CN112495394A - Hydrodechlorination catalyst and preparation method of chlorotrifluoroethylene - Google Patents
Hydrodechlorination catalyst and preparation method of chlorotrifluoroethylene Download PDFInfo
- Publication number
- CN112495394A CN112495394A CN202011454875.0A CN202011454875A CN112495394A CN 112495394 A CN112495394 A CN 112495394A CN 202011454875 A CN202011454875 A CN 202011454875A CN 112495394 A CN112495394 A CN 112495394A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- chlorotrifluoroethylene
- carrier
- auxiliary agent
- hydrodechlorination
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 abstract description 11
- 229910052718 tin Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- VFGPKMMQBBQIST-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane;zinc Chemical compound [Zn].FC(F)(F)C(Cl)(Cl)Cl VFGPKMMQBBQIST-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 trifluoroethylene, difluoroethylene, difluorochloroethylene Chemical group 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Landscapes
- 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
本发明涉及一种加氢脱氯催化剂及三氟氯乙烯的制备方法，加氢脱氯催化剂包括载体、主催化剂和助剂，主催化剂和助剂负载于载体上，主催化剂为Pd和Cu，助剂添加Sn或Mn以抑制团聚，并对负载量进行优化。该方法采用上述加氢脱氯催化剂制备三氟氯乙烯。本发明中的催化剂稳定性好、活性高、反应选择性和适用反应温度友好、寿命长，用于制备三氟氯乙烯时，更有利于工业规模生产。The invention relates to a hydrodechlorination catalyst and a preparation method of chlorotrifluoroethylene. The hydrodechlorination catalyst comprises a carrier, a main catalyst and an auxiliary, the main catalyst and the auxiliary are supported on the carrier, and the main catalyst is Pd and Cu, Additives Sn or Mn are added to suppress agglomeration and optimize the loading. The method adopts the above hydrodechlorination catalyst to prepare chlorotrifluoroethylene. The catalyst in the present invention has good stability, high activity, friendly reaction selectivity and applicable reaction temperature, and long service life. When used for preparing chlorotrifluoroethylene, it is more favorable for industrial scale production.
Description
Technical Field
The invention relates to a catalyst composition and a preparation method of chlorotrifluoroethylene, in particular to a catalyst composition for preparing chlorotrifluoroethylene by trichlorotrifluoroethane hydrodechlorination and a preparation method of chlorotrifluoroethylene.
Background
Chlorotrifluoroethylene (CTFE) is one of important monomers for synthesizing fluorine-containing materials, and the telomerization reaction of the CTFE has wide application value in industries such as aviation, construction, military industry, electronic industry and the like. The cost, purity and industrial feasibility of chlorotrifluoroethylene synthesis are major factors influencing the development of chlorotrifluoroethylene and fluoropolymer materials. Therefore, the development of a chlorotrifluoroethylene preparation process with high purity, low cost and environmental protection is of great significance.
The preparation method of chlorotrifluoroethylene with industrial application value at present mainly comprises the following steps: 1) zinc trichlorotrifluoroethane (CFC-113) powder reduction dechlorination method; 2) a catalytic hydrogenation and dechlorination method of trifluorotrichloroethane. The trifluorotrichloroethane zinc powder reduction dechlorination method has the disadvantages of large production equipment, low efficiency, difficult control of production rate, use of a large amount of alcohol substances and zinc powder which are difficult to recover in the reaction process, difficult recovery and treatment of byproducts including trifluoroethylene, difluoroethylene, difluorochloroethylene and the like, and high pollution treatment cost.
Aiming at a zinc powder reduction dechlorination method, a trifluorotrichloroethane gas-phase catalytic hydrogenation dechlorination method for preparing chlorotrifluoroethylene appears in the 50 th century. In the method, under the action of a catalyst, trifluorotrichloroethane and hydrogen undergo an oxidation-reduction reaction to generate chlorotrifluoroethylene and hydrogen chloride, but the types of the used catalysts are different, and the production efficiency, the purity and the preparation cost of the chlorotrifluoroethylene have larger differences. The catalyst can be roughly classified into a non-noble metal type and a noble metal type. The non-noble metal mostly takes metal oxide as an active component, and the catalyst needs to adopt higher reaction temperature and has shorter service life. The reaction temperature of the noble metal is lower, and the side reaction is less. Although the active components and reaction conditions of the catalyst are continuously optimized at present, the catalyst still has a larger promotion space in the aspects of catalyst stability, use cost, conversion rate, reaction selectivity and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrodechlorination catalyst and a preparation method of chlorotrifluoroethylene, and the catalyst is added with Sn or Mn on the basis of a Pd-Cu system catalyst to inhibit agglomeration, so that the performance of the catalyst is improved, when the catalyst is used for preparing the chlorotrifluoroethylene, the beneficial effects of environmental protection and cost reduction can be realized, and the market demand can be better met.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows:
a hydrodechlorination catalyst comprises a carrier, a main catalyst and an auxiliary agent;
the carrier is active carbon and Al2O3Or SiO2The main catalyst and the auxiliary agent are loaded on a carrier;
the main catalyst is Pd and Cu;
preferably, the amount of Pd is 0.5-3% of the total mass of the catalyst, the amount of Cu is 2.0-10.5% of the total mass of the catalyst, and the amount of the auxiliary agent is 0.2-3.0% of the total mass of the catalyst.
According to a further preferable scheme, the auxiliary agent is Sn and/or Mn, and the amount of Sn and/or Mn accounts for 0.2-3.0% of the total mass of the catalyst.
As a further preferable scheme, the auxiliary agent comprises one to three of Zn, Zr, Ag, Ti, Cd, Hg, In, Pb and Bi besides Sn and/or Mn; the dosage of the auxiliary agent is 0.2-3.0% of the total mass of the catalyst, and the dosage of Sn and/or Mn accounts for 0.1-2.0% of the total mass of the catalyst. The addition of auxiliary components such as Zn, Zr, Ag, Ti, Cd, Hg, In, Pb, Bi and the like further adjusts the surface property of the catalyst, and improves the dispersibility and the associativity of Sn and/or Mn, Pd and Cu on the carrier.
Optionally, the auxiliary agent is Sn or Zn. Optionally, the auxiliary agent is Mn or Zn. Optionally, the auxiliary agent is Sn, Mn, Zn.
Optionally, the auxiliary agent is Sn, Zn or Ti. Optionally, the auxiliary agent is Mn, Zn, Ti. Optionally, the auxiliary agent is Sn, Mn, Zn, Ti.
Optionally, the assistant is Sn, Zr, Cd, Bi. Optionally, the auxiliary agent is Mn, Zr, Cd, Bi. Optionally, the assistant is Sn, Mn, Zr, Cd, Bi.
Optionally, the auxiliary agent is Sn, Ag, Hg, In. Optionally, the auxiliary agent is Mn, Ag, Hg, In. Optionally, the auxiliary agent is Sn, Mn, Ag, Hg, In.
The preparation method of the catalyst comprises the following steps: and (3) soaking the carrier in the active component and auxiliary agent soaking solution.
As a further preferable scheme, the active component and auxiliary agent impregnation liquid comprises an active component and an auxiliary agent soluble salt; the pH value of the impregnation liquid is 3-9.5. More preferably, the pH of the impregnation solution is in the range of 7 to 9.
As a further preferred scheme, the active component and the auxiliary agent soluble salt can be chloride salt or nitrate salt.
As a further preferable scheme, the carrier is activated carbon, and the activated carbon is subjected to high-temperature pretreatment and acid/alkali washing pretreatment before the active components and the auxiliary agents are impregnated. The high-temperature pretreatment and the acid washing/alkali washing pretreatment can improve the stability of the activated carbon carrier and the binding capacity of the supported components.
More preferably, when the activated carbon is used as the carrier, the specific surface area of the activated carbon is 800-1500m2/g。
More preferably, when activated carbon is used as the carrier, the carrier is subjected to an acid washing pretreatment using nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, hydrofluoric acid, or the like.
More preferably, when activated carbon is used as the carrier, an alkali washing pretreatment is performed using ammonia water, potassium hydroxide, or the like.
More preferably, when activated carbon is used as the carrier, the activated carbon is pretreated at a high temperature, which may be 1700-2000 ℃. The high-temperature pretreatment time is 2-6 hours, and the vacuum environment is adopted.
The invention also discloses a preparation method of chlorotrifluoroethylene, which comprises the step of reacting trifluorotrichloroethane, hydrogen and the hydrodechlorination catalyst at the temperature of 150-300 ℃ by using the hydrodechlorination catalyst to obtain chlorotrifluoroethylene.
As a further preferable mode, the reaction pressure is controlled to be 1 to 1.5 MPa.
As a further preferred embodiment, the residence time is controlled to be 15 to 25 s.
As a further preferable mode, the hydrogen gas flow rate is 30 to 60ml/min in order to contact the reactants with the catalyst sufficiently and to react sufficiently.
More preferably, the molar ratio of the hydrogen to the trifluorotrichloroethane is (1.5-3.1): 1.
as a further preferable scheme, the space velocity of the raw materials is 10-1300h-1More preferably 10-1100h-1。
Compared with the prior art, the invention has the following technical effects:
(1) the catalyst has the advantages of good stability, high activity, reaction selectivity, friendly applicable reaction temperature, long service life and the like.
(2) The preparation method of the chlorotrifluoroethylene can realize the beneficial effects of environmental protection and cost reduction due to the improved performance of the catalyst, and is more beneficial to industrial scale production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1: pretreatment of activated carbon
Taking a certain amount of active carbon, wherein the specific surface area of the active carbon is 910m2(ii) in terms of/g. Treating at 1800 deg.C under vacuum for 2 hr, cooling, soaking in diluted 20% nitric acid, stirring, heating to 100 deg.C, and refluxing in 90 deg.C constant temperature water bath for 5 hr. And after the constant-temperature water bath is finished, washing the activated carbon carrier with deionized water to be neutral, and drying the activated carbon carrier at 110 ℃ for 8 hours to obtain the pretreated activated carbon carrier for later use.
Example 2: catalyst preparation
Preparing an immersion liquid: mixing the active component and the assistant soluble chloride solution, and adjusting the pH value to 9 by using ammonia water.
The carrier is immersed in the immersion liquid for 2h at 60 ℃ and then dried for 12h at 90 ℃. The catalyst was reduced with hydrogen at 200 ℃ for 2h before use.
The components of the catalyst are shown in table 1.
TABLE 1 catalyst Components
Example 3
The catalyst prepared in the example 2 is subjected to trichlorotrichloroethane hydrodechlorination reaction, hydrogen and trichlorotrichloroethane are introduced after the catalytic reaction temperature is controlled to be 280 ℃, and the molar ratio of the hydrogen to the trichlorotrichloroethane is 1.8: 1, the reaction pressure is 1.1Mpa, the residence time is 20 seconds, the hydrogen gas velocity is 40ml/min, and the space velocity of the raw material is 500h-1. And carrying out quenching, alkali washing, water washing, drying, compression and rectification on the reaction product to obtain the chlorotrifluoroethylene. The reaction results are shown in table 2.
Table 2 catalyst test results
Claims (10)
1. The hydrodechlorination catalyst comprises a carrier, a main catalyst and an auxiliary agent, wherein the carrier is active carbon and Al2O3Or SiO2The catalyst comprises a carrier, a main catalyst and an auxiliary agent, wherein the main catalyst is Pd and Cu, and the auxiliary agent comprises Sn and/or Mn.
2. The catalyst of claim 1 wherein the promoter further comprises one to three of Zn, Zr, Ag, Ti, Cd, Hg, In, Pb, Bi.
3. The catalyst according to claim 1 or 2, wherein the Pd is used in an amount of 0.5 to 3% by mass, the Cu is used in an amount of 2.0 to 10.5% by mass, and the promoter is used in an amount of 0.2 to 3.0% by mass, based on the total mass of the catalyst.
4. The catalyst according to claim 1, wherein the amount of Sn and/or Mn is 0.2 to 3.0% by mass based on the total mass of the catalyst.
5. The catalyst according to claim 2, wherein the amount of Sn and/or Mn is 0.1 to 2.0% by mass based on the total mass of the catalyst.
6. The catalyst as claimed in claim 1, wherein the specific surface area of the activated carbon is 800-1500m when the activated carbon is used as a carrier2/g。
7. A method for preparing chlorotrifluoroethylene, the method using the catalyst of any one of claims 1 to 6, wherein chlorotrifluoroethane, hydrogen, and the hydrodechlorination catalyst are reacted at a temperature of 150 to 300 ℃ to obtain chlorotrifluoroethylene.
8. The production method according to claim 7, wherein the reaction pressure is controlled to 1 to 1.5 MPa.
9. The production method according to claim 7, wherein the residence time is controlled to 15 to 25 s.
10. The method according to claim 7, wherein the hydrogen gas flow rate is 30 to 60 ml/min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011454875.0A CN112495394A (en) | 2020-12-10 | 2020-12-10 | Hydrodechlorination catalyst and preparation method of chlorotrifluoroethylene |
| PCT/CN2021/117090 WO2022121398A1 (en) | 2020-12-10 | 2021-09-08 | Hydrodechlorination catalyst and application thereof in preparation of chlorotrifluoroethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011454875.0A CN112495394A (en) | 2020-12-10 | 2020-12-10 | Hydrodechlorination catalyst and preparation method of chlorotrifluoroethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112495394A true CN112495394A (en) | 2021-03-16 |
Family
ID=74973525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011454875.0A Pending CN112495394A (en) | 2020-12-10 | 2020-12-10 | Hydrodechlorination catalyst and preparation method of chlorotrifluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112495394A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745552A (en) * | 2021-08-17 | 2021-12-03 | 西安交通大学 | Carbon-supported palladium tin tantalum nitride nano electro-catalyst for direct ethanol and methanol fuel cell and preparation method thereof |
| WO2022121398A1 (en) * | 2020-12-10 | 2022-06-16 | 中化蓝天集团有限公司 | Hydrodechlorination catalyst and application thereof in preparation of chlorotrifluoroethylene |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0416615A1 (en) * | 1989-09-06 | 1991-03-13 | Daikin Industries, Limited | Process for preparing chlorotrifluoroethylene |
| CN1065261A (en) * | 1991-01-25 | 1992-10-14 | 索尔维公司 | The catalyst composition for preparing the method for a chlorotrifluoroethylene and trifluoro-ethylene and be used for this method |
| US5637548A (en) * | 1995-07-07 | 1997-06-10 | The Dow Chemical Company | Preparation of bimetallic catalysts for hydrodechlorination of chlorinated hydrocarbons |
| CN101143328A (en) * | 2007-10-26 | 2008-03-19 | 江苏工业学院 | Catalyst for preparing tetrachlorethylene and its preparation method and use |
| US20100160696A1 (en) * | 2008-12-22 | 2010-06-24 | E. I. Du Pont De Nemours And Company | Method of hydrodechlorination to produce dihydrofluorinated olefins |
| CN102211028A (en) * | 2010-04-08 | 2011-10-12 | 中化蓝天集团有限公司 | Hydrogenation dechlorinating catalyst for synthesizing trifluoroethylene and novel preprocessing process of carrier of catalyst |
| CN104402668A (en) * | 2014-12-15 | 2015-03-11 | 宜宾天原集团股份有限公司 | Method for preparing chloroethylene monomer from dichloromethane |
| CN105457651A (en) * | 2014-09-05 | 2016-04-06 | 浙江蓝天环保高科技股份有限公司 | Hydrodechlorination catalyst and application thereof in preparation of chlorotrifluoroethylene |
| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
| CN106140193A (en) * | 2015-04-01 | 2016-11-23 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of the catalyst for CFC and HCFC hydrogenation-dechlorination |
| CN106660908A (en) * | 2014-08-25 | 2017-05-10 | 旭硝子株式会社 | Method for producing hydrofluoroolefin |
-
2020
- 2020-12-10 CN CN202011454875.0A patent/CN112495394A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0416615A1 (en) * | 1989-09-06 | 1991-03-13 | Daikin Industries, Limited | Process for preparing chlorotrifluoroethylene |
| CN1065261A (en) * | 1991-01-25 | 1992-10-14 | 索尔维公司 | The catalyst composition for preparing the method for a chlorotrifluoroethylene and trifluoro-ethylene and be used for this method |
| US5637548A (en) * | 1995-07-07 | 1997-06-10 | The Dow Chemical Company | Preparation of bimetallic catalysts for hydrodechlorination of chlorinated hydrocarbons |
| CN101143328A (en) * | 2007-10-26 | 2008-03-19 | 江苏工业学院 | Catalyst for preparing tetrachlorethylene and its preparation method and use |
| US20100160696A1 (en) * | 2008-12-22 | 2010-06-24 | E. I. Du Pont De Nemours And Company | Method of hydrodechlorination to produce dihydrofluorinated olefins |
| CN102211028A (en) * | 2010-04-08 | 2011-10-12 | 中化蓝天集团有限公司 | Hydrogenation dechlorinating catalyst for synthesizing trifluoroethylene and novel preprocessing process of carrier of catalyst |
| CN106660908A (en) * | 2014-08-25 | 2017-05-10 | 旭硝子株式会社 | Method for producing hydrofluoroolefin |
| CN105457651A (en) * | 2014-09-05 | 2016-04-06 | 浙江蓝天环保高科技股份有限公司 | Hydrodechlorination catalyst and application thereof in preparation of chlorotrifluoroethylene |
| CN104402668A (en) * | 2014-12-15 | 2015-03-11 | 宜宾天原集团股份有限公司 | Method for preparing chloroethylene monomer from dichloromethane |
| CN106140193A (en) * | 2015-04-01 | 2016-11-23 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of the catalyst for CFC and HCFC hydrogenation-dechlorination |
| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022121398A1 (en) * | 2020-12-10 | 2022-06-16 | 中化蓝天集团有限公司 | Hydrodechlorination catalyst and application thereof in preparation of chlorotrifluoroethylene |
| CN113745552A (en) * | 2021-08-17 | 2021-12-03 | 西安交通大学 | Carbon-supported palladium tin tantalum nitride nano electro-catalyst for direct ethanol and methanol fuel cell and preparation method thereof |
| CN113745552B (en) * | 2021-08-17 | 2024-04-09 | 西安交通大学 | Carbon-supported palladium-tin tantalum nitride nano electrocatalyst for direct ethanol and methanol fuel cells and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103191729B (en) | The preparation method of trifluoro-ethylene, and catalyst and preparation method | |
| CN104549360B (en) | Catalyst for producing chlorine by catalytic oxidation of hydrogen chloride | |
| CN102274734B (en) | Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof | |
| CN112495394A (en) | Hydrodechlorination catalyst and preparation method of chlorotrifluoroethylene | |
| CN101357337B (en) | Hydrogen chloride oxidation catalyst and preparation method thereof | |
| CN111389423A (en) | Modified copper-based catalyst for acetylene hydrochlorination and preparation method thereof | |
| CN113713841B (en) | Acetylene copper chloride-based catalyst and preparation method and application thereof | |
| CN112547093B (en) | Hydrodechlorination catalyst and preparation method and application thereof | |
| CN111330621A (en) | Supported mercury-free catalyst for synthesizing chloroethylene and preparation method thereof | |
| CN106140193A (en) | A kind of preparation method of the catalyst for CFC and HCFC hydrogenation-dechlorination | |
| CN112206801B (en) | A kind of nitrogen-doped palladium-carbon catalyst and its preparation method and application in CFC-113 hydrodechlorination | |
| CN111346662B (en) | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst | |
| CN1460549A (en) | Catalyst for producing chlorotrifluoroethylene and trifluoroethylene by catalytic hydrodechlorination of CFC-113 and its preparation method | |
| CN111774077A (en) | Non-supported catalyst and preparation method of chlorotrifluoroethylene or trifluoroethylene | |
| CN1146471C (en) | Catalystic hydrogenation and dechlorination catalyst for preparing trifluorochloroethylene and trichloroethylene | |
| CN104014335B (en) | Catalyst, its preparation method and the application of a fluoromethane are prepared for monofluorodichloromethane hydrogenation-dechlorination | |
| CN115430425B (en) | High-stability copper-based catalyst for catalyzing hydrochlorination of acetylene, preparation and application thereof | |
| WO2022121398A1 (en) | Hydrodechlorination catalyst and application thereof in preparation of chlorotrifluoroethylene | |
| CN111672525A (en) | In-situ synthesis layered mesoporous zirconium phosphate modified copper-based acetylene hydrochlorination catalyst on activated carbon and preparation method thereof | |
| CN115007214A (en) | Copper-based metal organic framework catalyst prepared by mechanochemical method and preparation method | |
| CN114713244B (en) | Hydrodechlorination catalyst, preparation method and application thereof | |
| CN107754802A (en) | A kind of catalyst and preparation method and application for ethylene carbonate ester through hydrogenation | |
| CN109293470B (en) | Process method for HCFC-142b catalytic cracking and acetylene hydrochlorination coupling reaction | |
| CN102701901B (en) | Method for producing HFC-32 (difluoromethane) by catalytic hydrogenation dechlorination of CFC-12 (dichlorodifluoromethane) | |
| CN102633591A (en) | Catalytic conversion technology for carbon tetrachloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210316 |
|
| RJ01 | Rejection of invention patent application after publication |