CN106694000A - Green catalyst for preparing tetrachlorethylene as well as preparation and use methods of green catalyst - Google Patents
Green catalyst for preparing tetrachlorethylene as well as preparation and use methods of green catalyst Download PDFInfo
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- CN106694000A CN106694000A CN201611254216.6A CN201611254216A CN106694000A CN 106694000 A CN106694000 A CN 106694000A CN 201611254216 A CN201611254216 A CN 201611254216A CN 106694000 A CN106694000 A CN 106694000A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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Abstract
The invention relates to a green catalyst for preparing tetrachlorethylene as well as preparation and use methods of the green catalyst. The non-toxic and harmless supported dehydrochlorination catalyst is prepared from two or more of FeCl3, AlCl3, CuCl2, CuCl and TiCl4 as active ingredients and activated carbon as a carrier with an impregnation method. The catalyst is used for dehydrochlorination of pentachloroethane, the conversion per pass can reach 95%, and the tetrachlorethylene selectivity can reach 99%. The green catalyst for preparing tetrachlorethylene has the advantages that few steps are required, the process is simple, the catalyst is non-toxic and harmless, and the green preparation of tetrachlorethylene can be truly realized.
Description
Technical field
The present invention relates to chemical catalyst area, more particularly to a kind of green catalyst for producing tetrachloro-ethylene and its preparation
And application method.
Background technology
Tetrachloro-ethylene is a kind of important organic chlorides, because tetrachloro-ethylene is smaller to the damage capability of ozone layer, ODP
(depletion of the ozone layer index) be 0.15, the aspects such as organic solvent, dry cleaning agent, metal degreasing agent application widely, there are about
80% tetrachloro-ethylene is used as dry cleaning agent, and it has excellent laundry washing effects.In addition, tetrachloro-ethylene can be used as fats extraction
Agent and the intermediate of refrigerant HCFC-123, HCFC-124, HFC-125.In addition, research is it has also been found that tetrachloro-ethylene is to coal
In organic sulfur also there is good removing to act on.Application of the tetrachloro-ethylene at aspects such as solvent, cleaning agent, foaming agent and refrigerants
Increasingly wider, demand increases year by year, and annual demand is concentrated mainly on Europe and China, as molten more than 1,000,000 tons
Agent, cleaning agent and foaming agent and production refrigerant.
The forties in 20th century, foreign countries begin to that the one-step chlorination of acetylene two first is obtained into pentachloroethane, pentachloroethane removing chlorination
Hydrogen obtains tetrachloro-ethylene.The Wa Ke companies of Germany are catalyst using the activated carbon containing 30% (mass fraction) BaCl2, using five
Chloroethanes catalysis dechlorination hydrogen method prepares tetrachloro-ethylene.The eighties in 20th century, market is to trichloro ethylene and the demand of tetrachloro-ethylene
Amount increases, and in order to meet market needs, while environmental protection, western developed country successively closes the life with acetylene method as raw material
Route is produced, is increasingly turned to C1~C3 etc. as raw material, using thermal chlorination, oxychlorination, pyrolysis method coproduction trichloro ethylene and tetrachloro
Ethene.(the Applied Catalysis B such as Delannoy:Environmental,2002,37(2):161-173) have studied
Dehydrogenation reaction is hydrogenated with by carbon tetrachloride in CH4/H2 gaseous mixtures and prepares tetrachloro-ethylene.They compare the platinum base of alumina load
Catalyst and the VIth B metal carbides WC, WC2, Mo2C are tested and found to the catalysis activity of the reaction, and the former activity is substantially
Less than the latter, but the life-span is preferably, while find that WC is best to the selectivity of product chloroform, and WC2 and Mo2C are to tetrachloro-ethylene
Selectivity it is good, at 300 DEG C, when Mo2C is catalyzed, the selectivity of tetrachloro-ethylene has reached 93%.Other scholars also enter to the technique
Go research, the reaction has been catalyzed with copper-based catalysts, equally achieve preferable effect.
(the European patents such as Shigetoshi：EP93109052A, 1993.) a kind of preparation method of tetrachloro-ethylene has been invented,
It is raw material with the hydrocarbon within three carbon, tetrachloro-ethylene is prepared using the method for fractional steps.It is hydrocarbon within first by three carbon
One or more in compound with carbon tetrachloride or chlorine in the reactor 500~700 DEG C at carry out chlorination reaction, from condensation
Mixture in carbon tetrachloride is recovered by distillation, separate and collect and obtain product tetrachloro-ethylene, and chlorine is recycled.
(the Russ Ps such as Villemson：RU2434837,2011. four chloroethenes) are prepared for by raw material of tetrachloroethanes
Alkene., with aluminum oxide as carrier, dry, hydrogen reducing is prepared for the alumina catalyzation of supported palladium under impregnated, nitrogen atmosphere for they
Agent.The reaction temperature that the method prepares tetrachloro-ethylene is 80~200 DEG C, and H2/C2H2Cl4 is 5~15, and time of contact is 3~10
Second.This procedure is simple, and product can be easily separated purifying, and the conversion ratio maximum of tetrachloroethanes can reach in experiment
80.5%, tetrachloro-ethylene has selectively reached 90%.
To meet domestic market needs, Jin Jiang River chemical research institute has used the time of 3 years to have developed suitable for industrial production
Load barium chloride activated-carbon catalyst, using chlorination of acetylene method production tetrachloroethanes, pentachloroethane, four, pentachloroethane gas
Phase catalysis dechlorination hydrogen produces trichloro ethylene and tetrachloro-ethylene.The method tetrachloroethanes and pentachloroethane mixing dehydrochlorination are produced
Trichloro ethylene, the selectivity of tetrachloro-ethylene and yield are higher, and the excellent performance of the catalyst causes that many enterprises draw to it
Enter production (chlorine industry, 2008,44 (1):31-35.).
Another method for producing tetrachloro-ethylene be using carbon tetrachloride by the method for catalytic hydrogenation can obtain chloroform,
The application value highest of the mixtures such as tetrachloro-ethylene, methane, wherein tetrachloro-ethylene.Therefore, the research to the technical process causes
The concern of people.(the Chinese patents such as Wei Junhai：CN103304369A, 2013.) exist in H2, O2, HCl and excess Cl2
Under the conditions of with carbon tetrachloride as raw material, produce tetrachloro-ethylene, the conversion ratio of reaction has reached more than 94%.Shi little Yu etc. is preceding
(Chinese patent on the basis of people's research：CN 101143328,2008.), carbon tetrachloride is employed for raw material, methane is hydrogen source,
Tetrachloro-ethylene co-production monochloro methane has been prepared using both coupled reactions, Pt-Cu/SiO2 bimetallic catalysts have been investigated
To the catalytic performance of the reaction, change the content and proportioning of metal, as a result show, the bimetallic containing 1%Pt-2%Cu/SiO2 is urged
Agent has activity and stability higher to the reaction.(the Chinese patents such as Zhang Dongbao：CN 101143328,2008.) research
With Al2O3, SiO2, ZrO2, one or two in TiO2 respectively as carrier, with Pt, Pd, Ni, Ag, Zn, Co, Cu, Fe
Compound in one or more be supported on carrier as active component, prepared catalyst is used for gas phase catalysis legal system
Standby tetrachloro-ethylene, obtains carbon tetrachloride conversion and tetrachloro-ethylene selectivity higher, while having the life-span more long.
Either domestic or external, the method for producing tetrachloro-ethylene is substantially used：(1) pentachloroethane dehydrochlorination
Method, i.e. acetylene method.(2) carbon tetrachloride, small molecule alkane and chlorine process for oxychlorination.The catalysis that pentachloroethane dehydrochlorination is used
Agent is BaCl2/ activated carbons, and BaCl2 is heavy metallic salt, due to the loss of catalyst activity component in production process, product and useless
The post processing of catalyst can produce baric waste water, pollute environment.Process for oxychlorination used catalyst is generally noble metal catalyst, is made
With high cost, by-product species are more, and product separates difficult, and some accessory substance application prospects are not clear, can only be as waste at
Reason, causes greatly waste.
The content of the invention
The purpose of the present invention is：Solve the deficiency of the catalyst of above-mentioned technology, there is provided one kind is with TiCl4、CuCl2、CaCl2、
AlCl3And SnCl4It is active component, with activated carbon as carrier, the support type dehydrochlorination catalyst prepared is nontoxic, nothing
Heavy metal pollution, without volatile slaine, does not easily cause environmental pollution.
Realizing the technical scheme of the object of the invention is：
1st, the preparation of catalyst：Catalyst is with FeCl3、AlCl3、CuCl2, CuCl and TiCl4In two or more for live
Property component, with activated carbon as carrier, impregnated, drying, the lower roasting of nitrogen protection prepare nontoxic supported catalyst
Agent.
2nd, the content of FeCl3, AlCl3, CuCl2, CuCl and TiCl4 is respectively in catalyst：0~3%, 0~6%, 0~
6%th, 0~8% and 0~5%.Wherein FeCl3 preferably without, 1%, 2% or 3%；AlCl3 preferably without, 1%, 2%,
3%th, 4%, 5% or 6%；CuCl2 preferably without, 1%, 2%, 3%, 4%, 5% or 6%；CuCl preferably without, 1%,
2%th, 3%, 4%, 5%, 6%, 7% or 8%；TiCl4 preferably without, 1%, 2%, 3% or 4%.The content 3 of active component
~28%, the content 72~97% of activated carbon.
3rd, active component aqueous impregnation activated carbon 24h is used at room temperature.
4th, the drying temperature of catalyst is 100~200 DEG C.
5th, catalyst sintering temperature under nitrogen protection is 250~450 DEG C.
6th, catalyst application method：Pentachloroethane is passed through the fixed bed reactors equipped with green catalyst, in catalyst
In the presence of pentachloroethane dehydrochlorination generation tetrachloro-ethylene.The temperature of pentachloroethane dehydrochlorination reaction is 150~350 DEG C,
The pressure of reaction is 0.1~0.5MPa, and the liquid air speed of pentachloroethane is 0.5~2.5h-1.
The present invention has positive effect：The support type dehydrochlorination catalyst that the present invention is prepared is nontoxic, without weight
Metallic pollution, without volatile slaine, does not easily cause environmental pollution, and tetrachloro-ethylene is produced using green catalyst of the invention,
Pentachloroethane conversion ratio between 70%~95%, tetrachloro-ethylene selectivity>98%；And step is few, process is simple, nontoxic nothing
Evil, can really realize the green production of tetrachloro-ethylene.
Specific embodiment
(embodiment 1)
By in 100g FeCl36H2O and 60kg AlCl36H2O addition 1.2kg water, stirring and dissolving obtains slaine
Concentration is the solution of 0.52M, adds activated carbon 1kg, 24h is impregnated at room temperature, 400 under filtering, 120 DEG C of drying 6h, N2 gas shieldeds
DEG C roasting 8h, obtain the dehydrochlorination catalyst that metalline is 8%.To be passed through under the conditions of 200 DEG C of pentachloroethane, 0.1MPa solid
Bed catalyst reactor reaction, pentachloroethane air speed is 1.5h-1, and pentachloroethane conversion ratio is 84%, tetrachloro-ethylene selectivity
It is 97%.
(embodiment 2)
90g FeCl36H2O, 50g AlCl36H2O, 50g CaCl22H2O and 40g TiCl4 are added into 1.2kg
In water, stirring and dissolving obtains the solution that metal salt concentrations are 0.65M, adds activated carbon 1kg, impregnates 24 hours at room temperature, mistake
Filter, 100 DEG C of drying 10h, the lower 300 DEG C of roastings 8h of nitrogen protection, obtain the dehydrochlorination catalyst that metalline is 11.5%.Will
Fix bed catalyst reactor reaction is passed through under the conditions of 280 DEG C of pentachloroethane, 0.2MPa, pentachloroethane air speed is 2.0h-1, five
Chloroethanes conversion ratio is 83%, and tetrachloro-ethylene is selectively 98%.
(embodiment 3)
50g AlCl36H2O, 50g CaCl22H2O, 40kg SnCl22H2O and 50g TiCl4 are added into 2kg
In water, stirring and dissolving obtains the solution that metal salt concentrations are 0.38M, adds activated carbon 2kg, and 24h is impregnated at room temperature, filter,
150 DEG C of drying 4h, the lower 500 DEG C of roastings 8h of nitrogen protection, obtain the acetylene hydrochlorination catalyst that metalline is 4.5%.By five
Fix bed catalyst reactor reaction is passed through under the conditions of 220 DEG C of chloroethanes, 0.1MPa, pentachloroethane air speed is 1.0h-1, pentachloro-
Ethane conversion is 72%, and tetrachloro-ethylene is selectively 98%.
(embodiment 4)
During 150g FeCl36H2O, 80g AlCl36H2O and 50g TiCl4 added into 1.2kg water, stirring and dissolving,
Obtain metal salt concentrations be 0.82M solution, add activated carbon 1kg, at room temperature impregnate 24 hours, filtering, 180 DEG C drying 4h,
The lower 450 DEG C of roastings 8h of N2 gas shieldeds, obtains the dehydrochlorination catalyst that metalline is 14%.By 250 DEG C of pentachloroethane,
Fix bed catalyst reactor reaction is passed through under the conditions of 0.2MPa, pentachloroethane air speed is 1.0h-1, and pentachloroethane conversion ratio is
93%, tetrachloro-ethylene is selectively 98%.
(embodiment 5)
By 180kg FeCl36H2O, 100g AlCl36H2O, 80g CaCl22H2O, 30g SnCl22H2O
In 80kg TiCl4 addition 1.2kg water, stirring and dissolving obtains the solution that metal salt concentrations are 1.7M, adds activated carbon 1kg,
Impregnate 24h at room temperature, filtering, 110 DEG C of drying 10h, the lower 4000C roastings 8h of nitrogen protection, obtain metalline be 25% it is de-
Chlorination hydrogen catalyst.Fix bed catalyst reactor reaction, pentachloroethane will be passed through under the conditions of 200 DEG C of pentachloroethane, 0.5MPa
Air speed is 1.0h-1, and pentachloroethane conversion ratio is 87%, and tetrachloro-ethylene is selectively 99%.
(embodiment 6)
By 150g FeCl36H2O, 80g AlCl36H2O, 80g CaCl22H2O, 50g SnCl22H2O and
30g TiCl4 are added in 1kg water, stirring and dissolving, obtain the solution that metal salt concentrations are 1.8M, add activated carbon 1kg, at room temperature
Dipping 24 hours, filtering, 160 DEG C of lower 400 DEG C of roastings 10h of drying 10h, N2 gas shielded, obtains the dechlorination that metalline is 21%
Change hydrogen catalyst.Fix bed catalyst reactor reaction will be passed through under the conditions of 220 DEG C of pentachloroethane, 0.1MPa, pentachloroethane is empty
Speed is 0.8h-1, and pentachloroethane conversion ratio is 95%, and tetrachloro-ethylene is selectively 99%.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail bright, should be understood that and the foregoing is only specific embodiment of the invention, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in guarantor of the invention
Within the scope of shield.
Claims (9)
1. a kind of green catalyst for producing tetrachloro-ethylene, it is characterised in that：The catalyst with FeCl3, AlCl3, CuCl2,
Two or more in CuCl and TiCl4 are active component, with activated carbon as carrier, four chloroethenes of production are prepared using infusion process
The green catalyst of alkene.
2. it is according to claim 1 production tetrachloro-ethylene green catalyst, it is characterised in that：In the green catalyst
The content of FeCl3, AlCl3, CuCl2, CuCl and TiCl4 is respectively：0~3%, 0~6%, 0~6%, 0~8% and 0~
5%；The content 3~28% of active component, the content 72~97% of activated carbon.
3. it is a kind of it is as claimed in claim 1 or 2 production tetrachloro-ethylene green catalyst production method, it is characterised in that：With
Two or more in FeCl3, AlCl3, CuCl2, CuCl and TiCl4 are active component, with activated carbon as carrier, impregnated,
Drying, the lower roasting of nitrogen protection, prepare the green catalyst of production tetrachloro-ethylene.
4. it is according to claim 3 production tetrachloro-ethylene green catalyst production method, it is characterised in that drying temperature
Spend is 100~200 DEG C.
5. it is according to claim 3 production tetrachloro-ethylene green catalyst production method, it is characterised in that：In nitrogen
Sintering temperature under protection is 300~500 DEG C.
6. it is a kind of it is as claimed in claim 1 or 2 production tetrachloro-ethylene green catalyst application method, it is characterised in that：Will
Pentachloroethane is passed through the fixed bed reactors of the green catalyst equipped with production tetrachloro-ethylene, five chloroethene in the presence of catalyst
Alkane dehydrochlorination generates tetrachloro-ethylene.
7. the application method of the green catalyst of production tetrachloro-ethylene according to claim 6, it is characterised in that：Pentachloro-
The temperature of ethane dehydrochlorination reaction is 150~350 DEG C.
8. it is according to claim 6 production tetrachloro-ethylene green catalyst application method, it is characterised in that：Reaction
Pressure is 0.1~0.5MPa.
9. it is according to claim 6 production tetrachloro-ethylene green catalyst application method, it is characterised in that：Five chloroethenes
The liquid air speed of alkane is 0.5~2.5h-1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759512A (en) * | 2017-11-06 | 2018-03-06 | 江苏中邦制药有限公司 | A kind of synthetic method of 2,3,6 trichloropyridine |
| CN107790158A (en) * | 2017-10-11 | 2018-03-13 | 南京红太阳股份有限公司 | A kind of preparation method of loaded catalyst, synthetic method and 2,3,5,6 4 chloro pyridines |
| CN107793352A (en) * | 2017-10-11 | 2018-03-13 | 南京红太阳股份有限公司 | A kind of preparation method of 2,3,5,6 4 chloro pyridine |
| CN109012676A (en) * | 2018-08-16 | 2018-12-18 | 山东东岳化工有限公司 | A kind of catalyst and the preparation method and application thereof preparing HF hydrocarbon for hydrofluoroalkane gas phase removal HF |
| CN113214044A (en) * | 2021-05-06 | 2021-08-06 | 重庆昊然节能环保技术咨询服务有限公司 | Preparation method of tetrachloroethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107790158A (en) * | 2017-10-11 | 2018-03-13 | 南京红太阳股份有限公司 | A kind of preparation method of loaded catalyst, synthetic method and 2,3,5,6 4 chloro pyridines |
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| CN109012676A (en) * | 2018-08-16 | 2018-12-18 | 山东东岳化工有限公司 | A kind of catalyst and the preparation method and application thereof preparing HF hydrocarbon for hydrofluoroalkane gas phase removal HF |
| CN109012676B (en) * | 2018-08-16 | 2021-07-20 | 山东东岳化工有限公司 | Catalyst for preparing hydrofluoroolefin by removing HF from hydrofluoroalkane gas phase, and preparation method and application thereof |
| CN113214044A (en) * | 2021-05-06 | 2021-08-06 | 重庆昊然节能环保技术咨询服务有限公司 | Preparation method of tetrachloroethylene |
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