EP0456879B1 - Process for the dehalogenation of organic compounds - Google Patents

Process for the dehalogenation of organic compounds Download PDF

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Publication number
EP0456879B1
EP0456879B1 EP90116143A EP90116143A EP0456879B1 EP 0456879 B1 EP0456879 B1 EP 0456879B1 EP 90116143 A EP90116143 A EP 90116143A EP 90116143 A EP90116143 A EP 90116143A EP 0456879 B1 EP0456879 B1 EP 0456879B1
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EP
European Patent Office
Prior art keywords
reaction
process according
organohalides
dehalogenation
catalyst
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP90116143A
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German (de)
English (en)
French (fr)
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EP0456879A1 (en
Inventor
Ilan Pri-Bar
David Azoulay
Ouri Buchman
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Israel Atomic Energy Commission
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Israel Atomic Energy Commission
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Definitions

  • the present invention relates to a process for the dehalogenation of organic compounds. More particularly, the invention relates to the degradation and detoxification of organic compounds containing halogen atoms.
  • Organic halogenated compounds are obtained in relatively large amounts as by-products of various industrial processes.
  • Representative - but not limitative - examples of such compounds are chloro- or bromo-aromatic compounds, such as polychlorinated and polybrominated biphenyls (PCBs and PBBs), polychloro heterocyclic compounds, such as p-hexachlorocyclohexane, and organic solvents such as chlorobenzene.
  • PCBs and PBBs polychlorinated and polybrominated biphenyls
  • PBBs polychloro heterocyclic compounds
  • organic solvents such as chlorobenzene.
  • the first type of process includes the reductive dehalogenation, wherein the organic substances are treated with hydrogen gas (e.g., US-A-4,840,721, US-A-4,818,368, EP-A-306,164 and EP-A-299,149), or with other hydrogen donating compounds such as alkali hydride (GB-A-2,189,804), hypophosphite (US-A-4,618,686), sodium borohydride (US-A-4 804 779.
  • hydrogen gas e.g., US-A-4,840,721, US-A-4,818,368, EP-A-306,164 and EP-A-299,149
  • hydrogen gas e.g., US-A-4,840,721, US-A-4,818,368, EP-A-306,164 and EP-A-299,149
  • other hydrogen donating compounds such as alkali hydride (GB-A-2,189,804), hypophosphite (US-A-4,618,686), sodium borohydride
  • the second type of dehalogenation processes involves the reactions of metals, alkali earth metals, alkali metals, or compounds of these metals which are chemically capable of causing the degradation of a carbon-halogen bond, and which lead to the transformation of the organic halogen into an inorganic halogen bonded to the metal.
  • Some examples of such processes are the use of metal or metals compounds such as tin, lead, aluminum, chloroaluminates, titanium, aluminum oxide, etc. (EP-A-277,858, EP-A-184,342 and US-A-4,435,379).
  • alkali metals and alkali metal compounds such as sodium/sodium hydroxide (US-A-4,755,628, CA-A-1,185,265 and EP-A-99,951), sodium naphthalene, sodium polyethylene glycol (EP-A-140,999 and EP-A-60,089), sodium carbonate, bicarbonate, alcoholates, etc. (US-A-4,631,183 and EP-A-306,398).
  • dehalogenation usually involves high temperatures, in the order of 500-1000°C, which are needed for the cleavage of the stable carbon-chlorine bond, and for the purpose of bringing the metal into contact with the organic compound in the form of molten salt, fine dispersion, etc.
  • Active metallic compounds may react at lower temperatures, in the order of 300-600°C.
  • a large excess of expensive reagents are needed, and the process involves separation and purification steps which render it both complicated and expensive.
  • the process for the dehalogenation of organohalides according to the invention comprises reacting an organohalide or a mixture of two or more organohalides with an alkali hydroxide in an alcoholic solution and in the presence of a heterogeneous transfer hydrogenolysis catalyst and in the abscence of added hydrogen.
  • the alcohol found in the alcoholic solution is a lower alcohol.
  • the preferred alkali hydroxide is sodium or potassium hydroxide, although of course other hydroxides may be employed.
  • any transfer hydrogenolysis catalyst may be employed, as long as a catalytically effective amount is provided.
  • a preferred catalyst would be, e.g., palladium-on-carbon. This catalyst is usually provided as 5% or 10% palladium-on-carbon.
  • reaction temperatures are comprised between 50° and 150°C. Although higher temperatures could be employed, this is generally not required.
  • the reaction can proceed at low pressures, e.g., atmospheric pressure in an open vessel. Normally it will be preferred to carry out the reaction in a closed reactor at pressures lower than 3-4 atmospheres. This, as will be apparent to a skilled person, is a considerable advantage over the prior art, which requires considerably higher temperatures and pressures.
  • the process of the invention does not require anhydrous conditions and may be conveniently carried out in the presence of high water concentrations (e.g., 25%). This is an additional advantage of the invention, since anhydrous conditions require efforts and expenses.
  • the concentration of the organohalides in the reaction mixture is comprised between 0.1-10% of the reaction mixture, and the alkali hydroxide is present in a stoichiometric excess over the organohalides.
  • concentration of organohalides remaining in the reaction mixture under normal conditions is lower than the detection limits.
  • the catalyst used in the reaction can be quantitively recovered after completion of the reaction, washed with water, and reused in a subsequent reaction. Therefore, this process is highly efficient also from the point of view of catalyst usage.
  • the invention also encompasses a process for the purification and the reclamation of fluids which are contaminated with organohalides, which process comprises contacting the fluid to be purified with a stoichiometric excess of an alkali hydroxide, with respect to the organohalide, in an alcoholic solution and in the presence of a catalytically effective amount of a heterogeneous transfer hydrogenolysis catalyst.
  • contaminated fluids are, e.g., mineral oils, silicon oils, lube oils, gas oils, transformation oils, which may be contaminated, e.g., with chlorinated organic compounds in a concentration range of about 0.1-60%.
  • Example 1 was repeated but without introduction of catalyst. No change in the starting Pyralene was observed in GC-EC analysis and no biphenyl was detected, as observed in GC-FID and HPLC analysis.
  • Example 1 was repeated but without nitrogen purging. No residual Pyralene was observed, indicating less than 1.0 ppm PCBs contents. Biphenyl (24.5% weight) was determined by GC and HPLC, indicating total hydrogenolysis of PCBs.
  • Example 1 was repeated but 0.25 ml water was introduced in addition to the methanol. Biphenyl (25% weight) was determined after the reaction was concluded. GC analysis revealed that no residual Pyralene components were left. A sole product with low retention time (20 min.) was detected in a concentration scale 1/10,000 lower than the starting Pyralene.
  • Catalyst from example 5 was washed with water and with THF and then dried under vacuum at 100°C to constant weight (57 mg). This catalyst was added together with 1.54 gr Pyralene, 3.6 gr sodium hydroxide, 10 ml methanol and 2 ml water into the reaction flask. The mixture was heated to 80°C for 18 hours.
  • Example 1 was repeated but 0.5 ml mineral oil contaminated with 0.2 ml (280 mg) Pyralene were added to the dehalogenation mixture. After completion of the reaction, the oil was separated from the methanol by means of phase separation. The solid was washed with methanol and the combined methanol fractions were subjected to GC and HPLC analysis. The oil phase was dissolved in THF and was subjected to GC and HPLC analysis.
  • Organic products contain mainly benzene and biphenyl (68.6 mg), 24.5% weight of starting Pyralene.
  • Halogenated compound (1 mmol), 0.72 gr sodium hydroxide (18 mmol), and 10 mg 10% palladium on carbon (0.01 mAtom Pd) were placed in a glass reactor, and 2.5 ml of methanol were added to this mixture. The reactor was purged twice with nitrogen, sealed and heated to 100°C for 16 hours.
  • Example 1 was repeated, but with 1 gr (18 mmol) of potassium hydroxide as a base. After the conclusion of the reaction, no residual Pyralene was detected by GC (EC detector) analysis. Biphenyl (70.5 mg, 24.5% weight) was determined by GC and HPLC, indicating a highly efficient dehalogenation reaction.
  • Example 1 was repeated but with 2.5 ml of ethanol as a hydrogen donor and solvent. After the conclusion of the reaction no observable remainders of Pyralene were detected in the solution, using GC (EC detector) analysis. Biphenyl (70.0 mg, 24.8 weight %) and benzene were the main organic products in the GC and HPLC analysis. An additional, unidentified minor organic product was eluted at lower retention time (24 min.) in GC analysis.
  • Dehalogenated organic products may be used as a source of heat and contribute to an additional energy credit of the process.
  • Inorganic products are harmless salts such as sodium chloride and sodium formate. The latter is a useful and saleable product, and the resulting revenue may reduce operating costs.
  • FIG. 3 A schematic flow diagram for a dechlorination unit, according to one process of the invention, is shown in Fig. 3.
  • the work-up process after the conclusion of the reaction starts with the evaporation of the solvents through condenser (1) and recycling the methanol using a solvent still and condenser (2).
  • the non-volatile residue is washed with water into a liquid-liquid extraction unit, useful for the recovery of purified oils.
  • the basic aqueous solution may be reused in the following dehalogenation process or may be neutralized with hydrochloric acid, followed by evaporation of water to dryness. Methanol is then added, allowing separation of soluble sodium formate from sodium chloride, which is disposed to waste.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP90116143A 1990-05-15 1990-08-23 Process for the dehalogenation of organic compounds Expired - Lifetime EP0456879B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL9439790A IL94397A (en) 1990-05-15 1990-05-15 Process for the dehalogenation of organic compounds
IL94397 1990-05-15

Publications (2)

Publication Number Publication Date
EP0456879A1 EP0456879A1 (en) 1991-11-21
EP0456879B1 true EP0456879B1 (en) 1996-04-17

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EP90116143A Expired - Lifetime EP0456879B1 (en) 1990-05-15 1990-08-23 Process for the dehalogenation of organic compounds

Country Status (6)

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EP (1) EP0456879B1 (ja)
JP (1) JP2823950B2 (ja)
AT (1) ATE136801T1 (ja)
CA (1) CA2024107C (ja)
DE (1) DE69026605T2 (ja)
IL (1) IL94397A (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5196617A (en) * 1992-01-14 1993-03-23 Engelhard Corporation Method of hydrodehalogenating halogenated organic compounds in aqueous environmental sources
US5177268A (en) * 1992-04-06 1993-01-05 Engelhard Corporation Hydrodehalogenation of aromatic compounds
JP2006117533A (ja) * 2004-10-19 2006-05-11 National Institute Of Advanced Industrial & Technology ヘキサクロロシクロヘキサンの分解方法
JP5344684B2 (ja) * 2008-01-07 2013-11-20 公益財団法人名古屋産業科学研究所 芳香族ハロゲン化物の脱ハロゲン化方法
JP2011088077A (ja) * 2009-10-22 2011-05-06 Jfe Mineral Co Ltd 有機ハロゲン化合物の浄化材及び該浄化材を用いた浄化方法、該浄化材のリサイクル方法
JP5664030B2 (ja) * 2010-09-01 2015-02-04 エヌ・イーケムキャット株式会社 含フッ素化合物の脱フッ素化法
JP2015013832A (ja) * 2013-07-05 2015-01-22 日立化成株式会社 芳香族化合物の製造方法及び有機エレクトロニクス材料

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3595931A (en) * 1968-05-28 1971-07-27 Gulf Research Development Co Hydrogenolysis of aromatic halides
JPS5236650A (en) * 1975-09-12 1977-03-22 Oosakafu Method for treating polychlorobiphenyl
US4351978A (en) * 1980-07-21 1982-09-28 Osaka Prefectural Government Method for the disposal of polychlorinated biphenyls
US4618686A (en) * 1984-09-27 1986-10-21 Ciba-Geigy Corporation Process for dehalogenation of aryl and alpha-araliphatic halides
GB8515063D0 (en) * 1985-06-14 1985-07-17 Ici Plc Polyaromatic compounds
US4775475A (en) * 1985-10-28 1988-10-04 Uop Inc. Process for the removal of hydrocarbonaceous compounds from an aqueous stream and hydrogenating these compounds

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Publication number Publication date
CA2024107A1 (en) 1991-11-16
JPH0426632A (ja) 1992-01-29
EP0456879A1 (en) 1991-11-21
DE69026605T2 (de) 1996-10-24
CA2024107C (en) 1998-06-30
JP2823950B2 (ja) 1998-11-11
IL94397A0 (en) 1991-03-10
ATE136801T1 (de) 1996-05-15
IL94397A (en) 1994-10-07
DE69026605D1 (de) 1996-05-23

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