CN113813998A - Acetylene hydrochlorination ultralow-mercury catalyst and preparation method and application thereof - Google Patents
Acetylene hydrochlorination ultralow-mercury catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 63
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 47
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 41
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 21
- 239000011592 zinc chloride Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims abstract description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 229960002317 succinimide Drugs 0.000 claims description 27
- 238000007598 dipping method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000000243 solution Substances 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 18
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 18
- 229960002523 mercuric chloride Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- -1 succinimidyl Chemical group 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004376 Sucralose Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BAQAVOSOZGMPRM-QBMZZYIRSA-N sucralose Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 BAQAVOSOZGMPRM-QBMZZYIRSA-N 0.000 description 1
- 235000019408 sucralose Nutrition 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/28—Mercury
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Catalysts (AREA)
Abstract
The invention discloses an acetylene hydrochlorination ultra-low mercury catalyst and a preparation method and application thereof, wherein the catalyst is prepared from HgCl2、CuCl2、ZnCl2The catalyst is prepared by adopting a solution dilution impregnation and step heating drying mode, and has the advantages of low mercury chloride content, high effective mercury chloride content, multiple active point positions, high dispersity, stable catalytic active component valence state, strong carbon deposition resistance and long service life.
Description
Technical Field
The invention relates to the technical field of acetylene and hydrogen chloride addition reaction, in particular to a catalyst for the addition reaction of acetylene and hydrogen chloride.
Background
Mercury is a heavy metal, commonly known as "mercury", and is a toxic substance. In 2013, 19 months, the United states environmental planning agency passes the Water guarantee agency of the International convention for controlling and reducing the emission of mercury in the global scope, a detailed regulation is made on a specific emission range to reduce the damage of mercury to the environment and human health, the convention takes effect in 2017, 16 months and 16 days, China is added into the contracting nation of the convention as the first batch, China starts to fulfill all the terms of the convention in China and undertakes the responsibility and the task of performance, aiming at the production process of polyvinyl chloride by the calcium carbide method, a plurality of management requirements are proposed by the convention, wherein in 2020, the usage amount of mercury of a unit product of the calcium carbide method polyvinyl chloride is reduced by 50% compared with 2015 years, environmental protection of an environmental protection department officially starts 'reduction and minimization project of mercury production by the Global environmental fund-China polyvinyl chloride and the United states industry development organization (UNIDO demonstration)', the project has formally been in effect in month 1 of 2018,
after the project is implemented, the mercury consumption of polyvinyl chloride products of enterprises and units is required to be not higher than 48g/t PVC, and the enterprises are encouraged to reduce the mercury consumption to the maximum extent.
The reasons for the deactivation of the acetylene hydrochlorination ultra-low mercury catalyst are mainly as follows: firstly, in industrial application, the actual use temperature is 100-; secondly, carbon deposition is carried out, reactants of the catalyst are acetylene and hydrogen chloride, acetylene is easy to generate self-polymerization, and the catalyst is inactivated due to the fact that catalytic activity points are covered by self-polymerization; and thirdly, the mercury valence state of the mercuric chloride is changed, and in production and application, the reductive functional group on the activated carbon and the acetylene as a reactant are easy to reduce the mercuric chloride into mercurous chloride and metallic mercury, so that the catalytic activity is reduced. Hydrogen sulfide and phosphine in acetylene raw material gas are easy to react with mercuric chloride, and the catalyst is inactivated due to poisoning.
Disclosure of Invention
The invention aims to provide an acetylene hydrochlorination ultralow-mercury catalyst. The invention has the characteristics of low mercury chloride content, small pollution, high dispersity, high catalytic conversion rate and high thermal stability.
The technical scheme of the invention is as follows: an acetylene hydrochlorination ultra-low mercury catalyst, the organic ligand of which is succinimide.
The catalyst is prepared from HgCl2、CuCl2、ZnCl2KCl and an organic ligand succinimide.
The catalyst contains HgCl in one hundred parts by weight20.2-4 parts of CuCl21-10 parts of ZnCl21-8 parts of KCl1-3 parts of succinimide, and the balance of carrier active carbon.
The catalyst contains HgCl in one hundred parts by weight20.8-2 parts of CuCl23-7 parts of ZnCl24-6 parts of KCl, 1.5-2.5 parts of succinimide, and the balance of carrier active carbon.
The preparation method of the acetylene hydrochlorination ultra-low mercury catalyst comprises the following steps,
(a) adding HgCl2、CuCl2、ZnCl2Adding KCl and succinimide into hydrochloric acid aqueous solution with pH less than or equal to 1, and mixing uniformly to obtain product A;
(b) diluting the product A by 2-5 times to obtain a product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and heating and drying the product C, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
In the preparation method of the acetylene hydrochlorination ultralow-mercury catalyst, the heating drying is step-wise heating drying at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃ respectively, and the drying time of each temperature section is 1-2 h.
The application of acetylene hydrochlorination ultra-low mercury catalyst and the application of succinimide in preparing acetylene hydrochlorination ultra-low mercury catalyst.
Has the advantages that: the applicant has found that the following effects can be obtained by adding the succinimide:
the catalyst has low mercury chloride content, high effective mercury chloride content and high catalytic conversion rate;
the addition of the succinimide is helpful to improve the dispersion degree of the main catalytic component and the auxiliary catalytic component and stabilize Hg2+、Zn2+、Cu2+The valence state of the metal ion inhibits the metal ion from being converted to the low valence state, and the catalytic performance is improved.
And the addition of the succinimide is beneficial to improving the adsorption capacity of the catalyst to hydrogen chloride, inhibiting the self-polymerization reaction of acetylene, improving the carbon deposition resistance and prolonging the service life of the catalyst.
The catalyst is impregnated under the condition of dilution of the solution, and the dilute concentration is helpful for improving the dispersity of the catalyst, namely the catalytic active components are loaded on the carrier in nano-scale size, but not in cluster form.
Metal ion Hg2+、Zn2+、Cu2+After the compound and succinimide form a stable complex, the conversion rate and selectivity of acetylene are obviously improved, and the loss rate of mercuric chloride is obviously reduced, mainly because:
①Hg2+、Zn2+、Cu2+respectively forms complexes with succinimide, reduces intermolecular force of mercuric chloride, increases dispersity of active components, enables the active components to be anchored on the surface of carrier active carbon more easily, and stabilizes Hg2+、Zn2 +、Cu2+The valence state of the metal ions is not easy to be reduced by acetylene and carry out valence-change reaction; and thirdly, the succinimide can preferentially adsorb hydrogen chloride and form hydrogen bonds with the hydrogen chloride, so that the catalytic conversion rate of the reaction of acetylene and the hydrogen chloride is increased.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the invention
Examples are given. An acetylene hydrochlorination ultra-low mercury catalyst, the organic ligand of which is succinimide.
More specifically, the catalyst is prepared from HgCl2、CuCl2、ZnCl2KCl and the organic ligand succinimidyl.
More preferably, the catalyst contains HgCl in every one hundred parts by weight20.2-4 parts of CuCl21-10 parts of ZnCl21-8 parts of KCl1-3 parts of succinimide, and the balance of carrier active carbon.
More preferably, the catalyst contains HgCl in every one hundred parts by weight20.8-2 parts of CuCl23-7 parts of ZnCl24-6 parts of KCl, 1.5-2.5 parts of succinimide, and the balance of carrier active carbon.
The preparation method of the acetylene hydrochlorination ultra-low mercury catalyst comprises the following steps,
(a) adding HgCl2、CuCl2、ZnCl2Adding KCl and succinimide into hydrochloric acid aqueous solution with pH less than or equal to 1, and mixing uniformly to obtain product A;
(b) diluting the product A by 2-5 times to obtain a product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and heating and drying the product C, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
More preferably, the temperature-rising drying is carried out in a stepwise manner at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, and the drying time of each temperature section is 1-2 h.
The application of acetylene hydrochlorination ultra-low mercury catalyst, in particular to the application of succinimide in preparing acetylene hydrochlorination ultra-low mercury catalyst.
The technical solution is further illustrated by the following specific examples:
example 1. The catalyst contains HgCl in one hundred parts by weight24 parts of CuCl210 parts of ZnCl22 parts of KCl3 parts, 5 parts of succinimide and the balance of carrier activated carbon.
The ultra-low mercury catalyst for acetylene hydrochlorination is prepared according to the following method:
(a) adding HgCl2、CuCl2、ZnCl2KCl and succinimide are added with hydrochloric acid water with pH less than or equal to 1Mixing the solution to obtain product A;
(b) diluting the product A by 2-5 times to obtain a product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and (3) performing step-by-step heating drying on the product C at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, wherein the drying time of each temperature period is 1h, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
The catalyst prepared from the raw materials in parts by weight is used for the addition reaction of acetylene and hydrogen chloride, and the acetylene space flow rate is 30h at the temperature of 140 DEG C-1The molecular ratio of acetylene to hydrogen chloride is 1: under the condition of 1.05, the catalytic conversion rate is measured to be 99.8%, the selectivity of chloroethylene is measured to be 99.8%, and the loss rate of mercuric chloride is measured to be 1.3%.
Comparative test example 1
The catalyst contains HgCl in one hundred parts by weight24 parts of CuCl210 parts of ZnCl22 parts of KCl3 parts of the raw materials, and the balance of carrier activated carbon.
The ultra-low mercury catalyst for acetylene hydrochlorination is prepared according to the following method:
(a) adding HgCl2、CuCl2、ZnCl2Adding KCl into hydrochloric acid aqueous solution with pH less than or equal to 1, and mixing uniformly to obtain product A;
(b) dividing the product A into 6-8 equal parts, and diluting by 2-5 times to obtain product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and (3) performing step-by-step heating drying on the product C at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
The catalyst prepared from the raw materials in parts by weight is used for the addition reaction of acetylene and hydrogen chloride, and the acetylene space flow rate is 30h at the temperature of 140 DEG C-1The molecular ratio of acetylene to hydrogen chloride is 1: under the condition of 1.05, the catalytic conversion rate is determined to be 93.4 percent, the selectivity of the chloroethylene is determined to be 98.2 percent, and the mercuric chloride is determined to beThe loss rate is 4.3%;
comparative test example 2
According to the patent CN201910521037.1, the chlorine-doped defect activated carbon obtained by mixing and molding carbon powder, sucralose and metal nitrate is used as a carrier, and then the chlorine-doped defect activated carbon is prepared by loading mercuric chloride, the prepared ultralow-mercury catalyst with the content of 4.0% is prepared, and acetylene hydrochlorination reaction evaluation is carried out on a fixed bed reactor: at the temperature of 140 ℃ and the acetylene space flow rate of 30h-1Hydrogen chloride: acetylene 1.05: 1, the reaction conversion rate is 97.5%, the selectivity of chloroethylene is 99.6%, and the loss rate of mercuric chloride is 2.5%.
Example 2
The catalyst contains HgCl in one hundred parts by weight23 parts of CuCl26 parts of ZnCl24 parts of KCl3 parts, 5 parts of succinimide and the balance of carrier activated carbon.
The acetylene hydrochlorination ultra-low mercury catalyst is prepared by the following method:
(a) adding HgCl2、CuCl2、ZnCl2Adding KCl and succinimide into hydrochloric acid aqueous solution with pH less than or equal to 1, and mixing uniformly to obtain product A;
(b) diluting the product A by 3 times to obtain a product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and (3) performing step-by-step heating drying on the product C at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, wherein the drying time of each temperature period is 2 hours, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
The catalyst prepared from the raw materials in parts by weight is used for the addition reaction of acetylene and hydrogen chloride, and the flow rate in an acetylene space is 30h-1The molecular ratio of acetylene to hydrogen chloride is 1: under the condition of 1.1, the catalytic conversion rate is measured to be 99.6%, and the loss rate of mercuric chloride is measured to be 1.2%.
Comparative test example 3
An acetylene hydrochlorination ultra-low mercury catalyst comprises the following components in parts by weight,each hundred parts of HgCl23 parts of CuCl26 parts of ZnCl24 parts of KCl3 parts of the raw materials, and the balance of carrier activated carbon.
The acetylene hydrochlorination ultra-low mercury catalyst is prepared by the following method:
(a) adding HgCl2、CuCl2、ZnCl2Adding KCl into hydrochloric acid aqueous solution with pH less than or equal to 1, and mixing uniformly to obtain product A;
(b) dividing the product A into 6-8 equal parts, and diluting by 2-5 times to obtain product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and (3) performing step-by-step heating drying on the product C at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
The catalyst prepared from the raw materials in parts by weight is used for the addition reaction of acetylene and hydrogen chloride, and the flow rate in an acetylene space is 30h-1The molecular ratio of acetylene to hydrogen chloride is 1: under the condition of 1.1, the catalytic conversion rate is determined to be 89.1 percent, the selectivity of chloroethylene is determined to be 98.1 percent, and the loss rate of mercuric chloride is determined to be 3.5 percent;
comparative test example 4
An ultra-low mercury catalyst according to patent cn202010297857.x, comprising the steps of: 1) preparing nitrogen-doped activated carbon: dipping the activated carbon in an amino resin dipping solution, drying and carbonizing to obtain nitrogen-doped activated carbon; the amino resin impregnation liquid is prepared by reacting an amino compound with an aldehyde compound; 2) preparation of ultra-low mercury catalyst: carrying out acetylene hydrochlorination evaluation on the nitrogen-doped activated carbon loaded mercury chloride and an auxiliary agent prepared by drying the nitrogen-doped activated carbon loaded mercury chloride and the auxiliary agent to obtain an ultralow-mercury catalyst with the content of 3.0 percent on a fixed bed reactor: at the temperature of 125 ℃ and the acetylene space flow rate of 30h-1Hydrogen chloride: acetylene 1.1: 1, the reaction conversion rate is 87.8 percent, the selectivity of the chloroethylene is 99.84 percent, and the loss rate of the mercuric chloride is 1.4 percent.
As can be seen from the comparison of the tests, the catalyst of the invention has better reaction conversion rate, vinyl chloride selectivity and mercury chloride loss rate than similar products. The main reason is thatThe catalyst has many catalytic active sites, high dispersion degree and metal ions Hg2+、Zn2+、Cu2+Form stable complex with succinimide, stabilize the valence state of metal ions, preferentially adsorb hydrogen chloride, inhibit the oxidation-reduction reaction of acetylene and metal ions, and load the catalytic active component on the carrier in nano-scale size.
Claims (7)
1. An acetylene hydrochlorination ultralow-mercury catalyst is characterized in that: the organic ligand of the catalyst is succinimide.
2. The ultra-low mercury catalyst for acetylene hydrochlorination according to claim 1, characterized in that: the catalyst consists of HgCl2、CuCl2、ZnCl2KCl and an organic ligand succinimide.
3. The ultra-low mercury catalyst for acetylene hydrochlorination according to claim 1, characterized in that: the catalyst contains HgCl in one hundred parts by weight20.2-4 parts of CuCl21-10 parts of ZnCl21-8 parts of KCl1-3 parts of succinimide, and the balance of carrier active carbon.
4. The ultra-low mercury catalyst for acetylene hydrochlorination according to claim 3, characterized in that: the catalyst contains HgCl in one hundred parts by weight20.8-2 parts of CuCl23-7 parts of ZnCl24-6 parts of KCl, 1.5-2.5 parts of succinimide, and the balance of carrier active carbon.
5. The method for preparing an acetylene hydrochlorination ultra-low mercury catalyst according to any one of claims 1 to 4, characterized in that: comprises the following steps of (a) carrying out,
(a) adding HgCl2、CuCl2、ZnCl2Adding KCl and succinimide into hydrochloric acid aqueous solution with pH less than or equal to 1, and mixing uniformly to obtain product A;
(b) diluting the product A by 2-5 times to obtain a product B;
(c) dipping the carrier active carbon by using the product B to obtain a product C;
(d) and heating and drying the product C, and volatilizing hydrochloric acid and water to obtain the acetylene hydrochlorination ultra-low mercury catalyst.
6. The ultra-low mercury catalyst for acetylene hydrochlorination according to claim 1, characterized in that: the temperature-rising drying is carried out in a stepwise manner at 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃, and the drying time of each temperature section is 1-2 h.
7. Use of an acetylene hydrochlorination ultra-low mercury catalyst according to any of claims 1-4, characterized in that: the application of succinimide in preparing acetylene hydrochlorination ultra-low mercury catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382579A (en) * | 2022-09-01 | 2022-11-25 | 贵州重力科技环保股份有限公司 | Acetylene copper hydrochloride catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380407A (en) * | 2011-08-25 | 2012-03-21 | 成都惠恩精细化工有限责任公司 | Low-mercury catalyst for acetylene hydrochlorination |
| CN104338561A (en) * | 2013-07-31 | 2015-02-11 | 中昊(大连)化工研究设计院有限公司 | Composite low-mercury complex catalyst used in vinyl chloride synthesis, and preparation method thereof |
| CN108295876A (en) * | 2018-01-30 | 2018-07-20 | 浙江工业大学 | A kind of preparation method of low-mercury catalyst and application |
| CN111203278A (en) * | 2020-03-05 | 2020-05-29 | 石河子大学 | Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
| CN111715253A (en) * | 2019-03-22 | 2020-09-29 | 南开大学 | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination and preparation and use methods thereof |
-
2021
- 2021-08-11 CN CN202110919931.1A patent/CN113813998A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380407A (en) * | 2011-08-25 | 2012-03-21 | 成都惠恩精细化工有限责任公司 | Low-mercury catalyst for acetylene hydrochlorination |
| CN104338561A (en) * | 2013-07-31 | 2015-02-11 | 中昊(大连)化工研究设计院有限公司 | Composite low-mercury complex catalyst used in vinyl chloride synthesis, and preparation method thereof |
| CN108295876A (en) * | 2018-01-30 | 2018-07-20 | 浙江工业大学 | A kind of preparation method of low-mercury catalyst and application |
| CN111715253A (en) * | 2019-03-22 | 2020-09-29 | 南开大学 | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination and preparation and use methods thereof |
| CN111203278A (en) * | 2020-03-05 | 2020-05-29 | 石河子大学 | Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115382579A (en) * | 2022-09-01 | 2022-11-25 | 贵州重力科技环保股份有限公司 | Acetylene copper hydrochloride catalyst and preparation method and application thereof |
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