CN102895976A - Silicon-containing intermetallic compound hydrodechlorination catalyst, preparation method and application - Google Patents
Silicon-containing intermetallic compound hydrodechlorination catalyst, preparation method and application Download PDFInfo
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- CN102895976A CN102895976A CN2012103869908A CN201210386990A CN102895976A CN 102895976 A CN102895976 A CN 102895976A CN 2012103869908 A CN2012103869908 A CN 2012103869908A CN 201210386990 A CN201210386990 A CN 201210386990A CN 102895976 A CN102895976 A CN 102895976A
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Abstract
The invention discloses a silicon-containing intermetallic compound catalyst, a preparation method and hydrodechlorination application in a chlorine-containing organic compound. The hydrodechlorination catalyst is a silicon-containing intermetallic compound M-Si, wherein M is a transition metal such as Ni, Cu, Fe, Co, Mo, W, Pd, Pt, Ru, Au or Nb. The method comprises the following steps of: adding an organic silane monomer SiClx(CH3)4-x in the atmosphere of nitrogen with the flow rate of 50 to 200sccm by using a nano metal or a metal oxide as a precursor, wherein X is 0, 1, 2, 3 or 4; performing constant temperature reaction for 2 to 5 hours at the temperature of between 200 and 800 DEG C, cooling to room temperature in the atmosphere of hydrogen, purging in an inert atmosphere, and thus obtaining the catalyst. The prepared silicon-containing intermetallic compound catalyst has high activity and stability on hydrodechlorination of the chlorine-containing compound in industrial production under the typical industrial application condition, and has a good industrial application prospect.
Description
Technical field
The present invention relates to compound Hydrodechlorinating catalyst, preparation method and application between employed a kind of siliceous metal in the hydrogenation-dechlorination of chlorine-containing organic compounds.Compound catalyst can make with the organosilan monomer reaction under atmosphere of hydrogen by nano metal or metal oxide between siliceous metal, the hydrogenation-dechlorination of the chlorine-containing compound that compound catalyst produces in to industrial production under typical commercial Application condition between prepared siliceous metal has very high active and stable, has good prospects for commercial application.
Background technology
Because the chloride volatility organic waste that the industries such as machinery industry, surface anticorrosion, petrochemical industry, pharmaceutical industry, coatings decoration industry produce discharges the destruction that not only causes ozone layer, and with airborne NO
xReact and generate chemical fumes etc. chemical substance, stimulate people's eyes, cause breathing problem, even cause global warming.In addition, in many industrial process of chemistry of silicones, there is the dechlorination purifying of chloride unit organosilicon precursor equally in the purifying of organosilicon precursor.Process chloride volatile organic matter than conventional catalyst burning and absorption method, hydrogenation-dechlorination has important economic benefit and environment protection significance.
Between siliceous metal in the compound, a little less than silicon atom and the metallic atom bonding, bonding between the silicon atom is stronger, metallic atom is between the construction unit of silicon atom, make it have unique physics, chemical property, such as: unique structure, electric property, magnetic performance and catalytic performance etc. show greater activity and selective to hydrogen-involved reaction.Yet compound is bright in reporting so far as the application of a kind of new catalyst in the hydrogenation-dechlorination reaction between siliceous metal.Compound between the prepared siliceous metal of the present invention, not only the preparation method is simple, mild condition, synthetic cost is low, and prepared material is to hydrogen-involved reaction, especially in the hydrogenation-dechlorination catalytic reaction, have higher catalytic activity and target product is had fine selective, effectively process industrial organic waste water and waste gas, reduce the harm to human and environment.Following known technology all comes with some shortcomings:
United States Patent (USP), publication number: US005716590A introduces the hydrogenation-dechlorination of tetrels chlorine-containing compound, and its catalyst system therefor is the nickle silicide catalyst, but preparation technology is loaded down with trivial details, and used reaction temperature is too high in the hydrogenated dechlorination process, and is strict to equipment requirement.
Chinese patent, publication number: CN101007280A introduces a kind of load and non-loading type NiPd alloy hydrogenation dechlorination catalyst, but uses noble metal, and is not only expensive, and easily fluorine poisoning and inactivation.
Chinese patent, publication number: CN11356550 introduces a kind of palladium-carbon catalyst and be used for the fluorochlorohydrocarbon hydrogenation-dechlorination, but this catalyst exists activity and selectivity low, and the deficiency such as service life is short.
Summary of the invention
The invention provides compound Hydrodechlorinating catalyst, preparation method and application between a kind of siliceous metal.The hydrogenation-dechlorination of the chlorine-containing compound that compound catalyst produces in to industrial production under typical commercial Application condition between the preparation siliceous metal under temperate condition has very high active and stable, has good prospects for commercial application.
Hydrodechlorinating catalyst of the present invention is compound M-Si between siliceous metal, and wherein M is transition metal, such as Ni, Cu, Fe, Co, Mo, W, Pd, Pt, Ru, Au, Nb etc., adopts wherein a kind of.
Between above-mentioned siliceous metal compound Hydrodechlorinating catalyst preparation method take compound catalyst between siliceous metal can nano metal or metal oxide as presoma, be to carry organic silane monomer SiCl under the 50-200sccm atmosphere of hydrogen at flow
x(CH
3)
4-xAt 200-800
oIsothermal reaction 2-5h under the C drops to room temperature after finishing under hydrogen atmosphere, purge passivation under inert atmosphere, namely obtains compound catalyst between corresponding siliceous metal.Machine silane monomer SiCl wherein
x(CH
3)
4-xMiddle X is 0,1,2,3 or 4, namely can be respectively silicon tetrachloride, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, tetramethylsilane.
Compound catalyst is used for the hydrogenated dechlorination process of chlorine-containing compound between above-mentioned siliceous metal, and chlorine-containing compound is R
xSiCl
4-xOr R
xCCl
4-x, wherein the R representative contains alkyl, the phenyl of 1-6 carbon atom, and X represents 0,1,2,3,4.Hydrogenation-dechlorination to the chlorine-containing compound in industrial organic waste water and the waste gas under typical commercial Application condition has very high activity and stable.
The invention provides a kind of at normal pressure, the method for preparing compound Hydrodechlorinating catalyst between siliceous metal under the moderate temperature conditions, the atomic ratio of the specific area of its prepared material, metal and silicon etc. have very important impact to the formation of chemical combination between siliceous metal, catalytic activity etc.It is of the present invention that preparation is simple, mild condition, and synthetic cost is low.The hydrogenation-dechlorination of the chlorine-containing compound that compound catalyst produces in to industrial production under typical commercial Application condition between prepared siliceous metal has very high active and stable, has good prospects for commercial application.
Description of drawings
Accompanying drawing is the process chart of compound catalyst between the preparation siliceous metal.
The specific embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1: the preparation of compound catalyst between siliceous metal
The nano metal precursor of getting the 0.3g high-specific surface area places quartz reactor.At first purge to wherein passing into Ar, then switch to H
2, be to carry organic silane monomer SiCl under the 50-200sccm atmosphere of hydrogen at flow
x(CH
3)
4-xAt 200-800
oIsothermal reaction 2-5h under the C drops to room temperature after finishing under hydrogen atmosphere, purge passivation under inert atmosphere, namely obtains compound catalyst between corresponding siliceous metal.Under different silication temperature, the difference of different silication times and selected silicon source precursor can be prepared compound catalyst between the siliceous metal of different proportion.The process chart of compound catalyst such as Fig. 1 between used siliceous metal.Actual conditions sees the following form:
Embodiment 2: nickel-silicon intermetallic compound catalyst is to the carrene hydrogenation-dechlorination
Take the 1000ppm carrene as substrate, investigate active and stable in the hydrogenation-dechlorination reaction of nickel-silicon intermetallic compound catalyst, reaction is carried out in fixed bed reactors.
Reaction condition is: nickel-silicon intermetallic compound catalyst: 0.2g, temperature, 150-250
oC, pressure: normal pressure, be time of contact: 1 kg
Cat./ mol, hydrogen-oil ratio is: 100.Total gas speed: 100sccm.Product analysis adopts gas-chromatography, hydrogen flame detector.Along with reaction temperature reaches 250
oC, the conversion ratio of carrene is by reaching 93%, and product is mainly methane.
Embodiment 3: copper-silicon intermetallic compound catalyst is to the silicon tetrachloride hydrogenation-dechlorination
Take the 1000ppm silicon tetrachloride as substrate, investigate active and stable in the hydrogenation-dechlorination reaction of copper-silicon intermetallic compound catalyst, reaction is carried out in fixed bed reactors.
Reaction condition is: nickel-silicon intermetallic compound catalyst: 0.2g, temperature, 600
oC, pressure: normal pressure, be time of contact: 1 kg
Cat./ mol, hydrogen-oil ratio is: 100.Total gas speed: 100sccm.Product analysis adopts gas-chromatography, hydrogen flame detector.The conversion ratio of silicon tetrachloride reaches 25%, and product is mainly trichlorosilane.
Embodiment 4: nickel-silicon intermetallic compound catalyst is to the methyl trichlorosilane hydrogenation-dechlorination
Take the 1000ppm methyl trichlorosilane as substrate, investigate active and stable in the hydrogenation-dechlorination reaction of nickel-silicon intermetallic compound catalyst, reaction is carried out in fixed bed reactors.
Reaction condition is: nickel-silicon intermetallic compound catalyst: 0.2g, temperature, 400
oC, pressure: normal pressure, be time of contact: 1 kg
Cat./ mol, hydrogen-oil ratio is: 100.Total gas speed: 100sccm.Product analysis adopts gas-chromatography, hydrogen flame detector.The conversion ratio of methyl trichlorosilane is by reaching 90%, and product is mainly allyl chloride.
Embodiment 5: iron-silicon intermetallic compound catalyst is to the carrene hydrogenation-dechlorination
Take the 1000ppm diethyl dichlorosilane as substrate, investigate active and stable in the hydrogenation-dechlorination reaction of iron-silicon intermetallic compound catalyst, reaction is carried out in fixed bed reactors.
Reaction condition is: iron-silicon intermetallic compound catalyst: 0.2g, temperature: 600
oC, pressure: normal pressure, be time of contact: 1 kg
Cat./ mol, hydrogen-oil ratio is: 100.Total gas speed: 100sccm.Product analysis adopts gas-chromatography, hydrogen flame detector.The conversion ratio of diethyl dichlorosilane is by reaching 95%.
Claims (5)
1. compound Hydrodechlorinating catalyst between a siliceous metal is characterized in that Hydrodechlorinating catalyst is compound M-Si between siliceous metal, and wherein M is transition metal.
2. compound Hydrodechlorinating catalyst between a kind of siliceous metal according to claim 1 is characterized in that, described transition metal M is Ni, Cu, Fe, Co, Mo, W, Pd, Pt, Ru, Au or Nb.
3. the preparation method of compound Hydrodechlorinating catalyst between claim 1 or 2 described a kind of siliceous metals, it is characterized in that, compound catalyst employing nano metal or metal oxide are presoma between siliceous metal, are to carry organic silane monomer SiCl under the 50-200sccm atmosphere of hydrogen at flow
x(CH
3)
4-x, wherein X is 0,1,2,3 or 4; At 200-800
oIsothermal reaction 2-5h under the C drops to room temperature after finishing under hydrogen atmosphere, purge passivation under inert atmosphere, namely obtains compound catalyst between corresponding siliceous metal.
4. preparation method according to claim 3 is further characterized in that described machine silane monomer is silicon tetrachloride, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane or tetramethylsilane.
5. the compound Hydrodechlorinating catalyst is further characterized in that for the hydrogenated dechlorination process of chlorine-containing compound chlorine-containing compound is R between claim 1 or 2 described a kind of siliceous metals
xSiCl
4-xOr R
xCCl
4-x, wherein R is chlorine, contains the alkyl or phenyl of 1-6 carbon atom, X is 0,1,2,3 or 4.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104492480A (en) * | 2014-12-15 | 2015-04-08 | 武汉科林精细化工有限公司 | Catalyst for removing organic chloride out of plastic oil and preparation method thereof |
CN114425328A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
CN1350885A (en) * | 2000-10-31 | 2002-05-29 | 舒德化学公司 | Catalyst for preparing chloroform by hydrogenation dechlorination of carbon tetrachloride |
-
2012
- 2012-10-14 CN CN2012103869908A patent/CN102895976A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
CN1350885A (en) * | 2000-10-31 | 2002-05-29 | 舒德化学公司 | Catalyst for preparing chloroform by hydrogenation dechlorination of carbon tetrachloride |
Non-Patent Citations (1)
Title |
---|
HOLGER WALTER ET AL: "Mechanism of the silicide-catalysed hydrodehalogenation of silicon tetrachloride to trichlorosilane", 《J. CHEM. SOC.,FARADAY TRANS.》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104492480A (en) * | 2014-12-15 | 2015-04-08 | 武汉科林精细化工有限公司 | Catalyst for removing organic chloride out of plastic oil and preparation method thereof |
CN114425328A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof |
CN114425328B (en) * | 2020-09-27 | 2024-01-26 | 中国石油化工股份有限公司 | Alpha, alpha-dimethylbenzyl alcohol hydrogenolysis catalyst and preparation method and application thereof |
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