CN117680153B - Co-Sb-M ternary intermetallic compound catalyst and preparation method and application thereof - Google Patents
Co-Sb-M ternary intermetallic compound catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 170
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 93
- 239000002184 metal Substances 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 44
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 229910020712 Co—Sb Inorganic materials 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical group [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000007812 deficiency Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 abstract description 36
- 239000000463 material Substances 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000002950 deficient Effects 0.000 abstract 1
- 229910018989 CoSb Inorganic materials 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 29
- 229910017850 Sb—Ni Inorganic materials 0.000 description 28
- 239000007787 solid Substances 0.000 description 24
- 229910021642 ultra pure water Inorganic materials 0.000 description 24
- 239000012498 ultrapure water Substances 0.000 description 24
- 238000001132 ultrasonic dispersion Methods 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 9
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 9
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
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- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
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- 239000013078 crystal Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910017847 Sb—Cu Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 230000008569 process Effects 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
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- 230000002195 synergetic effect Effects 0.000 description 4
- 229910002514 Co–Co Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910020068 MgAl Inorganic materials 0.000 description 2
- 229910003322 NiCu Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 1
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 assistants Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
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- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- 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
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a Co-Sb-M ternary intermetallic compound catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Preparing a mixed metal nitrate solution by taking a nitrate of Co, M, mg, al as a metal precursor, and preparing a Co/M/Mg/Al quaternary layered hydroxide U by adopting a coprecipitation method; in the mixed metal nitrate solution, the molar ratio of Co, M, mg, al ions is 1:1 (9-11): 4-6; (2) Grinding and mixing the material U and the inert metal Sb powder uniformly to obtain Co/M/Sb/Mg/Al pentabasic layered hydroxide VU; (3) The material VU is subjected to thermal reduction treatment to prepare the Co-Sb-M ternary intermetallic compound catalyst. In the catalyst, the carrier is magnesium aluminum metal mixed oxide, co-Sb-M ternary nano alloy particles are anchored on the carrier, the molar ratio of metal Co, M and Sb loading is 1:1:2, and the unique Co-Sb of electron-rich Sb isolated electron-deficient Co/M is formed 2 The M quadruple site structure realizes complete conversion of alkyne at low temperature, and has good alkene selectivity and catalytic stability.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a Co-Sb-M ternary intermetallic compound catalyst, and a preparation method and application thereof.
Background
The low-carbon olefin is the most important and basic chemical raw material for synthesizing organic materials and is also the basic stone of the modern chemical industry. Among them, ethylene and propylene are widely used for the synthesis of fine chemicals such as dyes, paints, assistants, pesticides, medicines, and the like. Naphtha steam cracking is the main process for obtaining low-carbon olefin, but the obtained olefin contains a small amount of alkyne or diene, which seriously jeopardizes the quality of products for producing polymer-grade olefin at the downstream. Thus, removal of alkyne impurities from olefins is of great value for the production of downstream chemicals. The selective catalytic hydrogenation can directionally catalyze and convert alkyne in the presence of a large amount of alkene, and the alkene is increased to a certain extent while removing impurities, so that the method is a process technology mainly adopted by industry. However, in the hydrogenation process, the problem of alkyne over-hydrogenation to alkane and oligomerization of alkyne to form "green oil" remains to be solved. In addition, improving the service life of the catalyst is also a challenge in catalyst design, while ensuring high olefin selectivity.
Pd-based catalysts are widely applied to alkyne catalytic hydrogenation processes, and have good hydrogenation activity and stability. In order to solve the problem of alkyne excessive hydrogenation, the electronic structure and the space structure of Pd active sites are often regulated and controlled by introducing guest metals, so that the adsorption behavior of substrates is changed to improve the selectivity of olefins. For example, journal document ACS Nano 2022, 16 (10): 16869-16879 reports modification of Pd active sites by guest metal Bi, inhibiting subsurface hydrogen formation and adsorption of product propylene, thereby increasing propylene selectivity. However, the cost problem caused by high loading (1% -5%) in Pd-based catalysts makes the related research of non-noble metal catalysts widely paid attention to. Ni-based catalysts are considered to be effective alternatives to Pd-based catalysts due to their high hydrogenation activity and low cost. Journal literature ACS catalysis, 2023, 13 (3): 1952-1963 synthesizes a supported NiCu alloy catalyst, revealing Al 2 O 3 Interaction of the carrier and the NiCu alloy; the formed Ni with stable structure and long-range order 1 Cu 1 The site is more beneficial to ethylene desorption, and the ethylene selectivity is remarkably improved. However, for Ni-based catalysts, the complete conversion temperature of alkynes is often up to 200 ℃, more prone to the formation of "green oil" leading to catalyst deactivation and mismatch with existing process conditions; alternatively, the olefin selectivity is not high at low temperature full conversion. Therefore, there is a need to further improve the hydrogenation activity of Ni-based catalysts, while achieving high alkyne conversion, high olefin selectivity, and low temperature reaction conditions.
In summary, the Pd-based catalyst in the existing alkyne hydrogenation catalyst has the cost problem caused by high noble metal loading; while Ni-based catalysts have difficulty maintaining high conversion and selectivity under low temperature reaction conditions. To solve the above problems, there is a need to develop a novel non-noble metal catalyst for selective hydrogenation of alkynes or dienes.
Disclosure of Invention
In order to solve the problems, the invention provides a Co-Sb - According to the M ternary intermetallic compound catalyst and the preparation method thereof, the space structure and the electronic structure of active sites of Co and M are directionally optimized through the p-d orbit hybridization between metal Sb and metal Co and M, so that complete conversion of alkyne under a low-temperature condition is realized, high olefin selectivity is considered, and the problem that low-temperature alkyne is difficult to convert in a non-noble metal catalyst is effectively solved.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a Co-Sb-M ternary intermetallic compound catalyst is characterized in that a catalyst carrier is magnesium-aluminum metal mixed oxide, co-Sb-M ternary nano alloy particles are anchored on the carrier, metal Sb is inert metal, and active metal M is selected from one of Ni, cu or Fe.
The invention is further arranged that the magnesium aluminum metal mixed oxide comprises MgO and MgAl 2 O 4 。
The inert metal is only inert with respect to the active metal in the selective hydrogenation process of alkyne in the Co-Sb-M ternary intermetallic compound catalyst prepared by the method.
The invention further provides that the high electronegativity p-region metal Sb in the catalyst is modifiedLow electronegativity active metals Co and M are decorated to form unique Co-Sb rich in electrons Sb and isolated in electrons and M 2 -M quadruple site structure, wherein the molar ratio of metal Co, M and Sb loadings is 1:1:2.
The invention provides a preparation method of a Co-Sb-M ternary intermetallic compound catalyst, which comprises the following steps:
(1) Preparing a mixed metal nitrate solution by taking a nitrate of Co, M, mg, al as a metal precursor, and preparing a Co/M/Mg/Al quaternary layered hydroxide U by adopting a coprecipitation method;
(2) Grinding and mixing the Co/M/Mg/Al quaternary layered hydroxide U and inert metal Sb powder uniformly to obtain Co/M/Sb/Mg/Al pentary layered hydroxide VU;
(3) Carrying out thermal reduction treatment on the Co/M/Sb/Mg/Al pentabasic layered hydroxide VU to obtain the Co-Sb-M ternary intermetallic compound catalyst;
in the step (1), the molar ratio of Co, M, mg, al ions in the mixed metal nitrate solution is 1:1 (9-11): 4-6.
The invention further provides that in the step (1), the ion concentration of the metal Co and the metal M in the mixed metal nitrate solution is 0.015-0.035 mol/L.
The invention further provides that in the step (1), the nitrates of Co, mg and Al are Co (NO) 3 ) 2 ·6H 2 O、Mg(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O; the nitrate of the metal M is Ni (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·6H 2 O or Fe (NO) 3 ) 3 ·9H 2 One of O.
The invention is further arranged that in the step (1), the temperature of a reaction system is maintained to be 55-75 ℃, a pH regulator and a mixed metal nitrate solution are added into a precipitator at the same time under the stirring condition, the pH value of the reaction system is controlled to be 10+/-1, and the adding rate of the mixed metal nitrate solution is controlled to be 0.8-1.2 ml/min; and after the feeding is finished, continuing to stir and react for 10-16 hours, and finally filtering, washing and drying to obtain the Co/M/Mg/Al quaternary layered hydroxide U.
The invention is further arranged that the precipitating agent is selected from Na 2 CO 3 Solution of NaHCO 3 Solutions or K 2 CO 3 One of the solutions. The molar concentration of the precipitant is 0.3-0.5 mol/L.
The invention further provides that the pH regulator is selected from one of NaOH solution or KOH solution. The molar concentration of the pH regulator is 2.4-2.6 mol/L.
The invention further provides that in the step (1), the drying condition is 100-120 ℃ and the drying time is 12-20 hours. The quaternary layered hydroxide U of Co/M/Mg/Al mixed with the inert metal Sb powder in the step (2) is the quaternary layered hydroxide U of Co/M/Mg/Al dried under the drying condition.
The invention is further provided that in the step (2), the Co/M/Mg/Al quaternary layered hydroxide U and the inert metal Sb powder are mixed according to the mole ratio of Co, M and Sb of 1:1 (1-3).
The invention further provides that in the step (3), the thermal reduction treatment condition is that in H 2 And N 2 Reducing for 3-5 hours at 800-1000 ℃ in a mixed atmosphere.
The invention also provides application of the Co-Sb-M ternary intermetallic compound catalyst, which is used for the reaction of preparing olefin by selective hydrogenation of alkyne or diene.
The Co-Sb-M ternary intermetallic compound catalyst is further used for the reaction of preparing ethylene by selective hydrogenation of acetylene and preparing propylene by selective hydrogenation of propyne.
The Co-Sb-M ternary intermetallic compound catalyst prepared by the invention forms unique Co-Sb rich in electron Sb and in isolation and electron deficiency of Co and M through the strong hybridization of d orbitals of active metals Co and M and p orbitals of inert metals Sb at the Fermi level 2 And the M quadruple site structure simultaneously combines adsorption activation of electrophilic alkyne and timely desorption of nucleophilic alkene, realizes complete alkyne conversion at low temperature, and has good alkene selectivity and catalytic stability.
The invention is further configured that the catalytic reaction conditions are: the reaction temperature is 80-150 ℃, the reaction pressure is normal pressure, the total air inflow flow is 20-50 mL/min, and the raw material gas is 0.4-0.6% of C 2 H 2 35.0 to 45.0 percent of C 2 H 4 8.0% -12.0% of H 2 The rest gas is N 2 The method comprises the steps of carrying out a first treatment on the surface of the Or 1.5% -2.5% of C 3 H 4 8.0% -12.0% of C 3 H 6 8.0% -12.0% of H 2 The rest gas is N 2 。
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the cost performance of the catalyst is greatly improved by using non-noble metal Co; by introducing the inert metal Sb, the p-d orbital hybridization between the metal Sb and the metal Co and M is utilized to optimize the Co-Sb 2 -surface structure of M quadruplets. The Co-Sb 2 Co and M active sites in the M quadruple sites are isolated by metal Sb, and the substrate adsorption behavior can be regulated. By Co-Sb 2 The synergistic effect of the M quadruple sites can improve the catalytic hydrogenation performance, realize complete alkyne conversion under the low-temperature condition, and have high olefin selectivity; the Co-Sb-M ternary intermetallic compound catalyst with high cost performance has great industrial application value.
Drawings
FIG. 1 is an XRD spectrum of Co single metal catalyst U2-900 and CoSb intermetallic compound catalyst V2U2-900 prepared in comparative example.
Fig. 2 is a simulated XRD pattern of Co single metal catalyst and CoSb intermetallic catalyst.
FIG. 3 a is a transmission electron microscope image and a corresponding Fourier image of Co single-metal catalyst U2-900 prepared in comparative example of the present invention; b is a statistical graph of the particle size distribution of the metal particles; and c is a corresponding transmission electron microscope EDS line scanning element analysis chart.
FIG. 4 a is a transmission electron micrograph and a corresponding Fourier plot of CoSb intermetallic catalyst V2U2-900 prepared in comparative example of the present invention; b is a statistical graph of the particle size distribution of the metal particles; and c is a corresponding transmission electron microscope EDS line scanning element analysis chart.
FIG. 5 is a photograph of a transmission electron microscopic elemental analysis of Co single metal catalyst U2-900 prepared in comparative example of the present invention.
FIG. 6 is a photograph of a transmission electron microscope elemental analysis of CoSb intermetallic compound catalyst V2U2-900 produced in comparative example of the present invention.
FIG. 7a is an XPS spectrum of Co 2p orbitals and Sb 4d orbitals of the CoSb intermetallic compound catalyst V2U2-900 prepared in the comparative example of the present invention; b is Co k side normalized XANES spectrograms of Co foil, co single metal catalyst U2-900 and CoSb intermetallic compound catalyst V2U 2-900; c is the Fourier transform k 2 Weighted EXAFS spectra; d is the EXAFS oscillation function of the Co k side; e is k of Co k edge 3 Wavelet transform map of weighted EXAFS signal.
FIG. 8 is a photograph of a transmission electron microscope elemental analysis of Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in the example of the present invention.
FIG. 9a is a view of a spherical aberration electron microscope of Co-Sb-Ni intermetallic compound catalyst V1U1-900 according to the embodiment of the present invention; b is the atomic image intensity profile shown along the purple arrow in a; c is an enlarged view of the yellow rectangular mark region in a and corresponds to the crystal model projected by [010] crystal band axis; d is a Fourier plot of Co-Sb-Ni intermetallic compounds.
FIG. 10 is a two-dimensional differential charge map of Co-Sb-Ni intermetallic catalyst V1U1-900 produced by the example of the invention.
FIG. 11 is a graph showing the density of states of Co-Sb-Ni intermetallic compound catalysts V1U1-900 produced in the examples of the present invention.
FIG. 12 is a schematic diagram showing H of CoSb intermetallic compound catalyst V2U2-900 produced in comparative example of the present invention, co-Sb-Ni intermetallic compound catalyst V1U1-900 produced in example, and Co-Sb-Cu intermetallic compound catalyst V7U7-900 2 -TPD map.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which specific embodiments are shown. It is to be understood that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
The preparation of the Co-Sb-M ternary intermetallic compound catalyst specifically comprises the following steps:
(1) 0.73 g of Ni (NO 3 ) 2 ·6H 2 O、0.73 g Co(NO 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, and the molar ratio of Co, ni, mg, al ions is 1:1:10:4; transferring the required precipitant into a 500 mL three-neck flask, placing the flask in an oil bath at 65 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 120 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, and the pH value of a reaction system in the three-neck flask is controlled to be constant at 10.5; continuously and vigorously stirring for 12 hours at the synthesis temperature of 65 ℃ after the material feeding is completed, then carrying out vacuum suction filtration, and washing for multiple times until the pH value is neutral to obtain a yellow-pink massive solid Co/Ni/Mg/Al quaternary LDH material, wherein the mark is U1.
Wherein the precipitant is prepared by mixing 2.12 g of Na 2 CO 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 10.00 g of NaOH powder in 100 mL ultrapure water for ultrasonic dispersion.
(2) Drying the yellow powder massive solid U1 prepared in the step (1) at 100 ℃ for 16 hours; 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried yellow powder solid U1 and fully ground, and the molar ratio of Sb to Ni to Co is 2:1:1, so that the Co/Ni/Sb/Mg/Al five-membered LDH material is prepared, and is marked as V1U1.
(3) The five-membered layered hydroxide V1U1 of the step (2) is reacted with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the Co-Sb-Ni intermetallic compound catalyst which is marked as V1U1-900.
Comparative example 1
The preparation of the Co single-metal catalyst specifically comprises the following steps:
(1) 1.46 g Co (NO) 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion and is recorded as mixed metal nitrate solution, and the molar ratio of Co, mg and Al ions is 1:5:2; transferring the required precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 120 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the pH of a reaction system in a three-neck flask is controlled to be constant at 10.5, continuous and vigorous stirring is continued for 12 hours at the synthesis temperature of 65 ℃ after the material feeding is completed, then vacuum suction filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a pink massive solid Co/Mg/Al ternary LDH material is obtained, and the ternary LDH material is marked as U2;
wherein the precipitant is prepared by mixing 2.12 g of Na 2 CO 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 10.00 g of NaOH powder in 100 mL ultrapure water for ultrasonic dispersion.
(2) U2 prepared in the step (1) is treated with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the Co single-metal catalyst which is marked as U2-900.
Comparative example 2
The preparation of the CoSb intermetallic compound catalyst specifically comprises the following steps:
(1) Drying the pink solid U2 prepared in step (1) of comparative example 1 at 100℃for 16 hours; then 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried pink solid U2 and fully ground, and the molar ratio of Sb to Co is 1:1, so that the Co/Sb/Mg/Al quaternary LDH material is prepared and is marked as V2U2.
(2) The V2U2 is prepared under H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the CoSb intermetallic compound catalyst which is marked as V2U2-900.
Example 2
The preparation of the Co-Sb-M ternary intermetallic compound catalyst specifically comprises the following steps:
(1) 0.73 g of Ni (NO 3 ) 2 ·6H 2 O、0.73 g Co(NO 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, and the molar ratio of Co, ni, mg, al ions is 1:1:10:4; transferring the required precipitant into a 500 mL three-neck flask, placing the flask in an oil bath at 55 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 110 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.2 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the pH of a reaction system in a three-neck flask is controlled to be constant at 10.5, continuous and vigorous stirring is continued for 16 hours at the synthesis temperature of 55 ℃ after the material feeding is completed, then vacuum suction filtration is carried out, the mixture is washed for multiple times until the pH is neutral, and a yellow-pink massive solid Co/Ni/Mg/Al quaternary LDH material is obtained, and is marked as U3.
Wherein the precipitant is a solution of 2.76 g K 2 CO 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; obtaining a precipitant; the pH regulator is prepared by dissolving 14.00 g KOH powder in 100 mL ultrapure water and performing ultrasonic dispersion.
(2) Drying the yellow powder massive solid U3 prepared in the step (1) at 120 ℃ for 12 hours; 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried yellow powder solid U3 and fully ground, and the molar ratio of Sb to Ni to Co is 2:1:1, so that the Co/Ni/Sb/Mg/Al five-membered LDH material is prepared, and is marked as V3U3.
(3) The five-membered layered hydroxide V3U3 of the step (2) is reacted with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the Co-Sb-Ni intermetallic compound catalyst which is marked as V3U3-900.
Comparative example 3
The preparation of the Co single-metal catalyst specifically comprises the following steps:
(1) 1.46 g Co (NO) 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion and is recorded as mixed metal nitrate solution, and the molar ratio of Co, mg and Al ions is 1:5:2; transferring the required precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 55 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 110 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.2 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the pH of a reaction system in a three-neck flask is controlled to be constant at 10.5, continuous and vigorous stirring is continued for 16 hours at the synthesis temperature of 55 ℃ after the material feeding is completed, then vacuum suction filtration is carried out, and the mixture is washed for multiple times until the pH is neutral, so that a pink massive solid Co/Mg/Al ternary LDH material is obtained, and the ternary LDH material is marked as U4;
wherein the precipitant is a solution of 2.76 g K 2 CO 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 14.00 g KOH powder in 100 mL ultrapure water and performing ultrasonic dispersion.
(2) U4 prepared in the step (1) is treated with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the single metal Co catalyst which is marked as U4-900.
Comparative example 4
The preparation of the CoSb intermetallic compound catalyst specifically comprises the following steps:
(1) Drying the pink solid U4 prepared in step (1) of comparative example 3 at 120℃for 12 hours; then 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried pink solid U4 and fully ground, the mole ratio of Sb to Co is 1:1, and the Co/Sb/Mg/Al quaternary LDH material is prepared and is marked as V4U4.
(2) The prepared V4U4 is treated with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the CoSb intermetallic compound catalyst which is marked as V4U4-900.
Example 3
The preparation of the Co-Sb-Ni ternary intermetallic compound catalyst specifically comprises the following steps:
(1) 0.73 g of Ni (NO 3 ) 2 ·6H 2 O、0.73 g Co(NO 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 5.63 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, and the molar ratio of Co, ni, mg, al ions is 1:1:10:6; transferring the required precipitant into a 500 mL three-neck flask, placing the flask in an oil bath at 75 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 150 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.8 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the pH of a reaction system in a three-neck flask is controlled to be constant at 10.5, continuous and vigorous stirring is continued for 10 hours at the synthesis temperature of 75 ℃ after the material feeding is completed, then vacuum suction filtration is carried out, the mixture is washed for multiple times until the pH is neutral, and a yellow-pink massive solid Co/Ni/Mg/Al quaternary LDH material is obtained, and the mixture is marked as U5.
Wherein the precipitant is NaHCO 1.68 g 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 10.00 g of NaOH powder in 100 mL ultrapure water for ultrasonic dispersion.
(2) Drying the yellow powder bulk solid U5 prepared in the step (1) at 110 ℃ for 20 hours; 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried yellow powder solid U5 and fully ground, and the molar ratio of Sb to Ni to Co is 2:1:1, so that the Co/Ni/Sb/Mg/Al five-membered LDH material is prepared, and is marked as V5U5.
(3) The five-membered layered hydroxide V5U5 of the step (2) is reacted with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the Co-Sb-Ni intermetallic compound catalyst which is marked as V5U5-900.
Comparative example 5
The preparation of the Co single-metal catalyst specifically comprises the following steps:
(1) 1.46 g Co (NO) 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, and the molar ratio of Co, mg and Al ions is 1:5:3; transferring the required precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 75 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 150 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 0.8 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, the pH of a reaction system in a three-neck flask is controlled to be constant at 10.5, continuous and vigorous stirring is continued for 10 hours at the synthesis temperature of 75 ℃ after the material feeding is completed, then vacuum suction filtration is carried out, the mixture is washed for multiple times until the pH is neutral, and a pink massive solid Co/Mg/Al ternary LDH material is obtained, wherein the ternary LDH material is marked as U6;
wherein the precipitant is NaHCO 1.68 g 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 10.00 g of NaOH powder in 100 mL ultrapure water for ultrasonic dispersion.
(2) U6 prepared in the step (1) is treated with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the single metal Co catalyst which is marked as U6-900.
Comparative example 6
The preparation of the CoSb intermetallic compound catalyst specifically comprises the following steps:
(1) Drying the pink solid U6 prepared in step (1) of comparative example 5 at 110℃for 20 hours; then 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried pink solid U6 and fully ground, the mole ratio of Sb to Co is 1:1, and the Co/Sb/Mg/Al quaternary LDH material is prepared and is marked as V6U6.
(2) The prepared V6U6 is treated with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the CoSb intermetallic compound catalyst which is marked as V6U6-900.
Example 4
The preparation of the Co-Sb-Cu ternary intermetallic compound catalyst specifically comprises the following steps:
(1) 0.73 g Co (NO) 3 ) 2 ·6H 2 O、0.74 g Cu(NO 3 ) 2 ·6H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, and the molar ratio of Co, cu, mg, al ions is 1:1:10:4; transferring the required precipitant into a 500 mL three-neck flask, placing the flask in an oil bath at 65 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 120 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, and the pH value of a reaction system in the three-neck flask is controlled to be constant at 10.5; after the material feeding is completed, continuously and vigorously stirring for 12 hours at the synthesis temperature of 65 ℃, then carrying out vacuum suction filtration, and washing for multiple times until the pH value is neutral, thus obtaining the purple pink massive solid Co/Cu/Mg/Al quaternary LDH material, and the mark is U7.
Wherein the precipitant is prepared by mixing 2.12 g of Na 2 CO 3 Dissolving the powder in 50mL of ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 10.00 g of NaOH powder in 100 mL ultrapure water for ultrasonic dispersion.
(2) Drying the purple pink solid U7 prepared in the step (1) at 100 ℃ for 16 hours; 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried purple pink solid U7 and fully ground, and the molar ratio of Sb to Cu to Co is 2:1:1, so that the Co/Cu/Sb/Mg/Al five-membered LDH material is prepared, and is marked as V7U7.
(3) V7U7 prepared in the step (2) is treated with H at 900 DEG C 2 And N 2 The mixture was reduced in a mixed atmosphere (volume ratio: 1:4) for 4 hours to obtain a Co-Sb-Cu intermetallic compound catalyst, which was designated as V7U7-900.
Example 5
The preparation of the Co-Sb-Fe ternary intermetallic compound catalyst specifically comprises the following steps:
(1) 0.73 g Co (NO) 3 ) 2 ·6H 2 O、1.01 g Fe(NO 3 ) 3 ·9H 2 O、6.41 g Mg(NO 3 ) 2 ·6H 2 O and 3.75 g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100 mL ultrapure water for ultrasonic dispersion, and is recorded as mixed metal nitrate solution, and the molar ratio of Co, fe, mg, al ions is 1:1:10:4; transferring the required precipitant into a 500 mL three-neck flask, placing the three-neck flask in an oil bath at 65 ℃ for constant temperature treatment for 1 h, then dropwise adding the prepared mixed metal nitrate solution under the condition of the rotating speed of 120 r/min, and controlling the flow rate of the mixed metal nitrate solution to be 1.0 mL/min by using a constant flow pump; meanwhile, a constant flow pump is used for adding a pH regulator, and the pH value of a reaction system in the three-neck flask is controlled to be constant at 10.5; after the material feeding is completed, continuously and vigorously stirring for 12 hours at the synthesis temperature of 65 ℃, then carrying out vacuum suction filtration, and washing for multiple times until the pH value is neutral, thus obtaining the pale pink blocky solid Co/Fe/Mg/Al quaternary LDH material, and the mark is U8.
Wherein the precipitant is prepared by mixing 2.12 g of Na 2 CO 3 Dissolving the powder in 50mL ultrapure water, and performing ultrasonic dispersion to obtain the powder; the pH regulator is prepared by dissolving 10.00 g of NaOH powder in 100 mL ultrapure water for ultrasonic dispersion.
(2) Drying the light pink solid U8 prepared in the step (1) at 100 ℃ for 16 hours; 0.609. 0.609 g inert metal Sb powder is weighed, mixed with the dried light pink solid U8 and fully ground, and the molar ratio of Sb to Fe to Co is 2:1:1, so that the Co/Fe/Sb/Mg/Al five-membered LDH material is prepared, and is marked as V8U8.
(3) V8U8 prepared in the step (2) is treated with H at 900 DEG C 2 And N 2 Reducing for 4 hours in a mixed atmosphere (volume ratio of 1:4) to obtain the Co-Sb-Fe intermetallic compound catalyst which is marked as V8U8-900.
Co single metal catalyst and CoSb intermetallic catalyst characterization
Characterization of the catalyst prepared above, as shown in fig. 1, the XRD spectrum of the Co single metal catalyst U2-900 prepared in comparative example 1 had distinct diffraction peaks at 44.3 °, 51.7 ° and 76.1 °, corresponding to the diffraction peaks of (111), (200) and (220) faces of the single metal Co standard card (ICSD 150806), respectively. The XRD spectrum of the CoSb intermetallic compound catalyst V2U2-900 prepared in the comparative example 2 shows diffraction peaks with different intensities at 31.6 degrees, 34.6 degrees, 44.0 degrees, 46.5 degrees, 57.3 degrees, 60.1 degrees and 66.0 degrees, and the diffraction peaks of the standard card (ICSD 164409) of the CoSb intermetallic compound can be respectively attributed to the diffraction peaks of the (101), (002), (102), (110), (201), (103) and (202) planes. In addition, the XRD patterns of fig. 1 are consistent with the simulated XRD patterns of fig. 2, indicating successful preparation of Co single metal catalysts and CoSb intermetallic catalysts.
The Co single-metal catalyst U2-900 prepared in comparative example 1 is observed by a transmission electron microscope, the microscopic morphology is shown in figure 3, the measured lattice spacing is 0.205 and nm, and the lattice spacing corresponds to the (111) plane of single-metal Co; the transmission electron microscope of the CoSb intermetallic compound catalyst V2U2-900 obtained in comparative example 2 showed a crystal face having a lattice spacing of 0.283 nm in FIG. 4, corresponding to the (101) face of the CoSb intermetallic compound. According to the corresponding EDS line scanning analysis chart, the Co single-metal catalyst U1-900 does not contain Sb elements, the Co and Sb elements in the CoSb intermetallic compound catalyst V2U2-900 are uniformly distributed, and the element ratio of Co to Sb is close to 1:1. And, FIGS. 3 and 4 show that Co single metal catalysts U2-900 and CoSb intermetallic compound catalysts V2U2-900 have similar particle size distribution, indicating that the introduction of the inert metal Sb did not significantly change the particle size of the Co-based catalyst.
The Co single metal catalyst U2-900 and the CoSb intermetallic compound catalyst V2U2-900 are continuously subjected to element analysis, and the results are shown in the figures 5 and 6, wherein Co, mg and Al elements in the figure 5 are uniformly distributed, and Sb elements are not observed, wherein the Mg and Al elements correspond to MgO and MgAl 2 O 4 A carrier; the Co, sb, mg, al elements in fig. 6 are uniformly distributed and are consistent with EDS line scan results. The above characterization results illustrate that the single metal Co crystal phase and CoSb alloy crystal phase are formed in comparative example 1 and comparative example 2, respectively.
The electron structure of the CoSb intermetallic compound catalyst V2U2-900 obtained in comparative example 2 was analyzed by XPS spectrum technique, and the result is shown in FIG. 7a, in which Co in the CoSb intermetallic compound catalyst V2U2-900 is compared with Co single metal catalyst U2-900 0 2p 3/2 The corresponding signal peak in the XPS spectrum of (a) shifts to higher binding energies; meanwhile, in XPS spectrum of Sb 4d, sb 4d 5/2 Sb 4d 3/2 Signal peak, compared with single metal SbIts binding energy is shifted in a lower direction. The shift of the signal peaks shows that strong electron interaction exists between Co element and Sb element in the CoSb intermetallic compound, namely, electrons are transferred from Co atoms to adjacent Sb atoms.
The electronic localization structure of CoSb intermetallic catalyst V2U2-900 was continued to be revealed by XAS characterization technology. As shown in fig. 7b, compared with the control Co foil and the prepared Co single metal catalyst U2-900, the normalized X-ray absorption near-edge spectrum corresponding to the Co k edge in the CoSb intermetallic compound shifted to the position of high photon energy and the corresponding white edge height was higher, indicating that the Co atoms in the CoSb catalyst transferred electrons to the adjacent Sb atoms to reduce the electron density of the Co atoms, which is completely consistent with the XPS result. In addition, as shown in FIG. 7c, in the EXAFS spectrum of the Co k side in the CoSb intermetallic compound, it is difficult to observe a signal peak of Co-Co coordination scattering and a main signal peak related to Co-Sb coordination can be clearly observed in the vicinity of 2.4A, compared to the Co single metal catalyst. The EXAFS oscillation function of the Co k side further verifies the geometric characteristics of the Co site. As shown in FIG. 7d, the characteristic of the short period and small amplitude of the EXAFS oscillation function at the Co k-edge in the CoSb catalyst, compared to the Co foil and Co single metal catalyst, suggests that the Co-Sb coordination distance in the CoSb catalyst is long and the Co-Co coordination number is low. WT analysis based on the EXAFS oscillation function of Co k-edge FIG. 7e shows that the corresponding WT-EXAFS contour plot of the control Co foil and Co single metal catalyst is at 8.0A -1 The vicinity shows one of the strongest signal peaks, which is attributed to scattering of the Co-Co bonds. In contrast, the WT-EXAFS contour plot of the CoSb intermetallic catalyst is at 10.5A -1 The left and right show scattering signals associated with Co-Sb coordination. The above electronic structural characterization reveals the modification of Co by the inert metal Sb, forming a Co site structure in the CoSb intermetallic catalyst that is isolated by the Sb site.
Co-Sb-Ni intermetallic catalyst characterization
As shown in FIG. 8, elemental analysis was performed on the Co-Sb-Ni intermetallic compound catalyst V1U1-900 obtained in example 1, and it was found that the element Co, ni, sb, mg, al was uniformly distributed, indicating that a Co-Sb-Ni ternary alloy crystal phase was formed. Relay(s)This was further characterized by a spherical aberration electron microscope, and as a result, as shown in fig. 9, the lattice spacing in the purple arrow direction in fig. 9a was 0.31 and nm, which corresponds to the (101) plane of the CoSb intermetallic compound. The radii of the element Ni and Co atoms are close, so that the Ni atoms replace Co sites in the parent alloy CoSb catalyst, and the lattice spacing is not changed significantly. FIG. 9c further shows that the atomic arrangement of the catalyst particles is highly matched to the results of the simulation in Co-Sb-Ni intermetallic compounds, indicating that the Co sites and Ni sites are ordered and isolated by the inert metal Sb, forming Co-Sb 2 Quadruple site structure of Ni. The Co-Sb-Ni intermetallic compound catalyst V1U1-900 was subjected to charge analysis, and as a result (figure 10) showed that charges were concentrated around Sb atoms, which illustrates the transfer of electrons from metal Co, ni to Sb atoms, and the isolated structure of Co sites and Ni sites in Co-Sb-Ni intermetallic compounds was demonstrated. It is to be noted that by plotting the density of states of the Co-Sb-Ni intermetallic compound (FIG. 11), it is possible to explain that the modification of Co and Ni active sites by the inert metal Sb is derived from orbital hybridization of Co d orbitals, ni d orbitals and Sb p orbitals at the Fermi level.
Hydrogen adsorption behavior of CoSb intermetallic catalyst and Co-Sb-M intermetallic catalyst
Hydrogen programmed desorption experiments were performed on Co-Sb-Ni intermetallic compound catalysts V1U1-900 prepared in example 1, co-Sb-Cu intermetallic compound catalysts V7U7-900 prepared in example 4, and CoSb intermetallic compound catalysts V2U2-900 prepared in comparative example 2, respectively, and the results are shown in FIG. 12. Wherein the CoSb catalyst V2U 2-900H 2 The TPD curve shows obvious desorption peak at 90 ℃ which is obviously lower than the desorption peak temperature of the Co-Sb-Ni catalyst V1U1-900 (105 ℃) and the Co-Sb-Cu catalyst V7U7-900 (165 ℃), which shows that the Co-Sb is characterized by 2 The M quadruple site structure can influence the adsorption behavior of hydrogen through the synergistic effect of metal Co and M so as to further improve the selective hydrogenation performance of the Co-based catalyst.
Evaluation of catalytic hydrogenation Performance of acetylene
Co-Sb-M intermetallic compound catalysts prepared in examples 1-5, co single-metal catalysts and CoSb intermetallic compound catalysts prepared in comparative examples 1-6 were used for acetylene catalytic hydrogenation performance evaluation, wherein:
the components in the reactants and products were analyzed on-line using a four-way Micro-chromatograph Micro GC 3000 (INFICON corporation, germany);
H 2 and N 2 Using a molecular sieve column, C 2 H 2 Using a Plot-U column, C 2 H 4 And C 2 H 6 Using an alumina column, C 4 The components are analyzed by using an OV-1 capillary chromatographic column, a detector is a thermal conductivity cell detector, and carrier gas is Ar and He;
evaluation conditions: the total flow of the inlet air is 30mL/min, and the raw material gas is 0.5 percent of C 2 H 2 40.0% of C 2 H 4 10.0% H 2 The rest gas is N 2 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 120 ℃; the reaction pressure is normal pressure. Catalyst loading 500 mg.
Weighing 500 mg catalyst sample and filling the catalyst sample in a constant temperature zone in a stainless steel reaction tube, after the catalyst is filled, firstly detecting the leak of the reaction system, and introducing a certain pressure N into the reaction system 2 (10 bar), if the pressure can be kept constant, it indicates that the reaction system has good sealability, and an evaluation experiment can be performed.
Setting N 2 The flow is 20 ml/min, and the temperature is raised to the reduction temperature; then turn off N 2 Set H 2 The flow is 20 ml/min, and H is closed after the reaction is performed for a certain time 2 The method comprises the steps of carrying out a first treatment on the surface of the Setting N 2 The flow rate is 20 ml/min, the temperature is reduced to the reaction temperature, and the pressure required by the reaction is set. After the reaction conditions are stable, the flow rate of each reaction component is set, and a Furnace six-way valve is cut into a bypass, so that the mixed gas directly enters the chromatograph to detect the concentration of each component before the reaction. After stabilization, the Furnace six-way valve is switched back to the main circuit to enable the mixed gas to enter the reaction tube to start reaction, and online chromatographic detection is carried out on the gas at the outlet of the reaction tube.
Acetylene conversion C (C) over catalyst 2 H 2 ) Ethylene selectivity S (C) 2 H 4 ) Yield Y (C) 2 H 4 ) To evaluate the selective hydrogenation of acetylene by the catalystCatalytic performance of ethylene production reaction, wherein:
C(C 2 H 2 ) = ；
S(C 2 H 4 ) = ；
Y(C 2 H 4 ) = ；
the results of evaluating the catalytic performance of the catalysts prepared in the examples and comparative examples are shown in the following table 1:
TABLE 1 evaluation results of catalytic Performance of catalysts at 120 ℃
As can be seen from Table 1, the CoSb intermetallic compound catalyst prepared in the comparative example had higher ethylene selectivity at 120℃under the condition that the raw material gas was introduced into ethylene, which was far superior to the Co single-metal catalyst prepared in the comparative example. The isolated Co sites formed in the CoSb catalyst can promote ethylene desorption and avoid excessive hydrogenation to ethane, and the use of an inert metal Sb modified Co-based catalyst is an effective strategy for improving ethylene selectivity. The Co-Sb-Ni intermetallic compound catalyst prepared by the embodiment 1-3 not only realizes complete conversion of acetylene at low temperature (120 ℃), but also has high ethylene selectivity; the performance is far better than that of the CoSb catalyst prepared in the comparative example. As is readily understood by those skilled in the art, the Co-Sb-Ni intermetallic compound catalyst prepared by the invention directionally optimizes Co-Sb by the p-d orbital hybridization between the inert metal Sb and the metal Co and Ni 2 Surface structure of Ni quadruple site. In Co-Sb 2 In the Ni quadruple site synergistic catalysis process, the problem of high-temperature reaction conditions of the Ni-based catalyst is avoided, and the catalytic advantages of low-temperature catalysis of metal Co and high hydrogenation activity of metal Ni are fully exerted.
Co-Sb-M intermetallic catalysts prepared by incorporating Cu or Fe as the second active component into CoSb catalysts 2 The M quadruple site structure, as shown in examples 4 and 5, also has superior low temperature selective hydrogenation properties. The Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in example 1 is found to have optimal performance by transversely comparing three Co-Sb-M intermetallic compound catalysts, and the ethylene selectivity is up to 98% when acetylene is completely converted, which shows that the synergistic catalytic effect between Co and Ni sites isolated by Sb sites is most competitive. In conclusion, the Co-Sb-M intermetallic compound catalyst prepared by the method has good low-temperature hydrogenation activity and ethylene selectivity, and provides a thinking for industrial application of non-noble metal catalysts.
Evaluation of stability of acetylene in catalytic hydrogenation
Evaluation of the hydrogenation stability of acetylene on Co-Sb-Ni intermetallic Compound catalyst V1U1-900 prepared in example 1 the stability of the catalyst was evaluated according to the catalyst Performance test method of the above-described test for the catalytic hydrogenation performance of acetylene, C (C) 2 H 2 )、S(C 2 H 4 ) And Y (C) 2 H 4 ) The data results are shown in table 2:
TABLE 2 evaluation of catalytic hydrogenation stability of V1U1-900 acetylene
As can be seen from the data of Table 2, the Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in example 1 was subjected to the reaction evaluation of 48 h, the conversion of acetylene was always maintained at 98.2% or more, the selectivity for ethylene was also maintained at 97.0% or more and the ethylene yield was maintained at 96.3% or more. The results show that the Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in example 1 has good stability.
Evaluation of propyne catalytic hydrogenation stability
Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in example 1 was used for propyne catalytic hydrogenation performance evaluation, wherein:
the components in the reactants and products were analyzed on-line using four-way Micro GC Fusion (INFICON corporation, germany);
C 3 H 4 using Rt-U-Bond column, C 3 H 6 And C 3 H 8 Using Alumen Na 2 SO 4 The detector is a thermal conductivity cell detector, and the carrier gas is He;
evaluation conditions: the total flow of air intake is 30mL/min, and the raw material gas is 2.0 percent of C 3 H 4 10.0% of C 3 H 6 10.0% H 2 The rest gas is N 2 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 120 ℃; the reaction pressure is normal pressure. Catalyst loading 500 mg.
A 500 mg sample of the catalyst was weighed and packed into a constant temperature zone in a stainless steel reaction tube. After the catalyst is filled, firstly leak detecting is carried out on the reaction system, and a certain pressure N is introduced into the reaction system 2 (10 bar). If the pressure can be kept constant, the reaction system has good tightness, and an evaluation experiment can be carried out.
Setting N 2 The flow is 20 ml/min, and the temperature is raised to the reduction temperature; then turn off N 2 Set H 2 The flow is 20 ml/min, and H is closed after the reaction is performed for a certain time 2 The method comprises the steps of carrying out a first treatment on the surface of the Setting N 2 The flow rate is 20 ml/min, the temperature is reduced to the reaction temperature, and the pressure required by the reaction is set. After the reaction conditions are stable, the flow rate of each reaction component is set, and a Furnace six-way valve is cut into a bypass, so that the mixed gas directly enters the chromatograph to detect the concentration of each component before the reaction. After stabilization, the Furnace six-way valve is switched back to the main circuit to enable the mixed gas to enter the reaction tube to start reaction, and online chromatographic detection is carried out on the gas at the outlet of the reaction tube.
Propyne conversion C (C) by testing the catalyst prepared in example 1 3 H 4 ) Propylene selectivity S (C 3 H 6 ) Yield Y (C) 3 H 6 ) To evaluate the catalytic performance of the catalyst on the reaction of propylene preparation by selective hydrogenation of propyne, wherein:
C(C 3 H 4 ) = ；
S(C 3 H 6 ) = ；
Y(C 3 H 6 ) = the method comprises the steps of carrying out a first treatment on the surface of the The results of the catalytic performance are shown in Table 3.
TABLE 3 evaluation of catalytic hydrogenation stability of V1U1-900 propyne
As can be seen from the data in Table 3, the Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in example 1 was subjected to the reaction evaluation of 48 h, the conversion of propyne was always 96.5% or more, the selectivity for propylene was maintained at 97.0% or more, and the propylene yield was maintained at 94.0% or more. The results show that the Co-Sb-Ni intermetallic compound catalyst V1U1-900 prepared in the example 1 has good propyne selective hydrogenation catalytic stability.
In conclusion, the Co-Sb-M intermetallic compound catalyst prepared by the method has good catalytic stability, can be used for selective hydrogenation of acetylene and propyne under the low-temperature condition, reduces the use cost of the catalyst, and has potential value for industrial application of non-noble metal catalysts.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A Co-Sb-M ternary intermetallic compound catalyst for preparing olefin by selective hydrogenation of alkyne or diene is characterized in that the catalyst carrier is magnesium-aluminum metal mixtureA composite oxide, co-Sb-M ternary nano alloy particles are anchored on the carrier, metal Sb is inert metal, co and M are active metals, and M is selected from one of Ni, cu or Fe; the molar ratio of the loading of the metal Co, the metal M and the metal Sb in the catalyst is 1:1:2, co sites and M sites are orderly arranged and isolated by inert metal Sb, and the catalyst has high electronegativitypZone metal Sb modified low electronegativity active metals Co and M to form Co-Sb rich in electrons Sb and isolated in electron deficiency Co and M 2 -M quadruple site structure.
2. A method for preparing the Co-Sb-M ternary intermetallic compound catalyst according to claim 1, comprising the steps of:
(1) Preparing a mixed metal nitrate solution by taking a nitrate of Co, M, mg, al as a metal precursor, and preparing a Co/M/Mg/Al quaternary layered hydroxide U by adopting a coprecipitation method;
(2) Grinding and mixing the Co/M/Mg/Al quaternary layered hydroxide U and inert metal Sb powder uniformly to obtain Co/M/Sb/Mg/Al pentary layered hydroxide VU;
(3) Carrying out thermal reduction treatment on the Co/M/Sb/Mg/Al pentabasic layered hydroxide VU to obtain the Co-Sb-M ternary intermetallic compound catalyst;
in the step (1), the molar ratio of Co, M, mg, al ions in the mixed metal nitrate solution is 1:1 (9-11): 4-6.
3. The method for preparing a Co-Sb-M ternary intermetallic compound catalyst according to claim 2, wherein in the step (1), the nitrates of Co, mg and Al are Co (NO 3 ) 2 ·6H 2 O、Mg(NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O; the nitrate of the metal M is Ni (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·6H 2 O or Fe (NO) 3 ) 3 ·9H 2 One of O.
4. The method for preparing a Co-Sb-M ternary intermetallic compound catalyst according to claim 2, wherein in the step (1), the temperature of a reaction system is maintained to be 55-75 ℃, a pH regulator and a mixed metal nitrate solution are added to a precipitator at the same time under the condition of stirring, the pH value of the reaction system is controlled to be 10+/-1, and the adding rate of the mixed metal nitrate solution is controlled to be 0.8-1.2 ml/min; and after the feeding is finished, continuing to stir and react for 10-16 hours, and finally filtering, washing and drying to obtain the Co/M/Mg/Al quaternary layered hydroxide U.
5. The method for preparing a Co-Sb-M ternary intermetallic compound catalyst according to claim 4, wherein the precipitant is selected from Na 2 CO 3 Solution of NaHCO 3 Solutions or K 2 CO 3 One of the solutions; the pH regulator is selected from one of NaOH solution or KOH solution.
6. The method for preparing a Co-Sb-M ternary intermetallic compound catalyst according to claim 4, wherein in the step (1), the drying conditions are: and drying for 12-20 hours at 100-120 ℃.
7. The preparation method of the Co-Sb-M ternary intermetallic compound catalyst according to claim 2, wherein in the step (2), the Co/M/Mg/Al quaternary layered hydroxide U and the inert metal Sb powder are mixed according to the molar ratio of Co, M and Sb of 1:1 (1-3).
8. The method for producing a Co-Sb-M ternary intermetallic compound catalyst according to claim 2, wherein in the step (3), the heat-reducing treatment conditions are as follows 2 And N 2 Reducing for 3-5 hours at 800-1000 ℃ in a mixed atmosphere.
9. The use of a Co-Sb-M ternary intermetallic compound catalyst prepared according to the method for preparing a Co-Sb-M ternary intermetallic compound catalyst according to any one of claims 2 to 8, characterized in that it is used for the reaction of preparing olefins by selective hydrogenation of alkynes or dienes.
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| CN106861691A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation of hydrogenation catalyst and hydrogenation catalyst and application |
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