CN113663740A - Passivation type ultralow-content gold catalyst - Google Patents
Passivation type ultralow-content gold catalyst Download PDFInfo
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- CN113663740A CN113663740A CN202110859223.3A CN202110859223A CN113663740A CN 113663740 A CN113663740 A CN 113663740A CN 202110859223 A CN202110859223 A CN 202110859223A CN 113663740 A CN113663740 A CN 113663740A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 32
- 239000010931 gold Substances 0.000 title claims abstract description 32
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002161 passivation Methods 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002344 gold compounds Chemical class 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 238000007038 hydrochlorination reaction Methods 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940080818 propionamide Drugs 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052753 mercury Inorganic materials 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- -1 gold halide Chemical class 0.000 abstract 1
- 229910001922 gold oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 206010024769 Local reaction Diseases 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910015723 MoP Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
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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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a passivated ultra-low content gold catalyst, in particular to a non-mercury catalyst suitable for synthesizing chloroethylene by acetylene hydrochlorination, which adopts monoamide as a passivating agent of a gold-based catalyst, takes one or more of simple substance gold, chloroauric acid, gold halide and gold oxide as main active components, and then compounds of more than one of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin as auxiliary active components; the prepared gold compound catalyst remarkably reduces the cost of the noble metal catalyst, overcomes the defects of high heat point, concentrated hot points, easy occurrence of side reaction, carbon deposit and inactivation of the noble metal catalyst, and greatly improves the performance of the catalyst.
Description
Technical Field
The invention belongs to the field of gold-based catalysts for synthesizing vinyl chloride by hydrochlorinating acetylene, and particularly relates to a passivated ultralow-content gold catalyst.
Background
The vinyl chloride monomer is an important synthetic raw material of polyvinyl chloride, the polyvinyl chloride is one of synthetic resins with the largest consumption and yield in China, and the basic national situation of more coal and less oil in China determines that the vinyl chloride produced by the acetylene hydrochlorination method still occupies the leading position in China. The main problems faced by the acetylene hydrochlorination method for synthesizing vinyl chloride are environmental pollution caused by the use of mercury catalyst and large consumption of mercury resources. With the increasing enhancement of environmental awareness and the increasing tension of international mercury-limiting treaties, the development of mercury-free catalysts is imperative for maintaining the living space of calcium carbide-process PVC.
At present, the research focus of the mercury-free catalyst focuses on the research and development of non-noble metal and noble metal mercury-free catalysts. Research and development of non-noble metal catalysts have also made certain research progress, for example, CN101497046, CN101671293, and CN102151581A are catalytic systems using non-noble metals such as Cu, Bi, and MoP as main active components, respectively, but the non-noble metal mercury-free catalysts still have major problems of low activity and short lifetime.
The development participation units of the noble metal mercury-free catalyst comprise development units of Sichuan university, Tianjin staphyla, Huadong university, Ak technology Limited, south China university, Qinghua university, Xinjiang celestial group, Dalian institute, Shihui university, Tianjin university, Xinjiang university, Zhejiang university and the like, so that the development of the noble metal mercury-free catalyst is greatly researched and developed, but the noble metal mercury-free catalyst has high conversion rate, but one of the main problems of the noble metal mercury-free catalyst is that the conversion rate of the catalyst is too high, the reaction of the catalyst is concentrated, the hot spot is too high, the local reaction heat transfer is not carried out, the catalyst sintering, carbon accumulation and side reaction are increased, the active component is inactivated and the like, and the one-time investment cost of the catalyst is high, so that the popularization and the application of the noble metal mercury-free catalyst are limited.
Aiming at the problems of the noble metal mercury-free catalyst, the invention firstly greatly reduces the content of the noble metal catalyst and the first investment and use cost of the noble metal catalyst, but aims at solving the problems of sintering, carbon deposit, side reaction increase, active component inactivation and the like of the catalyst caused by high reaction heat point, concentrated reaction and partial reaction heat transfer which still exist in the ultra-low content noble metal gold catalyst, thereby reducing the service life of the catalyst. The invention develops a passivator of a noble metal gold catalyst, which reduces the initial activity of the noble metal catalyst and prolongs the induction period of the catalyst by adding the passivator, and gradually releases the activity of the catalyst along with the progress of catalytic reaction, thereby reducing the hot spot temperature of the catalyst, prolonging the reaction bandwidth of the catalyst, reducing the side reaction of the catalyst, lightening the carbon deposit and the sintering condition of the catalyst, and prolonging the service life of the catalyst.
Disclosure of Invention
The invention aims to solve the problems that the high-toxicity mercury catalyst is used in the production of polyvinyl chloride by a calcium carbide acetylene method, the mercury consumption in the production is high, the environmental pollution is serious, the reaction heat point of the existing noble metal catalyst is high, the reaction is concentrated, the local reaction heat is not transferred, the catalyst sintering, carbon deposition and side reaction are increased, the active component is inactivated, and the one-time investment cost is high.
The passivated ultra-low gold catalyst has the advantages that the main active component of the catalyst is a noble metal gold compound; the auxiliary active component is one or a mixture of any more of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin compounds, the catalyst passivator is a monoamide compound, and the carrier is activated carbon.
In the passivated ultra-low gold catalyst, the gold compound is one or two of chloroauric acid and gold chloride.
The passivated ultra-low gold catalyst has gold content of one ten-thousandth to five ten-thousandth of the activated carbon.
The passivated ultra-low gold catalyst has the auxiliary active components of chlorides and nitrates of compounds of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin.
The content of the auxiliary active component simple substance is 1-50% of the active carbon.
In the above-mentioned passivated ultra-low gold catalyst, the monoamide compound is one or more of formamide, acetamide, propionamide, N-dimethylformamide, benzamide, tetracyclic amide, pentacyclic amide, hexacyclic amide, tetracyclic amide derivative, pentacyclic amide derivative and hexacyclic amide derivative.
The mass ratio of the passivating agent to the active carbon of the passivated ultralow-content gold catalyst is 0.01-0.3.
The preparation method of the passivated ultra-low gold catalyst comprises the steps of firstly impregnating the auxiliary active component of the catalyst, then impregnating the main active component of the catalyst and the passivating agent.
The drying condition of the passivated ultra-low content gold catalyst is drying for 8-72 hours at the temperature of 30-80 ℃, and drying for 8-48 hours at the temperature of 105-125 ℃.
The passivated catalyst with ultralow gold content is used in the reaction process of synthesizing vinyl chloride by hydrochlorinating acetylene and is used for producing vinyl chloride by acetylene and hydrogen chloride.
The preparation method of the high-dispersity gold-loaded catalyst provided by the invention is carried out for 30-360 h-1When the space velocity reaction is carried out, the initial conversion rate reaches 80-100%, the conversion rate is kept stable after the reaction is carried out for 8-1000 h, and the selectivity of chloroethylene reaches more than 98%, so that the problems that the high-toxicity mercury catalyst is used in the production of polyvinyl chloride by a calcium carbide acetylene method, the mercury consumption in the production is high, the environmental pollution is serious, the hot spots of the existing noble metal catalyst are concentrated, the hot spot temperature is high, the reaction is concentrated, the local reaction heat is not transferred, the catalyst sintering, carbon deposition, side reaction increase, the active component inactivation and the one-time investment cost are high are solved.
Detailed Description
To better illustrate the present invention, the following examples are given. The scope of the invention is not to be limited by the examples, but rather is to be defined by the claims appended hereto.
Firstly, preparing a chloroauric acid solution, namely dissolving 1g of chloroauric acid in 100ml of deionized water to prepare the chloroauric acid solution, and preparing for subsequent sample preparation. Secondly, pretreatment of the carrier: 200g of activated carbon is weighed and repeatedly washed by deionized water until the supernatant of the water solution of the activated carbon is clear and bright, and then dried at 120 ℃ for later use.
Example 1
0.6224g of chloroauric acid solution and 0.2904g of ferric chloride were weighed into a beaker, and then diluted with 26ml of deionized water. Adding 0.2ml of formamide into the solution, stirring uniformly, adding 10g of activated carbon, stirring uniformly, soaking at normal temperature for 24h, drying at 50 ℃ for 12h, and drying at 125 ℃ for 24 h. The initial conversion of this catalyst reached 75%.
Example 2
0.6224g of chloroauric acid solution and 0.2203g of cobalt chloride are weighed in a beaker, 26ml of deionized water is added for dilution, 0.2ml of formamide is added into the solution, 10g of activated carbon is added after the mixture is uniformly stirred, the mixture is uniformly stirred and dipped for 24 hours at normal temperature, and then the mixture is dried for 12 hours at the temperature of 50 ℃ and 24 hours at the temperature of 125 ℃. 0.6224g of chloroauric acid solution was weighed out and added to 20ml of water, and the above dried catalyst was added to carry out secondary impregnation, followed by impregnation and drying under the above conditions. The initial conversion of this catalyst reached 78%.
Example 3
1.2448g of chloroauric acid solution and 0.4416g of nickel chloride were weighed into a beaker, followed by dilution with 26ml of deionized water. And then 2g of acetamide is taken and added into the solution, after the mixture is uniformly stirred, 10g of activated carbon is added, the mixture is uniformly stirred, the mixture is immersed for 24 hours at normal temperature, and then the mixture is dried for 12 hours at 50 ℃ and 24 hours at 125 ℃. The initial conversion of this catalyst reached 83%.
Example 4
1.8672g of chloroauric acid solution and 0.7991g of copper chloride were weighed into a beaker, and then diluted with 26ml of deionized water. And adding 3g of propionamide into the solution, uniformly stirring, adding 10g of activated carbon, uniformly stirring, soaking at normal temperature for 24 hours, drying at 50 ℃ for 12 hours, and drying at 125 ℃ for 24 hours. The initial conversion of this catalyst reached 80%.
Example 5
2.4896g of chloroauric acid solution and cesium chloride 1.0141 were weighed into a beaker and then diluted by adding 26ml of deionized water. And then adding 2ml of N, N-dimethylformamide into the solution, stirring uniformly, adding 10g of activated carbon, stirring uniformly, soaking at normal temperature for 24h, then drying at 50 ℃ for 12h, and drying at 125 ℃ for 24 h. The initial conversion of this catalyst reached 85%.
Example 6
3.1112g of chloroauric acid solution and 3.1171 g of lanthanum nitrate were weighed into a beaker, and then diluted with 26ml of deionized water. And then 0.6g of benzamide is added into the solution, after the stirring is uniform, 10g of activated carbon is added, the stirring is uniform, the impregnation is carried out for 24h at the normal temperature, then the drying is carried out for 12h at the temperature of 50 ℃, and the drying is carried out for 24h at the temperature of 125 ℃. The initial conversion of this catalyst reached 95%.
Example 7
0.6224g of chloroauric acid solution and 3.4912 g of cerium nitrate were weighed into a beaker, followed by dilution with 26ml of deionized water. And then 2ml of 2-pyrrolidone is added into the solution, after the mixture is uniformly stirred, 10g of activated carbon is added, the mixture is uniformly stirred, the mixture is soaked for 24 hours at normal temperature, and then the mixture is dried for 12 hours at the temperature of 50 ℃ and 24 hours at the temperature of 125 ℃. The initial conversion of this catalyst reached 76%.
Example 8
1.2448g of chloroauric acid solution and stannous chloride 3.8017 were weighed into a beaker and then diluted with 26ml of deionized water. And then 0.5ml of 2-piperidone is added into the solution, after the mixture is uniformly stirred, 10g of activated carbon is added, the mixture is uniformly stirred, the mixture is soaked for 24 hours at normal temperature, and then the mixture is dried for 12 hours at the temperature of 50 ℃ and dried for 24 hours at the temperature of 125 ℃. The initial conversion of this catalyst reached 90%.
Example 9
1.8672g of chloroauric acid solution and 1.2599 g of silver nitrate were weighed into a beaker, and then diluted by adding 26ml of deionized water. And then adding 0.5g of caprolactam into the solution, stirring uniformly, adding 10g of activated carbon, stirring uniformly, soaking at normal temperature for 24 hours, then drying at 50 ℃ for 12 hours, and drying at 125 ℃ for 24 hours. The initial conversion of this catalyst reached 86%.
Claims (10)
1. A passivated ultra-low gold catalyst is characterized in that the catalyst comprises a main active component and a noble metal gold compound; auxiliary active component, one or mixture of any more of iron, cobalt, nickel, copper, cesium, lanthanum, cerium and tin compounds; a catalyst deactivator, a monoamide compound; the carrier is active carbon.
2. A passivated ultra low gold catalyst according to claim 1 wherein the noble metal gold compound is one or both of chloroauric acid and gold chloride.
3. A passivated ultra low gold catalyst according to claim 1 wherein the gold is present in an amount of one to five ten thousandths of an activated carbon.
4. A passivated ultra low gold catalyst as claimed in claim 1 wherein the ancillary active components are chlorides and nitrates of one or any of the compounds of iron, cobalt, nickel, copper, cesium, lanthanum, cerium, tin.
5. The passivated ultra-low gold catalyst of claim 1 wherein the auxiliary active component element content is 1-50% of the activated carbon.
6. The passivated ultra low gold catalyst according to claim 1 wherein said mono-amide compound is one or more of formamide, acetamide, propionamide, N dimethylformamide, benzamide, tetracyclic amide, pentacyclic amide, hexacyclic amide, tetracyclic amide derivatives, pentacyclic amide derivatives, hexacyclic amide derivatives.
7. The passivated ultra-low gold catalyst according to claim 6 wherein the mass ratio of passivating agent to activated carbon is 0.01 to 0.3.
8. A passivated ultra low gold catalyst according to claim 1 wherein the catalyst is prepared by impregnating the secondary active component of the catalyst followed by the primary active component of the catalyst and the passivating agent.
9. The passivated ultra-low gold catalyst of claim 1 wherein the drying conditions are 30-80 ℃ for 8-72 hours and 105-125 ℃ for 8-48 hours.
10. The passivated ultra low gold catalyst of claim 1 wherein said catalyst is used in the reaction of acetylene hydrochlorination to vinyl chloride.
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| US4912271A (en) * | 1988-04-30 | 1990-03-27 | Huels Aktiengesellschaft | Process for the manufacture of vinyl chloride by reaction of acetylene with hydrogen chloride |
| CN102698806A (en) * | 2012-04-14 | 2012-10-03 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Non-mercury catalyst for synthesizing chloroethylene through acetylene in hydrochlorinate mode |
| CN103191760A (en) * | 2013-04-25 | 2013-07-10 | 新疆天业（集团）有限公司 | Acetylene-hydrochlorinated low-content gold compound catalyst |
| CN109622036A (en) * | 2018-12-25 | 2019-04-16 | 南开大学 | A kind of preparation method for the Au-based catalyst preparing vinyl chloride for acetylene hydrochlorination method |
| CN109876864A (en) * | 2019-02-14 | 2019-06-14 | 西安凯立新材料股份有限公司 | A kind of super low loading noble metal composite catalyst and preparation method thereof for acetylene hydrochlorination reaction |
| 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 |
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2021
- 2021-07-28 CN CN202110859223.3A patent/CN113663740A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4912271A (en) * | 1988-04-30 | 1990-03-27 | Huels Aktiengesellschaft | Process for the manufacture of vinyl chloride by reaction of acetylene with hydrogen chloride |
| CN102698806A (en) * | 2012-04-14 | 2012-10-03 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Non-mercury catalyst for synthesizing chloroethylene through acetylene in hydrochlorinate mode |
| CN103191760A (en) * | 2013-04-25 | 2013-07-10 | 新疆天业（集团）有限公司 | Acetylene-hydrochlorinated low-content gold compound catalyst |
| CN109622036A (en) * | 2018-12-25 | 2019-04-16 | 南开大学 | A kind of preparation method for the Au-based catalyst preparing vinyl chloride for acetylene hydrochlorination method |
| CN109876864A (en) * | 2019-02-14 | 2019-06-14 | 西安凯立新材料股份有限公司 | A kind of super low loading noble metal composite catalyst and preparation method thereof for acetylene hydrochlorination reaction |
| 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 |
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