CN115626863A - Method for using low-content ruthenium-based catalyst in reaction of preparing vinyl chloride through fixed bed acetylene hydrochlorination - Google Patents
Method for using low-content ruthenium-based catalyst in reaction of preparing vinyl chloride through fixed bed acetylene hydrochlorination Download PDFInfo
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- CN115626863A CN115626863A CN202211270243.8A CN202211270243A CN115626863A CN 115626863 A CN115626863 A CN 115626863A CN 202211270243 A CN202211270243 A CN 202211270243A CN 115626863 A CN115626863 A CN 115626863A
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- vinyl chloride
- acetylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 209
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 82
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 64
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 57
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000007038 hydrochlorination reaction Methods 0.000 title claims description 34
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000012495 reaction gas Substances 0.000 claims abstract description 12
- AVJBQMXODCVJCJ-UHFFFAOYSA-M 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C=[N+](C=2C(=CC=CC=2C(C)C)C(C)C)C=C1 AVJBQMXODCVJCJ-UHFFFAOYSA-M 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 87
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 45
- 239000012452 mother liquor Substances 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000007605 air drying Methods 0.000 claims description 20
- 238000005470 impregnation Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 17
- 244000060011 Cocos nucifera Species 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000004570 mortar (masonry) Substances 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- IJLQXRDUIISBEE-UHFFFAOYSA-N 1-[2,6-di(propan-2-yl)phenyl]-1h-imidazol-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1[NH+]1C=NC=C1 IJLQXRDUIISBEE-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229920000742 Cotton Polymers 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052753 mercury Inorganic materials 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000012327 Ruthenium complex Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- OTOSIXGMLYKKOW-UHFFFAOYSA-M 1,3-bis(2,4,6-trimethylphenyl)imidazol-1-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1C=[N+](C=2C(=CC(C)=CC=2C)C)C=C1 OTOSIXGMLYKKOW-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229910019854 Ru—N Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 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 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
-
- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for applying a low-content ruthenium-based catalyst to a reaction for preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed, belonging to the technical field of catalyst preparation and application. The method takes 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride as a ligand, mixes and stirs with a ruthenium precursor, then impregnates the mixture on a carrier in an incipient wetness manner, and dries the obtained mixture in an oven to obtain the required catalyst. The catalyst has extremely high activity and vinyl chloride selectivity in the reaction of preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed, is low in cost and free of mercury pollution, and the preparation method is simple and can be expanded, so that the catalyst has a great potential industrial application value. The load capacity of ruthenium is 0.3 percent, and the space velocity of reaction gas is 170h ‑1 ，V (C2H2) /V (HCl) 1.15, under the condition that the reaction temperature is 180 ℃, the acetylene conversion rate can reach 93.2%, and the selectivity of vinyl chloride is more than 99%.
Description
Technical Field
The invention belongs to the field of catalyst preparation technology and application, and particularly relates to a method for applying a low-content ruthenium-based catalyst to a reaction for preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed.
Background
Polyvinyl chloride (PVC) is a polymer formed by polymerization of Vinyl Chloride Monomer (VCM), and is widely used in building materials, industrial products, daily necessities, flooring, packaging films, foamed materials, and the like. The calcium carbide method is a main method for producing vinyl chloride monomer in China, and is mainly determined by the energy structure characteristics of rich coal, poor oil and little gas in China. The traditional acetylene hydrochlorination process is to load HgCl on activated carbon 2 As a catalyst. However, mercury is highly volatile and toxic and can easily pose a hazard to the environment and human health. Since 2013, there have been 140 countries signed the Water industry Commission and call for mercury ban globally in 2025. Therefore, the development of a new mercury-free catalyst with low cost, high activity and high stability has become the most urgent and arduous task of vinyl chloride industry.
In recent decades, a series of mercury-free catalysts, namely acetylene hydrochlorination activity, are researched and mainly classified into three types: noble metal catalysts, non-noble metal catalysts, metal-free catalysts. At present, noble metal catalysts are mainly focused on the research and development of gold-based and ruthenium-based catalysts. Hutching et al found that there was a relatively significant positive correlation between the catalytic activity of the metal ions and the corresponding standard electrode potential, and predicted that Au had a relatively high catalytic performance. Furthermore, hutching (J.Am. Chem.Soc.2015,137, 14548-14557) developed Na 3 Au(S 2 O 3 ) 2 Supported catalysts (Au loading 0.1 wt%) and commercial production of the catalysts was achieved with Johnson-Mattey. The factory line of the catalyst also achieves the yield of 1000kgVCM/kg catalyst, the testing time is above 4500h, the conversion rate is always maintained above 90%, and the selectivity is above 99%. From the perspective of reaction process, the Au-based catalyst can be used as an excellent option for replacing a mercury catalyst, provides a feasible scheme, and has potential application value.
Although gold-based catalysts exhibit excellent catalytic activity and stability, there still exist significant problems such as: high cost, rare reserves, large recycling difficulty and the like. The ruthenium-based catalyst is low in price, green and efficient, and becomes a research hotspot of researchers in recent years. For example, patent CN107803222.A invented a supported ruthenium complex catalyst (ruthenium loading 0.3%). The catalyst is prepared by matching polypyridine compound with ruthenium, adding metal auxiliary agent and ionic liquid for stabilizing active component, and the catalyst has the temperature of 160 ℃, the pressure of 0.1MPa and V (HCl)/V (C) 2 H 2 ) =1.0/1, and the space velocity of acetylene is 50h -1 . At the initial stage of the reaction, the conversion of acetylene was 99.5% and the selectivity of vinyl chloride was 99.94%. The addition of the complex and the ionic liquid is favorable for improving the stability of the ruthenium-based catalyst, simultaneously reduces the loading amount of ruthenium and saves the cost, but the process is too complex and the acetylene space velocity is lower.
The patent CN109331869.B discloses a low content ruthenium-based catalyst for acetylene hydrochlorination, which takes oxalic acid as an auxiliary agent, the loading capacity of ruthenium is 0.25wt%,in V (HCl)/V (C) 2 H 2 )＝1.15，T＝170℃，GHSV(C 2 H 2 )＝180h -1 Performance testing experiments were performed under the conditions. The test results found that 0.25% Ru/AC had an acetylene conversion of 58.8%, all ruthenium-based catalysts modified with oxalic acid had higher activity than 0.25% Ru/AC catalyst, where 0.25% Ru-15/AC catalyst showed the best performance, with an acetylene conversion of 80.9%, 22.1% higher than the unmodified catalyst, 0.25 Ru/AC. The catalyst has low content, effectively saves the cost, but has low space velocity and low acetylene conversion rate.
The patent CN 113058594A discloses a ruthenium-based catalyst, which is prepared by wrapping a precursor with polymers such as polydopamine, polyethyleneimine and the like and calcining at 100-300 ℃. The catalyst has a loading of 1wt%, at T =180 ℃, C 2 H 2 (GHSV)＝180h -1 、 C 2 H 2 Under the reaction condition of/HCl = 1.15, the conversion rate of acetylene reaches 98.17%, the selectivity reaches 99.74%, and the catalyst contains a Ru-N structure, so that an active component Ru in the catalyst is more stable and is not easy to run off. However, the catalyst has high loading capacity of ruthenium and high cost.
Disclosure of Invention
The technical problem solved by the invention is as follows: provides a method for using a low-content ruthenium-based catalyst in the reaction of preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed. The invention uses an incipient wetness impregnation method, prepares a catalyst with low ruthenium content, high activity and better stability by adding 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride ligand, adjusting the molar ratio of the ligand to ruthenium to be 4, stirring for 5h and the like, and the loading amount of ruthenium is 0.3 percent, and the airspeed of reaction gas is 170h -1 ， V (C2H2) /V (HCl) 1.15, under the condition that the reaction temperature is 180 ℃, the acetylene conversion rate can reach 93.2%, the selectivity of chloroethylene is more than 99%, and a unique and effective solution is provided for industrially producing chloroethylene with low cost and high efficiency.
In order to solve the technical problem of the invention, the technical scheme is as follows: a method for using a low-content ruthenium-based catalyst in a reaction for preparing vinyl chloride by fixed bed acetylene hydrochlorination comprises the following steps:
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99 percent) solid is dissolved in 10ml of distilled water, oscillated and ultrasonically treated, and the solution is fixed into a 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor, ru:2.6935mg/ml;
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 Dispersing in O, adding 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride at room temperature by a magnetic stirrer at 350rpm, stirring at room temperature, covering a beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature for 350rpm for 5h;
(3) Preparing a catalyst by an impregnation method: 1.2g of activated carbon is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) Putting the ground catalyst in a forced air drying oven for drying for 12-24h;
(5) The prepared ruthenium-based catalyst is used for the reaction of preparing chloroethylene by fixed bed acetylene hydrochlorination.
Preferably, step (1) uses distilled water as solvent, and the appropriate amount of ruthenium trichloride (RuCl) is added at room temperature 3 Not less than 99%) dissolved in distilled water, shaking for 10min with a mixing instrument, and performing ultrasonic treatment for 30min to obtain RuCl 3 The mother liquor of (2.69356 mg/ml) is sealed, shielded from light and stored at low temperature.
Preferably, the ligand in step (2) is 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride.
Preferably, the ligand and the ruthenium precursor are reacted in the step (2) for 5h.
Preferably, the molar ratio of ligand to ruthenium in step (2) is 4.
Preferably, the step (3) is one of non-pretreated wood activated carbon, coconut shell activated carbon and coal activated carbon.
Preferably, in the step (3), the activated carbon is in the shape of column, powder or sheet, the particle size is 200 meshes, and the specific surface area is 800-1500, preferably 1200-1500.
Preferably, the ratio of the impregnation liquid to the carrier is adjusted as follows: the carrier and RuCl in the step (3) 3 The solution should be guaranteed in the ratio carrier/g: solution/ml =0.5.
Preferably, the catalyst ground in step (3) should ensure smooth surface, and then dried in a 90 ℃ forced air drying oven.
Preferably, the step (5) is specifically as follows:
(1) Filling a catalyst: padding a layer of quartz cotton with the thickness of 10mm at the middle position of a quartz reaction tube with the diameter of 10mm, adding a catalyst into the reaction tube and ensuring the catalyst to be flat, and then padding a layer of quartz cotton with the thickness of 10 mm;
(2) Before reaction: the whole pipeline takes 20mL min -1 N of (A) 2 Purging with flow rate for 60min to remove air and water in the system, and simultaneously controlling the temperature, raising to 150 deg.C at 5 deg.C/min and maintaining for 30min, and raising to 180 deg.C at 5 deg.C/min; then, hydrogen chloride was introduced at a flow rate of V =20mL/min and maintained for 30min, followed by V (C) 2 H 2 ) Introducing reaction gas at a flow rate of =16mL/min and V (HCl) =16.8mL/min, keeping for 10min, ensuring that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride, and then introducing V (C) 2 H 2 ) The ratio of/V (HCl) = 1.15 decreases the reaction gas flow rate, and detection is started after ten minutes of holding at the reaction flow rate;
(3) After the reaction: the gas phase product was first freed of excess HCl by passing through an absorption flask containing NaOH solution and then analyzed on-line by gas chromatography (GC-9790 II) to evaluate the acetylene conversion and selectivity to VCM.
The invention has the following beneficial effects:
the invention provides a preparation method of a low-content ruthenium-based catalyst, which greatly reduces the preparation cost, is simpler to operate and can be expanded compared with other methods. The technical scheme adopted by the invention for solving the technical problem is as follows: 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride is used as a ligand, the reaction time and the molar ratio of the ligand and ruthenium are changed, water is selected as a solvent, the ratio between the solvent and a carrier is determined, the content of Ru in the catalyst is greatly reduced, and the low-content ruthenium-based catalyst is prepared. The production cost is effectively saved; the catalyst prepared by the method has excellent catalytic performance on acetylene hydrochlorination and has potential industrial application value.
(1) Specifically, the invention provides a ruthenium complex catalyst for hydrochlorination of acetylene, which takes active carbon as a catalyst carrier and loads RuCl 3 And a ligand. Screening the ligand 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, tetrabutylammonium chloride, pyridine carboxylic acid, vitamin b1, ethylene diamine tetraacetic acid, 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium chloride in the step (2) through a large number of experiments; the ligand is preferably 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride
(2) The ligands used in the present invention: 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium chloride is selected as a ligand. Under the same condition, the ligand can stabilize the electronic environment of high-valence ruthenium so as to stabilize the active center, and can improve the dispersion of ruthenium, improve the catalytic activity and reduce the inactivation rate. Compared with the prior art: firstly, the selected ligand is non-toxic and harmless, and the price is low; secondly, the ligand of the invention has small usage amount and low cost; in addition, the method is simple to operate, green and environment-friendly, and reduces energy consumption. In a word, the method provided by the invention has the advantages that the catalytic activity and stability of the catalyst are obviously improved by adding the ligand, the excellent catalytic activity can be shown by the synthesis method in the technology, and the method has potential industrial application value.
(3) According to the invention, in the step (2), the reaction time of the ligand and ruthenium is kept to be 5h, so that the ruthenium complex is obtained, and the performance of the catalyst is better than that of the catalyst prepared by 1h, 3h and 7h.
(4) In the step (2), the reaction molar ratio of the ligand to the ruthenium is kept to be 4:1, obtaining a ruthenium complex, wherein the performance of the catalyst is better than that of a catalyst prepared by mixing 1.
(5) In step (3) of the present invention, the catalyst was ground to a smooth state in a clockwise direction within 10min, and then dried in a 90 ℃ forced air drying oven. The grinding is carried out in a short time till the catalyst is smooth, the contact between the catalyst and air at normal temperature can be reduced, and the loading rate and the dispersity of the active components are improved.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a graph of acetylene conversion versus reaction time for various ligand catalysts.
FIG. 2 is a graph of selectivity versus reaction time for various ligand catalysts.
FIG. 3 is a graph of acetylene conversion versus reaction time for catalysts with different molar ratios of ruthenium to ligand.
FIG. 4 is a graph of selectivity versus reaction time for catalysts with different molar ratios of ruthenium to ligand.
FIG. 5 is a graph of acetylene conversion versus reaction time for catalysts with different reaction times for the ligand and ruthenium.
FIG. 6 is a graph of selectivity versus reaction time for catalysts with different reaction times for the ligand and ruthenium.
Detailed Description
Example 1 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) was weighed 3 Not less than 99 percent) solid is dissolved in 10ml of distilled water, oscillated and ultrasonically treated, and the solution is fixed into a 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 48mg of tetrabutylammonium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature (350 rpm) for 5h.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% Ru-N1/AC (H) 2 O)。
(5) The method for using the low-content ruthenium-based catalyst in the reaction for preparing vinyl chloride by fixed bed acetylene hydrochlorination comprises the following steps:
1. loading a catalyst: padding a layer of quartz cotton with the thickness of 10mm at the middle position of a quartz reaction tube with the diameter of 10mm, adding 500mg of catalyst into the reaction tube and ensuring the catalyst to be flat, and then padding a layer of quartz cotton with the thickness of 10 mm;
2. before reaction: the whole pipeline is at 20mL min -1 N of (2) 2 Blowing at flow rate for 60min to remove air and water in the system, and simultaneously controlling the temperature to rise to 150 deg.C at 5 deg.C/min and keep for 30min, and then to rise to 180 deg.C at 5 deg.C/min; then, hydrogen chloride was introduced at a flow rate of V =20mL/min and maintained for 30min, followed by V (C) 2 H 2 ) Introducing reaction gas at a flow rate of =16mL/min and V (HCl) =16.8mL/min, keeping for 10min, ensuring that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride, and then introducing V (C) 2 H 2 ) The ratio/V (HCl) = 1.15 the reaction gas flow rate is reduced and detection is started after ten minutes at the reaction flow rate;
3. after the reaction: the gas phase product was first freed of excess HCl by passing through an absorption flask containing NaOH solution and then analyzed on-line by gas chromatography (GC-9790 II) to evaluate the acetylene conversion and selectivity to VCM.
Example 2 catalyst preparation
(2) 1.37ml of the mother liquor was dissolved in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 42mg of ethylenediamine tetraacetic acid, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature (350 rpm) for 5h.
(3) And preparing the catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N2/AC.
The procedure for the use of a low ruthenium-based catalyst in the fixed-bed hydrochlorination of acetylene to vinyl chloride is as in example 1 and will not be repeated.
Comparative example 3 catalyst preparation
(2) 1.37ml of the mother liquor was dissolved in 1ml of H 2 O, then 1.8mg of 2-picolinic acid was added thereto and stirred at room temperature with a magnetic stirrer (350 rpm) at room temperature, the beaker was covered with a sealing film and then covered with foil paper, and stirred at room temperature (350 rpm) for 5 hours.
(3) And preparing the catalyst by an impregnation method: spreading 1.2g of coconut shell powdered activated carbon in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a forced air drying oven for 12-24 h.
Catalyst designation ru-N3/AC%.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Example 4 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99%) solid is dissolved in 10ml distilled water, oscillated and ultrasonically treated, and the volume is determined to 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) 1.37ml of the mother liquor was dissolved in 1ml of H 2 O, then 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride is added into the mixture and stirred at room temperature in a magnetic stirrer (350 rpm), the beaker is covered by a sealing film and then covered by tinfoil paper, and the mixture is stirred at room temperature (350 rpm) for 5 hours.
(3) And preparing the catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (200 meshes, the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N4/AC.
(5) The method for using the low-content ruthenium-based catalyst in the reaction of preparing vinyl chloride by fixed bed acetylene hydrochlorination comprises the following steps:
1. loading a catalyst: padding a layer of quartz cotton with the thickness of 10mm at the middle position of a quartz reaction tube with the diameter of 10mm, adding 500mg of catalyst into the reaction tube and ensuring the catalyst to be flat, and then padding a layer of quartz cotton with the thickness of 10 mm;
2. before reaction: the whole pipeline takes 20mL min -1 N of (A) 2 Purging with flow rate for 60min to remove air and water in the system, and simultaneously controlling the temperature, raising to 150 deg.C at 5 deg.C/min and maintaining for 30min, and raising to 180 deg.C at 5 deg.C/min; then, hydrogen chloride was introduced at a flow rate of V =20mL/min and maintained for 30min, followed by V (C) 2 H 2 ) Introducing reaction gas at a flow rate of =16mL/min and V (HCl) =16.8mL/min, keeping for 10min, ensuring that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride, and then introducing V (C) 2 H 2 ) The ratio of/V (HCl) = 1.15 decreases the reaction gas flow rate, and detection is started after ten minutes of holding at the reaction flow rate;
3. after the reaction: the gas phase product was first passed through an absorption flask containing NaOH solution to remove excess HCl and then on-line analyzed by gas chromatography (GC-9790 ii) to evaluate acetylene conversion and selectivity to VCM.
EXAMPLE 4-1 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99 percent) solid is dissolved in 10ml of distilled water, oscillated and ultrasonically treated, and the solution is fixed into a 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 Dispersing in O, stirring with magnetic stirrer (350 rpm) at room temperature, adding 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with sealing film, and adding tinThe foil is covered and stirred (350 rpm) at room temperature for 1h.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% Ru-N4-1 h/AC.
The procedure for the use of a low ruthenium-based catalyst in the fixed-bed hydrochlorination of acetylene to vinyl chloride is as in example 1 and will not be repeated.
Example 4-2 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) was weighed 3 Not less than 99%) solid is dissolved in 10ml distilled water, oscillated and ultrasonically treated, and the volume is determined to 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, then 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride is added and stirred at room temperature in a magnetic stirrer (350 rpm), the beaker is covered with a sealing film and then covered with tinfoil paper, and the mixture is stirred at room temperature (350 rpm) for 3 hours.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% Ru-N4-3 h/AC.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Examples 4-3 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99 percent) solid is dissolved in 10ml of distilled water, oscillated and ultrasonically treated, and the solution is fixed into a 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature (350 rpm) for 7h.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% Ru-N4-7 h/AC.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Examples 4-4 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99%) solid is dissolved in 10ml distilled water, oscillated and ultrasonically treated, and the volume is determined to 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, then, 15mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added thereto and stirred at room temperature with a magnetic stirrer (350 rpm), the beaker was covered with a sealing film and then covered with a tinfoil paper, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N4- (1)/AC.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Examples 4-5 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99%) solid is dissolved in 10ml distilled water, oscillated and ultrasonically treated, and the volume is determined to 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 30.27mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature (350 rpm) for 5h.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N4- (1)/AC.
The procedure for the use of a low ruthenium-based catalyst in the fixed-bed hydrochlorination of acetylene to vinyl chloride is as in example 1 and will not be repeated.
Examples 4-6 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99 percent) solid is dissolved in 10ml of distilled water, oscillated and ultrasonically treated, and the solution is fixed into a 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, then 45.41mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride was added and stirred at room temperature with a magnetic stirrer (350 rpm), the beaker was covered with a sealing film and then with tinfoil paper, and stirred at room temperature (350 rpm) for 5 hours.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N4- (1)/AC.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Examples 4-7 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) was weighed 3 Not less than 99%) solid is dissolved in 10ml distilled water, oscillated and ultrasonically treated, and the volume is determined to 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 75.68mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil, and stirring at room temperature (350 rpm) for 5h.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N4- (1).
The procedure for the use of a low ruthenium-based catalyst in the fixed-bed hydrochlorination of acetylene to vinyl chloride is as in example 1 and will not be repeated.
Examples 4-8 catalyst preparation
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99 percent) solid is dissolved in 10ml of distilled water, oscillated and ultrasonically treated, and the solution is fixed into a 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor (Ru: 2.6935 mg/ml).
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature (350 rpm) for 5h.
(3) Preparing a catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% Ru-N4/AC-II.
(5) The method for using the low-content ruthenium-based catalyst in the reaction for preparing vinyl chloride by fixed bed acetylene hydrochlorination comprises the following steps:
1. loading a catalyst: padding a layer of quartz cotton with the thickness of 10mm at the middle position of a quartz reaction tube with the diameter of 10mm, adding 1.00g of catalyst into the reaction tube and ensuring the catalyst to be flat, and then padding a layer of quartz cotton with the thickness of 10 mm;
2. before reaction: the whole pipeline is at 20mL min -1 N of (A) 2 Blowing at flow rate for 60min to remove air and water in the system, and simultaneously controlling the temperature to rise to 150 deg.C at 5 deg.C/min and keep for 30min, and then to rise to 180 deg.C at 5 deg.C/min; then, at V =20Hydrogen chloride was introduced at a flow rate of mL/min for 30min, followed by V (C) 2 H 2 ) Introducing reaction gas at a flow rate of =16mL/min and V (HCl) =16.8mL/min, keeping for 10min, ensuring that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride, and then introducing V (C) 2 H 2 ) The ratio of/V (HCl) = 1.15 decreases the reaction gas flow rate, and detection is started after ten minutes of holding at the reaction flow rate;
3. after the reaction: the gas phase product was first freed of excess HCl by passing through an absorption flask containing NaOH solution and then analyzed on-line by gas chromatography (GC-9790 II) to evaluate the acetylene conversion and selectivity to VCM.
Example 5 catalyst preparation
(2) 1.37ml of the mother liquor was dissolved in 1ml of H 2 O, magnetic stirrer (350 rpm) at room temperature, then 48mg Vb1 was added and stirred at room temperature, the beaker was covered with a sealing film and then covered with tinfoil paper, and stirred at room temperature (350 rpm) for 5 hours.
(3) And preparing the catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N5/AC.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Example 6 catalyst preparation
(2) 1.37ml of the mother liquor was dissolved in 1ml of H 2 O, stirring at room temperature with a magnetic stirrer (350 rpm), adding 49mg of 1, 3-bis (2, 4, 6-trimethylphenyl) imidazolium chloride, stirring at room temperature, covering the beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature (350 rpm) for 5h.
(3) And preparing the catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And (3) drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h.
The catalyst was named 0.3% ru-N6/AC.
The procedure for the fixed bed hydrochlorination of acetylene to vinyl chloride using a low ruthenium-based catalyst is the same as in example 1 and will not be repeated.
Comparative example 1 preparation of catalyst
(2) 1.37ml of the mother liquor was dissolved in 1ml of H 2 O, the beaker was covered with a sealing film and then with tinfoil paper using a magnetic stirrer (350 rpm) at room temperature, and stirred (350 rpm) at room temperature for 5 hours.
(3) And preparing the catalyst by an impregnation method: 1.2g of coconut shell powdered activated carbon (> 200 meshes, and the specific surface area is about 1200) is flatly laid in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) And drying the ground catalyst in a 90 ℃ forced air drying oven for 12-24 h. The catalyst was named 0.3% ru/AC.
TABLE 1 acetylene hydrochlorination Activity test
TABLE 2 acetylene hydrochlorination stability test
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the claims of the invention.
Claims (10)
1. A method for using a low-content ruthenium-based catalyst in a reaction of preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed is characterized in that the preparation method of the low-content ruthenium-based catalyst comprises the following steps:
(1) Preparing a precursor solution: first, 0.2764g of ruthenium trichloride (RuCl) is weighed 3 Not less than 99%) solid is dissolved in 10ml distilled water, oscillated and ultrasonically treated, and the volume is determined to 50ml brown round-bottom flask to obtain RuCl 3 Mother liquor, ru:2.6935mg/ml;
(2) Dissolving 1.37ml of the mother liquor in 1ml of H 2 Dispersing in O, adding 60mg1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride at 350rpm of a magnetic stirrer at room temperature, stirring at room temperature, covering a beaker with a sealing film, covering with tinfoil paper, and stirring at room temperature for 350rpm for 5h;
(3) Preparing a catalyst by an impregnation method: spreading 1.2g of activated carbon in a mortar; uniformly dropwise adding the solution prepared in the step (2) on an activated carbon carrier, and fully grinding the catalyst along the clockwise direction until the surface is smooth, wherein the ratio of ruthenium in the catalyst: the mass ratio of the carrier is 0.3:99.70.
(4) Putting the ground catalyst in a forced air drying oven for drying for 12-24h;
(5) The prepared ruthenium-based catalyst is used for the reaction of preparing vinyl chloride by fixed bed acetylene hydrochlorination.
2. The method for using the low content ruthenium-based catalyst in the reaction of preparing vinyl chloride by fixed bed acetylene hydrochlorination according to claim 1, characterized in that: step (1) using distilled water as solvent, adding proper amount of ruthenium trichloride (RuCl) at room temperature 3 Not less than 99%) dissolved in distilled water, shaking for 10min with a mixing instrument, and performing ultrasonic treatment for 30min to obtain RuCl 3 The mother liquor of (2.69356 mg/ml) is sealed, shielded from light and stored at low temperature.
3. The method for using the low content ruthenium-based catalyst in the reaction of preparing vinyl chloride by fixed bed acetylene hydrochlorination according to claim 1, characterized in that: the ligand in the step (2) is 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride.
4. The method for the reaction of preparing vinyl chloride by the hydrochlorination of acetylene with low content of ruthenium-based catalyst according to claim 1, wherein the ligand is reacted with the ruthenium precursor for 5 hours in the step (2).
5. The method for preparing vinyl chloride through fixed bed acetylene hydrochlorination by using the low-content ruthenium-based catalyst according to claim 1, wherein the molar ratio of the ligand to the ruthenium in the step (2) is 4.
6. The method for preparing vinyl chloride through fixed bed acetylene hydrochlorination by using the low-content ruthenium-based catalyst according to claim 1, wherein the step (3) is one of non-pretreated wood activated carbon, coconut shell activated carbon and coal activated carbon.
7. The method for preparing vinyl chloride through fixed bed acetylene hydrochlorination by using the ruthenium-based catalyst with low content as claimed in claim 1, wherein in the step (3), the activated carbon is in the shape of column, powder or sheet, has the particle size of 200 meshes, and has the specific surface area of 800-1500, preferably 1200-1500.
8. The method for preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed by using the low-content ruthenium-based catalyst according to claim 1, which is characterized by adjusting the ratio of the impregnation liquid to the carrier: the carrier and RuCl in the step (3) 3 The solution should be guaranteed in the ratio carrier/g: solution/ml =0.5.
9. The method for preparing vinyl chloride through fixed bed hydrochlorination of acetylene according to claim 1, wherein the catalyst ground in step (3) is dried in a 90 ℃ forced air drying oven after the surface is smooth.
10. The method for using the low-content ruthenium-based catalyst in the reaction for preparing vinyl chloride by fixed bed acetylene hydrochlorination according to claim 1, which is characterized in that: the step (5) is specifically as follows:
(1) Loading a catalyst: padding a layer of quartz cotton with the thickness of 10mm at the middle position of a quartz reaction tube with the diameter of 10mm, adding a catalyst into the reaction tube and ensuring the catalyst to be flat, and then padding a layer of quartz cotton with the thickness of 10 mm;
(2) Before reaction: the whole pipeline takes 20mL min -1 N of (A) 2 Blowing at flow rate for 60min to remove air and water in the system, and simultaneously controlling the temperature to rise to 150 deg.C at 5 deg.C/min and keep for 30min, and then to rise to 180 deg.C at 5 deg.C/min; then, hydrogen chloride was introduced at a flow rate of V =20mL/min and maintained for 30min, followed by V (C) 2 H 2 ) Introducing reaction gas at a flow rate of =16mL/min and V (HCl) =16.8mL/min, keeping for 10min, ensuring that the catalyst is in a gas atmosphere of acetylene and hydrogen chloride, and then introducing V (C) 2 H 2 ) The ratio of/V (HCl) = 1.15 decreases the reaction gas flow rate, and detection is started after ten minutes of holding at the reaction flow rate;
(3) After the reaction: the gas phase product was first freed of excess HCl by passing through an absorption flask containing NaOH solution and then analyzed on-line by gas chromatography (GC-9790 II) to evaluate the acetylene conversion and selectivity to VCM.
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| CN101716528A (en) * | 2009-10-30 | 2010-06-02 | 于志勇 | Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof |
| WO2012113778A1 (en) * | 2011-02-24 | 2012-08-30 | Solvay Sa | Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
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