CN105521801A - Catalyst for ethyne hydrochlorination for synthesis of chloroethylene and preparation method thereof - Google Patents
Catalyst for ethyne hydrochlorination for synthesis of chloroethylene and preparation method thereof Download PDFInfo
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- CN105521801A CN105521801A CN201510934275.7A CN201510934275A CN105521801A CN 105521801 A CN105521801 A CN 105521801A CN 201510934275 A CN201510934275 A CN 201510934275A CN 105521801 A CN105521801 A CN 105521801A
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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
- B01J27/08—Halides
- B01J27/122—Halides of copper
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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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
- B01J27/08—Halides
- B01J27/10—Chlorides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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Abstract
The invention discloses a catalyst for ethyne hydrochlorination for synthesis of chloroethylene and a preparation method thereof. The catalyst of the invention is prepared by impregnation of an active carbon carrier, metallic compound active components and a hydroxyl-containing water-soluble carboxylic acid competitive adsorbent. The active components contain at least one component selected from chloride, nitrate, sulfate or phosphate of cobalt, copper, manganese, zinc, bismuth, barium and potassium. The competitive adsorbent contains citric acid, malic acid, salicylic acid, oxalic acid, tartaric acid and lactic acid. The prepared catalyst has characteristics of high activity, good selectivity, simple production method and low cost. By adding the hydroxyl-containing water-soluble carboxylic acid competitive adsorbent, the active components are greatly fixed to the carrier, and high temperature transfer of the active components is reduced; by roasting decomposition of the competitive adsorbent, rich pore structures are generated, and gas dispersion in the reaction process is improved; and dispersity of the active components is improved, catalyst poisoning is alleviated, and life of the catalyst is prolonged.
Description
Technical field
The invention belongs to catalytic field, particularly relate to a kind of Catalysts and its preparation method for acetylene hydrochlorination synthesizing chloroethylene.
Background technology
Along with growing continuously and fast of national economy, the production capacity of polyvinyl chloride is increasing.China's Production of PVC mainly carbide acetylene method, main use mercury catalyst mercury in Vinyl Chloride Synthesis.On the one hand, the loss of mercury causes serious environmental pollution, and on the other hand, the scarcity of mercury resource, also limit the use of China's mercury catalyst.
Catalyst without mercury exploitation is the fundamental way solved the problem, but catalyst without mercury is in development, there is not yet industrialization report up to now.At present, the best catalyst without mercury of application prospect is noble metal catalyst, and this catalyst shows active and stability preferably, but the combination property of its industrial applications needs to be confirmed further.Non-precious metal catalyst cannot be broken through and not show obvious progress because of active and stability.
A lot of colleges and universities, scientific research institutions and enterprise are at research and development catalyst without mercury, and series is issued without mercury non-precious metal catalyst achievement.Luo Yun etc. disclose a kind of catalyst without mercury system CN201010574802.5, take cocoanut active charcoal as carrier, stannous chloride is main active substances, and the mass percentage of stannous chloride is 15%-30%, is added with at least one additive in barium chloride, zinc chloride and copper chloride.Li Wei discloses a kind of catalyst without mercury system in CN201110040369.1, catalyst adopt active carbon be carrier, active component is phosphorized copper, auxiliary agent be copper chloride, nickel chloride, barium chloride one or more.Xinjiang University Wang Feng etc. also discloses a kind of catalyst without mercury system in CN201110257699.6, catalyst with coconut husk charcoal, fruit shell carbon, coal mass active carbon for carrier, active component be copper, nickel, bismuth, zinc-manganese, molybdenum one or more, metal is with form loads such as oxide, chloride, nitrate, acetate.Zhao Yonglu etc. disclose a kind of technology preparing vinyl chloride without mercury non-precious metal catalyst in patent CN201510108335.X, the dealuminzation molecular sieve adopting steam treatment is carrier, with copper, tin, bismuth, cobalt for main active component, the load capacity of main active component accounts for the 1%-25% of carrier quality, catalyst prepared by load, finally by corresponding temperature calcination, obtained final catalyst, existing patent enters Substantive Examination Stage.The many catalyst of other industry have employed competitive Adsorption method in preparation process, but there is not yet the report that acetylene hydrochlorination catalysts adopts competitive adsorbate.Fu Qiang etc. disclose the preparation of catalyst being applied to methyl alcohol, dimethyl ether low-carbon alkene at CN200910210328.5, activity component metal ion and competitive adsorbate are contacted, finally carry out silanization treatment.Rock assistant Thailand waits the catalyst disclosing co selective oxidation application in CN201080022746.2, and complete the load to ruthenium by competitive Adsorption method, load capacity is 30%-70%.The gorgeous catalyst disclosing a kind of year Pd producing hydrogen peroxide by direct synthesis of Guizhou University Pan Hong in patent CN104475092A, adopts γ-A1
2o
3carrier, PdC1
2solution and competitive adsorbate solvent process 2h under ultrasonic power is 500W, and roasting in oxygen atmosphere after dry, under hydrogen, reduction is obtained, is now in Substantive Examination Stage.Patent CN101524643 is Sino-Korean beautiful etc. discloses a kind of preparation method producing o-phenyl phenol catalyst, adopt incipient impregnation, first with competitive adsorbate to Vehicle element, competitive adsorbate is conventional organic acid and inorganic acid, flood again after drying, dry activation, auxiliary agent add, roasting, the catalyst that obtained o-phenyl phenol is produced, at high temperature has high activity, high selectivity and stiff stability.
Summary of the invention
Object of the present invention provides a kind of Catalysts and its preparation method for acetylene hydrochlorination synthesizing chloroethylene.
It is carrier that a kind of Catalysts and its preparation method for acetylene hydrochlorination synthesizing chloroethylene comprises with active carbon, metallic compound is active component, the water-soluble carboxylic acid of hydroxyl is competitive adsorbate, active component and competitive adsorbate are made into mixed solution, again carrier active carbon is put into mixed solution and carry out dip loading, finally drying roasting is prepared from again.
As mentioned above, the competitive adsorbate of the water-soluble carboxylic acid of described hydroxyl comprises citric acid, malic acid, salicylic acid, oxalic acid, tartaric acid and lactic acid.
As mentioned above, the competitive adsorbate of the water-soluble carboxylic acid of hydroxyl accounts for carrier gross mass 2% ~ 20%.
As mentioned above, described active component and competitive adsorbate are made into the pH value of mixed solution 0.5 ~ 4.
As mentioned above, described metallic compound active component is cobalt, copper, manganese, zinc, bismuth, barium, the chloride of potassium, nitrate, sulfate or phosphatic at least one, accounts for 3 ~ 50% of catalyst carrier gross weight.
As mentioned above, carrier active carbon put into mixed solution carry out dip loading active component and competitive adsorbate composition mixed solution dipping temperature be 18 DEG C ~ 70 DEG C, dip time is 4-14h.
As mentioned above, adopt inert gas shielding during described roasting, sintering temperature is 200 ~ 600 DEG C, and roasting time is 1 ~ 8h.
The invention discloses a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene.This catalyst is jointly flooded by absorbent charcoal carrier, metallic compound active component and competitive adsorbate and is prepared from, active component is cobalt, copper, manganese, zinc, bismuth, barium, the chloride of potassium, nitrate, sulfuric acid or phosphatic at least one, and the carboxylic acid competitive adsorbate of hydroxyl comprises citric acid, malic acid, salicylic acid, oxalic acid, tartaric acid and lactic acid.
A kind of Catalysts and its preparation method for acetylene hydrochlorination synthesizing chloroethylene involved in the present invention, its principle is, first the first Application in acetylene hydrochlorination catalyst preparing of organic acid competitive adsorbate, and by experiment to the selection of its different specific functional groups structure.
Catalyst prepared by the present invention has active high, and side reaction is few, selective height, and preparation method is simple, feature with low cost.The carboxylic acid of hydroxyl has special functional group, adds catalyst can produce a lot of wholesome effect as competitive adsorbate.Hydroxyl in competitive adsorbate and the grafting of carboxyl energy are on absorbent charcoal carrier, add the oxygen-containing functional group of active carbon, active component is better fastened on carrier, decreases high temperature (roasting and the reaction) migration of active component, improve the agglomeration of active component.Competitive adsorbate thermal decomposition in catalyst roasting process, the pore structure that some are new is produced after gas overflowing, increase the specific area (see attached list 1, Fig. 1, Fig. 2) of carrier, abundant pore structure is beneficial to the gas diffusion in course of reaction, meanwhile, the unformed charcoal that competitive adsorbate pyrolytic generates better secures active component.The use of competitive adsorbate, increases the load capacity (seeing attached list 2) of active component, improves the distribution of active component, make active component be deep into carrier inside, slow down catalyst poisoning, extend the life-span of catalyst.
Accompanying drawing explanation
Fig. 1 is that after not adding competitive adsorbate roasting, BET schemes;
Fig. 2 is that after not adding competitive adsorbate roasting, BET schemes.
Detailed description of the invention
In order to better the present invention is described, enumerate related example below.But the scope of the invention is not limited in example, its claimed scope is recorded in claim.
Embodiment 1:
Take copper chloride dihydrate 2.65g, take tartaric acid 2g, add 30ml deionized water, stirring and dissolving, with salt acid for adjusting pH value to 2, by electric jacket computer heating control maceration extract temperature 40 DEG C.Add dry activated carbon 15g, normal temperature dipping 8h, 105 DEG C of dry 8h, in tube furnace, nitrogen atmosphere roasting 2h, obtains acetylene hydrochlorination catalyst, and conversion of alkyne is 100%.By carrying out to not adding the tartaric acid sample sample (adding tartaric acid competitive adsorbate) that therewith prepared by case 1 contrast that BET relevant characterization draws table 1 and Fig. 1, Fig. 2.
Embodiment 2:
Take bismuth chloride 1.58g, take oxalic acid 2g, add 30ml deionized water, stirring and dissolving, adopt salt acid for adjusting pH value to 1.5, by electric jacket computer heating control maceration extract temperature 35 DEG C.Add dry activated carbon 15g, normal temperature dipping 6h, 110 DEG C of oven drying 9h, in tube furnace, nitrogen atmosphere roasting 1.5h, obtains acetylene hydrochlorination catalyst, and conversion of alkyne is 90%.By catalyst prepared by this case and the catalyst that do not add competitive adsorbate oxalic acid adopt micro-wave digestion and Atomic absorption to catalyst bismuth element in the catalyst content carry out phenetic analysis in table 2.
Embodiment 3:
Take barium nitrate 2g, take citric acid 2g, add 30ml deionized water, stirring and dissolving, adopt salt acid for adjusting pH value to 1.5, by electric jacket computer heating control maceration extract temperature 50 C.Add dry activated carbon 15g, normal temperature dipping 7h, 110 DEG C of oven drying 6.5h, in tube furnace, nitrogen atmosphere roasting 3h, obtains acetylene hydrochlorination catalyst, and conversion of alkyne is 67%.
Table 1 sample adds the BET table of comparisons before and after tartaric acid
Table 2 adds the difference of catalyst activity constituent content before and after competitive adsorbate
| Do not add product after competitive adsorbate roasting | Add competitive adsorbate, product after roasting | |
| Catalyst activity component bi content (%) | 5.0424 | 8.3001 |
| Active component bismuth is to carbon back ratio (%) | 5.3102 | 9.0514 |
Claims (8)
1. for a catalyst for acetylene hydrochlorination synthesizing chloroethylene, it is characterized in that: comprising with active carbon is carrier, and metallic compound is active component, the water-soluble carboxylic acid of hydroxyl is competitive adsorbate.
2. the preparation method of a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene according to claim 1, it is characterized in that: active component and competitive adsorbate are made into mixed solution, again carrier is put into mixed solution and carry out dip loading, be prepared from finally by drying and roasting.
3. a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene according to claim 1, is characterized in that: the competitive adsorbate of the water-soluble carboxylic acid of described hydroxyl comprises citric acid, malic acid, salicylic acid, oxalic acid, tartaric acid and lactic acid.
4., according to the arbitrary described a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene of claim 1,3, it is characterized in that: the competitive adsorbate of the water-soluble carboxylic acid of described hydroxyl accounts for carrier gross mass 2% ~ 20%.
5. the preparation method of a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene according to claim 2, is characterized in that: described active component and competitive adsorbate are made into the pH value of mixed solution 0.5 ~ 4.
6. a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene according to claim 1, it is characterized in that: described metallic compound active component is cobalt, copper, manganese, zinc, bismuth, barium, the chloride of potassium, nitrate, sulfate or phosphatic at least one, accounts for 3 ~ 50% of catalyst carrier gross weight.
7. the preparation method of a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene according to claim 2, it is characterized in that: carrier active carbon put into mixed solution carry out dip loading active component and competitive adsorbate composition mixed solution dipping temperature be 18 DEG C ~ 70 DEG C, dip time is 4-14h.
8. the preparation method of a kind of catalyst for acetylene hydrochlorination synthesizing chloroethylene according to claim 2, is characterized in that: adopt inert gas shielding during described roasting, sintering temperature is 200 ~ 600 DEG C, and roasting time is 1 ~ 8h.
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| CN201510934275.7A CN105521801B (en) | 2015-12-15 | 2015-12-15 | Application of catalyst in synthesis of vinyl chloride by hydrochlorination of acetylene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268963A (en) * | 2016-07-29 | 2017-01-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of service life length synthesis vinyl chloride without mercury catalyst and preparation method thereof |
| CN106582727A (en) * | 2016-12-06 | 2017-04-26 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Catalyst used for synthesizing vinyl chloride through acetylene hydrochlorination |
| CN107999140A (en) * | 2017-11-29 | 2018-05-08 | 宁夏新龙蓝天科技股份有限公司 | A kind of preparation method for the catalyst without mercury for reducing vinyl chloride synthesis reaction temperature |
| CN108993595A (en) * | 2018-06-27 | 2018-12-14 | 厦门中科易工化学科技有限公司 | A kind of copper-based catalysts and its preparation method and application for acetylene hydrochlorination synthesis vinyl chloride thereof |
| CN109331869A (en) * | 2018-09-28 | 2019-02-15 | 内蒙古自治区石油化工监督检验研究院 | A kind of low ruthenium content ruthenium-based catalyst for acetylene hydrochlorination reaction |
| CN112916049A (en) * | 2021-01-27 | 2021-06-08 | 南开大学 | Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN113617393A (en) * | 2021-07-28 | 2021-11-09 | 新疆至臻化工工程研究中心有限公司 | Catalyst for acetylene hydrochlorination metal organic framework material |
| CN113634235A (en) * | 2021-08-05 | 2021-11-12 | 德之昭科技(苏州)有限公司 | Hydroxyl carboxylate modified nano activated carbon material and preparation method and application thereof |
| CN113735076A (en) * | 2021-09-14 | 2021-12-03 | 宁波四明化工有限公司 | Method for preparing hydroxylamine salt |
| CN116809078A (en) * | 2023-08-31 | 2023-09-29 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst for organic liquid hydrogen storage material, and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268963A (en) * | 2016-07-29 | 2017-01-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of service life length synthesis vinyl chloride without mercury catalyst and preparation method thereof |
| CN106268963B (en) * | 2016-07-29 | 2018-12-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of synthesis vinyl chloride thereof with long service life no mercury catalyst and preparation method thereof |
| CN106582727A (en) * | 2016-12-06 | 2017-04-26 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Catalyst used for synthesizing vinyl chloride through acetylene hydrochlorination |
| CN107999140A (en) * | 2017-11-29 | 2018-05-08 | 宁夏新龙蓝天科技股份有限公司 | A kind of preparation method for the catalyst without mercury for reducing vinyl chloride synthesis reaction temperature |
| CN108993595B (en) * | 2018-06-27 | 2021-04-23 | 厦门中科易工化学科技有限公司 | Copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method and application thereof |
| CN108993595A (en) * | 2018-06-27 | 2018-12-14 | 厦门中科易工化学科技有限公司 | A kind of copper-based catalysts and its preparation method and application for acetylene hydrochlorination synthesis vinyl chloride thereof |
| CN109331869A (en) * | 2018-09-28 | 2019-02-15 | 内蒙古自治区石油化工监督检验研究院 | A kind of low ruthenium content ruthenium-based catalyst for acetylene hydrochlorination reaction |
| CN112916049A (en) * | 2021-01-27 | 2021-06-08 | 南开大学 | Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN113617393A (en) * | 2021-07-28 | 2021-11-09 | 新疆至臻化工工程研究中心有限公司 | Catalyst for acetylene hydrochlorination metal organic framework material |
| CN113634235A (en) * | 2021-08-05 | 2021-11-12 | 德之昭科技(苏州)有限公司 | Hydroxyl carboxylate modified nano activated carbon material and preparation method and application thereof |
| CN113634235B (en) * | 2021-08-05 | 2023-08-29 | 德之昭科技(苏州)有限公司 | Hydroxy carboxylate modified nano active carbon material and preparation method and application thereof |
| CN113735076A (en) * | 2021-09-14 | 2021-12-03 | 宁波四明化工有限公司 | Method for preparing hydroxylamine salt |
| CN116809078A (en) * | 2023-08-31 | 2023-09-29 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst for organic liquid hydrogen storage material, and preparation method and application thereof |
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