprise nitrogen bearing compounds, wherein the reductive decomposition produces amines and/or ammonia. As will be apparent, further reductive 10 decomposition of the amines will result in complete deni tr if ication and production of ammonia. The reductive decomposition methods of the invention may be employed with sulfur-containing compounds, both organic and inorganic. The sulfur-containing compounds 15 generally decompose to produce sulfides and/or elemental sulfur. Organic phosphorus and inorganic phosphorus compounds may be treated according to the present methods and, as a result of the reductive decomposition, yield phosphine and other reduced forms of phosphorus. 20 Complete dephosphorylation may be achieved if desired.

Oxygenated compounds, both organic and inorganic, may also be treated according to the present methods and undergo reductive decomposition to yield water and lower molecular weight non-oxygenated compounds. Examples of 25 organic oxygenated compounds include octanol, polyethylene glycol, methoxy-aromatics and the like. Generally, when inorganic compounds are treated according to the reductive decomposition methods of the present invention, they undergo reduction to yield 30 intermediate reduced forms of metal compounds, including hydrides and the like.

Generally, the methods of the invention comprise adding an alkali and/or alkaline earth metal compound, for example a carbonate, bicarbonate, oxide or 9 h 1 -A v £ J s J l, WO 94/20591 PCT/US93/02220 1 0 • hydroxide, or a compound which generates a carbonate, bicarbonate, oxide or hydroxide, to the pure chemical contaminant or to a contaminated medium containing one or more chemical contaminant compounds. The alkali or 5 alkaline earth metal compound, for example in the form of a carbonate, bicarbonate, oxide or hydroxide, may be added to the pure contaminant or to a contaminated medium in an aqueous solution or in a high boiling solvent. Alternatively, the alkali or alkaline earth 10 metal compound may be added in the form of a solid dispersion or suspension. When the alkali or alkaline earth metal compound is added in an aqueous solution or high boiling solvent, the water from the aqueous solution or the solvent assists in distributing the 15 metal compovmd homogeneously throughout the contaminant or contaminated medium. If the alkali or alkaline earth compound is added with a high boiling solvent, suitable solvents have a boiling point of at least 100°C, and preferably from about 200°C to about 500°C. Preferred 20 solvents include hydrocarbon compounds. In an additional embodiment, the alkali or alkaline earth metal 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 compound, for example a carbonate, bicarbonate, oxide or hydroxide is combined with the chemical contaminant in a molar ratio of from about 1:1 to about 10:1. The specific amount of alkali or alkaline earth metal compound which is 30 required is dependent on the specific contaminant to be decomposed. Any of the alkali and alkaline earth metals, or mixtures thereof may be employed in the present methods. Preferred alkali metals include lithium, sodium and potassium with sodium and potassium 1 l •&LU j o being particulary preferred.

The alkali and alkaline earth metal carbonates, bicarbonates and oxides are preferred for use in certain systems owing to their lower corrosive effects as 5 compared with alkali and alkaline earth metal hydroxides. However, the hydroxide and oxide compounds are preferred for use in systems where the contaminated medium is acidic in nature or comprises a hydrocarbon material.

In one embodiment, an alkali metal compound is used in combination with an alkaline earth metal compound in the present methods for the reductive decomposition of a chemical contaminant. More particularly, the alkali metal compounds are preferred to initiate the chemical 15 decomposition reaction. However, alkali metal compounds are generally more expensive than alkaline earth metal compounds. For example, many alkaline earth metal compounds are approximately 1/5 the cost of the corresponding alkali metal compounds. Thus, the 20 alkaline earth metal compounds, for example alkaline earth metal oxides, may be used in combination with the alkali metal compound to provide stoichiometric amounts of cations for reaction with anions liberated from the chemical contaminant, for example halogen ions liberated 25 from halogenated compounds in the reductive destruction of the halogenated compounds. When the alkali metal compound and the alkaline earth metal compound are used in combination, the alkaline earth metal compound also absorb indigenous and chemically formed water in the 30 reaction mixture. Accordingly, less of the more costly alkali metal compound may be used in combination with an alkaline earth metal compound in the present methods. As a result, the reductive decomposition may be effected at lower temperatures, faster rates and at a lower cost J I a £ > WO 94/20591 PCT7US93/02220 " 12 for raw materials. This embodiment is particularly preferred for treating organic compounds.

In accordance with an important feature of the invention, the contaminated medium further contains a 5 hydrogen donor compound. The hydrogen donor compound provides hydrogen ions for reaction with the chemical contaminant. The hydrogen donor compound may comprise an organic compound, a polymer, or a gas, for example hydrogen gas, and may be originally contained in a 10 contaminated medium together with the chemical contaminant. If the contaminant or contaminated medium to be treated does not already contain a hydrogen donor compound,, the hydrogen donor compound may be added to the contaminant or the contaminated medium together with 15 the alkali or alkaline earth metal compound. In one embodiment, the hydrogen donor compound may comprise a high boiling polar or nonpolar solvent, for example the solvent in which the alkali or alkaline earth metal compound is added. Suitable hydrogen donor compounds 20 include fatty acids, aliphatic alcohols or hydrocarbons, amines and the like. In one embodiment, the hydrogen donor compound may be modified to effect easier release of the hydrogen ion, whereby the method of the invention may be conducted at a lower temperature. For example, 25 the hydrogen donor compound may be treated with an alkylating agent which can produce tertiary hydrogen atoms in the modified hydrogen donor compound. The tertiary hydrogen atoms are more easily releasable to form hydrogen ions, whereby the methods may be conducted 30 at a lower temperature.

In order to activate the hydrogen donor compound to produce free radical hydrogen ions, a catalyst must be added, preferable either in solution or suspension. An inexpensive catalyst comprises a carbon source. One —rO.'J 94/20591 FeT/t5S93 1 3 * example of a carbon source which is water soluble and suitable for use in the invention comprises a carbohydrate, for example sucrose. Another example of a carbon source suitable for use in the present invention 5 comprises carbon black, or other carbon source having a relatively large surface area. In an alternate embodiment, the catalyst comprises a phase catalyst such as a polyalkylene glycol, for example polyethylene glycol. In a third embodiment, the catalyst may 10 comprise a combination of a carbon source and a phase catalyst such as polyethylene glycol. The catalyst is employed in the present methods in an amount sufficient to effect the desired reductive decomposition of the chemical contaminant.

Once the alkali and/or alkaline earth metal compound and the chemical contaminant are combined to form a reaction mixture which further contains an organic hydrogen donor compound and a catalyst for the formation of free radical hydrogen ions, the reaction 20 mixture is heated. Specifically, the mixture is heated at a temperature in a predetermined range for a time sufficient to cause formation of free radical hydrogen ions therein and effect reductive decomposition of the chemical contaminant. The heating step may be performed 25 at atmospheric pressure or at reduced or elevated pressures if so desired. The time required for the reductive decomposition of the chemical contaminant will depend upon the specific contaminant and its concentration. Generally, a time period of from about 30 0.5 to about 2 hours is sufficient.

The predetermined temperature range is from about 5 0 °C to about 4 00°C, depending on the chemical contaminant which is treated and the alkali and/or alkaline earth metal compounds which are employed. *•••■ r WO 94/20591 PCT/US93/02220^ 1 4 1 Preferably, when the chemical contaminant is an organic compound and an alkali metal compound or an alkaline earth metal compound is combined with the chemical contaminant, the predetermined temperature range is from 5 about 50° to less than 200°C. When the chemical contaminant is an organic compound and both an alkali metal compound and alkaline earth metal compound are combined with the chemical contaminant, the predetermined temperature range is from about 50° to 10 about 400°C. Finally, when the chemical contaminant is an inorganic compound, the predetermined temperature range is from about 50°C to 400°C. Generally, the dehalogenation or the dehydrogenation for nonaromatic compounds such as chlorof luorocarbons, halogenated 15 solvents and cyclic compounds may be conducted at temperatures up to less than 200°C. On the other hand, temperatures of from 150° to 400PC me,y be required to dehalogenate aromatic compounds. For a particular chemical contaminant, a lower temperature may be 20 employed by pretreating the hydrogen donor compound with an alkylation agent such as an aluminum compound, phosphoric acid or the like as discussed above.

When the reaction mixture containing the chemical contaminant is heated, the catalysts, for example a 25 carbon source (i.e., carbon black or a carbohydrate such as sucrose), causes the formation of a reactive hydrogen ion from the hydrogen donor compounds. This catalyzed reaction is represented by the following reaction formula: - R + M heat ^ R' + H* + M+ ■— Carbon wherein R is the hydrogen donor compounds, M is the metal compounds, Carbon * is the source of carbon, for 35 example a carbohydrate, and H" is the free radical 1 5 hydrogen Ion. The reactive free radical hydrogen ion then reacts with the chemical contaminant, for example a halogenated organic contaminant, according to the following reaction: H* + R-X + M+ heat - R-H + MX wherein R-X is the halogenated organic contaminant, X being the halogen atom, and R-H is the reduced form of 10 the contaminant compound.

Thus, the alkali or alkaline earth metal compounu catalyzes the dehalogenation and reduction of both the halogenated and non-halogenated contaminants.

Finally, when a contaminated medium is treated, the 15 medium may optionally be further treated with an acid for neutralization. Preferably, the acid is added in an 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 20 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 Na2S04 or sodium sulfate from use of sulfuric acid, NaH2P04, Na2HP04, Na3P04 or sodium 25 phosphates from the use of phosphoric acid, and NaN03 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 30 original environment if desired.

In an alternate embodiment of the methods of the present invention, chemical contaminants which may be stripped from contaminated mediums are collected in a condensate and extracted to a high boiling point oil. 35 The contaminants may then be destroyed by use of the 1 6 x i ■ ) < ;) l L present methods wherein alkali and/or alkaline earth metal compounds, a hydrogen donor compound and a catalyst are added to the ccntaminant and the resulting mixture is heated as described above.

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 10 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 15 solvent if used, there is no need to recover excess reagents for reuse. Moreover, because the present invention may employ water to wet a contaminated medium and to distribute the alkali or alkaline earth metal compounds therein, the present methods are significantly 20 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.

Moreover, the base-catalyzed decomposition methods according to the present invention are advantageous in that decomposition of both halogenated and non-halogenated organic contaminant compounds and inorganic chemical contaminants is achieved to higher degrees in 30 less time as compared with the prior art methods employing reagents derived form 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 i h i y y f .Ljf a &32 *tmrmQQ'X ff\m n WO 94/20591 rcT/tfs93^2220 1 7 ' methods could not be employed to effectively decompose or remove non-halogenated organic and inorganic contaminants from contaminated mediums.

It will also be apparent that the products of the 5 present methods may result in the production of compounds useful in other applications, whereby the present methods may be viewed as methods for synthesizing such compounds.

The methods of the present invention are 10 demonstrated in the following Examples: EXAMPLE 1 This example demonstrates the reductive decomposition of sulfur-containing organic compounds. Specifically, in a 250 ml flat bottom flask, 50 ml of a 15 hydrocarbon solvent (boiling point of 100-400°C), 0.1 g of a carbon catalyBt, 0.10 mole of dimethyl sulfoxide (DMSO) and 0.3 mole sodium hydroxide were combined. A magnetic stir bar was added to the reaction mixture and the flask was placed on a hot plate and connected with a 20 water-cooled condenser. The reaction mixture was then heated to between 50 and 100°C. As a result, the DMSO decomposed to produce sodium sulfide in an amount equal to the weight of sulfur introduced into the flask as DMSO. Additionally, a volatile component captured 25 during the reaction was determined to be methane produced from the reduction of the methyl groups of the DMSO. Both organic and inorganic sulfur compounds may be decomposed using analogous procedures to produce sulfides and elemental sulfur. Nitrogen, phosphorus and 30 oxygen-containing compounds may also be reductively decomposed according to this method using temperatures in a range of from 50°C to about 300°C. rA i h y WO 94/20591 PCI7BS93702220 1 8 EXAMPLE 2 This example demonstrates the reductive decomposition, specifically the dehalogenation, of a nonaromatic chlorocarbon, namely 1,1,1-trichloroethane. 5 In a 250 ml flat bottom flask, 100 ml of highly aromatic naphtha, O.Olg of a phase catalyst comprising polyethylene glycol (molecular weight of 60-1000), 1.0 g 1,1,1-trichloroethane and 2.0 g sodium hydroxide were combined. The reaction medium was then heated from room 10 temperature to about 100°C to effect complete dechlorination. In an alternate embodiment, a catalyst comprising a source of carbon can be employed either in place of or together with the polyethylene glycol phase catalyst. The phase catalyst is not consumed during the 15 reaction and the treatment process may be repeated without the addition of catalysts. Nitrogen, sulfur, phosphorus and oxygen-containing compounds may also be reductively decomposed using this method.

EXAMPLE 3 This example demonstrates the reductive decomposition of a halogenated aromatic compound using a combination of an alkali metal compound and an alkaline earth metal compound. In a 250 ml flat bottom flask, 100 ml of a hydrocarbon solvent (boiling point of 100-25 350°C), 0.3 M pentachlorophenol (PCP), 0.3 M sodium hydroxide, 0.3 M calcium oxide and 0.1 g of a carbon catalyst were combined. The reaction medium was heated to a temperature of 150°C to 350°C to effect complete dechlorination of the pentachlorophenol. The 30 dehalogenation reaction may be further improved when a carbon catalyst and a phase catalyst such as polyethylene glycol are combined.

Thus, the methods of the present invention are

Claims (25)

WO 94/20591 1 9 1 01 S93/omo advantageous for the reductive destruction of halogenated and non-halogenated organic compounds and inorganic compounds. The methods of the present invention employ relatively inexpensive compounds, 5 namely, the alkali or alkaline earth metal compounds, for example carbonates, bicarbonates, oxides and hydroxides, high boiling hydrocarbon solvents as hydrogen donor compounds, and a catalyst, for example a catalytic form of carbon preformed or obtained from a 10 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, bicarbonates and oxides employed in the methods of the present invention are less corrosive than 15 the alkali and alkaline earth metal hydroxides, although the hydroxides may be required or preferred in some instances. Thus, the methods of the present invention provide an improved process for destroying or reducing chemical contaminant compounds to non-detectable levels. 20 The organic 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. 25 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 30 will be apparent to one of ordinary skill in the art. 25 1 52 2 20 ' ~WHAT IS CLAIMED IS:

1. A method for.the reductive decomposition of a chemical contaminant, comprising (a) combining at leaBt one alkali or alkaline earth metal compound and the chemical contaminant to form a reaction mixture, said reaction mixture further containing a hydrogen donor compound and a catalyst which will cause the formation of a free radical hydrogen ion; and (b) heating the reaction mixture at a temperature in a predetermined range for a time sufficient to cause formation of a free radical hydrogen ion therein and effect reductive decomposition of the chemical contaminant, provided that (i) when the chemical contaminant is an organic compound, the predetermined temperature range is from substantially 50° to less than 20 0° and- (ii) when the chemical contaminant is an inorganic compound, the predetermined temperature range is from substantially 50°C to 400°C.

2. A method as defined by claim 1, wherein the chemical contaminant is an organic compound, and an alkali metal compound or an alkaline earth metal compound is combined with the chemical contaminant. 25 15 21

"3. A method as defined by claim 2, wherein the reaction mixture contains the alkali metal compound or alkaline earth metal compound and the chemical contaminant in a molar ratio of from substantially 1:1 to 10 :1.

4. A method as defined by claim 2, wherein the chemical contaminant comprises a nonaromatic organic compound.

5. A method as defined by claim 2, wherein the hydrogen donor compound comprises a polymer, a gas or a high boiling solvent selected from the group consisting of fatty acids, aliphatic alcohols, hydrocarbons and amines.

6. A method as defined by claim 2, wherein the catalyst comprises a source of carbon.

7. A method as defined by claim 6, wherein the catalyst comprises a carbohydrate or carbon black.

8. A method as defined by claim 2, wherein the catalyst comprises a polyalkylene glycol.

9. A method as defined by claim 1, wherein the chemical contaminant -is an organic compound, and an alkali metal compound and an alkaline earth metal compound are combined with the chemical contaminant. 251522 22

10. A method as defined by claim 9, wherein the reaction mixture contains the alkali metal compound and alkaline earth metal compound combined, and the chemical contaminant in a molar ratio of from substantially 1:1 to 10:1.

11. A method as defined by claim 9, wherein the chemical contaminant comprises a halogenated aromatic organic compound.

12. A method as defined by claim 9, wherein the hydrogen donor compound comprises a polymer, a gas or a high boiling solvent selected from the group consisting of fatty acids, aliphatic alcohols, hydrocarbons and amines.

13. A method as defined by claim 9, wherein the catalyst comprises a source of carbon.

14. A method as defined by claim 13, wherein the catalyst comprises a carbohydrate or carbon black.

15. A method as defined by claim 9, wherein the catalyst comprises a polyalkylene glycol.

16. A method as defined by claim l, wherein the chemical contaminant is am inorganic compound.

17. A method as defined by claim 16, wherein the reaction mixture contains the alkali metal compound or alkaline earth metal compound and the chemical contaminant in a molar ratio of from substantially 1:1 to /•' i::S "i t. . V f,;' I ^ <- c 23 10:1

18. A method as defined by claim 16, wherein the hydrogen donor compound comprises a polymer, a gas or a high boiling solvent selected from the group consisting of fatty acids, aliphatic alcohols, hydrocarbons and amines.

19. A method as defined by claim 16, wherein the catalyst comprises a source of carbon.

20. A method as defined by claim 19, wherein the catalyst comprises a carbohydrate or carbon black.

21. A method as defined by claim 16, wherein the catalyst comprises a polyalkylene glycol. f *.

22. A method as defined by claim 1, wherein the at least one alkali or alkaline earth metal compound is selected from the group consisting of carbonates, bicarbonates, oxides, hydroxides and compounds which generate carbonates, bicarbonates, oxides or hydroxides.

23. A method as defined by claim 1, wherein the hydrogen donor compound is treated with an alkylating agent prior to inclusion in the reaction mixture.

24. A method as defined in claim 1, wherein the chemical contaminant is an organic compound and the predetermined temperature range is from substantially " 50°C to 100°G.

25. A method according to claim 1 for the reductive decomposition of a chemical contaminant substantially as herein described with reference to the Examples. N Z PV.TrJiT OFFICE 1 5 MAY 1996 received