CN112452340B - Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof - Google Patents
Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof Download PDFInfo
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- CN112452340B CN112452340B CN202011320829.1A CN202011320829A CN112452340B CN 112452340 B CN112452340 B CN 112452340B CN 202011320829 A CN202011320829 A CN 202011320829A CN 112452340 B CN112452340 B CN 112452340B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 13
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000001294 propane Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 8
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 101710134784 Agnoprotein Proteins 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth 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
- B01J23/38—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
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a preparation method of a catalyst, in particular to a catalyst for preparing propylene by selective hydrogenation of propyne, a preparation method and application thereof, and belongs to the technical field of organic chemistry. A catalyst for preparing propylene by selective hydrogenation of propyne is a supported noble metal catalyst, which uses gamma-Al 2 O 3 As a main component of the catalyst carrier, mgO is attached to the surface of the carrier to form a composite metal oxide carrier; one or more noble metals Ru, pd and Pt are used as main active components, and the content of the noble metals is 0.1-3.0wt% based on the weight content of the final catalyst; one or more than one of non-noble metals Cu, zn and Co is used as auxiliary metal to modify noble metal, and the molar ratio of the noble metal to the non-noble metal is 1:1-10.
Description
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a catalyst for preparing propylene by selective hydrogenation of propyne, a preparation method and application thereof, and belongs to the technical field of organic chemistry.
Background
Propylene is the second largest basic chemical raw material of ethylene, the largest amount of propylene is polypropylene, and in addition, propylene can be used for producing acrylonitrile, isopropanol, phenol, acetone, butanol, octanol, acrylic acid and esters thereof, and propylene oxide, propylene glycol, epichlorohydrin, synthetic glycerol and the like. The main process route for producing propylene at present comprises the following steps: steam cracking process, catalytic cracking process, coal to olefins process, olefin disproportionation process and propane dehydrogenation process. Along with the trend of maturity of the propane dehydrogenation process technology and the large-scale application of the emerging energy shale gas, the process for preparing propylene by the propane dehydrogenation has strong advantages, causes the company at home and abroad to invest in disputes, and becomes a hot spot for the recent development of petrochemical industry.
Catalytic dehydrogenation of propane to produce propylene is an endothermic reaction that requires a large amount of heat to be supplied, often accompanied by excessive dehydrogenation of propane to produce propyne (MA) and Propadiene (PD). MAPD is a precursor of catalytic dehydrogenation catalyst poison coke, and is extremely easy to cause the phenomenon of coking of the catalyst and blockage of an internal network and an external network of the reactor when the circulating propane enters the reactor again; MAPD affects propylene polymerization when the product propylene enters downstream polypropylene units, resulting in reject polypropylene products. The boiling point of MAPD is very close to that of propane and propylene, and is difficult to remove from the cryogenic separation unit and the fractionating tower unit, so that hydrogenation equipment (SHP) is needed to be added after the liquid phase product is discharged from the cryogenic separation unit, so that trace MAPD (about 100 ppm) in the liquid phase product is hydrogenated and converted into propylene, and the product yield is increased. The most widely used catalyst in the current SHP units of the propane dehydrogenation process is Pd/Al 2 O 3 The catalyst shows good selective hydrogenation performance, but the catalyst has limited catalytic performance, and can not well convert MAPD into propylene when MAPD exceeds standard for abnormal process conditions; if the liquid hourly space velocity is selectively reduced to increase the conversion rate of MAPD, propylene is easy to generate propane through catalytic hydrogenation, and product loss is caused.
Disclosure of Invention
The invention aims to provide a catalyst for preparing propylene by selective hydrogenation of propyne, which solves the problems of narrow reaction range, easy carbon deposition of the catalyst, poor selectivity of the catalyst and the like in the prior art.
The technical scheme adopted for solving the technical problems is as follows:
a catalyst for preparing propylene by selective hydrogenation of propyne is a supported noble metal catalyst
By gamma-Al 2 O 3 As a main component of the catalyst carrier, mgO is attached to the surface of the carrier to form a composite metal oxide carrier;
one or more noble metals Ru, pd and Pt are used as main active components, and the content of the noble metals is 0.1-3.0wt% based on the weight content of the final catalyst;
one or more than one of non-noble metals Cu, zn and Co is used as auxiliary metal to modify noble metal, and the molar ratio of the noble metal to the non-noble metal is 1:1-10.
The invention uses noble metals Ru, pd and Pt as main active components, uses a composite metal oxide as a carrier, and prepares the selective hydrogenation catalyst with low noble metal loading, high dispersity and high mechanical strength by an isovolumetric impregnation method. The catalyst is used for preparing propylene by MAPD selective hydrogenation, has high conversion rate and selectivity, and has high industrial application value.
The supported noble metal catalyst provided by the invention can effectively solve the defects of narrow reaction range, easy carbon deposit, poor catalyst selectivity and the like of a catalytic hydrogenation catalyst in the existing propylene production process SHP device by propane dehydrogenation.
Preferably, the MgO loading is 5 to 30wt%. Further preferably, the catalyst carrier has more weak acid sites within the loading range, which is more favorable for the activation of hydrogen molecules, the timely desorption of propylene and the like.
Preferably, the MgO precursor is a 10-60 wt% aqueous solution of magnesium nitrate. Further preferred is 30wt% magnesium nitrate aqueous solution.
A method for preparing a catalyst for the selective hydrogenation of propyne to propylene, the method comprising the steps of:
（1）γ-Al 2 O 3 drying at 80-150 ℃ for 10-20 h, and dripping the MgO precursor aqueous solution into the dried gamma-Al under stirring 2 O 3 Dipping, dehydrating and drying,Roasting to obtain a composite oxide carrier;
(2) The noble metal salt and the non-noble metal salt are dissolved in a dilute hydrochloric acid aqueous solution to obtain a mixed metal impregnation solution;
(3) Slowly dripping the mixed metal impregnating solution in the step (2) onto the composite oxide carrier in the step (1) under stirring, and carrying out impregnation, washing, separation, drying and roasting to obtain a catalyst precursor;
(4) And (3) reducing the noble metal oxide in the catalyst precursor in the step (3) into a metal simple substance by using hydrogen so that the catalyst has catalytic activity and performs catalytic reaction. The catalyst activation in the step (4) is generally carried out in a tubular fixed bed during the reaction for preparing propylene by selectively hydrogenating propyne. The concentration of the diluted hydrochloric acid is generally about 1.0mmol/L.
Preferably, in the step (1) and the step (3), the soaking time is 12-24 hours, the drying temperature is 80-120 ℃, the drying time is 6-12 hours, and the roasting conditions are as follows: rate of temperature rise: and (3) 5-12 ℃/min, heating to 450-750 ℃ from room temperature, and keeping the temperature for 2-6 h.
Preferably, in the step (3), the washing step is specifically: the catalyst solution was neutral and chloride free by washing with deionized water.
Use of the catalyst of claim 1 for the selective catalytic hydrogenation of propyne to propylene.
Preferably, the liquid hourly space velocity is 20+/-5 h -1 And the dosage of the catalyst is 100-1000 mg. Most preferably 300mg (when the liquid hourly space velocity is 20.+ -. 2h -1 When).
Preferably, the method comprises the steps of:
loading the catalyst into a tubular fixed bed reactor, filling a constant temperature area in the middle of the tubular fixed bed with quantitative catalyst, filling the rest space with quartz sand, connecting the fixed pipes completely and hermetically, starting programmed temperature rise, firstly raising the temperature to 300-600 ℃ at a temperature rise rate of 5+/-1 ℃/min, keeping the temperature for 2-5 hours, activating the catalyst under the hydrogen pressure of 0.5-3 MPa, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; the mixture of propyne and cyclohexane is then fed into a tubular fixed bed reactor for hydrogenation with hydrogen.
Preferably, the hydrogenation reaction conditions are: reaction temperature: the temperature of 30-80 ℃ and the hydrogen pressure are as follows: 0.5-3 MPa, the molar concentration of propyne in cyclohexane is 0.01-1.0%, the molar ratio of hydrogen to propyne is 1.1-1.5, and the reaction Liquid Hourly Space Velocity (LHSV) is: 10-30 h -1 。
Compared with the prior art, the catalyst has the advantages that:
1. formed in the market as gamma-Al 2 O 3 The composite oxygen compound carrier synthesized by the invention has more weak acid sites, is more favorable for dissociation of hydrocarbon single bonds, and promotes hydrogen molecule activation, electron transfer and propylene desorption; dispersing the catalyst active metal; reducing carbon deposit on the surface of the catalyst.
2. The non-noble metal Co has an important modification effect on noble metal Pd, can change the electronic cloud state, dispersity and microstructure of the metal Pd, promotes propylene desorption and improves propylene selectivity.
3. The catalyst provided by the invention has the advantages of high selective hydrogenation performance, high process fluctuation resistance, good stability, high mechanical strength and good industrial application prospect.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The reagents used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Since Propadiene (PD) is extremely unstable and difficult to prepare and use in a large amount in a laboratory, in the present invention, catalyst performance test evaluation was performed using propyne (MA) dissolved in cyclohexane as a reaction substrate model, and the molar concentration of the propyne reactant is: 0.01 to 1.0%.
In the catalyst of the present invention, the catalyst carrier: gamma-Al 2 O 3 The product can be commercially available or prepared and synthesized in a laboratory according to the prior art.
The concentration of the dilute hydrochloric acid solution described in the examples below was 1.0mmol/L.
Example 1
The preparation method of the catalyst for preparing propylene by selectively hydrogenating propyne comprises the following specific steps:
1. accurately weighing 5g of dried gamma-Al 2 O 3 Placing the particles in a 250mL beaker (about 30 meshes), slowly adding a certain amount of 30wt% magnesium nitrate solution into a carrier beaker while stirring according to the MgO load of 10wt%, immersing and aging for 24 hours, placing the beaker in an oven at 120 ℃ for constant temperature drying for 12 hours, finally transferring the carrier precursor into the crucible, placing the crucible in a muffle furnace for roasting, heating to 650 ℃ at a heating rate of 5 ℃/min from room temperature, keeping the temperature constant for 4 hours, cooling to room temperature to obtain the composite catalyst carrier, and placing the composite catalyst carrier in a closed dryer for standby.
2. Accurately weighing 3g of composite catalyst carrier, and placing in a 100mL beaker; the loading of palladium and cobalt is as follows: 0.3wt% of solid PdCl is accurately weighed 2 And CoCl 2 ·6H 2 O (molar ratio of metal platinum to metal cobalt is 1:5) is dissolved in dilute hydrochloric acid solution, ultrasonic dissolution is carried out in an ultrasonic instrument for 30min, then 3g of composite catalyst carrier is slowly added into a beaker, stirring is carried out while adding, isovolumetric dipping and aging are carried out for 24h, then suction filtration is carried out, deionized water is used for washing until the solution is neutral, and AgNO is used for preparing the catalyst carrier 3 Detecting no white precipitate in the washing liquid, drying the solution in a beaker at a constant temperature of 120 ℃ for 12 hours, transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, and rising the temperature from room temperature to the temperature at a heating rate of 5 ℃/minKeeping the temperature at 650 ℃ for 2 hours, cooling to room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for standby.
Accurately weighing 0.3g of catalyst to be activated, tabletting, crushing, placing into a constant temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting a fixed pipe completely and hermetically, starting temperature programming, heating to 300 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, activating the prepared catalyst under the hydrogen pressure of 1MPa, completely reducing the catalyst, and cooling the tubular fixed bed reactor to room temperature; at the reaction temperature: the hydrogen pressure at 50 ℃ is: the molar concentration of propyne in cyclohexane at 2MPa is: 0.1 percent, the molar ratio of the hydrogen injection amount to propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) of: 20h -1 And (3) conveying the mixture of propyne and cyclohexane into a tubular fixed bed reactor through a high-pressure constant-flow micropump to react with hydrogen, collecting liquid products at intervals of 1h after the set reaction conditions are reached, analyzing the liquid products by using a gas chromatograph, sampling the liquid products in parallel for multiple times, taking the average value of the liquid products, and calculating the conversion rate and the selectivity under the current reaction working condition.
Example 2
With metallic ruthenium (RuCl) 3 ) The other steps are the same as in example 1, except that metallic palladium is used instead of metallic palladium in example 1.
Example 3
With platinum metal (K) 2 PtCl 6 ) The other steps are the same as in example 1, except that metallic palladium is used instead of metallic palladium in example 1.
Example 4
With metallic copper (CuCl) 2 ·2H 2 O) instead of the metallic cobalt of example 1, the other steps are the same as in example 1.
Example 5
With metallic zinc (ZnCl) 2 ) The other steps were the same as in example 1, except for replacing the metallic cobalt in example 1.
Example 6
The molar ratio of platinum to cobalt was 1:1 instead of 1:5 for example 1, and the other steps were the same as in example 1.
Example 7
The molar ratio of platinum to cobalt was 1:10 instead of 1:5 for example 1, and the other steps were the same as in example 1.
Example 8
The MgO loading of 20wt% was used instead of 10wt% of MgO in example 1, and the other steps were the same as in example 1.
Example 9
The MgO loading of 30wt% was used instead of 10wt% of MgO loading in example 1, and the other steps were the same as in example 1.
Example 10
The molar concentration of propyne in cyclohexane was 0.01% instead of 0.1% in example 1, the other steps being the same as in example 1.
Example 11
The molar concentration of propyne in cyclohexane was 1% instead of 0.1% in example 1, and the other steps were the same as in example 1.
Comparative example 1
Accurately weighing 3g of dried gamma-Al 2 O 3 (particles are about 30 mesh) and placed in a 100mL beaker; the loading of palladium and cobalt is as follows: 0.3wt% of solid PdCl is accurately weighed 2 And CoCl 2 ·6H 2 O (molar ratio of metal platinum to metal cobalt is 1:5) is dissolved in dilute hydrochloric acid solution, ultrasonic dissolution is carried out in an ultrasonic instrument for 30min, then 3g of composite catalyst carrier is slowly added into a beaker, stirring is carried out while adding, isovolumetric dipping and aging are carried out for 24h, then suction filtration is carried out, deionized water is used for washing until the solution is neutral, and AgNO is used for preparing the catalyst carrier 3 And detecting no white precipitate in the washing liquid, placing the beaker in an oven at a constant temperature of 120 ℃ for drying for 12 hours, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, heating to 650 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, cooling to the room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for standby.
Accurately weighing 0.3g of catalyst to be activated, tabletting, crushing, and placing into a tubular fixed bed reactorIn the warm area, the rest space is filled with quartz sand, after the fixed pipe is connected completely and airtight, the temperature programming is started, the temperature is raised to 300 ℃ at the temperature raising rate of 5 ℃/min, the temperature is kept constant for 3 hours, the hydrogen pressure is 1MPa, the prepared catalyst is subjected to activation treatment, and after the catalyst is completely reduced, the tubular fixed bed reactor is cooled to room temperature; at the reaction temperature: the hydrogen pressure at 50 ℃ is: the molar concentration of propyne in cyclohexane at 2MPa is: 0.1 percent, the molar ratio of the hydrogen injection amount to propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) of: 20h -1 And (3) conveying the mixture of propyne and cyclohexane into a tubular fixed bed reactor through a high-pressure constant-flow micropump to react with hydrogen, and collecting liquid products at intervals of 1h after the set reaction conditions are reached, and sampling and analyzing.
Comparative example 2
Accurately weighing 3g of dried MgO (commercial, chemical grade), and placing in a 100mL beaker; the loading of palladium and cobalt is as follows: 0.3wt% of solid PdCl is accurately weighed 2 And CoCl 2 ·6H 2 O (molar ratio of metal platinum to metal cobalt is 1:5) is dissolved in dilute hydrochloric acid solution, ultrasonic dissolution is carried out in an ultrasonic instrument for 30min, then 3g of composite catalyst carrier is slowly added into a beaker, stirring is carried out while adding, isovolumetric dipping and aging are carried out for 24h, then suction filtration is carried out, deionized water is used for washing until the solution is neutral, and AgNO is used for preparing the catalyst carrier 3 And detecting no white precipitate in the washing liquid, placing the beaker in an oven at a constant temperature of 120 ℃ for drying for 12 hours, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, heating to 650 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, cooling to the room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for standby.
Accurately weighing 0.3g of catalyst to be activated, tabletting, crushing, placing into a constant temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting a fixed pipe completely and hermetically, starting temperature programming, heating to 300 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, activating the prepared catalyst under the hydrogen pressure of 1MPa, completely reducing the catalyst, and cooling the tubular fixed bed reactor to room temperature; in the opposite directionThe temperature should be: the hydrogen pressure at 50 ℃ is: the molar concentration of propyne in cyclohexane at 2MPa is: 0.1 percent, the molar ratio of the hydrogen injection amount to propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) of: 20h -1 And (3) conveying the mixture of propyne and cyclohexane into a tubular fixed bed reactor through a high-pressure constant-flow micropump to react with hydrogen, and collecting liquid products at intervals of 1h after the set reaction conditions are reached, and sampling and analyzing.
Comparative example 3
Accurately weighing 5g of dried gamma-Al 2 O 3 (particles are 30 meshes or so) are placed in a 250mL beaker, and the loading amount of MgO is as follows: and (3) calculating 10 weight percent, weighing 30 weight percent magnesium nitrate solution with certain mass, slowly adding the solution into a carrier beaker while stirring, carrying out dipping and ageing for 24 hours, then placing the beaker into a baking oven at 120 ℃ for constant temperature drying for 12 hours, finally transferring a carrier precursor into a crucible, placing the crucible into a muffle furnace for baking, heating to 650 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature constant for 4 hours, cooling to room temperature to obtain a composite catalyst carrier, and placing the composite catalyst carrier into a closed dryer for standby.
Accurately weighing 3g of composite catalyst carrier, and placing in a 100mL beaker; the load of the metal palladium is as follows: 0.3wt% of solid PdCl is accurately weighed 2 Dissolving in dilute hydrochloric acid solution, ultrasonically dissolving in ultrasonic instrument for 30min, slowly adding 3g of composite catalyst carrier into beaker, stirring, soaking and aging for 24 hr under equal volume, vacuum filtering, washing with deionized water until the solution is neutral, and collecting the solution with AgNO 3 And detecting no white precipitate in the washing liquid, placing the beaker in an oven at a constant temperature of 120 ℃ for drying for 12 hours, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, heating to 650 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, cooling to the room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for standby.
Accurately weighing 0.3g of catalyst to be activated, tabletting, crushing, placing into a constant temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting the fixed tubes completely and air-tightly, starting programmed heating, heating to 300 ℃ at a heating rate of 5 ℃/min, and keeping constant temperature3h, the hydrogen pressure is 1MPa, the prepared catalyst is activated, and after the catalyst is completely reduced, the tubular fixed bed reactor is cooled to room temperature; at the reaction temperature: the hydrogen pressure at 50 ℃ is: the molar concentration of propyne in cyclohexane at 2MPa is: 0.1 percent, the molar ratio of the hydrogen injection amount to propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) of: 20h -1 And (3) conveying the mixture of propyne and cyclohexane into a tubular fixed bed reactor through a high-pressure constant-flow micropump to react with hydrogen, and collecting liquid products at intervals of 1h after the set reaction conditions are reached, and sampling and analyzing.
Performance testing
The liquid products of examples 1 to 11 and comparative examples 1 to 3 were subjected to qualitative and quantitative analysis by a gas chromatograph, and the conversion rate of propyne, the selectivity of propylene and the yield were calculated, and the results are shown in Table 1.
Table 1 results of the propyne hydrogenation reactions of examples 1 to 11 and comparative examples 1 to 3
| Sequence number | Propyne conversion/% | Propylene selectivity/% | Propylene yield/% |
| Example 1 | 99.6 | 87.2 | 86.9 |
| Example 2 | 85.1 | 70.8 | 60.3 |
| Example 3 | 99.8 | 82.4 | 82.2 |
| Example 4 | 97.0 | 83.1 | 80.6 |
| Example 5 | 98.2 | 78.7 | 77.3 |
| Example 6 | 99.5 | 81.5 | 81.1 |
| Example 7 | 90.7 | 88.4 | 80.2 |
| Example 8 | 99.8 | 90.0 | 89.8 |
| Example 9 | 98.3 | 85.9 | 84.4 |
| Example 10 | 99.4 | 85.5 | 85.0 |
| Example 11 | 97.0 | 88.6 | 85.9 |
| Comparative example 1 | 99.2 | 74.0 | 73.4 |
| Comparative example 2 | 86.1 | 67.9 | 58.5 |
| Comparative example 3 | 99.4 | 68.0 | 67.6 |
Table 1 illustrates the invention with noble metal Pd as the main active ingredient, metal Co as the auxiliary agent, and gamma-Al 2 O 3 And MgO composite oxide is used as a carrier, and the prepared supported catalyst has higher catalytic activity and selectivity for the reaction of preparing propylene by the selective hydrogenation of propyne, has strong process fluctuation resistance and shows good industrial application value. gamma-Al 2 O 3 The catalyst has higher mechanical strength and carbon deposit resistance through interaction with MgO, and the addition of the metal Co changes the valence state and the electron cloud state of noble metal Pd, so that the metal Pd particles are dispersed more uniformly, and the timely desorption of propylene is promoted.
The catalyst prepared by the method is used for the selective hydrogenation reaction of propyne, the main product is propylene, the byproduct is propane, and the propane can be separated out by a rectifying tower during industrial production, so that the propane can be recycled.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The catalyst for preparing propylene by the selective hydrogenation of propyne, the preparation method and the application thereof provided by the invention are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (5)
1. The application of the catalyst in preparing propylene by selectively catalyzing and hydrogenating propyne is characterized in that: the catalyst is a supported noble metal catalyst, and the catalyst
By gamma-Al 2 O 3 As a main component of the catalyst carrier, mgO is attached to the surface of the carrier to form a composite metal oxide carrier;
one or more noble metals Ru, pd and Pt are used as main active components, and the content of the noble metals is 0.1-3.0wt% based on the weight content of the final catalyst;
modifying noble metal by taking non-noble metal Co as auxiliary metal, wherein the molar ratio of the noble metal to the non-noble metal is 1:1-10;
the loading amount of MgO is 10-20wt%, and the MgO precursor is 10-60wt% of magnesium nitrate aqueous solution;
the preparation method of the catalyst comprises the following steps:
（1）γ-Al 2 O 3 drying at 80-150 ℃ for 10-20 h, and dripping the MgO precursor aqueous solution into the dried gamma-Al under stirring 2 O 3 Dipping, dehydrating, drying and roasting to obtain a composite oxide carrier;
(2) The noble metal salt and the non-noble metal salt are dissolved in a dilute hydrochloric acid aqueous solution to obtain a mixed metal impregnation solution;
(3) Slowly dripping the mixed metal impregnating solution in the step (2) onto the composite oxide carrier in the step (1) under stirring, and carrying out impregnation, washing, separation, drying and roasting to obtain a catalyst precursor;
(4) Reducing noble metal oxide in the catalyst precursor in the step (3) into metal simple substance by using hydrogen so that the catalyst has catalytic activity and performs catalytic reaction;
in the step (1) and the step (3), the soaking time is 12-24 hours, the drying temperature is 80-120 ℃, the drying time is 6-12 hours, and the roasting conditions are as follows: rate of temperature rise: 5-12 ℃/min, heating to 450-750 ℃ from room temperature, and keeping the temperature for 2-6 h;
in the step (3), the washing step is specifically: the catalyst solution was neutral and chloride free by washing with deionized water.
2. The use according to claim 1, characterized in that: the MgO precursor was 30wt% magnesium nitrate aqueous solution.
3. The use according to claim 1, wherein the catalyst is used in an amount of 100 to 1000mg.
4. Use according to claim 1, characterized in that the method comprises the steps of:
loading the catalyst into a tubular fixed bed reactor, filling a constant temperature area in the middle of the tubular fixed bed with quantitative catalyst, filling the rest space with quartz sand, connecting the fixed pipes completely and hermetically, starting programmed temperature rise, firstly raising the temperature to 300-600 ℃ at a temperature rise rate of 5+/-1 ℃/min, keeping the temperature for 2-5 hours, activating the catalyst under the hydrogen pressure of 0.5-3 MPa, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; the mixture of propyne and cyclohexane is then fed into a tubular fixed bed reactor for hydrogenation with hydrogen.
5. The process according to claim 4, wherein the hydrogenation reaction conditions are: reaction temperature: the temperature of 30-80 ℃ and the hydrogen pressure are as follows: 0.5-3 MPa, the molar concentration of propyne in cyclohexane is 0.01-1.0%, the molar ratio of hydrogen to propyne is 1.1-1.5, and the reaction liquid hourly space velocity is: 10-30 h -1 。
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