CN106902851A - A kind of catalyst, Its Preparation Method And Use - Google Patents

A kind of catalyst, Its Preparation Method And Use Download PDF

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Publication number
CN106902851A
CN106902851A CN201710119186.6A CN201710119186A CN106902851A CN 106902851 A CN106902851 A CN 106902851A CN 201710119186 A CN201710119186 A CN 201710119186A CN 106902851 A CN106902851 A CN 106902851A
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catalyst
carrier
hfc
fluoride
fluorine
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CN201710119186.6A
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CN106902851B (en
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董利
胡儒柱
陈朝晖
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Quanzhou Yuji New Material Technology Co.,Ltd.
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BEIJING YUJI TECHNOLOGY DEVELOPMENT Co
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

It is to solve the problem that reaction temperature is high, target product selectivity is relatively low present in 1,1,1, the 2 HFC-134a bromination synthesis HFC-134a process of 1,1 dibromo 1,2,2,2 the invention discloses a kind of catalyst, Its Preparation Method And Use.The catalyst is using one or more in Fe, Al, Cu, Sn, Zn, P halide as active component, it is carried on activated carbon, porous metals fluoride or oxyfluoride using infusion process, it is used for vapor- phase synthesis 1 after drying, 1 dibromo 1,2,2,2 HFC-134as react, and have the advantages that reaction temperature is low, target product selectivity is high.

Description

A kind of catalyst, Its Preparation Method And Use
Technical field
The present invention relates to a kind of catalyst, more particularly to a kind of catalyst, its preparation method and its in gas phase reaction preparation Application in the bromo- 1,2,2,2- HFC-134as of 1,1- bis-.
Background technology
1,3- hexachlorobutadiene is a kind of etching gas of excellent performance, the market in terms of semicon industry etching technics Demand sustainable growth.The method of synthesis 1,3- hexachlorobutadienes mainly has two kinds at this stage：One kind be by 1,2- bis- bromo- 1,2, 2- HFC-143as slough HBr generation bromotrifluoroethylenes, then are complexed to form trifluoro-ethylene based metal complex with metallic zinc, in Fe3+ In the presence of be coupled generation；It is another then be that by 1,1- bis- bromo- 1,2,2,2- HFC-134as are complexed with metallic zinc, in Fe3+Make Synthesized with lower coupling.Wherein second method due to reaction scheme it is short, it is simple to operate, with good prospects for commercial application.
The current bromo- 1,2,2,2- HFC-134as of 1,1- bis- are mainly by 1,1,1,2- HFC-134as and bromine at high temperature Substitution reaction synthesizes, except containing 1,1- bis- bromo- 1 in the product of the reaction, also substantial amounts of beyond 2,2,2- HFC-134as 1- bromo- 1,2,2,2- HFC-134as, and a small amount of 1,2- bis- bromo- 1,2,2- HFC-143as, wherein 1,2- bis- bromo- 1,2,2- tri- Fluoroethane is to be cracked to form trifluoro-ethylene at high temperature by HFA 134a, then with bromine addition reaction gained.Whole work Skill has that reaction temperature is higher, the relatively low problem of target product selectivity, it is therefore desirable to develop a kind of new catalyst The selectivity of target product is improved, and can further reduce reaction temperature, it is to avoid raw material occurs cracking and produces excessive pair Product.
The content of the invention
, for the deficiency of existing process condition, high especially for reaction temperature, target product selectivity is relatively low for the present invention A kind of problem, there is provided preparation process is simple, the efficient catalyst of reactivity worth can be used for scale and be combined to 1,1- bis- bromo- 1,2, 2,2- HFC-134as.
The technical solution adopted by the present invention is as follows：
A kind of catalyst, using one or more in Fe, Al, Cu, Sn, Zn, P halide as active component, using leaching Stain method is carried on carrier, load capacity 1~20%, is obtained after drying, the carrier be activated carbon, porous metals fluoride or Oxyfluoride.
The halide includes chloride and bromide.
The activated carbon includes coconut husk charcoal, coal charcoal processing, charcoal, bamboo charcoal, and its form can be powder, particle or extrusion bar Shape, carrier specific surface area 100-1000m2/g；The porous metals fluoride includes aluminum fluoride, magnesium fluoride, calcirm-fluoride, fluorination Chromium, the oxyfluoride is fluorine alumina, fluorine magnesia, fluorine chromium oxide, and its form can be powder, particle or extrude bar shaped, Carrier specific surface area 20-300m2/g。
It is described it is carrier loaded before need to be processed suddenly：Activated carbon used, porous metals fluoride or oxyfluoride carrier 3-10% salpeter solution boiling reflux 2-12h need to be first used, pH=7 is washed with distilled water to after filtering, 12h is dried at 80 DEG C.
The preparation method of above-mentioned carrier, comprises the following steps：
1) pretreatment of carrier
Activated carbon used, porous metals fluoride or oxyfluoride carrier need to first use 3-10% salpeter solution boiling refluxs 2- 12h, is washed with distilled water to pH=7 after filtering, 12h is dried at 80 DEG C.
2) preparation catalyst
One or more in Fe, Al, Cu, Sn, Zn, P halide salt are weighed, maceration extract is prepared according to a certain percentage, treat molten The catalyst carrier by pretreatment is added after the completion of solution, dipping 12-24h is stood.The catalyst filtration that will have been impregnated, 80-200 12-24h is dried at DEG C, it is stand-by.
Application of the described catalyst in fluorohydrocarbon bromo obtains fluorine bromine hydrocarbon.
The fluorohydrocarbon is fluoric ether, and fluorine bromine hydrocarbon is fluorobromohydrocarbon hydrocarbon.
The fluorohydrocarbon is 1,2,2,2- HFC-134as, and bromo agent is bromine, and fluorine bromine hydrocarbon is 1,1- bis- bromo- 1,2,2,2- tetra- Fluoroethane, wherein reaction temperature are 300-600 DEG C, and bromine is 0.8-5 with 1,2,2,2- HFC-134a mol ratios, and total air speed is 100-1500h-1。
Wherein reaction temperature is 350-450 DEG C, and bromine is 1.5-2.5, total air speed with 1,2,2,2- HFC-134a mol ratios It is 300-800h-1。
Catalyst of the present invention is used to synthesize 1,1- bis- bromo- 1, during 2,2,2- HFC-134a, using fixed bed reactors, Material be 99.5% alundum tube, internal diameter 20mm, length 2000mm, loaded catalyst is 300ml.Reaction temperature is 300-600 DEG C, preferably 350-450 DEG C, bromine is 0.8-5, preferably 1.5-2.5 with 1,2,2,2- HFC-134a mol ratios, and total air speed control exists 100-1500h-1, preferably 300-800h-1.Product carries out quantitative analysis after washing, alkali cleaning, drying with GC, calculates raw material Conversion ratio and the bromo- 1,2,2,2- HFC-134as selectivity of 1,1- bis-.
Beneficial effect：
1. the preparation process is simple of catalyst of the present invention is easy to operate, and catalyst reappearance is high；
2. catalyst of the present invention is used for bromination reaction process can significantly improve the selectivity of target product, can be significantly Improve production efficiency；
3. catalyst of the present invention can reduce reaction temperature, suppress the cracking of raw material, reduce side reaction generation, make Reaction condition is more gentle controllable.
Specific embodiment
With reference to embodiment, the present invention will be further described, but does not limit the invention to these specific embodiment parties Formula.
Embodiment 1 (sample 1)
300g coconut husk charcoals are weighed, 10% salpeter solution boiling reflux 6h is added, is washed with deionized after filtering to pH= 12h is dried at 7,80 DEG C, it is stand-by；
Weigh 17.3g FeCl3With 12.7g ZnCl2With deionized water dissolving, stirring is added to solution clarification passes through pre- place The coconut husk charcoal of reason stands dipping 12h.It is stand-by in 24h is dried at 80 DEG C after the catalyst filtration that will have been impregnated.
Embodiment 2 (sample 2)
300g aluminum fluorides are weighed, 10% salpeter solution boiling reflux 6h is added, is washed with deionized after filtering to pH= 12h is dried at 7,80 DEG C, it is stand-by；
Weigh 17.3g FeCl3With 12.7g ZnCl2With deionized water dissolving, stirring is added to solution clarification passes through pre- place The aluminum fluoride of reason stands dipping 12h.It is stand-by in 24h is dried at 80 DEG C after the catalyst filtration that will have been impregnated.
Embodiment 3 (sample 3)
300g magnesium fluorides are weighed, 10% salpeter solution boiling reflux 6h is added, is washed with deionized after filtering to pH= 12h is dried at 7,80 DEG C, it is stand-by；
Weigh 17.3g FeCl3With 12.7g ZnCl2With deionized water dissolving, stirring is added to solution clarification passes through pre- place The magnesium fluoride of reason stands dipping 12h.It is stand-by in 24h is dried at 80 DEG C after the catalyst filtration that will have been impregnated.
Embodiment 4 (sample 4)
300g charomic fluorides are weighed, 10% salpeter solution boiling reflux 6h is added, is washed with deionized after filtering to pH= 12h is dried at 7,80 DEG C, it is stand-by；
Weigh 17.3g FeCl3With 12.7g ZnCl2With deionized water dissolving, stirring is added to solution clarification passes through pre- place The charomic fluoride of reason stands dipping 12h.It is stand-by in 24h is dried at 80 DEG C after the catalyst filtration that will have been impregnated.
Embodiment 5 (sample 5)
300g aluminum fluorides are weighed, 10% salpeter solution boiling reflux 12h is added, is washed with deionized after filtering to pH= 12h is dried at 7,80 DEG C, it is stand-by；
Weigh 32.2g FeBr3With 12.8g CuCl2With deionized water dissolving, stirring is added to solution clarification passes through pre- place The aluminum fluoride of reason stands dipping 24h.It is stand-by in 24h is dried at 100 DEG C after the catalyst filtration that will have been impregnated.
Embodiment 6 (sample 6)
300g fluorine aluminas are weighed, 8% salpeter solution boiling reflux 6h is added, is washed with deionized after filtering to pH= 12h is dried at 7,120 DEG C, it is stand-by；
Weigh 7.7g SnCl4With 7.3g CuCl2With deionized water dissolving, stirring is added to solution clarification passes through pretreatment Fluorine alumina stand dipping 24h.It is stand-by in 24h is dried at 120 DEG C after the catalyst filtration that will have been impregnated.
Embodiment 7
300ml catalyst is loaded in 99.5% corundum pipe reactor, adjustment reaction temperature is 400 DEG C, bromine and 1,1,1, 2- HFC-134as raw materials components mole ratio is 2, and product carries out quantitative analysis after washing, alkali cleaning, drying with GC, calculates raw material and turns Rate and the bromo- 1,2,2,2- HFC-134as selectivity of 1,1- bis-.
The sample 1-6 reactivity worth of table 1 is contrasted
As can be seen from Table 1, sample 5 has optimal reactivity worth, and under conditions of 400 DEG C, feed stock conversion is reachable 97.4%, target product 1,1- bis- bromo- 1,2,2,2- HFC-134as are selectively 96.8%, and cleavage reaction product 1,2- bis- is bromo- 1,2,2- HFC-143as are selectively only 0.1%.

Claims (10)

1. a kind of catalyst, using one or more in Fe, Al, Cu, Sn, Zn, P halide as active component, using dipping Method is carried on carrier, load capacity 1~20%, is obtained after drying, and the carrier is activated carbon, porous metals fluoride or fluorine Oxide.
2. catalyst according to claim 1, the halide includes chloride and bromide.
3. catalyst according to claim 1, the activated carbon includes coconut husk charcoal, coal charcoal processing, charcoal, bamboo charcoal, its form Can be powder, particle or extrusion bar shaped, carrier specific surface area 100-1000m2/g；The porous metals fluoride includes fluorination Aluminium, magnesium fluoride, calcirm-fluoride, charomic fluoride, the oxyfluoride are fluorine alumina, fluorine magnesia, fluorine chromium oxide, and its form can be Powder, particle or extrusion bar shaped, carrier specific surface area 20-300m2/g。
4. catalyst according to claim 1, it is described it is carrier loaded before need to be processed suddenly：It is activated carbon used, porous Metal fluoride or oxyfluoride carrier need to first use 3-10% salpeter solution boiling reflux 2-12h, with distillation water washing after filtering To pH=7,12h is dried at 80 DEG C.
5. the preparation method of any carriers of claim 1-4, comprises the following steps：
1) pretreatment of carrier
Activated carbon used, porous metals fluoride or oxyfluoride carrier need to first use 3-10% salpeter solution boiling reflux 2-12h, PH=7 is washed with distilled water to after filtering, 12h is dried at 80 DEG C；
2) preparation catalyst
One or more in Fe, Al, Cu, Sn, Zn, P halide salt are weighed, water retting liquid is prepared according to a certain percentage, it is to be dissolved After the completion of add by pretreatment catalyst carrier, stand dipping 12-24h；The catalyst filtration that will have been impregnated, drying is standby With.
6. method according to claim 5, the step 2) in drying be to process 12-24h at 80-200 DEG C.
7. application of any described catalyst of claim 1-4 in fluorohydrocarbon bromo obtains fluorine bromine hydrocarbon.
8. application according to claim 7, the fluorohydrocarbon is fluoric ether, and fluorine bromine hydrocarbon is fluorobromohydrocarbon hydrocarbon.
9. application according to claim 8, the fluorohydrocarbon is 1,2,2,2- HFC-134as, and bromo agent is bromine, fluorine bromine Hydrocarbon is 1,1- bis- bromo- 1, and 2,2,2- HFC-134as, wherein reaction temperature are 300-600 DEG C, bromine and 1,2,2,2- HFC-134as Mol ratio is 0.8-5, and total air speed is 100-1500h-1。
10. application according to claim 9, wherein reaction temperature are 350-450 DEG C, bromine and 1,2,2,2- HFC-134as Mol ratio is 1.5-2.5, and total air speed is 300-800h-1。
CN201710119186.6A 2017-03-02 2017-03-02 A kind of catalyst, Its Preparation Method And Use Active CN106902851B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107999100A (en) * 2018-01-10 2018-05-08 中国科学院上海高等研究院 A kind of catalyst of light paraffins aromatisation and its preparation method and application
CN109569719A (en) * 2018-12-29 2019-04-05 中国科学院上海高等研究院 A kind of carbon base catalyst and preparation method thereof for light paraffins aromatisation
CN116139893A (en) * 2022-12-21 2023-05-23 西安近代化学研究所 Catalyst for synthesizing trifluoroethylene by selective hydrodechlorination and preparation method of trifluoroethylene

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5334705A (en) * 1976-09-13 1978-03-31 Central Glass Co Ltd Preparation of bromotrifluoromethane
CN1031220A (en) * 1987-07-10 1989-02-22 阿托化学公司 Synthesizing of perfluoroalkyl bromide
CN1814345A (en) * 2006-03-01 2006-08-09 那风换 Composite metal chloride catalyst and its production process
CN1876238A (en) * 2006-07-07 2006-12-13 宁夏大学 Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method
CN101229516A (en) * 2008-02-25 2008-07-30 中国石油化工集团公司 Catalyst for removing organic chloride contained in hydrocarbon and preparing method thereof
CN102069000A (en) * 2010-12-06 2011-05-25 宜宾天原集团股份有限公司 Non-mercury catalyst for production of vinyl chloride and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5334705A (en) * 1976-09-13 1978-03-31 Central Glass Co Ltd Preparation of bromotrifluoromethane
CN1031220A (en) * 1987-07-10 1989-02-22 阿托化学公司 Synthesizing of perfluoroalkyl bromide
CN1814345A (en) * 2006-03-01 2006-08-09 那风换 Composite metal chloride catalyst and its production process
CN1876238A (en) * 2006-07-07 2006-12-13 宁夏大学 Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method
CN101229516A (en) * 2008-02-25 2008-07-30 中国石油化工集团公司 Catalyst for removing organic chloride contained in hydrocarbon and preparing method thereof
CN102069000A (en) * 2010-12-06 2011-05-25 宜宾天原集团股份有限公司 Non-mercury catalyst for production of vinyl chloride and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107999100A (en) * 2018-01-10 2018-05-08 中国科学院上海高等研究院 A kind of catalyst of light paraffins aromatisation and its preparation method and application
CN107999100B (en) * 2018-01-10 2020-12-15 中国科学院上海高等研究院 Light alkane aromatization catalyst and preparation method and application thereof
CN109569719A (en) * 2018-12-29 2019-04-05 中国科学院上海高等研究院 A kind of carbon base catalyst and preparation method thereof for light paraffins aromatisation
CN109569719B (en) * 2018-12-29 2021-08-13 中国科学院上海高等研究院 Carbon-based catalyst for light alkane aromatization and preparation method thereof
CN116139893A (en) * 2022-12-21 2023-05-23 西安近代化学研究所 Catalyst for synthesizing trifluoroethylene by selective hydrodechlorination and preparation method of trifluoroethylene

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