CN111774094B - Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof - Google Patents

Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof Download PDF

Info

Publication number
CN111774094B
CN111774094B CN201910265291.XA CN201910265291A CN111774094B CN 111774094 B CN111774094 B CN 111774094B CN 201910265291 A CN201910265291 A CN 201910265291A CN 111774094 B CN111774094 B CN 111774094B
Authority
CN
China
Prior art keywords
inert gas
minutes
catalyst
chloride
activated carbon
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.)
Active
Application number
CN201910265291.XA
Other languages
Chinese (zh)
Other versions
CN111774094A (en
Inventor
李伟
关庆鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nankai University filed Critical Nankai University
Priority to CN201910265291.XA priority Critical patent/CN111774094B/en
Publication of CN111774094A publication Critical patent/CN111774094A/en
Application granted granted Critical
Publication of CN111774094B publication Critical patent/CN111774094B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method and a preparation method and a use method thereof, belonging to the technical field of catalysts. The catalyst takes trimethyl aluminum or silicon tetrachloride modified active carbon as a carrier, zinc chloride or ferric chloride as an auxiliary agent, and a complex formed by copper chloride and a nitrogen-containing or carbonyl-containing ligand as an active component. The catalyst shows good activity and stability in the hydrochlorination reaction of acetylene in a normal-pressure fixed bed.

Description

Copper-based mercury-free catalyst for producing vinyl chloride by calcium carbide method and preparation and use methods thereof
Technical Field
The invention provides a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method and a preparation method and a use method thereof, belonging to the technical field of catalysts. The catalyst takes trimethylaluminum or silicon tetrachloride modified active carbon as a carrier, zinc chloride or ferric chloride as an auxiliary agent, and a complex formed by copper chloride and a ligand containing nitrogen or carbonyl as an active component. The catalyst shows good activity and stability in the hydrochlorination reaction of acetylene in a normal-pressure fixed bed.
Background
Polyvinyl chloride (PVC) is one of five general resins in the world, and is widely applied to building materials, pipelines, daily consumer goods and the like. Chloroethylene is a monomer for producing PVC and is influenced by energy structures in China, and the production of chloroethylene mainly adopts a calcium carbide method (acetylene hydrochlorination method). The reaction process is very simple and can be realized only by one-step addition reaction of acetylene and hydrogen chloride. However, the catalyst adopted in the reaction is activated carbon-supported mercuric chloride, and the loss of mercury exists in the using process, so that the environment is seriously polluted, and the human health is threatened. Under the multiple pressure of environment, price and the like, the task of researching and developing mercury-free catalysts to replace mercury catalysts is urgent and is also the key for realizing the sustainable development of the chlor-alkali industry.
Since the last 70 s, the research and development of mercury-free catalysts for acetylene hydrochlorination began by the subject group of Chengrong and Wittig academy of south Kelvin university. In the next decades, mercury-free catalysts have been extensively studied by many groups of topics both at home and abroad. Most research has focused on noble metal catalysts such as gold and ruthenium. However, the precious metals are expensive and scarce, and if the existing mercury catalysts are replaced, the precious metals are a huge investment. Therefore, research on other conventional catalysts has also been receiving attention. Among conventional metal catalysts, copper-based catalysts have received much attention. Patent application CN201310289144.9 discloses a nitrogen-doped carbon material supported catalyst, wherein a nitrogen-doped carbon material is supported with a simple substance or a compound of one or more elements of gold, copper, manganese, bismuth or potassium. Patent application cn201710174566.X discloses a mercury-free catalyst with copper salt and lactam compound as active components and active carbon as a carrier. The catalyst composition structure and the preparation method proposed by the invention are obviously different from the technical contents disclosed above.
It is well known that a delicate synergy among the carrier, the auxiliary agent and the active component is very important for the supported catalyst. Only good active centers are far from sufficient, and it is difficult to obtain a catalyst with excellent properties without suitable carriers and auxiliaries. At present, the copper-based catalyst has the problems of good initial activity, but the catalyst is easy to deposit carbon, poor in stability and quick in inactivation, and the loss and reduction of a copper component also exist in the reaction process.
Disclosure of Invention
Aiming at the defects of the disclosed technology, the invention provides a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method and a preparation and use method thereof. The catalyst takes trimethylaluminum or silicon tetrachloride modified active carbon as a carrier, zinc chloride or ferric chloride as an auxiliary agent, and a complex formed by copper chloride and a ligand containing nitrogen or carbonyl as an active component.
The specific technical scheme of the invention is as follows:
scheme 1, a preparation method of a copper-based mercury-free catalyst for producing chloroethylene by a calcium carbide process, which is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas to vapor of trimethylaluminum at a temperature of 150-200 ℃ and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gasIs water vapor and is maintained for at least 10 minutes; then switching to inert gas again, and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain a pretreated activated carbon carrier;
(4) Dissolving copper chloride and an auxiliary agent in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and then completely drying a sample to obtain a catalyst; wherein the auxiliary agent is zinc chloride or chloridization
One or more of iron, copper chloride accounts for 5-40% of the mass of the catalyst, and the molar ratio of the copper chloride to the auxiliary agent is 1.0:0.05-0.5. scheme 2, a preparation method of a copper-based mercury-free catalyst for producing chloroethylene by a calcium carbide method, which is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas to vapor of trimethylaluminum at a temperature of 150-200 ℃ and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a nitrogen-containing ligand in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the nitrogen-containing ligand is one or more of imidazole, 1-methylimidazole, 2-methylimidazole, N-isopropylimidazole and N-methylpyrrole, and the copper chloride: auxiliary agent: the molar ratio of the nitrogen-containing ligands is 1.0:0.05-0.5:0.1-2.0.
scheme 3, a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas to vapor of trimethylaluminum at a temperature of 150-200 ℃ and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a ligand containing carbonyl in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the carbonyl-containing ligand is one or more of 4-amino-5-imidazole formamide, N-acetyl imidazole, N-dimethylformamide, N-dimethyl propylene urea, succinimide, cyclohexanone, cyclopentanone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, N-octyl pyrrolidone and 2-pyrrolidone, and the copper chloride: auxiliary agent: the molar ratio of the carbonyl-containing ligands is 1.0:0.05-0.5:0.1-2.0.
scheme 4, a preparation method of a copper-based mercury-free catalyst for producing chloroethylene by a calcium carbide method, which is characterized by comprising the following steps:
(1) Placing the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas, and maintaining for at least 10 minutes;
(2) Switching the inert gas into the vapor of silicon tetrachloride at the temperature of 150-200 ℃, and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Dissolving copper chloride and an auxiliary agent in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and then completely drying a sample to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, and the molar ratio of the copper chloride to the auxiliary agent is 1.0:0.05-0.5.
scheme 5, a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching inert gas into vapor of silicon tetrachloride at the temperature of 150-200 ℃, and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a nitrogen-containing ligand in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the nitrogen-containing ligand is one or more of imidazole, 1-methylimidazole, 2-methylimidazole, N-isopropylimidazole and N-methylpyrrole, and the copper chloride: auxiliary agent: the molar ratio of the nitrogen-containing ligand is 1.0:0.05-0.5:0.1-2.0.
scheme 6, a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Placing the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas, and maintaining for at least 10 minutes;
(2) Switching inert gas into vapor of silicon tetrachloride at the temperature of 150-200 ℃, and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again, and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a ligand containing carbonyl in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the carbonyl-containing ligand is one or more of 4-amino-5-imidazole formamide, N-acetyl imidazole, N-dimethylformamide, N-dimethyl propylene urea, succinimide, cyclohexanone, cyclopentanone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, N-octyl pyrrolidone and 2-pyrrolidone, and the copper chloride: auxiliary agent: the molar ratio of the carbonyl-containing ligands is 1.0:0.05-0.5:0.1-2.0.
scheme 7, a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide process, which is characterized by being prepared by using the preparation method of any one of schemes 1-6.
The method for using the copper-based mercury-free catalyst in the scheme 8 and the scheme 7 is characterized by comprising the following steps of:
(1) Loading the catalyst into a normal pressure fixed bed reactor, heating to 150-200 ℃ under flowing inert gas and keeping the temperature constant for at least 1 hour, wherein the volume space velocity of the inert gas is 20-320h –1 ；
(2) After the inert gas is closed, introducing hydrogen chloride gas and keeping the temperature for at least 1 hour, wherein the volume space velocity of the hydrogen chloride is 20-320 hours –1 ；
(3) Then acetylene gas is introduced, and the volume space velocity of the acetylene is 20-320h –1 The molar ratio of the hydrogen chloride to the acetylene is 1.05-1.2;
(4) The using temperature range of the catalyst is 120-200 ℃;
(5) The reaction products were analyzed using gas chromatography equipped with a TCD detector.
Compared with the prior art, the invention has the innovation points that:
(1) Trimethylaluminum or silicon tetrachloride is used as a raw material, the surface of the activated carbon is modified, and 1-10 atomic layers of aluminum hydroxide or orthosilicic acid can be controllably deposited on the surface of the activated carbon by utilizing the self-limiting characteristic of the reaction. Therefore, the content of hydroxyl functional groups on the surface of the activated carbon is greatly improved, which is beneficial to playing a better dispersing role on the active center and the auxiliary agent, and simultaneously, the interaction of the carrier, the active center and the auxiliary agent can be enhanced, and the loss of components is reduced. Meanwhile, the increase of the number of the hydroxyl on the surface of the activated carbon can improve the adsorption and enrichment effects on acetylene and hydrogen chloride, thereby improving the activity of the catalyst.
(2) The complex formed by the ligand containing nitrogen or carbonyl and the copper ions can enhance the interaction between the copper ions and the ligand, improve the content of monovalent copper ions in the catalyst, and prevent the copper ions from being reduced and inactivated at high temperature, thereby improving the stability of the catalyst. Meanwhile, the addition of the ligands can greatly reduce the content of divalent copper ions in the catalyst, thereby effectively reducing carbon deposition of the catalyst in the hydrochlorination reaction of acetylene.
Detailed Description
To better illustrate the patent, the following examples are now set forth. The following examples are intended to provide those skilled in the art with a more detailed understanding of the present invention, or to provide further insubstantial modifications and adaptations of the invention in light of the above teachings. However, the scope of the present invention is not limited by these examples.
Example 1
(1) The activated carbon was placed in a quartz tube furnace and heated to 200 ℃ under flowing argon and maintained for 10 minutes.
(2) Switching argon to vapor of trimethylaluminum at the temperature of 200 ℃, and treating the activated carbon for 10 minutes; then switching to argon and maintaining for 10 minutes; then the argon is switched to water vapor and maintained for 10 minutes; then switched to argon and maintained for 10 minutes; obtaining the pretreated activated carbon carrier; wherein the volume space velocity of the argon is 80h –1 。
(3) Dissolving copper chloride and zinc chloride in water at 60 ℃ to obtain a steeping liquor, then steeping the steeping liquor on the pretreated activated carbon carrier by an isometric steeping method, sealing and standing for 1 hour, and then completely drying a sample to obtain the catalyst, wherein the serial number of the obtained catalyst is Cat-1. Wherein the mass fraction of the copper chloride in the catalyst is 5%, and the molar ratio of the copper chloride to the zinc chloride is 1.0:0.05.
example 2
The procedure of example 2 was followed as in example 1 except that the argon volume space velocity in step (2) was changed to 300h –1 The catalyst obtained is numbered Cat-2.
Example 3
The procedure of example 3 was carried out in the same manner as in example 1 except that the zinc chloride in step (3) was changed to ferric chloride and the catalyst obtained was numbered Cat-3.
Example 4
The procedure of example 4 was followed in the same manner as in example 1 except that the mass fraction of copper chloride in the catalyst of step (3) was changed from 5% to 40%, and the catalyst thus obtained was named Cat-4.
Example 5
The procedure of example 5 was the same as in example 1 except that the molar ratio of copper chloride to zinc chloride in step (3) was changed from 1.0:0.05 to 1.0:0.5, the catalyst obtained is numbered Cat-5.
Example 6
Example 6 was prepared by the same procedure as in example 1 except that trimethylaluminum in step (2) was changed to silicon tetrachloride, and the catalyst obtained was numbered Cat-6.
Example 7
(1) The activated carbon was placed in a quartz tube furnace and heated to 200 ℃ under flowing argon and maintained for 10 minutes.
(2) Switching argon to vapor of trimethylaluminum at the temperature of 200 ℃, and treating the activated carbon for 10 minutes; then switching to argon and maintaining for 10 minutes; then the argon is switched to water vapor and maintained for 10 minutes; then switching to argon again and maintaining for 10 minutes; wherein the volume space velocity of the argon is 80h –1 。
(3) And (3) repeating the step (2) for 1 time to obtain the pretreated activated carbon carrier.
(4) Stirring and dissolving copper chloride, zinc chloride and imidazole in water at 40 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier by using an isometric impregnation method, sealing and standing for 1 hour, and completely drying a sample at 200 ℃ under flowing argon to obtain the catalyst, wherein the serial number of the obtained catalyst is Cat-7. Wherein the copper chloride accounts for 5 percent of the mass of the catalyst, and the weight percentage of the copper chloride is as follows: zinc chloride: molar ratio of imidazole 1.0:0.05:0.1.
example 8
Example 8 was prepared by the same procedure as in example 7 except that the zinc chloride in step (4) was changed to ferric chloride and the resulting catalyst was numbered Cat-8.
Example 9
The procedure for preparation of example 9 was the same as in example 7 except that the mass fraction of copper chloride in the catalyst in the step (4) was changed from 5% to 40%, and the catalyst obtained was numbered Cat-9.
Example 10
Example 10 the procedure was the same as in example 7 except that the copper chloride in step (4): zinc chloride: the molar ratio of imidazole is from 1.0:0.05:0.1 is changed to 1.0:0.5:2.0, the obtained catalyst was numbered Cat-10.
Example 11
Example 11 was prepared by the same procedure as in example 7 except that trimethylaluminum in step (2) was changed to silicon tetrachloride, and the obtained catalyst was numbered Cat-11.
Example 12
The procedure for preparation of example 12 was the same as in example 7 except that the operation in step (3) was repeated 1 time to 9 times, and the catalyst obtained was numbered Cat-12.
Example 13
Example 13 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to 1-methylimidazole, and the resulting catalyst was numbered Cat-13.
Example 14
The procedure for preparation of example 14 was the same as in example 7 except that the imidazole in step (4) was changed to 2-methylimidazole, and the resulting catalyst was numbered Cat-14.
Example 15
Example 15 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to N-isopropylimidazole, and the resulting catalyst was numbered Cat-15.
Example 16
Example 16 was prepared by the same procedure as in example 7 except that imidazole in step (4) was changed to N-methylpyrrole, and the catalyst obtained was numbered Cat-16.
Example 17
The procedure for preparation of example 17 was the same as in example 7 except that imidazole in step (4) was changed to 4-amino-5-imidazolecarboxamide, and the resulting catalyst was numbered Cat-17.
Example 18
Example 18 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to N-acetylimidazole and the resulting catalyst was numbered Cat-18.
Example 19
Example 19 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to N, N-dimethylformamide, and the resulting catalyst was numbered Cat-19.
Example 20
Example 20 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to N, N-dimethylpropylurea, and the catalyst obtained was numbered Cat-20.
Example 21
The procedure for preparation of example 21 was the same as in example 7 except that imidazole in step (4) was changed to succinimide, and the resulting catalyst was numbered Cat-21.
Example 22
The procedure for the preparation of example 22 was identical to that of example 7, except that the imidazole in step (4) was changed to cyclohexanone, and the resulting catalyst was numbered Cat-22.
Example 23
Example 23 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to N-methylpyrrolidone, and the catalyst obtained was numbered Cat-23.
Example 24
Example 24 was prepared by the same procedure as in example 7 except that the imidazole in step (4) was changed to 2-pyrrolidone and the resulting catalyst was numbered Cat-24.
Comparative example 1
The aim was to illustrate the effect of carrier pretreatment on catalyst activity.
Dissolving copper chloride and zinc chloride in water at 60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on an activated carbon carrier by using an isometric impregnation method, sealing and standing for 1 hour, and then completely drying a sample to obtain the catalyst, wherein the serial number of the obtained catalyst is Cat-25. Wherein the copper chloride accounts for 5 percent of the mass of the catalyst, and the molar ratio of the copper chloride to the zinc chloride is 1.0:0.05.
the procedure for the evaluation of the catalyst for the hydrochlorination of acetylene was as follows:
(1) Loading the catalyst into a normal pressure fixed bed reactor, heating to 180 ℃ under flowing argon and keeping the temperature for 1 hour, wherein the volume space velocity of the argon is 160h –1 ；
(2) After the argon is closed, introducing hydrogen chloride gas and keeping the temperature for 1 hour, wherein the volume space velocity of the hydrogen chloride is 80 hours –1 ；
(3) Then acetylene gas is introduced, and the volume space velocity of the acetylene is 160h –1 The molar ratio of hydrogen chloride to acetylene is 1.05;
comparative data for acetylene conversion and vinyl chloride selectivity for different copper-based mercury-free catalysts are shown in the table:
catalyst numbering Acetylene conversion (%) Vinyl chloride Selectivity (%)
Cat-1 40.3 99.6
Cat-2 40.2 99.5
Cat-3 41.1 99.1
Cat-4 92.8 99.6
Cat-5 48.2 99.4
Cat-6 42.9 99.5
Cat-7 48.9 99.6
Cat-8 49.1 99.3
Cat-9 95.6 99.3
Cat-10 58.3 99.5
Cat-11 50.7 99.3
Cat-12 49.3 99.6
Cat-13 49.6 99.5
Cat-14 49.5 99.5
Cat-15 50.5 99.6
Cat-16 52.7 99.5
Cat-17 55.0 99.6
Cat-18 54.3 99.5
Cat-19 57.2 99.5
Cat-20 57.0 99.6
Cat-21 57.3 99.4
Cat-22 59.5 99.6
Cat-23 60.4 99.5
Cat-24 62.1 99.6
Cat-25 30.1 99.2

Claims (8)

1. A preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Placing the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas, and maintaining for at least 10 minutes;
(2) Switching the inert gas to vapor of trimethylaluminum at a temperature of 150-200 ℃ and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again, and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain a pretreated activated carbon carrier;
(4) Dissolving copper chloride and an auxiliary agent in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and then completely drying a sample to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, and the molar ratio of the copper chloride to the auxiliary agent is 1.0:0.05-0.5.
2. a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Placing the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas, and maintaining for at least 10 minutes;
(2) Switching the inert gas to vapor of trimethylaluminum at a temperature of 150-200 ℃ and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again, and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a nitrogen-containing ligand in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the nitrogen-containing ligand is one or more of imidazole, 1-methylimidazole, 2-methylimidazole, N-isopropylimidazole and N-methylpyrrole, and the copper chloride: auxiliary agent: the molar ratio of the nitrogen-containing ligands is 1.0:0.05-0.5:0.1-2.0.
3. a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas to vapor of trimethylaluminum at a temperature of 150-200 ℃ and treating the activated carbon for at least 10 minutes; then the reaction is switched to inert gas,and maintained for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a ligand containing carbonyl in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the carbonyl-containing ligand is one or more of 4-amino-5-imidazole formamide, N-acetyl imidazole, N-dimethylformamide, N-dimethyl propylene urea, succinimide, cyclohexanone, cyclopentanone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, N-octyl pyrrolidone and 2-pyrrolidone, and the copper chloride: auxiliary agent: the molar ratio of the carbonyl-containing ligands is 1.0:0.05-0.5:0.1-2.0.
4. a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas into the vapor of silicon tetrachloride at the temperature of 150-200 ℃, and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again, and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Dissolving copper chloride and an auxiliary agent in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and then completely drying a sample to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, and the molar ratio of the copper chloride to the auxiliary agent is 1.0:0.05-0.5.
5. a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas into the vapor of silicon tetrachloride at the temperature of 150-200 ℃, and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a nitrogen-containing ligand in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the nitrogen-containing ligand is one or more of imidazole, 1-methylimidazole, 2-methylimidazole, N-isopropylimidazole and N-methylpyrrole, and the copper chloride: auxiliary agent: the molar ratio of the nitrogen-containing ligands is 1.0:0.05-0.5:0.1-2.0.
6. a preparation method of a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide method is characterized by comprising the following steps:
(1) Putting the activated carbon in a quartz tube furnace, heating to 150-200 ℃ under flowing inert gas and maintaining for at least 10 minutes;
(2) Switching the inert gas into the vapor of silicon tetrachloride at the temperature of 150-200 ℃, and treating the activated carbon for at least 10 minutes; then switching to inert gas and maintaining for at least 10 minutes; then switching the inert gas to water vapor and maintaining for at least 10 minutes; then switching to inert gas again and maintaining for at least 10 minutes; wherein the inert gas is one of nitrogen, argon and helium, and the volume space velocity of the inert gas is 80-300h –1 ；
(3) Repeating the step (2) for 0-9 times to obtain the pretreated activated carbon carrier;
(4) Stirring and dissolving copper chloride, an auxiliary agent and a ligand containing carbonyl in water at the temperature of 20-60 ℃ to obtain an impregnation solution, then impregnating the impregnation solution on the pretreated activated carbon carrier, sealing and standing for at least 1 hour, and completely drying a sample at the temperature of 150-200 ℃ in a flowing inert atmosphere to obtain a catalyst; wherein the auxiliary agent is one or more of zinc chloride or ferric chloride, the copper chloride accounts for 5-40% of the mass of the catalyst, the carbonyl-containing ligand is one or more of 4-amino-5-imidazole formamide, N-acetyl imidazole, N-dimethylformamide, N-dimethyl propylene urea, succinimide, cyclohexanone, cyclopentanone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, N-octyl pyrrolidone and 2-pyrrolidone, and the copper chloride: auxiliary agent: the molar ratio of the carbonyl-containing ligands is 1.0:0.05-0.5:0.1-2.0.
7. a copper-based mercury-free catalyst for producing vinyl chloride by a calcium carbide process, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. A method of using the copper-based mercury-free catalyst of claim 7, comprising the steps of:
(1) Loading the catalyst into a normal pressure fixed bed reactor, heating to 150-200 ℃ under flowing inert gas, and keeping the temperature for at least 1 hour, wherein the volume space velocity of the inert gas is 20-320h –1 ；
(2) After the inert gas is closed, introducing hydrogen chloride gas and keeping the temperature for at least 1 hour, wherein the volume space velocity of the hydrogen chloride is 20-320 hours –1 ；
(3) Then acetylene gas is introduced, and the volume space velocity of the acetylene is 20-320h –1 The molar ratio of hydrogen chloride to acetylene is 1.05-1.2;
(4) The application temperature range of the catalyst is 120-200 ℃;
(5) The reaction products were analyzed using gas chromatography equipped with a TCD detector.
CN201910265291.XA 2019-04-03 2019-04-03 Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof Active CN111774094B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910265291.XA CN111774094B (en) 2019-04-03 2019-04-03 Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910265291.XA CN111774094B (en) 2019-04-03 2019-04-03 Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof

Publications (2)

Publication Number Publication Date
CN111774094A CN111774094A (en) 2020-10-16
CN111774094B true CN111774094B (en) 2022-12-16

Family

ID=72754833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910265291.XA Active CN111774094B (en) 2019-04-03 2019-04-03 Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof

Country Status (1)

Country Link
CN (1) CN111774094B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115608415B (en) * 2021-07-16 2024-04-16 中国科学院大连化学物理研究所 Supported catalyst, preparation and application thereof
CN115608359B (en) * 2021-07-16 2024-04-05 中国科学院大连化学物理研究所 Copper catalyst and preparation method and application thereof
CN114146728B (en) * 2021-11-29 2023-12-05 内蒙古鄂尔多斯电力冶金集团股份有限公司 Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof
EP4197635A1 (en) 2021-12-17 2023-06-21 Johnson Matthey Public Limited Company Gold containing catalyst, method of preparation and use

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103551168B (en) * 2013-11-06 2015-09-02 南开大学 A kind ofly be applied to fixed bed catalyst without mercury preparing vinyl chloride and preparation method thereof
CN106975500A (en) * 2017-04-28 2017-07-25 武汉工程大学 Catalyst without mercury of vinyl chloride and preparation method thereof is produced for acetylene method
CN108097251B (en) * 2018-01-10 2021-03-26 南开大学 Catalyst for fixed bed acetylene hydrochlorination and use method thereof

Also Published As

Publication number Publication date
CN111774094A (en) 2020-10-16

Similar Documents

Publication Publication Date Title
CN111774094B (en) Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof
CN111715253B (en) Copper-based catalyst for preparing vinyl chloride by hydrochlorination of acetylene and preparation and use methods thereof
CN108097251B (en) Catalyst for fixed bed acetylene hydrochlorination and use method thereof
CN106944151B (en) A kind of catalyst without mercury and its preparation method and application for acetylene hydrochlorination synthesis vinyl chloride thereof
CN110813359B (en) Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof
CN113713841B (en) Acetylene copper chloride-based catalyst and preparation method and application thereof
CN110773156A (en) Transition metal monatomic catalyst, preparation method and application thereof
CN107519872A (en) A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method
CN110813380B (en) Copper ketone complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination
CN111330621A (en) Supported mercury-free catalyst for synthesizing chloroethylene and preparation method thereof
CN111346662B (en) Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst
CN114177940A (en) Preparation and application of monoatomic Cu-anchored covalent organic framework material
CN107321389B (en) Preparation method of ultralow-mercury catalyst for catalytic synthesis of chloroethylene
CN113501895A (en) Preparation method of catalyst for mercury-free synthesis of polyvinyl chloride
CN108043467B (en) Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof
CN113426490A (en) Method for preparing mercury-free catalyst by adding dichloroethane
CN116651505A (en) Ruthenium-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof
CN109647523B (en) Preparation method and use method of metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in fixed bed
CN112876336B (en) Preparation method of chlorotrifluoroethylene
CN112435858A (en) Nitrogen and oxygen containing metal doped porous carbon material and preparation method and application thereof
CN108067282B (en) Catalyst for hydrochlorination of acetylene and using method
CN117181314A (en) Preparation method and application method of Cu-based catalyst for preparing vinyl chloride by hydrochlorination of acetylene in fixed bed
CN116037173B (en) Catalyst for selective hydrodechlorination of acetic acid chlorinated solution, preparation method and application
CN110624578A (en) Preparation method of supported catalyst for synthesizing 1,1,2,3, 3-pentachloropropane
CN115106093B (en) Preparation method and application of metal covalent organic framework catalyst

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
GR01 Patent grant
GR01 Patent grant