EP0380782A1 - Liquid dehalogenation agents - Google Patents
Liquid dehalogenation agents Download PDFInfo
- Publication number
- EP0380782A1 EP0380782A1 EP89122423A EP89122423A EP0380782A1 EP 0380782 A1 EP0380782 A1 EP 0380782A1 EP 89122423 A EP89122423 A EP 89122423A EP 89122423 A EP89122423 A EP 89122423A EP 0380782 A1 EP0380782 A1 EP 0380782A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid
- carbon atoms
- dehalogenating
- alcohol
- alkali
- Prior art date
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000005695 dehalogenation reaction Methods 0.000 title abstract description 9
- 239000003921 oil Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract 1
- 239000010913 used oil Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- MXVMODFDROLTFD-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCOCCOCCOCCOCCO MXVMODFDROLTFD-UHFFFAOYSA-N 0.000 description 5
- 150000002334 glycols Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KSAQCJQZQISASG-UHFFFAOYSA-N 2,4,6-trimethyloctan-1-ol Chemical compound CCC(C)CC(C)CC(C)CO KSAQCJQZQISASG-UHFFFAOYSA-N 0.000 description 1
- FETZOWIQWWEBTN-UHFFFAOYSA-N 3,4-diethylhexan-1-ol Chemical compound CCC(CC)C(CC)CCO FETZOWIQWWEBTN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 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
- 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
Definitions
- the invention relates to liquid dehalogenating agents based on alkali alcoholates, the production of the dehalogenating agents and their use for the dehalogenation of waste oils.
- Lubricating oils accumulate metal abrasion and degradation and oxidation products of their components during use. Nonetheless, used lubricating oils are not considered waste products, since they can be processed to such an extent by filtration, distillation or refining with concentrated sulfuric acid that valuable lubricants are formed after additional additives. However, contaminants on chlorinated hydrocarbons, such as polychlorinated biphenyls (PCB), which are toxicologically harmful, are not removed in this way.
- PCB polychlorinated biphenyls
- alkali alcoholates of alcohols with 1 to 5 carbon atoms, polyoxyalkylene glycols with 4 to 20 carbon atoms, polyols with 2 to 5 carbon atoms and 2 to 3 hydroxyl groups or of monoalkyl ethers of these polyols with alcohols 1 to 4 carbon atoms are suitable as dehalogenating agents.
- the reaction is carried out in the presence of one half to one equivalent of associated free alcohol. It is preferably dehalogenated with sodium glycolate / ethylene glycol and with sodium methylate / methanol.
- DE-A-36 21 175 the dehalogenation of hydrocarbon oils with alkali metal alcoholates having 6 to 25 carbon atoms, at 120 to 400 ° C is performed.
- the alcoholates can contain small amounts of the associated alcohol.
- the known alcohol enthalogenation agents are sensitive to oxidation and hydrolysis, especially at elevated temperatures. When cooling to room temperature, they also become solid or excrete solid components. To avoid deposits, they have to passed through heated pipes and pumps. They must also always be kept hot until they are used as intended.
- the object of the present invention is to provide easy-to-handle and, moreover, less oxidation and hydrolysis sensitive dehalogenating agents.
- liquid dehalogenating agents which contain the following components: 30 to 70% alkali alcoholate with 6 to 20 carbon atoms, up to 12% alcohol with 6 to 20 carbon atoms, 5 to 40% polyether of the structure wherein R1 is hydrogen or alkyl having 1 to 15 carbon atoms, R2 is hydrogen or alkyl having 1 to 5 carbon atoms, X is hydrogen or alkyl having 1 to 5 carbon atoms and n is a number from 2 to 50, and 10 to 65% halogen-free hydrocarbon oil.
- the dehalogenating agents which are liquid even at room temperature, preferably contain 40 to 60% alkali alcoholate, up to 10% related alcohol, 5 to 30% polyethers of structure I and 20 to 55% halogen-free hydrocarbon oil.
- the alcohols on which the alcoholates are based are, for example, hexanol, octanol, 2-ethylhexanol, decanol, 3,4-diethylhexanol, 2,4,6-trimethyloctanol, dodecanol, tetradecanol, hexadecanol or octadecanol.
- the alcoholates preferably contain 8 to 14 carbon atoms.
- Alcohol latexes of 2-ethylhexanol-1 are very particularly preferred.
- Sodium and potassium alcoholates are preferably used as alkali alcoholates.
- alkali alcoholates can be prepared by all known processes. For example, alkali metal can be reacted with alcohol, alkali hydroxide with alcohol, or a lower alcoholate with a higher alcohol, the latter reaction (salting) proceeding at a sufficient rate from about 220 ° C.
- the alkali alcoholate can contain small amounts of the associated free alcohol due to the production process.
- Polyalkylene oxide glycols and their mono- and dialkyl ethers are used as polyethers of structure I in the mixtures.
- Mono- and dialkyl ethers of polyethylene oxide and polypropylene oxide glycols are preferably used.
- Alkyl ethers of copolymers of ethylene oxide and propylene oxide are also suitable.
- R1 is, for example, hydrogen or methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl and tetradecyl.
- R 1 is preferably alkyl having 1 to 8 carbon atoms.
- the degree of polymerization n is preferably 3 to 15.
- the polyethers are monobutyl ethers of polyethylene oxide or polypropylene oxide glycols with a degree of polymerization n of 3 to 6.
- the polyethers used generally have a boiling point above 200 ° C.
- Suitable halogen-free hydrocarbon oils are, for example, saturated paraffins, lubricating and insulating oils as well as paraffin, aromatic and naphthene-based neutral oils.
- the alkali metal alcoholate which may contain small amounts of alcohol, is first dissolved in a polyether of structure I at 100 to 200 ° C.
- the dissolving process is usually spontaneous. It ends after 15 minutes at the latest. At temperatures below 100 o C the dissolving is too slow. At temperatures above 200 o C when using polyalkylene oxide glycols and their monoalkyl ethers there is a risk that salting will take place to a significant extent. Then free alcohol and alkali salt of the polyether would be formed.
- the alkali alcoholate is preferably dissolved at 160 to 200 o C.
- the halogen-free hydrocarbon oil is then mixed in.
- a temperature of 30 to 200 o C is generally used, 100 to 160 o C being preferred.
- the amounts are chosen so that mixtures with the abovementioned proportions are formed.
- waste oils can be dehalogenated.
- the dehalogenation is carried out generally at 200 to 400 o C, are preferably used per mole of halogen in the waste oil 0.5 to 10 moles of alkali metal alcoholate.
- Hydrocarbon oil and polyether are essential for the dehalogenating agents according to the invention. Only in the hydrocarbon oil would the alkali alcoholate not be soluble at room temperature, and it could not be stored without sedimentation. Only dissolved in the polyether would the alkali alcoholate not be sufficiently resistant to oxidation and hydrolysis.
- this dehalogenation reagent 20 g are mixed with 200 ml of diethyl ether and stirred for 30 minutes at room temperature. Then it is filtered through silica gel (slurried with diethyl ether) and the filter cake is washed with diethyl ether. After distillation of the diethyl ether, 10.3 g of high-boiling residue are obtained from the eluate, which consists of neutral oil, tetraethylene glycol monobutyl ether and a few percent of 2-ethylhexanol-1.
- the dehalogenating reagent has a viscosity of 820 mPa s at 20 o C and is composed as follows: 50.6% Na ethyl hexoxide 5.3% 2-ethylhexanol-1 20.1% Bu-O- (C2H4O) 4-H 24.0% neutral oil
Abstract
Description
Die Erfindung betrifft flüssige Enthalogenierungsmittel auf der Basis von Alkalialkoholaten, die Herstellung der Enthalogenierungsmittel sowie ihre Verwendung zur Enthalogenierung von Altölen.The invention relates to liquid dehalogenating agents based on alkali alcoholates, the production of the dehalogenating agents and their use for the dehalogenation of waste oils.
Schmieröle reichern während des Gebrauches Metallabrieb und Abbau- und Oxidationsprodukte ihrer Bestandteile an. Dennoch gelten gebrauchte Schmieröle nicht als Abfallprodukte, da sie durch Filtration, Destillation oder Raffination mit konzentrierter Schwefelsäure so weit aufbereitet werden können, daß nach erneuter Additivierung wertvolle Schmierstoffe entstehen. Verunreinigungen an chlorierten Kohlenwasserstoffen, wie beispielsweise an polychlorierten Biphenylen (PCB), die in toxikologischer Hinsicht bedenklich sind, werden auf diese Weise jedoch nicht entfernt.Lubricating oils accumulate metal abrasion and degradation and oxidation products of their components during use. Nonetheless, used lubricating oils are not considered waste products, since they can be processed to such an extent by filtration, distillation or refining with concentrated sulfuric acid that valuable lubricants are formed after additional additives. However, contaminants on chlorinated hydrocarbons, such as polychlorinated biphenyls (PCB), which are toxicologically harmful, are not removed in this way.
Es ist bekannt, daß man Verunreinigungen an organischen Halogenverbindungen in Altölen durch Behandlung mit Alkalialkoholaten entfernen kann. So sind nach EP-B-21 294 Alkalialkoholate von Alkoholen mit 1 bis 5 C-Atomen, Polyoxyalkylenglykolen mit 4 bis 20 C-Atomen, Polyolen mit 2 bis 5 C-Atomen und 2 bis 3 Hydroxylgruppen oder von Monoalkylethern dieser Polyole mit Alkoholen mit 1 bis 4 C-Atomen als Enthalogenierungsmittel geeignet. Die Reaktion wird in Gegenwart von einem halben bis einem Äquivalent an zugehörigem freien Alkohol durchgeführt. Vorzugsweise wird mit Natriumglykolat/Ethylenglykol sowie mit Natriummethylat/Methanol enthalogeniert.It is known that impurities in organic halogen compounds in waste oils can be removed by treatment with alkali alcoholates. According to EP-B-21 294, alkali alcoholates of alcohols with 1 to 5 carbon atoms, polyoxyalkylene glycols with 4 to 20 carbon atoms, polyols with 2 to 5 carbon atoms and 2 to 3 hydroxyl groups or of monoalkyl ethers of these polyols with alcohols 1 to 4 carbon atoms are suitable as dehalogenating agents. The reaction is carried out in the presence of one half to one equivalent of associated free alcohol. It is preferably dehalogenated with sodium glycolate / ethylene glycol and with sodium methylate / methanol.
In DE-A-36 21 175 wird die Enthalogenierung von Kohlenwasserstoffölen mit Alkalialkoholaten mit 6 bis 25 C-Atomen bei 120 bis 400 oC durchgeführt. Dabei können die Alkoholate kleine Mengen des zugehörigen Alkohols enthalten.In DE-A-36 21 175, the dehalogenation of hydrocarbon oils with alkali metal alcoholates having 6 to 25 carbon atoms, at 120 to 400 ° C is performed. The alcoholates can contain small amounts of the associated alcohol.
Die bekannten Alkoholatenthalogenierungsmittel sind vor allem bei erhöhten Temperaturen oxidations- und hydrolyseempfindlich. Beim Abkühlen auf Raumtemperatur werden sie außerdem fest oder scheiden feste Bestandteile aus. Um Ablagerungen zu vermeiden, müssen sie durch beheizte Rohre und Pumpen geleitet werden. Sie müssen außerdem bis zu ihrem bestimmungsgemäßen Verbrauch stets heiß gelagert werden.The known alcohol enthalogenation agents are sensitive to oxidation and hydrolysis, especially at elevated temperatures. When cooling to room temperature, they also become solid or excrete solid components. To avoid deposits, they have to passed through heated pipes and pumps. They must also always be kept hot until they are used as intended.
Aufgabe der vorliegenden Erfindung ist es, gut handhabbare und außerdem weniger oxidations- und hydrolyseempfindliche Enthalogenierungsmittel bereitzustellen.The object of the present invention is to provide easy-to-handle and, moreover, less oxidation and hydrolysis sensitive dehalogenating agents.
Die Aufgabe wird erfindungsgemäß durch flüssige Enthalogenierungsmittel gelöst, die folgende Bestandteile enthalten:
30 bis 70 % Alkalialkoholat mit 6 bis 20 C-Atomen,
bis zu 12 % Alkohol mit 6 bis 20 C-Atomen,
5 bis 40 % Polyether der Struktur
10 bis 65 % halogenfreies Kohlenwasserstofföl.The object is achieved according to the invention by liquid dehalogenating agents which contain the following components:
30 to 70% alkali alcoholate with 6 to 20 carbon atoms,
up to 12% alcohol with 6 to 20 carbon atoms,
5 to 40% polyether of the structure
10 to 65% halogen-free hydrocarbon oil.
Die auch bei Raumtemperatur flüssigen Enthalogenierungsmittel enthalten vorzugsweise
40 bis 60 % Alkalialkoholat,
bis zu 10 % zugehörigen Alkohol,
5 bis 30 % Polyether der Struktur I und
20 bis 55 % halogenfreies Kohlenwasserstofföl.The dehalogenating agents, which are liquid even at room temperature, preferably contain
40 to 60% alkali alcoholate,
up to 10% related alcohol,
5 to 30% polyethers of structure I and
20 to 55% halogen-free hydrocarbon oil.
Die den Alkoholaten zugrunde liegenden Alkohole sind beispielsweise Hexanol, Octanol, 2-Ethylhexanol, Decanol, 3,4-Diethylhexanol, 2,4,6-Trimethyloctanol, Dodecanol, Tetradecanol, Hexadecanol oder Octadecanol. Vorzugsweise enthalten die Alkoholate 8 bis 14 C-Atome. Alkoho late von 2-Ethylhexanol-1 werden dabei ganz besonders bevorzugt.The alcohols on which the alcoholates are based are, for example, hexanol, octanol, 2-ethylhexanol, decanol, 3,4-diethylhexanol, 2,4,6-trimethyloctanol, dodecanol, tetradecanol, hexadecanol or octadecanol. The alcoholates preferably contain 8 to 14 carbon atoms. Alcohol latexes of 2-ethylhexanol-1 are very particularly preferred.
Als Alkalialkoholate werden vorzugsweise Natrium- und Kaliumalkoholate verwendet.Sodium and potassium alcoholates are preferably used as alkali alcoholates.
Die Alkalialkoholate können nach allen dafür bekannten Verfahren hergestellt werden. So kann man beispielsweise Alkalimetall mit Alkohol, Alkalihydroxid mit Alkohol oder ein niederes Alkoholat mit einem höheren Alkohol umsetzen, wobei die letztgenannte Reaktion (Umsalzung) ab etwa 220 oC mit ausreichender Geschwindigkeit abläuft.The alkali alcoholates can be prepared by all known processes. For example, alkali metal can be reacted with alcohol, alkali hydroxide with alcohol, or a lower alcoholate with a higher alcohol, the latter reaction (salting) proceeding at a sufficient rate from about 220 ° C.
Das Alkalialkoholat kann herstellungsbedingt kleine Mengen an zugehörigem freien Alkohol enthalten.The alkali alcoholate can contain small amounts of the associated free alcohol due to the production process.
Als Polyether der Struktur I werden in den Mischungen Polyalkylenoxidglykole und ihre Mono- und Dialkylether verwendet. Vorzugsweise werden Mono- und Dialkylether von Polyethylenoxid- und Polypropylenoxidglykolen eingesetzt. Geeignet sind auch Alkylether von Copolymeren aus Ethylenoxid und Propylenoxid.Polyalkylene oxide glycols and their mono- and dialkyl ethers are used as polyethers of structure I in the mixtures. Mono- and dialkyl ethers of polyethylene oxide and polypropylene oxide glycols are preferably used. Alkyl ethers of copolymers of ethylene oxide and propylene oxide are also suitable.
In Struktur I ist R₁ beispielsweise Wasserstoff oder Methyl, Ethyl, Propyl, Isopropyl, Butyl, Hexyl, Octyl, Decyl, Dodecyl und Tetradecyl. Vorzugsweise ist R₁ Alkyl mit 1 bis 8 C-Atomen.In structure I, R₁ is, for example, hydrogen or methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl and tetradecyl. R 1 is preferably alkyl having 1 to 8 carbon atoms.
Der Polymerisationsgrad n ist vorzugsweise 3 bis 15.The degree of polymerization n is preferably 3 to 15.
In einer besonders bevorzugten Ausführungsform sind die Polyether Monobutylether von Polyethylenoxid- oder Polypropylenoxidglykolen mit einem Polymerisationsgrad n von 3 bis 6.In a particularly preferred embodiment, the polyethers are monobutyl ethers of polyethylene oxide or polypropylene oxide glycols with a degree of polymerization n of 3 to 6.
Die verwendeten Polyether weisen im allgemeinen einen Siedepunkt von über 200 oC auf.The polyethers used generally have a boiling point above 200 ° C.
Geeignete halogenfreie Kohlenwasserstofföle sind beispielsweise gesättigte Paraffine, Schmier- und Isolieröle sowie paraffin-, aromaten- und naphthenbasische Neutralöle.Suitable halogen-free hydrocarbon oils are, for example, saturated paraffins, lubricating and insulating oils as well as paraffin, aromatic and naphthene-based neutral oils.
Zur Herstellung der flüssigen Enthalogenierungsmittel löst man zunächst das Alkalialkoholat, das kleine Mengen an Alkohol enthalten kann, bei 100 bis 200 oC in einem Polyether der Struktur I. Der Lösevorgang erfolgt meist spontan. Er ist spätestens nach 15 Minuten beendet. Bei Temperaturen unter 100 oC erfolgt das Lösen zu langsam. Bei Temperaturen über 200 oC besteht bei Verwendung von Polyalkylenoxidglykolen und ihren Monoalkylethern die Gefahr, daß eine Umsalzung in signifikantem Ausmaße stattfindet. Dann würden freier Alkohol und Alkalisalz des Polyethers gebildet werden.To prepare the liquid dehalogenating agents, the alkali metal alcoholate, which may contain small amounts of alcohol, is first dissolved in a polyether of structure I at 100 to 200 ° C. The dissolving process is usually spontaneous. It ends after 15 minutes at the latest. At temperatures below 100 o C the dissolving is too slow. At temperatures above 200 o C when using polyalkylene oxide glycols and their monoalkyl ethers there is a risk that salting will take place to a significant extent. Then free alcohol and alkali salt of the polyether would be formed.
Das Alkalialkoholat wird vorzugsweise bei 160 bis 200 oC gelöst.The alkali alcoholate is preferably dissolved at 160 to 200 o C.
Anschließend wird das halogenfreie Kohlenwasserstofföl zugemischt. Dabei wird im allgemeinen eine Temperatur von 30 bis 200 oC angewandt, wobei 100 bis 160 oC bevorzugt werden.The halogen-free hydrocarbon oil is then mixed in. A temperature of 30 to 200 o C is generally used, 100 to 160 o C being preferred.
Bei der Herstellung der flüssigen Enthalogenierungsmittel werden die Mengen so gewählt, daß Mischungen mit den obengenannten Anteilen entstehen.In the production of the liquid dehalogenating agents, the amounts are chosen so that mixtures with the abovementioned proportions are formed.
Mit diesen bei Raumtemperatur flüssigen Produkten können Altöle enthalogeniert werden. Die Enthalogenierung erfolgt im allgemeinen bei 200 bis 400 oC, wobei vorzugsweise pro Mol Halogen im Altöl 0,5 bis 10 Mole Alkalialkoholat verwendet werden.With these products, which are liquid at room temperature, waste oils can be dehalogenated. The dehalogenation is carried out generally at 200 to 400 o C, are preferably used per mole of halogen in the waste oil 0.5 to 10 moles of alkali metal alcoholate.
Für die erfindungsgemäßen Enthalogenierungsmittel sind Kohlenwasserstofföl und Polyether essentiell. Nur in dem Kohlenwasserstofföl wäre das Alkalialkoholat bei Raumtemperatur nicht löslich, es könnte auch nicht ohne Sedimentation gelagert werden. Nur in dem Polyether gelöst wäre das Alkalialkoholat nicht ausreichend oxidations- und hydrolysebeständig. Durch die Kombination von Polyether und Kohlenwasserstofföl, in der der Polyether auch als Lösevermittler wirkt, werden flüssige Enthalogenierungsmittel mit folgenden Eigenschaften erhalten:
- verbessert hydrolyse- und oxidationsbeständig,
- bei Raumtemperatur homogen, nicht sedimentierend und deshalb la gerstabil,
- flüssig, pumpfähig, gut dosierbar, die Produkte können in unbeheizten Rohren und Pumpen verbleiben, ohne Ablagerungen oder Verstopfungen zu verursachen.Hydrocarbon oil and polyether are essential for the dehalogenating agents according to the invention. Only in the hydrocarbon oil would the alkali alcoholate not be soluble at room temperature, and it could not be stored without sedimentation. Only dissolved in the polyether would the alkali alcoholate not be sufficiently resistant to oxidation and hydrolysis. The combination of polyether and hydrocarbon oil, in which the polyether also acts as a solubilizer, gives liquid dehalogenating agents with the following properties:
- improves resistance to hydrolysis and oxidation,
- Homogeneous at room temperature, not sedimenting and therefore la stable,
- Liquid, pumpable, easy to dose, the products can remain in unheated pipes and pumps without causing deposits or blockages.
Die folgenden Beispiel sollen die Erfindung verdeutlichen.The following examples are intended to illustrate the invention.
Eine Mischung aus 211,3 g Na-Ethylhexylat und 6,2 g 2-Ethylhexanol-1, hergestellt aus Natriummethylat und 2-Ethylhexanol-1, wird bei 190 oC mit 88 g Tetraethylenglykol-monobutylether versetzt, wobei unter Rühren in 10 Minuten eine homogene Lösung entsteht. Anschließend werden bei 130 oC unter Rühren 131,5 g Neutralöl (2,5o E/50) zugetropft, worauf unter Rühren auf Raumtemperatur abgekühlt wird. Man erhält ein klares Enthalogenierungsreagenz mit einer Viskosität von 840 mPa s bei 20 oC.A mixture of 211.3 g Na-ethylhexylate and 6.2 g of 2-ethylhexanol-1, prepared from sodium methoxide and 2-ethylhexanol-1, is treated at 190 o C with 88 g of tetraethylene glycol monobutyl ether, and with stirring, in 10 minutes a homogeneous solution is created. 131.5 g of neutral oil are then at 130 o C with stirring was added dropwise (2.5 o E / 50), followed by cooling with stirring to room temperature. A clear dehalogenating reagent with a viscosity of 840 mPa s at 20 o C. is obtained.
48,4 % Na-Ethylhexylat
1,4 % 2-Ethylhexanol-1
20,1 % Bu-O-(C₂H₄O)₄-H
30,1 % Neutralöl48.4% Na ethyl hexoxide
1.4% 2-ethylhexanol-1
20.1% Bu-O- (C₂H₄O) ₄-H
30.1% neutral oil
20 g dieses Enthalogenierungsreagenzes werden mit 200 ml Diethylether versetzt und 30 Minuten bei Raumtemperatur gerührt. Dann wird durch Kieselgel (mit Diethylether aufgeschlämmt) filtriert und der Filterkuchen mit Diethylether gewaschen. Aus dem Eluat werden nach Destillation des Diethylethers 10,3 g hochsiedender Rückstand erhalten, der aus Neutralöl, Tetraethylenglykol-monobutylether und wenigen Prozenten 2-Ethylhexanol-1 besteht.20 g of this dehalogenation reagent are mixed with 200 ml of diethyl ether and stirred for 30 minutes at room temperature. Then it is filtered through silica gel (slurried with diethyl ether) and the filter cake is washed with diethyl ether. After distillation of the diethyl ether, 10.3 g of high-boiling residue are obtained from the eluate, which consists of neutral oil, tetraethylene glycol monobutyl ether and a few percent of 2-ethylhexanol-1.
Bei der Hydrolyse des Filterkuchens mit Wasser entstehen 2 Phasen, wobei die obere Phase aus 2-Ethylhexanol-1 besteht und die untere Phase eine mit 2-Ethylhexanol-1 gesättigte Natronlauge ist.Hydrolysis of the filter cake with water creates 2 phases, the upper phase consisting of 2-ethylhexanol-1 and the lower phase being a sodium hydroxide solution saturated with 2-ethylhexanol-1.
Dieser Test zeigt, daß Tetraethylenglykol-monobutylether nicht als Salz vorliegt, daß also keine Umsalzung stattgefunden hat.This test shows that tetraethylene glycol monobutyl ether is not in the form of a salt, that is to say that no salting has taken place.
211,3 g Na-Ethylhexylat und 9,2 g 2-Ethylhexanol-1 werden bei 170 oC mit 85 g Triethylenglykol-dimethylether versetzt. Nach 10 Minuten liegt eine klare Lösung vor. Nun werden bei 120 oC 128 g Neutralöl (2,5o E/50) zugegeben, worauf unter Rühren auf Raumtemperatur abgekühlt wird. Man erhält ein bei Raumtemperatur gut fließfähiges Reagenz der Zusammensetzung:
48,8 % Na-Ethylhexylat
2,1 % 2-Ethylhexanol-1
19,6 % Me-O-(C₂H₄O)₃-Me
29,5 % Neutralöl211.3 g of Na-ethylhexylate and 9.2 g of 2-ethylhexanol-1 are mixed with 85 g of triethylene glycol dimethyl ether at 170 ° C. After 10 minutes there is a clear solution. Now at 120 o C 128 g neutral oil (2.5 o E / 50) are added, whereupon the mixture is cooled to room temperature with stirring. A reagent of the composition which is readily flowable at room temperature is obtained:
48.8% Na ethyl hexoxide
2.1% 2-ethylhexanol-1
19.6% Me-O- (C₂H₄O) ₃-Me
29.5% neutral oil
211,3 g Na-Ethylhexylat und 21,9 g 2-Ethylhexanol-1 werden bei 190 oC mit 84 g Tetraethylenglykol-monobutylether und nach Erhalt einer homogenen Lösung bei 150 oC mit 100 g Neutralöl (2,5o E/50) versetzt, worauf die Mischung auf Raumtemperatur abgekühlt wird. Das Enthalogenierungsreagenz hat eine Viskosität von 820 mPa s bei 20 oC und ist wie folgt zusammengesetzt:
50,6 % Na-Ethylhexylat
5,3 % 2-Ethylhexanol-1
20,1 % Bu-O-(C₂H₄O)₄-H
24,0 % Neutralöl211.3 g Na-ethylhexylate and 21.9 g of 2-ethylhexanol-1 at 190 o C with 84 g of tetraethylene glycol monobutyl ether, and after obtaining a homogeneous solution at 150 ° C with 100 g of neutral oil (2.5 o E / 50 ) added, whereupon the mixture is cooled to room temperature. The dehalogenating reagent has a viscosity of 820 mPa s at 20 o C and is composed as follows:
50.6% Na ethyl hexoxide
5.3% 2-ethylhexanol-1
20.1% Bu-O- (C₂H₄O) ₄-H
24.0% neutral oil
250.4 g Na-Decanolat und 27.7 g Decanol-1 werden bei 200 oC mit 113 g Tetraethylenglykol-monobutylether versetzt. Innerhalb von 10 Minuten hat sich eine klare Lösung gebildet. Bei 140 oC werden 142 g naphthenreiches Neutralöl zugegeben und unter Rühren auf Raumtemperatur abgekühlt. Das bei 25 oC gut fließfähige Gemisch hat die Zusammensetzung
47,0 % Na-Decanolat
5,2 % Decanol-1
21,2 % Bu-O-(C₂H₄O)₄-H
26,6 % Neutralöl250.4 g Na-Decanolat and 27.7 g of decanol-1 are treated at 200 o C and 113 g tetraethylene glycol monobutyl ether. A clear solution was formed within 10 minutes. At 140 o C 142 g of naphthenic neutral oil are added and cooled to room temperature with stirring. The mixture, which is readily flowable at 25 ° C., has the composition
47.0% Na decanolate
5.2% decanol-1
21.2% Bu-O- (C₂H₄O) ₄-H
26.6% neutral oil
100 g Altöl mit den in Tabelle 1 genannten Chlorgehalten werden bei 300 bzw. 330 oC in 30 bzw. 60 Minuten entchloriert. Dabei wird in den Versuchen 1 bis 3 das Produkt von Beispiel 1 und in den Versuchen 4 und 5 das Produkt von Beispiel 2 verwendet.
Die Versuche belegen, daß die erfindungsgemäßen flüssigen Produkte sehr gut als Enthalogenierungsmittel geeignet sind.The tests prove that the liquid products according to the invention are very suitable as dehalogenating agents.
Claims (8)
30 bis 70 % Alkalialkoholat mit 6 bis 20 C-Atomen,
0 bis 12 % Alkohol mit 6 bis 20 C-Atomen,
5 bis 40 % Polyether der Struktur
R₁ = H oder Alkyl mit 1 bis 15 C-Atomen,
R₂ = H oder Alkyl mit 1 bis 5 C-Atomen,
X = H oder Alkyl mit 1 bis 5 C-Atomen,
n = 2 bis 50 ist,
und
10 bis 65 % halogenfreies Kohlenwasserstofföl
enthalten.1. Liquid dehalogenating agents that
30 to 70% alkali alcoholate with 6 to 20 carbon atoms,
0 to 12% alcohol with 6 to 20 carbon atoms,
5 to 40% polyether of the structure
R₁ = H or alkyl with 1 to 15 carbon atoms,
R₂ = H or alkyl with 1 to 5 carbon atoms,
X = H or alkyl with 1 to 5 carbon atoms,
n = 2 to 50,
and
10 to 65% halogen-free hydrocarbon oil
contain.
40 bis 60 % Alkalialkoholat,
0 bis 10 % Alkohol,
5 bis 30 % Polyether der Struktur I und
20 bis 55 % halogenfreiem Kohlenwasserstofföl.2. Liquid dehalogenating agent according to claim 1 with
40 to 60% alkali alcoholate,
0 to 10% alcohol,
5 to 30% polyethers of structure I and
20 to 55% halogen-free hydrocarbon oil.
dadurch gekennzeichnet,
daß Alkalialkoholat und Alkohol 8 bis 14 C-Atome aufweisen und das Alkalialkoholat ein Natrium und/oder Kaliumalkoholat ist.3. Liquid dehalogenating agent according to claim 1,
characterized,
that alkali alcoholate and alcohol have 8 to 14 carbon atoms and the alkali alcoholate is a sodium and / or potassium alcoholate.
dadurch gekennzeichnet,
daß im Polyether der Struktur I
R₁ = Alkyl mit 1 bis 8 C-Atomen,
R₂ = H oder Methyl,
X = H oder Methyl und
n = 3 bis 15
ist.4. Liquid dehalogenating agent according to claim 1,
characterized,
that in the polyether of structure I
R₁ = alkyl with 1 to 8 carbon atoms,
R₂ = H or methyl,
X = H or methyl and
n = 3 to 15
is.
dadurch gekennzeichnet,
daß man 30 bis 70 Teile Alkalialkoholat und bis zu 12 Teile Alkohol in 5 bis 40 Teilen Polyether der Struktur I bei 100 bis 200 oC löst und danach 10 bis 65 Teile halogenfreies Kohlenwasserstofföl zusetzt.5. A process for the preparation of liquid dehalogenating agents according to claim 1,
characterized,
that 30 to 70 parts of alkali alcoholate and up to 12 parts of alcohol are dissolved in 5 to 40 parts of polyether of structure I at 100 to 200 ° C. and then 10 to 65 parts of halogen-free hydrocarbon oil are added.
dadurch gekennzeichnet,
daß man bei 160 bis 200 oC löst.6. The method according to claim 5,
characterized,
that one solves at 160 to 200 o C.
dadurch gekennzeichnet,
daß man pro Mol Halogen im Altöl 0,5 bis 10 Mole Alkalialkoholat einsetzt.8. Use of the liquid dehalogenating agent according to claim 7,
characterized,
that 0.5 to 10 moles of alkali metal alcoholate are used per mole of halogen in the waste oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT89122423T ATE90217T1 (en) | 1989-02-02 | 1989-12-05 | LIQUID DEHALOGENING AGENTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3903105A DE3903105A1 (en) | 1989-02-02 | 1989-02-02 | LIQUID ENTHALOGEN |
| DE3903105 | 1989-02-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0380782A1 true EP0380782A1 (en) | 1990-08-08 |
| EP0380782B1 EP0380782B1 (en) | 1993-06-09 |
Family
ID=6373301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89122423A Expired - Lifetime EP0380782B1 (en) | 1989-02-02 | 1989-12-05 | Liquid dehalogenation agents |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5132006A (en) |
| EP (1) | EP0380782B1 (en) |
| JP (1) | JPH0390173A (en) |
| AT (1) | ATE90217T1 (en) |
| CA (1) | CA2009007A1 (en) |
| DE (2) | DE3903105A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4327804A1 (en) * | 1992-08-18 | 1994-02-24 | Toshiba Kawasaki Kk | Decomposition of organic halogen cpds. - by exposing soln. to UV light then adding alkali to ppte. salt, for economical destruction of e.g. tri:chloroethylene, poly:chloro-bi:phenyl and chloro-fluorocarbon cpds. |
| AU661096B2 (en) * | 1992-06-05 | 1995-07-13 | Mitsui & Co., Ltd. | Method of removing halogenated aromatic compound from hydrocarbon oil |
| ES2112706A1 (en) * | 1994-05-06 | 1998-04-01 | Centralair Sa | Torque limiting servomechanism |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2638483B2 (en) * | 1994-06-30 | 1997-08-06 | 株式会社関西テック | Method for treating polychlorinated aromatic compounds |
| US5534124A (en) * | 1995-09-19 | 1996-07-09 | Chem-Pro | On-site electrochemical dehalogenation process and system |
| DE19711762A1 (en) * | 1997-03-21 | 1998-09-24 | Huels Chemische Werke Ag | Process for the preparation of bishydroxymethyl compounds |
| US6024737A (en) | 1998-02-25 | 2000-02-15 | Advanced Cardiovascular Systems, Inc. | Stent crimping device |
| CN114058433B (en) * | 2021-12-07 | 2022-11-18 | 湖北润驰环保科技有限公司 | Method for dechlorinating waste lubricating oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021294A1 (en) * | 1979-06-15 | 1981-01-07 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
| EP0250748A1 (en) * | 1986-06-25 | 1988-01-07 | Hüls Aktiengesellschaft | Process for the dehalogenation of hydrocarbon oils |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4351718A (en) * | 1981-06-01 | 1982-09-28 | General Electric Company | Method for removing polyhalogenated hydrocarbons from nonpolar organic solvent solutions |
| US4532028A (en) * | 1983-10-24 | 1985-07-30 | Niagara Mohawk Power Corporation | Method for reducing content of halogenated aromatics in hydrocarbon solutions |
| DE3900159A1 (en) * | 1989-01-04 | 1990-07-05 | Geut Ag | METHOD FOR REFURBISHING ALTOEL |
-
1989
- 1989-02-02 DE DE3903105A patent/DE3903105A1/en not_active Withdrawn
- 1989-11-03 US US07/431,437 patent/US5132006A/en not_active Expired - Fee Related
- 1989-12-05 AT AT89122423T patent/ATE90217T1/en not_active IP Right Cessation
- 1989-12-05 DE DE8989122423T patent/DE58904641D1/en not_active Expired - Fee Related
- 1989-12-05 EP EP89122423A patent/EP0380782B1/en not_active Expired - Lifetime
-
1990
- 1990-01-31 CA CA002009007A patent/CA2009007A1/en not_active Abandoned
- 1990-02-02 JP JP2022335A patent/JPH0390173A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021294A1 (en) * | 1979-06-15 | 1981-01-07 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
| EP0250748A1 (en) * | 1986-06-25 | 1988-01-07 | Hüls Aktiengesellschaft | Process for the dehalogenation of hydrocarbon oils |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU661096B2 (en) * | 1992-06-05 | 1995-07-13 | Mitsui & Co., Ltd. | Method of removing halogenated aromatic compound from hydrocarbon oil |
| DE4327804A1 (en) * | 1992-08-18 | 1994-02-24 | Toshiba Kawasaki Kk | Decomposition of organic halogen cpds. - by exposing soln. to UV light then adding alkali to ppte. salt, for economical destruction of e.g. tri:chloroethylene, poly:chloro-bi:phenyl and chloro-fluorocarbon cpds. |
| ES2112706A1 (en) * | 1994-05-06 | 1998-04-01 | Centralair Sa | Torque limiting servomechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0390173A (en) | 1991-04-16 |
| ATE90217T1 (en) | 1993-06-15 |
| CA2009007A1 (en) | 1990-08-02 |
| US5132006A (en) | 1992-07-21 |
| DE58904641D1 (en) | 1993-07-15 |
| DE3903105A1 (en) | 1990-08-09 |
| EP0380782B1 (en) | 1993-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2715671C2 (en) | Lubricant composition | |
| DE1295124B (en) | Hydraulic fluids, heat exchange fluids, lubricating and cutting oils based on glycol or glycol ether | |
| EP0380782B1 (en) | Liquid dehalogenation agents | |
| DE3611027A1 (en) | COLD ROLLING OIL FOR STEEL | |
| DE2915071A1 (en) | BETAINE COMPOUNDS CONTAINING FLUORINE | |
| DE1946432C3 (en) | Silicone grease | |
| CH377029A (en) | Process for the production of a magnesium-containing additive for lubricants | |
| DE1139228B (en) | Lubricants and processes for their manufacture | |
| DE2046368A1 (en) | Additive for lubricant mixture | |
| EP0376236B1 (en) | Use of 1,2-butylene oxide compounds added to amines as lubricants, and lubricants containing the same | |
| DE1032242B (en) | Process for the preparation of di-aryl-substituted adipic acids | |
| DE3715574A1 (en) | ADDITIVES FOR DRILLING LIQUIDS, METHOD FOR THE PRODUCTION AND USE THEREOF | |
| DE1594384B1 (en) | Lubricant or hydraulic oil based on polyisobutylene | |
| DE875384C (en) | High pressure lubricating oils | |
| DE3117839A1 (en) | Polyethers, their preparation, and their use as lubricants | |
| DE942524C (en) | Additives to lubricants | |
| DE879443C (en) | Process for the production of lubricating oil improvers which act as detergents and / or inhibitors | |
| DE2162286B2 (en) | Triaryl phosphate mixtures and functional fluids containing them | |
| DE1594488B2 (en) | LUBRICANT FOR LUBRICANT MACHINES | |
| DE767842C (en) | Process for the production of polyglycol ethers | |
| DE843584C (en) | Stable metal soap lubricants, especially greases | |
| DE949678C (en) | Grease | |
| DE1518747C3 (en) | Condensed phosphoric acid esters of polyhydric alcohols and process for their preparation | |
| DE2202732B2 (en) | Hydraulic fluids | |
| DE1926176A1 (en) | Process for cold rolling aluminum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
| 17P | Request for examination filed |
Effective date: 19900727 |
|
| 17Q | First examination report despatched |
Effective date: 19921105 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19930609 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19930609 |
|
| REF | Corresponds to: |
Ref document number: 90217 Country of ref document: AT Date of ref document: 19930615 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 58904641 Country of ref document: DE Date of ref document: 19930715 |
|
| ET | Fr: translation filed | ||
| ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19930805 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19931124 Year of fee payment: 5 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19931205 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19931214 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19931217 Year of fee payment: 5 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19931231 Ref country code: CH Effective date: 19931231 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19931231 Year of fee payment: 5 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19940127 Year of fee payment: 5 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19941205 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19941231 |
|
| BERE | Be: lapsed |
Owner name: HULS A.G. Effective date: 19941231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19950701 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19941205 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19950831 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19950701 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19950901 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051205 |