CN114471618B - Sulfur-doped carbon-supported nickel-based catalyst, preparation method and application - Google Patents
Sulfur-doped carbon-supported nickel-based catalyst, preparation method and application Download PDFInfo
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- CN114471618B CN114471618B CN202011152640.6A CN202011152640A CN114471618B CN 114471618 B CN114471618 B CN 114471618B CN 202011152640 A CN202011152640 A CN 202011152640A CN 114471618 B CN114471618 B CN 114471618B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- -1 isooctyl aldehyde Chemical class 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 120
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- KYXCWBOZEWMWSY-UHFFFAOYSA-N 6-methylhept-2-enal Chemical compound CC(C)CCC=CC=O KYXCWBOZEWMWSY-UHFFFAOYSA-N 0.000 claims description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 13
- 239000004815 dispersion polymer Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 20
- 238000011068 loading method Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 229910019993 S1-Ni Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- PYLMCYQHBRSDND-VURMDHGXSA-N (Z)-2-ethyl-2-hexenal Chemical compound CCC\C=C(\CC)C=O PYLMCYQHBRSDND-VURMDHGXSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- GZLCNRXKVBAALW-UHFFFAOYSA-N O=[Ru](=O)=O Chemical compound O=[Ru](=O)=O GZLCNRXKVBAALW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WCYAALZQFZMMOM-UHFFFAOYSA-N methanol;sulfuric acid Chemical compound OC.OS(O)(=O)=O WCYAALZQFZMMOM-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a sulfur-doped carbon-supported nickel-based catalyst, a preparation method and application thereof. The catalyst comprises: the carbon carrier generated in situ, ni and sulfur loaded on the carbon carrier generated in situ by coordination; based on 100% of the total catalyst weight, the Ni content is 50-60%, and the sulfur content is 0.01-0.1%. The carbon carrier generated in situ is obtained by carbonizing imidazole polymer at high temperature in an anaerobic atmosphere. The catalyst of the invention can obtain isooctyl aldehyde with high selectivity under the condition of liquid phase hydrogenation. The Ni metal catalyst provided by the invention has low cost and high selectivity. Because of the coordination effect of sulfur element and nickel metal in the carbon material generated in situ, certain toxicity can be generated on the nickel component, the hydrogenation activity of nickel is reduced, and the hydrogenation selectivity of nickel is improved. In addition, the carbon-based carrier generated in situ has fewer acid sites, so that side reactions are reduced.
Description
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a sulfur-doped carbon-supported nickel-based catalyst, a preparation method and application thereof.
Background
Isooctanoic acid and important fine chemicals are mainly used as various unsaturated polyester resin accelerators and catalysts, paint and ink driers, polyvinyl chloride processing aids, metal processing and lubricating aids, oil additives and rubber vulcanization accelerators, and can be used as intermediates for synthesizing medicines, dyes, pesticides, fragrances and the like. Some European and American companies mostly adopt isooctyl aldehyde oxidation technology to produce isooctanoic acid, and the technology is green and environment-friendly, high in yield and high in product quality, but has higher requirements on isooctyl aldehyde.
Currently, the industrial isooctyl aldehyde preparation mainly comprises a propylene oxo process and an acetaldehyde aldol condensation process. The propylene oxo process is to obtain butyraldehyde with propylene and synthetic gas under the action of cobalt or ruthenium catalyst, to condense and dewater to obtain 2-ethyl-2-hexenal, and to obtain isooctyl aldehyde through selective hydrogenation. The aldol condensation method uses acetaldehyde as raw material, and uses condensation, dehydration and hydrogenation to obtain butyraldehyde, and the subsequent process is identical to propylene oxo synthesis method. Therefore, in the preparation of isooctyl aldehyde, the selective hydrogenation of isooctyl aldehyde is a key process.
Pd/Al is used for industrial selective hydrogenation catalyst 2 O 3 A catalyst. For example, the yield of isooctyl aldehyde prepared by catalyzing isooctyl aldehyde hydrogenation can reach 98% and the selectivity can reach 99% at the reaction temperature of 85-95 ℃. Patent CN110433802a also discloses a palladium catalyst with ruthenium trioxide, manganese oxide, rhenium heptaoxide, antimony trioxide, bismuth trioxide and selenium dioxide as auxiliary agents, which can obtain isooctyl aldehyde with high selectivity. However, noble metal palladium is expensive and has high production cost.
The metal Ni catalyst is widely used hydrogenation catalyst in oil refining and chemical industry, but the activity of the Ni catalyst is too high, so that unsaturated aldehyde is easy to be completely hydrogenated to generate saturated alcohol, and the yield of the unsaturated aldehyde is low.
Patent GB 1102796A discloses a Ni/diatomite catalyst which adopts a mode of partially poisoning the Ni catalyst by sulfide to improve the selectivity of saturated aldehyde. When the catalyst is used for hydrogenation reaction of isooctene aldehyde, the conversion rate of isooctene aldehyde reaches 98%, and the selectivity reaches 97%. However, the reaction is a gas phase hydrogenation reaction, which requires a higher temperature of 225 ℃ and has a side reaction of raw material cracking.
In summary, the Ni metal hydrogenation catalyst has a cost advantage, but the gas phase hydrogenation process has high reaction temperature, high energy consumption, and side reactions.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a sulfur-doped carbon-supported nickel-based catalyst, a preparation method and application. The method has mild reaction conditions and realizes high selectivity of liquid-phase isooctyl aldehyde.
It is an object of the present invention to provide a sulfur-doped carbon supported nickel-based catalyst.
The carbon carrier generated in situ, ni and sulfur loaded on the carbon carrier generated in situ by coordination;
based on 100% of the total catalyst weight, the Ni content is 50-60%, and the sulfur content is 0.01-0.1%.
Wherein,,
the carbon carrier generated in situ is obtained by carbonizing imidazole polymer at high temperature in an anaerobic atmosphere.
The second object of the invention is to provide a method for preparing the sulfur-doped carbon-supported nickel-based catalyst.
The method comprises the following steps:
(1) Preparing imidazole polymer dispersion liquid;
(2) Preparing nickel salt and sulfuric acid solution;
(3) Dropwise adding nickel salt and sulfuric acid solution into imidazole polymer dispersion liquid;
(4) Filtering and washing the solution;
(5) The solid is obtained to be carbonized at high temperature in an anaerobic atmosphere.
In a preferred embodiment of the present invention,
the solvent of the imidazole polymer dispersion liquid is methanol or ethanol; more preferably methanol; and/or the number of the groups of groups,
the solvent of the nickel salt and sulfuric acid solution is methanol or ethanol; more preferably methanol; and/or the number of the groups of groups,
the imidazole polymer is polyvinyl imidazole or a vinyl imidazole-divinylbenzene copolymer; more preferably polyvinylimidazole; and/or the number of the groups of groups,
the nickel salt is selected from nickel nitrate or nickel carbonate, more preferably nickel nitrate;
in a preferred embodiment of the present invention,
step (1), the concentration of the imidazole polymer dispersion liquid is 0.01-0.1g/ml;
in a preferred embodiment of the present invention,
step (2), the concentration of the nickel salt solution is 0.01-0.1g/ml; sulfuric acid concentration of 4 x 10 -6 ～4*10 -5 g/ml。
In a preferred embodiment of the present invention,
step (3), the volume ratio of the imidazole polymer dispersion liquid to the nickel salt and sulfuric acid solution is (0.2-20): 1.
in a preferred embodiment of the present invention,
step (5), the anaerobic atmosphere is nitrogen or argon atmosphere; and/or
The carbonization temperature is 450-600 ℃.
It is a further object of the present invention to provide a catalyst obtainable by said process.
It is a fourth object of the present invention to provide the use of the catalyst or the catalyst obtained by the process for the preparation of isooctyl aldehyde.
Under the condition of hydrogen, isooctenal is used as a raw material, and under the action of a catalyst, isooctenal is subjected to selective hydrogenation reaction to obtain isooctenal;
the hydrogen pressure is 1-10Mpa, the reaction temperature is 70-150 DEG C
The catalyst is one of the objects of the invention or the catalyst obtained by the two methods of the object of the invention.
The invention adopts the following technical scheme:
a preparation method of a sulfur-doped carbon-supported nickel catalyst.
The method comprises the following steps:
(1) Preparing a methanol dispersion of the imidazole polymer;
(2) Preparing nickel nitrate and a methanol sulfate solution;
(3) Dropwise adding nickel nitrate and a sulfuric acid methanol solution into a methanol dispersion liquid of the imidazole polymer;
(4) Filtering and washing the solution;
(5) The solid is obtained to be carbonized at high temperature in an anaerobic atmosphere.
The catalyst comprises an in-situ generated carbon carrier, ni and sulfur which are coordinately loaded on the in-situ generated carbon carrier, wherein the content of Ni is 50-60% by weight of the total weight of the catalyst, the content of sulfur (calculated by sulfuric acid) is 0.01-0.1%, and the balance is the in-situ generated carbon carrier. The carbon carrier generated in situ is obtained by carbonizing imidazole polymer at a high temperature of 450-600 ℃ in an anaerobic atmosphere.
Use of the sulfur-doped carbon-supported nickel catalyst.
Under the condition of hydrogen, isooctenal is used as a raw material, methanol is used as a solvent, and the hydrogen pressure is controlled to be 1-10Mpa, the reaction temperature is 70-150 ℃, and isooctenal is subjected to selective hydrogenation reaction in a high-pressure reaction kettle filled with the sulfur-doped carbon-loaded nickel catalyst to obtain isooctenal.
Effects of the invention
The catalyst of the invention can obtain isooctyl aldehyde with high selectivity under the condition of liquid phase hydrogenation. The Ni metal catalyst provided by the invention has low cost and high selectivity. Because of the coordination effect of sulfur element and nickel metal in the carbon material generated in situ, certain toxicity can be generated on the nickel component, the hydrogenation activity of nickel is reduced, and the hydrogenation selectivity of nickel is improved. In addition, the carbon-based carrier generated in situ has fewer acid sites, so that side reactions are reduced.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In the examples, all materials were commercially available except for the specific descriptions.
Example 1
Taking 20ml of methanol solution with the concentration of 0.05g/ml of polyvinyl imidazole; nickel nitrate and sulfuric acid with concentration of 0.05g/ml and 2 x 10 respectively are taken -5 10ml of a g/ml methanol solution; in the state of stirring, the stirring device can stir,dropwise adding a methanol solution of nickel nitrate and sulfuric acid into a methanol solution of polyvinyl imidazole, and keeping stirring for 4 hours; the solution was filtered and washed 3 times with methanol and dried in vacuo at 80 ℃; the obtained solid powder is roasted for 4 hours at 450 ℃ in nitrogen atmosphere, and the S1-Ni/C-450 catalyst with the sulfur content of 0.1% and the nickel loading amount of 50% is obtained.
Before use, after the S1-Ni/C-450 catalyst is reduced by hydrogen at 450 ℃, 0.5g, 0.1g and 9.9g of S1-Ni/C-450, isooctenal and methanol are respectively added into a stainless steel reaction kettle, the reaction kettle is completely sealed, and the air in the reaction kettle is replaced by high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 100 ℃ and the hydrogen pressure of 3Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
Example 2
Taking 100ml of methanol solution with the concentration of 0.01g/ml of polyvinyl imidazole; nickel nitrate and sulfuric acid with concentration of 0.1g/ml and 4 x 10 respectively are taken -6 5ml of a methanol solution of g/ml; dropwise adding a methanol solution of nickel nitrate and sulfuric acid into a methanol solution of polyvinyl imidazole under stirring, and keeping stirring for 4 hours; the solution was filtered and washed 3 times with methanol and dried in vacuo at 80 ℃; the obtained solid powder is roasted for 8 hours at 450 ℃ in nitrogen atmosphere, and the S2-Ni/C-450 catalyst with the sulfur content of 0.01% and the nickel loading amount of 50% is obtained.
Before use, after the S2-Ni/C-450 catalyst is reduced by hydrogen at 450 ℃, 0.5g, 0.1g and 9.9g of S2-Ni/C-450, isooctenal and methanol are respectively added into a stainless steel reaction kettle, the reaction kettle is completely sealed, and the air in the reaction kettle is replaced by high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 70 ℃ and the hydrogen pressure of 10Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
Example 3
Taking 10ml of methanol solution with the concentration of 0.1g/ml of polyvinyl imidazole; nickel nitrate and sulfuric acid with concentration of 0.01g/ml and 4 x 10 respectively are taken -6 50ml of a g/ml methanol solution; dropwise adding methanol solution of nickel nitrate and sulfuric acid into polyvinyl imidazole under stirringIs kept stirring for 4 hours; the solution was filtered and washed 3 times with methanol and dried in vacuo at 80 ℃; the obtained solid powder is roasted for 12 hours at 450 ℃ in nitrogen atmosphere, and the S3-Ni/C-450 catalyst with the sulfur content of 0.1% and the nickel loading amount of 50% is obtained.
Before use, after the S3-Ni/C-450 catalyst is reduced by hydrogen at 450 ℃, 0.5g, 0.1g and 9.9g of S3-Ni/C-450, isooctenal and methanol are respectively added into a stainless steel reaction kettle, the reaction kettle is completely sealed, and the air in the reaction kettle is replaced by high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 150 ℃ and the hydrogen pressure of 1Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
Example 4
Taking 20ml of methanol solution with the concentration of 0.05g/ml of polyvinyl imidazole; nickel nitrate and sulfuric acid with concentration of 0.05g/ml and 2 x 10 respectively are taken -5 10ml of a g/ml methanol solution; dropwise adding a methanol solution of nickel nitrate and sulfuric acid into a methanol solution of polyvinyl imidazole under stirring, and keeping stirring for 4 hours; the solution was filtered and washed 3 times with methanol and dried in vacuo at 80 ℃; the obtained solid powder is roasted for 4 hours at 600 ℃ in nitrogen atmosphere, and the S1-Ni/C-600 catalyst with the sulfur content of 0.1% and the nickel loading amount of 60% is obtained.
Before use, after reducing the S1-Ni/C-600 catalyst with hydrogen at 450 ℃, adding 0.5g, 0.1g and 9.9g of S1-Ni/C-600, isooctenal and methanol into a stainless steel reaction kettle respectively, completely sealing, and replacing the air in the reaction kettle with high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 100 ℃ and the hydrogen pressure of 3Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
Example 5
Taking 100ml of methanol solution with the concentration of 0.01g/ml of polyvinyl imidazole; nickel nitrate and sulfuric acid with concentration of 0.1g/ml and 4 x 10 respectively are taken -6 5ml of a methanol solution of g/ml; dropwise adding a methanol solution of nickel nitrate and sulfuric acid into a methanol solution of polyvinyl imidazole under stirring, and keeping stirring for 4 hours; passing the above solution throughFiltering and washing with methanol for 3 times, and vacuum drying at 80deg.C; the obtained solid powder is roasted for 8 hours at 600 ℃ in nitrogen atmosphere, and the S2-Ni/C-600 catalyst with the sulfur content of 0.01% and the nickel loading amount of 60% is obtained.
Before use, after reducing the S2-Ni/C-600 catalyst with hydrogen at 450 ℃, adding 0.5g, 0.1g and 9.9g of S2-Ni/C-600, isooctenal and methanol into a stainless steel reaction kettle respectively, completely sealing, and replacing the air in the reaction kettle with high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 70 ℃ and the hydrogen pressure of 10Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
Example 6
Taking 10ml of ethanol solution with the concentration of the vinylimidazole-divinylbenzene copolymer of 0.1g/ml; nickel carbonate and sulfuric acid with concentration of 0.01g/ml and 4 x 10 respectively are taken -6 50ml of a g/ml ethanol solution; dropwise adding ethanol solution of nickel carbonate and sulfuric acid into ethanol solution of vinylimidazole-divinylbenzene copolymer under stirring, and keeping stirring for 4 hours; filtering the solution, washing with ethanol for 3 times, and vacuum drying at 80deg.C; the obtained solid powder is roasted for 12 hours at 600 ℃ in nitrogen atmosphere, and the S3-Ni/C-600 catalyst with the sulfur content of 0.1% and the nickel loading amount of 60% is obtained.
Before use, after reducing the S3-Ni/C-600 catalyst with hydrogen at 450 ℃, adding 0.5g, 0.1g and 9.9g of S3-Ni/C-600, isooctenal and methanol into a stainless steel reaction kettle respectively, completely sealing, and replacing the air in the reaction kettle with high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 150 ℃ and the hydrogen pressure of 1Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
Comparative example 1
Use of Ni/Al with an industrial nickel loading of 20% 2 O 3 The hydrogenation catalyst is a comparative catalyst
Ni/Al of traditional supported nickel hydrogenation catalyst prepared by adopting equivalent impregnation method 2 O 3 . 10ml of nickel nitrate aqueous solution with nickel concentration of 0.2g/ml was taken, 10g of alumina was added thereto, and immersedAfter 2h, the mixture was dried at 110℃for 4h. Finally roasting at 400 ℃ to prepare Ni/Al with 20 percent nickel loading 2 O 3 A hydrogenation catalyst.
Before use, the Ni/Al alloy is treated with hydrogen at 450 DEG C 2 O 3 After the catalyst is reduced, ni/Al is added 2 O 3 0.5g, 0.1g and 9.9g of isooctenal and methanol are respectively added into a stainless steel reaction kettle, the reaction kettle is completely closed, and the air in the reaction kettle is replaced by high-purity hydrogen for 3 times. The reaction is carried out for 4 hours at the reaction temperature of 100 ℃ and the hydrogen pressure of 3Mpa and the stirring speed of 400 r/min, thus obtaining the product containing isooctyl aldehyde. The experimental results are shown in Table 1.
TABLE 1 hydrogenation Activity and Selectivity of catalysts
The hydrogenation activity of nickel metal is reduced due to the doping of sulfur element, but the hydrogenation selectivity is improved. The yield of isooctyl aldehyde is obviously improved.
Claims (10)
1. A sulfur-doped carbon-supported nickel-based catalyst, characterized in that the catalyst comprises:
the carbon carrier generated in situ, ni and sulfur loaded on the carbon carrier generated in situ by coordination;
based on 100 percent of the total weight of the catalyst, the content of Ni is 50 to 60 percent, and the content of sulfur is 0.01 to 0.1 percent;
the carbon carrier generated in situ is obtained by carbonizing an imidazole polymer at a high temperature in an anaerobic atmosphere;
the catalyst is prepared by a method comprising the following steps:
(1) Preparing imidazole polymer dispersion liquid;
(2) Preparing nickel salt and sulfuric acid solution;
(3) Dropwise adding nickel salt and sulfuric acid solution into imidazole polymer dispersion liquid;
(4) Filtering and washing the solution;
(5) The solid is obtained to be carbonized at high temperature in an anaerobic atmosphere.
2. A method for preparing the sulfur-doped carbon-supported nickel-based catalyst according to claim 1, comprising:
(1) Preparing imidazole polymer dispersion liquid;
(2) Preparing nickel salt and sulfuric acid solution;
(3) Dropwise adding nickel salt and sulfuric acid solution into imidazole polymer dispersion liquid;
(4) Filtering and washing the solution;
(5) The solid is obtained to be carbonized at high temperature in an anaerobic atmosphere.
3. The method of manufacturing as claimed in claim 2, wherein:
the solvent of the imidazole polymer dispersion liquid is methanol or ethanol; and/or the number of the groups of groups,
the solvent of the nickel salt and sulfuric acid solution is methanol or ethanol; and/or the number of the groups of groups,
the imidazole polymer is polyvinyl imidazole or a vinyl imidazole-divinylbenzene copolymer; and/or the number of the groups of groups,
the nickel salt is selected from nickel nitrate or nickel carbonate.
4. The method of manufacturing as claimed in claim 2, wherein:
step (1), the concentration of the imidazole polymer dispersion liquid is 0.01-0.1g/mL.
5. The method of manufacturing as claimed in claim 2, wherein:
step (2), the concentration of the nickel salt solution is 0.01-0.1g/mL, and the concentration of sulfuric acid is 4 x 10 -6 ～4*10 -5 g/mL。
6. The method of manufacturing as claimed in claim 2, wherein:
step (3), the volume ratio of the imidazole polymer dispersion liquid to the nickel salt and sulfuric acid solution is (0.2-20): 1.
7. the method of manufacturing as claimed in claim 2, wherein:
step (5), the anaerobic atmosphere is nitrogen or argon atmosphere; and/or the number of the groups of groups,
the carbonization temperature is 450-600 ℃.
8. A catalyst obtainable by the process of any one of claims 2 to 7.
9. Use of the catalyst according to claim 1 or obtainable by the process according to any one of claims 2 to 7 for the preparation of isooctyl aldehyde.
10. The use according to claim 9, wherein:
under the condition of hydrogen, isooctenal is used as a raw material, and under the action of a catalyst, isooctenal is subjected to selective hydrogenation reaction to obtain isooctenal;
the hydrogen pressure is 1-10Mpa, and the reaction temperature is 70-150 ℃.
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