IE63083B1 - Chemical process for destroying halogenated organic products - Google Patents
Chemical process for destroying halogenated organic productsInfo
- Publication number
- IE63083B1 IE63083B1 IE267088A IE267088A IE63083B1 IE 63083 B1 IE63083 B1 IE 63083B1 IE 267088 A IE267088 A IE 267088A IE 267088 A IE267088 A IE 267088A IE 63083 B1 IE63083 B1 IE 63083B1
- Authority
- IE
- Ireland
- Prior art keywords
- process according
- halogenated
- ppm
- products
- aleoholate
- Prior art date
Links
- 238000001311 chemical methods and process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 28
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- -1 halogenated aryl compound Chemical class 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 239000002480 mineral oil Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000002013 dioxins Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004826 dibenzofurans Chemical class 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 4
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 235000017168 chlorine Nutrition 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000004074 biphenyls Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UVROAJFELBNMRA-UHFFFAOYSA-N (1-chloro-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(Cl)CC1=CC=CC=C1 UVROAJFELBNMRA-UHFFFAOYSA-N 0.000 description 1
- MEIUXJOXEUYBRW-UHFFFAOYSA-N 1,2-dichloro-3-(1,1-dichloro-2-phenylethyl)benzene Chemical compound ClC1=CC=CC(C(Cl)(Cl)CC=2C=CC=CC=2)=C1Cl MEIUXJOXEUYBRW-UHFFFAOYSA-N 0.000 description 1
- WZTJFRVXSHGGEF-UHFFFAOYSA-N 1-chloro-4-(2-phenylethyl)benzene Chemical compound C1=CC(Cl)=CC=C1CCC1=CC=CC=C1 WZTJFRVXSHGGEF-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
Landscapes
- 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)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fire-Extinguishing Compositions (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Insulating Materials (AREA)
- Processing Of Solid Wastes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
A process for the destruction of halogenated products and more particularly of chlorinated aromatic products or of oils containing these products, for example unchlorinated dielectric fluids contaminated with PCBs. The process is characterised in that these products are subjected to the action of an alcoholate and preferably sodium methylate at a temperature of between 250 and 290 DEG C.
Description
The present invention relates to a chemical process for destroying halogenated aryl compounds contained in a non-halogenated organic material, for example chlorinated aromatic products such as PCBs (polychlorobiphenyls), which are possibly present in a mixture with non-halogenated organic compounds.
The removal of PCBs present in dielectric transformer oils or lubricating oils by extraction with methanol has already been proposed in the prior art (US Patent 4,387,018). The methanol is then separated from the PCBs by distillation and is then recycled. This process enables the quantity of PCB to be reduced by 70%. European Patent EP 99,951 discloses the treatment of similar products with sodium dispersed as particles larger than 10 pm. European Patent Application EP 107,404 describes the treatment of a transformer oil containing 652 ppm of PCB with sodium salts of a polyethylene glycol. The disadvantage of these processes is that they require separations and recycling operations or the handling of sodium. European Patent Application EP 21,294 describes the destruction of dioxins, in particular chlorinated anisoles containing 39.7 ppm of 2,3,7,8-tetrachlorodibenzo-p-dioxin, by reacting these products under pressure with sodium methylate in methanol at 160°C. Moreover, a paper by Gyula Pfeifer and Terez Flora in the Hungarian journal Magy. Kem. Folyoirat 71 (8), 343-6 (1965) explains that sodium methylate can decompose from 120 to 140°C. A much simpler and highly efficient process has now been found.
The present invention relates to a process for destroying one or more halogenated aryl compounds contained in a non-halogenated organic material which process comprises bringing the material into contact with an anhydrous alkali metal alcoholate in powder form at a temperature of at least 220°C such that halogenated aryl compound is converted into inorganic halide, the alcoholate being used in an excess with respect to the stoichiometry based on the quantity of halogen and being chosen from the methylate, ethylate, propylate or isopropylate of sodium, lithium or potassium; and recovering the non-halogenated organic material by distillation.
The invention applies to all halogenated compounds, for example chlorine- and/or bromine-substituted aryl hydrocarbons. These include, for example, chlorinated or brominated dioxins, chlorinated or brominated dibenzofurans, (polychloro)biphenyls, (polybromo)biphenyls, (polybromo)diphenyl ethers, and (polychloro)diphenyl ethers. These compounds may be present singly or mixed together, with non-halogenated organic products such as polyarylalkanes, or mineral oils.
Although the invention makes it possible to destroy any halogenated aryl compound, the process is generally used for such materials comprising 1% or less, for example 1000 ppm or less by weight of halogen.
Anhydrous sodium methylate in powder form is particularly suitable.
In general the aleoholate is added to the halogenated aryl compounds or the mixture comprising them.
When the stoichiometry of the process is one aleoholate group * per atom of halogen to be removed, the aleoholate is used in excess with respect to this stoichiometry. Very good dehalogenation can be achieved by employing an excess of, for example, 5 to 10 times the stoichiometry. For example, if a mixture contains PCBs in a proportion of 100 ppm, expressed as chlorine, a quantity of sodium methylate of 0.14% is suitably employed.
It is also possible to use, together with the aleoholate, one or more additional reagents capable of converting organic chlorine into an inorganic chloride.
Suitable examples include sodium carbonate and other alkaline reagents.
The halogenated aryl compounds are generally brought into contact with the aleoholate with agitation, for example in a stirred reactor or a packed column, or by any other means which affords sufficient agitation to disperse the aleoholate thoroughly whilst allowing adequate contact between the reactants to destroy the halogenated compounds.
The reaction may be carried out continuously or noncontinuously. The reaction kinetics increase with * k temperature. A suitable temperature is from 220 to 300°C, for example from 250 to 29,0°C. Depending on the physical properties of the products (for example vapour pressure) the operation is suitably carried out at atmospheric pressure or at a higher pressure. The reaction time is a function of the quantities of organic halogen, of temperature, of the quantity of alcoholate, and of the agitation conditions for obtaining good contact between the reactants; it is usually from 30 minutes to 10 hours.
The Invention is applied to the destruction of halogenated aryl products present in a mixture, such as a non-halogenated dielectric liquid or a mineral oil containing PCBs. When the process of the invention is applied to such a material containing PCBs or other halogenated aryl compounds, the inorganic halogenated products are separated from the other products by distillation. A mineral oil or a dielectric liquid free from organic chlorine is thus obtained.
An excess of alcoholate is employed to ensure that the dehalogenation process is as complete as possible. When a dielectric fluid comprising a few hundred ppm of aromatic chlorinated compounds is treated, the products obtained at the end of the reaction comprise the dielectric, the chloride NaCl, the conversion products of the aromatic chlorinated compounds and unreacted alcoholate. This mixture is generally distilled to recover the pure dielectric no longer containing aromatic chlorine.
When the alcoholate employed is sodium methylate, it is usual not to exceed a residence time of 12 hours at 295°C in the distillation apparatus to avoid a decomposition of v the methylate.
It is possible to use the process of the present invention as an adjunct to a sodium carbonate process.
Sodium carbonate is very easy to handle but only enables aliphatic halogens and the most labile aryl halogen to be removed.
The process of the invention makes it possible to obtain a product with an aryl halogen content of less than 10 ppm. The advantages of this process are that it is applicable to compounds containing relatively unreactive halogen atoms and it does not require the use of solvents; that is to say, it suffices to add an alcoholate, for example to the oil containing the PCBs, in the absence of the corresponding alcohol, as in EP 21,294. Furthermore, this process does not require a preliminary separation of the excess alcoholate, in particular of sodium methylate, at the end of the treatment, before recovery of the dehalogenated products.
Another advantage of the process is that the v byproducts formed, such as the chloride NaCl, the aryl halogenated products converted by the aleoholate and the remaining unreacted aleoholate, can be easily destroyed by incineration without giving rise to toxic products.
The following Examples further illustrate the invention.
EXAMPLE 1 1000 g of dibenzyl toluene (DBT) containing 300 ppm of aromatic chlorine in the form of monochlorobenzyltoluene are taken. This mixture is placed in a reactor fitted with a rotary stirrer, a reflux condenser and a nitrogen injector. After purging with a stream of nitrogen at 100°C for 15 minutes, 1X by weight (i.e. 10 g) of sodium methylate is added. The mixture is heated to reflux at 285°C with stirring and nitrogen purging for 3 hours. The product is then distilled, vacuum being applied progressively, down to 2 mm of mercury so as not to exceed 300°C in the heel. The' distillate obtained has a total aromatic chlorine content of 3 ppm.
By way of comparison, when the same product containing the same chlorinated products is treated with sodium carbonate, a product which has a total aromatic chlorine content of the order of 100 ppm is obtained.
EXAMPLE 2 DBT is treated as in Example 1 but with NaOCzHs, KOCH3, KOC2H5 and NaOCH(CH3)2 in the conditions of Example 1. The results are given in the table.
EXAHPLE 3 v a) DBT containing 1000 ppm of PCB is treated with 1Z of sodium methylate for 3 hours at 280°C. A product containing less than 15 ppm of chlorine is obtained. b) Identical with a), except that the DBT contains 1000 ppm of tetrachlorobenzyltoluene.
The results are given in the table.
EXAHPLE 4 a) A mineral oil containing 1000 ppm of PCB is treated with 1% of CHjONa for 3 hours at 280°C. A product containing less than 15 ppm of halogen is obtained. b) Identical with a), except that the mineral oil contains 1000 ppm of octabromobiphenyl.
The results are given in the table.
EXAHPLE 5 1600 g of DBT and 32 g of sodium methylate ,are placed in a reactor fitted with a rotary stirrer, a condenser and a nitrogen injector. The mass is heated to reflux <290°C) under a nitrogen purge and with stirring.
The nitrogen stream is then stopped and the condenser outlet is connected to a vessel containing water. After ξ treatment for 70 hours at 290°C, no gas release is observed. After cooling and filtration, the reaction mixture shows: that there is no sign of light products in the filtrate, according to chromatographic analysis, and that the infrared spectrum on the solid after washing with monochIorobenzene and with hexane and after drying in the absence of air (weight collected = 952 of the weight of methylate employed) is precisely that of sodium methylate.
Nature of the product treated ! ΣΧ/ΚΡ-ΧΕ. 2 j DBT + 300 ppm of chlorine j in the form of monochloro-. j benzy 11 oluene ι 1 EXAMPLE. 3 ! BT 100 4 1000 ppm of PCB • (6.5 chlorines) * BT 100 + 1000 ppm of tetra* chLorobenzyltoluene i EXAMPLE 4 • Mineral oil ♦ 1000 ppm j of PCB 6.5 chlorines (*) » Mineral oil + 1000 ppm j of octabromobiphenyl(**) !_ J Alcoholate I ί employed _ X C B.OKa 0.5 2 cLoK 0.5 X C.B^OK 0.5 2 (CHp^CHONa 2 CR^ONa 1 2 CH^ONa ! I ! 1 2 CB ONa j 3 ! 1 2 CB ONa j 3 ! j Weight content j ί of hafc-o'gen in 1 the treated and j distilled product ? < 15 ppm ! < 15 ppa ! < 15 ppm ! ppm ! < 15 ppm < 15 ppm < 15 ppm < 15 ppm (*) Determination of 580 ppm of chlorine in the form of chloride in the distillation residue, relative to the quantity of oil employed.
(**) Determination of 846 ppm of bromine in the form of bromide in the distillation residue, relative to the quantity of oil employed.
Claims (10)
1. A process for destroying one or more halogenated aryl compounds contained in a non-halogenated organic material which process comprises bringing the material into contact with an anhydrous alkali metal aleoholate in powder form at a temperature of at least 220°C such that halogenated aryl compound is converted into inorganic halide, the aleoholate being used in an excess with respect to the stoichiometry based on the guantity of halogen and being chosen from the methylate, ethylate, propylate or isopropylate of sodium, lithium or potassium; and recovering the non-halogenated organic material by distillation.
2. A process according to claim 1 in which he alkali metal aleoholate is sodium methylate.
3. A process according to claim 1 or 2 in which the halogenated aryl compound is a chlorine- or brominesubstituted aryl hydrocarbon.
4. A process according to claim 3 in which the aryl hydrocarbon material comprises benzyltoluene, triphenylmethane or a higher homologue thereof.
5. A process according to any one of claims 1 to 3 in which the aryl hydrocarbon material comprises polychlorobiphenyls, dioxins or dibenzofurans. ’
6. A process according to any one of the preceding claims in which the non-halogenated organic materials are polyarylalkanes or mineral oils.
7. A process according to any one of the preceding claims in which the temperature is from 220 to 300°C.
8. A process according to claim 7 in which the 5 temperature is from 250° to 290°C.
9. A process according to claim 1 substantially as described in any one of the Examples.
10. A substantially dehalogenated hydrocarbon material whenever produced by the process according to any 10 one of claims 1 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8712248A FR2620055B1 (en) | 1987-09-03 | 1987-09-03 | CHEMICAL PROCESS OF DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE882670L IE882670L (en) | 1989-03-03 |
| IE63083B1 true IE63083B1 (en) | 1995-03-22 |
Family
ID=9354601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE267088A IE63083B1 (en) | 1987-09-03 | 1988-09-02 | Chemical process for destroying halogenated organic products |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0306398B1 (en) |
| JP (1) | JPH0667409B2 (en) |
| KR (1) | KR910000196B1 (en) |
| CN (1) | CN1016142B (en) |
| AT (1) | ATE85229T1 (en) |
| CA (1) | CA1336981C (en) |
| DE (1) | DE3878098T2 (en) |
| DK (1) | DK169377B1 (en) |
| ES (1) | ES2053784T3 (en) |
| FI (1) | FI97276C (en) |
| FR (1) | FR2620055B1 (en) |
| IE (1) | IE63083B1 (en) |
| NO (1) | NO176749C (en) |
| PT (1) | PT88421B (en) |
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| US10542777B2 (en) | 2014-06-27 | 2020-01-28 | British American Tobacco (Investments) Limited | Apparatus for heating or cooling a material contained therein |
| US11064725B2 (en) | 2015-08-31 | 2021-07-20 | British American Tobacco (Investments) Limited | Material for use with apparatus for heating smokable material |
| US11241042B2 (en) | 2012-09-25 | 2022-02-08 | Nicoventures Trading Limited | Heating smokeable material |
| US11452313B2 (en) | 2015-10-30 | 2022-09-27 | Nicoventures Trading Limited | Apparatus for heating smokable material |
| US11659863B2 (en) | 2015-08-31 | 2023-05-30 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US11672279B2 (en) | 2011-09-06 | 2023-06-13 | Nicoventures Trading Limited | Heating smokeable material |
| US11825870B2 (en) | 2015-10-30 | 2023-11-28 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US11924930B2 (en) | 2015-08-31 | 2024-03-05 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2656603B1 (en) * | 1989-12-28 | 1993-05-21 | Atochem | METHODS OF SYNTHESIS OF BENZYLTOLUENE AND LOW CHLORINE DIBENZYLTOLUENE. |
| US5490919A (en) * | 1990-08-14 | 1996-02-13 | State Of Isreal, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
| US5093011A (en) * | 1990-12-12 | 1992-03-03 | Chemical Waste Management, Inc. | Process for dehalogenation of contaminated waste materials |
| JPH04253875A (en) * | 1991-02-01 | 1992-09-09 | Chiyoda Kohan Kk | Decomposition and removal of chlorinated compound |
| DE4109639C2 (en) * | 1991-03-23 | 1994-06-01 | Metallgesellschaft Ag | Process for the decomposition of polyhalogenated organo compounds |
| JP2638483B2 (en) * | 1994-06-30 | 1997-08-06 | 株式会社関西テック | Method for treating polychlorinated aromatic compounds |
| ES2297829T3 (en) | 1994-09-30 | 2008-05-01 | Arkema France | USE FOR DISTRIBUTION TRANSFORMERS OF A POLYARILALCAN BASED DIELECTRIC COMPOSITION WITH IMPROVED DIELECTRIC PROPERTIES. |
| JP4537539B2 (en) * | 2000-06-20 | 2010-09-01 | 利夫 半谷 | Decomposition treatment method and treatment equipment for hazardous substances |
| JP2003001220A (en) * | 2001-06-25 | 2003-01-07 | Kansai Electric Power Co Inc:The | Method for separating polychlorinated aromatic compound from contaminated material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4327027A (en) * | 1979-06-15 | 1982-04-27 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
| AU555461B2 (en) * | 1983-03-10 | 1986-09-25 | Sea Marconi Decontamination S.R.L. | Process for the decomposition and decontamination of organic substances and halogenated toxic materials |
| US4574013A (en) * | 1985-04-18 | 1986-03-04 | Galson Research Corporation | Method for decontaminating soil |
| CH668709A5 (en) * | 1985-12-06 | 1989-01-31 | Ciba Geigy Ag | METHOD FOR ENTHALOGENATING POLYHALOGENATED ALIPHATIC AND AROMATIC COMPOUNDS. |
| DE3621175A1 (en) * | 1986-06-25 | 1988-01-07 | Huels Chemische Werke Ag | METHOD FOR ENTHALOGENATING HYDROCARBON OILS |
-
1987
- 1987-09-03 FR FR8712248A patent/FR2620055B1/en not_active Expired - Lifetime
-
1988
- 1988-08-23 CA CA000575896A patent/CA1336981C/en not_active Expired - Lifetime
- 1988-08-29 AT AT88402176T patent/ATE85229T1/en not_active IP Right Cessation
- 1988-08-29 DE DE8888402176T patent/DE3878098T2/en not_active Expired - Lifetime
- 1988-08-29 ES ES88402176T patent/ES2053784T3/en not_active Expired - Lifetime
- 1988-08-29 EP EP88402176A patent/EP0306398B1/en not_active Expired - Lifetime
- 1988-09-01 NO NO883893A patent/NO176749C/en not_active IP Right Cessation
- 1988-09-01 JP JP63219600A patent/JPH0667409B2/en not_active Expired - Lifetime
- 1988-09-02 FI FI884055A patent/FI97276C/en not_active IP Right Cessation
- 1988-09-02 PT PT88421A patent/PT88421B/en not_active IP Right Cessation
- 1988-09-02 DK DK488488A patent/DK169377B1/en not_active IP Right Cessation
- 1988-09-02 IE IE267088A patent/IE63083B1/en not_active IP Right Cessation
- 1988-09-03 CN CN88106409A patent/CN1016142B/en not_active Expired
- 1988-09-03 KR KR1019880011407A patent/KR910000196B1/en not_active IP Right Cessation
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11672279B2 (en) | 2011-09-06 | 2023-06-13 | Nicoventures Trading Limited | Heating smokeable material |
| US12041968B2 (en) | 2011-09-06 | 2024-07-23 | Nicoventures Trading Limited | Heating smokeable material |
| US11241042B2 (en) | 2012-09-25 | 2022-02-08 | Nicoventures Trading Limited | Heating smokeable material |
| US10036574B2 (en) | 2013-06-28 | 2018-07-31 | British American Tobacco (Investments) Limited | Devices comprising a heat source material and activation chambers for the same |
| US10542777B2 (en) | 2014-06-27 | 2020-01-28 | British American Tobacco (Investments) Limited | Apparatus for heating or cooling a material contained therein |
| US11064725B2 (en) | 2015-08-31 | 2021-07-20 | British American Tobacco (Investments) Limited | Material for use with apparatus for heating smokable material |
| US11659863B2 (en) | 2015-08-31 | 2023-05-30 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US11924930B2 (en) | 2015-08-31 | 2024-03-05 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US11452313B2 (en) | 2015-10-30 | 2022-09-27 | Nicoventures Trading Limited | Apparatus for heating smokable material |
| US11825870B2 (en) | 2015-10-30 | 2023-11-28 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US12016393B2 (en) | 2015-10-30 | 2024-06-25 | Nicoventures Trading Limited | Apparatus for heating smokable material |
Also Published As
| Publication number | Publication date |
|---|---|
| NO883893D0 (en) | 1988-09-01 |
| FI97276C (en) | 1996-11-25 |
| KR890004780A (en) | 1989-05-09 |
| FR2620055B1 (en) | 1991-05-10 |
| DE3878098T2 (en) | 1993-06-09 |
| DK488488A (en) | 1989-03-04 |
| CA1336981C (en) | 1995-09-12 |
| FI884055A0 (en) | 1988-09-02 |
| FR2620055A1 (en) | 1989-03-10 |
| FI97276B (en) | 1996-08-15 |
| JPS6470084A (en) | 1989-03-15 |
| DK488488D0 (en) | 1988-09-02 |
| FI884055A (en) | 1989-03-04 |
| DE3878098D1 (en) | 1993-03-18 |
| EP0306398B1 (en) | 1993-02-03 |
| PT88421A (en) | 1989-07-31 |
| CN1016142B (en) | 1992-04-08 |
| PT88421B (en) | 1992-10-30 |
| IE882670L (en) | 1989-03-03 |
| ES2053784T3 (en) | 1994-08-01 |
| NO176749B (en) | 1995-02-13 |
| DK169377B1 (en) | 1994-10-17 |
| KR910000196B1 (en) | 1991-01-23 |
| NO883893L (en) | 1989-03-06 |
| JPH0667409B2 (en) | 1994-08-31 |
| CN1032109A (en) | 1989-04-05 |
| ATE85229T1 (en) | 1993-02-15 |
| NO176749C (en) | 1995-05-24 |
| EP0306398A1 (en) | 1989-03-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK9A | Patent expired |