CN116803503A - Catalyst, preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenation - Google Patents
Catalyst, preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenation Download PDFInfo
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 135
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 239000001384 succinic acid Substances 0.000 title claims abstract description 66
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 41
- 239000012295 chemical reaction liquid Substances 0.000 description 22
- 238000005470 impregnation Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000004364 calculation method Methods 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910018496 Ni—Li Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- -1 polybutylene terephthalate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 229910017539 Cu-Li Inorganic materials 0.000 description 1
- 229910002528 Cu-Pd Inorganic materials 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention provides a catalyst, a preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenation, and belongs to the technical field of catalyst preparation. The expression of the catalyst is Co-X-M/SiO 2 Wherein SiO is 2 And X is selected from one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, and M is selected from one of alkali metal oxide and alkaline earth metal oxide. The invention also provides a preparation method of the catalyst, and the invention also provides an application of the catalyst in preparing 1, 4-butanediol by succinic acid hydrogenation. The invention adopts the non-noble metal catalyst, has simple preparation, low price and high catalytic activity, and is 1, 4-butanediumThe alcohol has good selectivity, can prepare the 1, 4-butanediol at lower reaction temperature and moderate hydrogen pressure within shorter reaction time, and has the yield reaching more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst, a preparation method and application thereof in preparing 1, 4-butanediol by succinic acid hydrogenation.
Background
1, 4-butanediol is an important raw material for industrially producing chemicals such as tetrahydrofuran, N-vinyl pyrrolidone and the like, is also a basic raw material for producing polybutylene terephthalate engineering plastics and fibers, and is widely used in the fields of pesticides, medicines, cosmetics and the like. In recent years, the demand for 1, 4-butanediol has been greatly increased and the price has been greatly increased as a core material for producing degradable plastics such as adipic acid butanediol diformate and poly (butylene succinate). The industrial preparation method of the 1, 4-butanediol mainly comprises four methods, namely an alkynal method, a butadiene method, a propylene oxide method and a maleic anhydride method. The alkynal method is a more traditional method, and the process has the advantages of wider application, harder preparation of raw materials, higher cost, higher safety risk and larger influence on the environment. The butadiene method has the advantages of rich raw material sources and mild reaction conditions, but the process adopts a noble metal catalyst, and has longer flow, large overall investment and high energy consumption. The catalyst in the epoxypropane method can be repeatedly used, has long service life, and the yield of 1, 4-butanediol can be adjusted, but the isomerisation product allyl alcohol has certain toxicity. The maleic anhydride method has the advantages of cheap raw materials and lower production cost, but adopts an acid process for production, and has higher requirement on corrosion resistance of equipment. At present, the methods take fossil resources as raw materials, and various problems exist. With the development of the chemical industry and the increasing demand for 1, 4-butanediol, further development of green synthesis and renewable synthesis processes of 1, 4-butanediol is required.
Succinic acid is an important renewable biomass-based platform molecule, and is one of the potential raw materials for the production of renewable 1, 4-butanediol. In recent years, the development and utilization of renewable resources such as biomass are gradually increased in China. Succinic acid can be produced from a lignocellulosic biomass feedstock, and succinic acid has been industrially produced by a biological method. Therefore, it is necessary, feasible, and of great research and application value to develop efficient techniques for the production of 1, 4-butanediol from succinic acid. Le et al prepared Cu-Pd/HAP catalyst by co-impregnation method for preparing 1, 4-butanediol by succinic acid hydrogenation. The Cu and Pd have synergistic effect in the alloying process, the fine alloy structure with high Cu content is beneficial to preparing 1, 4-butanediol, when the Cu and Pd content is 8wt.% and 2wt.% respectively, the succinic acid conversion rate and the 1, 4-butanediol selectivity are 100% and 82% respectively under the hydrogen pressure condition of 8MPa at 200 ℃&Engineering,2019, 7:18483-18492). Preparation of Re-Pd/TiO by continuous impregnation and catalytic reduction method by Tapin and the like 2 The catalyst has the 1, 4-butanediol yield of 80 percent under the hydrogen pressure condition of 160 ℃ and 15MPa90% (Materials Chemistry and Physics,2020,252: 123225). Di and the like prepare Re-Ru/C bimetallic catalyst for succinic acid hydrogenation reaction by adopting a microwave pyrolysis method. Re-Ru bimetallic interaction changes the adsorption and activation of active components on the surface of the catalyst, and the yield of 1, 4-butanediol is 70.1% under the hydrogen pressure condition of 160 ℃ and 8MPa (Industrial)&Engineering Chemistry Research,2017, 56:4672-4683). The Ru-Sn/AC catalyst is prepared by the dipping method by Vardon et al and is used for the hydrogenation reaction of succinic acid aqueous phase. The catalytic activity is best when the metal mass ratio of Ru to Sn is 1:1, and the 1, 4-butanediol yield is 82% under the hydrogen pressure condition of 10MPa at 180 ℃ (ACS Catalysis,2017, 7:6207-6219). The Pt-Fe bimetallic catalyst is adopted in the process of muu and the like, and 1, 4-butanediol is prepared through succinic acid hydrogenation. The reaction was carried out at 180℃under a hydrogen pressure of 5MPa for 5, 10 and 30 hours, with yields of 1, 4-butanediol of 22, 40.7 and 90.7% (CN 104368358A), respectively. In the above studies, it is generally considered that gamma-butyrolactone is an intermediate in the hydrogenation of succinic acid to 1, 4-butanediol, and gamma-butyrolactone and tetrahydrofuran are major by-products in the reaction for producing 1, 4-butanediol. One U.S. patent reports that when gamma-butyrolactone is subjected to a gas phase hydrogenation reaction over a magnesium silicate supported Cu-Pd-KOH catalyst, wherein Cu, pd, KOH mass% is 12, 0.5, 2% respectively, the 1, 4-butanediol selectivity can reach 99.0% when the conversion of gamma-butyrolactone is 96.5% under hydrogen pressure conditions of 160 ℃ and 6.2MPa (US 4797382). In one Japanese patent, fuchigami et al used Pd/C catalyst in the presence of tetrabutylammonium rhenium oxide to catalyze the hydrogenation of gamma-butyrolactone with a mixture of water and ethanol as the solvent to produce 1, 4-butanediol. The reaction was carried out at 180℃under a hydrogen pressure of 10MPa for 16 hours, with a conversion of gamma-butyrolactone and a selectivity of 1, 4-butanediol of 98% and 88.6%, respectively (JP 7082188).
In summary, in the reaction of preparing 1, 4-butanediol by taking succinic acid as a raw material, a noble metal catalyst is mainly adopted, the reaction temperature is 160-200 ℃, the hydrogen pressure is 5-15MPa, and the yield of 1, 4-butanediol can reach 80% -90%. The reaction conditions are severe and generally require higher hydrogen pressures and longer reaction times. In view of the high price of noble metal catalysts, the production costs are greatly increased. Therefore, the development and application of non-noble metal catalysts, and the catalytic hydrogenation of succinic acid to prepare 1, 4-butanediol at lower temperature and hydrogen pressure, are effective ways of realizing industrial application of the reaction.
Disclosure of Invention
The invention aims to provide a catalyst, a preparation method and application thereof in preparing 1, 4-butanediol by hydrogenating succinic acid, wherein the catalyst can prepare the 1, 4-butanediol under relatively low temperature and hydrogen pressure and in a short reaction time.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention firstly provides a catalyst, the expression formula of which is Co-X-M/SiO 2 Wherein SiO is 2 And X is selected from one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, and M is selected from one of alkali metal oxide and alkaline earth metal oxide.
Preferably, in the catalyst, siO 2 The content of the carrier is 60-89wt.%, the content of Co component is 5-30wt.%, the content of X component is 1-15wt.%, and the content of M component is 5-20wt.%.
Preferably, M is selected from Li 2 O, mgO or CaO.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
step one: impregnating SiO with a metal solution of an alkali metal or alkaline earth metal 2 In the carrier, M/SiO is obtained after drying and calcining 2 A catalyst;
step two: impregnating the mixed metal solution of Co and metal component X into the M/SiO prepared in the step one according to the method of the step one 2 In the process, the catalyst Co-X-M/SiO is obtained after drying, calcining and reducing 2。
Preferably, the impregnating in the first step is specifically: dropwise and uniformly dripping a metal solution of alkali metal or alkaline earth metal into SiO 2 Evaporating solution at 65-75deg.C under tungsten lamp irradiation to obtain SiO 2 Stirring SiO after drying 2 Until the mixture is uniform, the next dripping is carried out, and the process is repeated until the metal solution is exhausted.
Preferably, the calcination temperature of the first step is 200-800 ℃, the calcination time is 1-6h, the calcination temperature of the second step is 200-600 ℃, and the calcination time is 1-6h.
Preferably, the reduction temperature of the second step is 200-600 ℃ and the reduction time is 0.5-4h.
The invention also provides application of the catalyst in preparing 1, 4-butanediol by succinic acid hydrogenation.
Preferably, the method for preparing the 1, 4-butanediol by hydrogenating the succinic acid comprises the following steps:
by H 2 Succinic acid hydrogenation reaction is carried out for a hydrogen source, and reduced Co-X-M/SiO is carried out 2 Adding the catalyst, succinic acid and the solvent into a reaction kettle to react to prepare the 1, 4-butanediol.
Preferably, the reaction temperature is 140-200 ℃, the hydrogen pressure is 3-10MPa, and the reaction time is 1-28h.
The beneficial effects of the invention are that
The invention provides a catalyst, a preparation method and application in preparing 1, 4-butanediol by succinic acid hydrogenation, wherein the catalytic activity can be greatly improved by adding two components of X and M into a Co-based catalyst, and the 1, 4-butanediol is prepared under the conditions of relatively low temperature and hydrogen pressure and in a relatively short reaction time. The use and the dependence on fossil raw materials in the production of 1, 4-butanediol can be reduced; meanwhile, the prepared 1, 4-butanediol has higher selectivity and milder reaction conditions, the 1, 4-butanediol can be prepared under lower temperature and hydrogen pressure conditions, convenience can be provided for the subsequent separation process in industrial production, and the difficulty and energy consumption of the separation process can be reduced.
Detailed Description
The invention firstly provides a catalyst, the expression formula is Co-X-M/SiO 2 Wherein Co is the main metal component, siO 2 As the carrier, X and M respectively represent two other components, X is selected from one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, M is selected from one of alkali metal oxide and alkaline earth metal oxide, preferably Li 2 O, mgO or CaO.
According to the invention, in the catalyst, siO 2 The content of the carrier is preferably 60-89wt.%, the content of the Co component is 5-30wt.%, the content of the X component is 1-15wt.%, and the content of the M component is 5-20wt.%, more preferably: siO (SiO) 2 The content of the carrier is preferably 65-70wt.%, the content of the Co component is 15-22wt.%, the content of the X component is 3-10wt.%, and the content of the M component is 5-10wt.%.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
step one: impregnating SiO with a metal solution of an alkali metal or alkaline earth metal 2 In the carrier, the impregnation is particularly preferably: dropwise and uniformly dripping a metal solution of alkali metal or alkaline earth metal into SiO 2 The surface is dripped in small amount each time, the solution is evaporated under the irradiation of a tungsten lamp at 65-75 ℃ until SiO is obtained 2 Stirring SiO after drying 2 Until uniform, then dripping again, repeating until the metal solution is exhausted, and drying, preferably drying at 110deg.C for one night, and calcining to obtain M/SiO 2 A catalyst; the calcination temperature is preferably 200-800 ℃, more preferably 400-600 ℃, and the calcination time is preferably 1-6 hours, more preferably 3-4 hours;
the metal solution of the alkali metal or alkaline earth metal is nitrate solution or acetate solution of the alkali metal or alkaline earth metal, and the concentration of the metal solution is preferably 0.03-0.15g/ml; the metal solution and SiO 2 The mass ratio of the carrier is preferably 5-30:1, a step of;
step two: impregnating the mixed metal solution of Co and metal component X into the M/SiO prepared in the step one according to the method of the step one 2 And then dried, preferably at 110 ℃ for one night, and calcined, preferably at a temperature of 200-600 ℃, more preferably 300-500 ℃, for a time of preferably 1-6 hours, more preferably 3-4 hours, and a catalystBefore use, the calcined catalyst is reduced in hydrogen atmosphere to obtain Co-X-M/SiO 2 The catalyst, the reduction temperature in the hydrogen atmosphere is preferably 200-600 ℃, more preferably 300-500 ℃, the reduction time is preferably 0.5-4 hours, more preferably 1-2 hours;
the mixed metal solution of Co and the metal component X is nitrate solution or acetate solution of Co and the metal component X, and the concentration of the mixed metal solution is preferably 0.03-0.15g/ml; the mixed metal solution and SiO 2 The mass ratio of the carrier is preferably 5-30:1.
the invention also provides application of the catalyst in preparing 1, 4-butanediol by succinic acid hydrogenation.
The method for preparing the 1, 4-butanediol by hydrogenating the succinic acid preferably comprises the following steps:
by H 2 Succinic acid hydrogenation reaction is carried out for a hydrogen source, and reduced Co-X-M/SiO is carried out 2 The catalyst, the succinic acid and the solvent are added into a reaction kettle for reaction, wherein the reaction temperature is preferably 140-200 ℃, more preferably 160-180 ℃, the hydrogen pressure is preferably 3-10MPa, more preferably 5-7MPa, the reaction time is preferably 1-28h, more preferably 4-8h, and the 1, 4-butanediol is prepared.
According to the invention, the solvent is preferably selected from the group consisting of 1, 4-dioxane, water and alcohol solvents. The mass ratio of the solvent to the succinic acid is preferably 1-50:1, the mass ratio of succinic acid to the catalyst is preferably 1-40:1.
the invention is further illustrated by the following specific examples, which do not limit the scope of the invention.
Comparative example 1
4g of SiO with an average pore diameter of 10nm are weighed out by an analytical balance 2 The carrier is placed in an evaporating dish, the SiO 2 The vector was purchased from FujiSilycia Chemical ltd. 4.26g of cobalt nitrate hexahydrate is added into a volumetric flask, 25ml of distilled water is added to prepare a cobalt nitrate aqueous solution, and ultrasonic oscillation is carried out for 30min. SiO was adjusted by placing the crucible under a 375W tungsten lamp 2 The surface temperature reached about 70 ℃. Drop-wise adding 25ml of the prepared aqueous solution of cobalt nitrate to SiO 2 Surface, solution added dropwise at a timeVolume of about 0.3ml, to be SiO 2 After the surface is completely dried, siO 2 The carrier is evenly stirred, then the next dripping is carried out, and the operation is circulated until the dripping of the cobalt nitrate aqueous solution is completed. The impregnated catalyst was dried at 110℃for 12h and subsequently calcined at 300℃for 3h. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co/SiO with Co loading of 25wt.% is prepared after cooling 2 A catalyst sample.
Comparative example 2
4g of SiO with an average pore diameter of 10nm are weighed out by an analytical balance 2 The support was placed in an evaporation dish. 1.23g of lithium nitrate is added into a volumetric flask, 25ml of distilled water is added to prepare a lithium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. SiO was adjusted by placing the crucible under a 375W tungsten lamp 2 The surface temperature reached about 70 ℃. Drop-wise adding 25ml of the prepared aqueous lithium nitrate solution to SiO 2 On the surface, the volume of the solution added dropwise was about 0.3ml for each time, and SiO was to be obtained 2 After the surface is completely dried, siO 2 The carrier is evenly stirred, then the next dripping is carried out, and the operation is circulated until the dripping of the lithium nitrate aqueous solution is completed. Drying the impregnated catalyst at 110deg.C for 12 hr, and calcining at 500deg.C for 3 hr to obtain Li 2 O/SiO 2 . 4g of the obtained Li was weighed with an analytical balance 2 O/SiO 2 Placed in an evaporation dish. Into a volumetric flask, 4.26g of cobalt nitrate hexahydrate was added, and 25ml of distilled water was further added to prepare an aqueous solution of cobalt nitrate for secondary impregnation, followed by ultrasonic vibration for 30 minutes. Placing crucible under 375W tungsten lamp to regulate Li 2 O/SiO 2 The surface temperature reached about 70 ℃. Drop-wise adding 25ml of the prepared aqueous cobalt nitrate solution to Li 2 O/SiO 2 The surface, the volume of the solution added dropwise each time was about 0.3ml, and after the surface was completely dried, li was added 2 O/SiO 2 Stirring uniformly, then dripping the mixture next time, and circularly operating until the cobalt nitrate aqueous solution is dripped. The impregnated catalyst was dried at 110℃for 12h and subsequently calcined at 300℃for 3h. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co and Li are prepared after cooling 2 Co-Li with O loading of 25wt.% and 10wt.% respectively 2 O/SiO 2 CatalystAnd (3) a sample.
Example 1
Li was prepared by the same method as comparative example 2 2 O/SiO 2 . 4g of the obtained Li was weighed with an analytical balance 2 O/SiO 2 Placed in an evaporation dish. 3.52g of cobalt nitrate hexahydrate and 0.35g of copper nitrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and copper nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110℃for 12 hours and then calcined at 300℃for 3 hours. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co, cu and Li are prepared after cooling 2 The O loadings were 22wt.%,3wt.% and 10wt.% Co-Cu-Li, respectively 2 O/SiO 2 A catalyst sample.
Example 2
Li was prepared by the same method as comparative example 2 2 O/SiO 2 . 4g of the obtained Li was weighed with an analytical balance 2 O/SiO 2 Placed in an evaporation dish. 3.20g of cobalt nitrate hexahydrate and 1.12g of ferric nitrate nonahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and ferric nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110℃for 12 hours and then calcined at 300℃for 3 hours. Before the reaction, the catalyst is reduced for 1h under the condition of 500 ℃ and hydrogen atmosphere, and Co, fe and Li are prepared after cooling 2 The O loadings were 20wt.%,5wt.% and 10wt.% Co-Fe-Li, respectively 2 O/SiO 2 A catalyst sample.
Example 3
Li was prepared by the same method as comparative example 2 2 O/SiO 2 . 4g of the obtained Li was weighed with an analytical balance 2 O/SiO 2 Placed in an evaporation dish. 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. Catalysis after secondary impregnationThe agent was dried at 110℃for 12h and subsequently calcined at 300℃for 3h. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co, ni and Li are prepared after cooling 2 The O loadings were 20wt.%,5wt.% and 10wt.% Co-Ni-Li, respectively 2 O/SiO 2 A catalyst sample.
Example 4
Li was prepared by the same method as comparative example 2 2 O/SiO 2 . 4g of the obtained Li was weighed with an analytical balance 2 O/SiO 2 Placed in an evaporation dish. 3.52g of cobalt nitrate hexahydrate and 0.60g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110℃for 12 hours and then calcined at 300℃for 3 hours. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co, ni and Li are prepared after cooling 2 The O loadings were 22wt.%,3wt.% and 10wt.% Co-Ni-Li, respectively 2 O/SiO 2 A catalyst sample.
Example 5
Li was prepared by the same method as comparative example 2 2 O/SiO 2 . 4g of the obtained Li was weighed with an analytical balance 2 O/SiO 2 Placed in an evaporation dish. 2.40g of cobalt nitrate hexahydrate and 2.00g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110℃for 12 hours and then calcined at 300℃for 3 hours. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co, ni and Li are prepared after cooling 2 The O loadings were 15wt.%,10wt.% and 10wt.% Co-Ni-Li, respectively 2 O/SiO 2 A catalyst sample.
Example 6
Weigh 4g SiO with analytical balance 2 The support was placed in an evaporation dish. Adding 0.62g of lithium nitrate into a volumetric flask, and adding 25ml of distilled water to prepare a lithium nitrate aqueous solutionAnd (5) vibrating for 30min by ultrasonic waves. SiO was adjusted by placing the crucible under a 375W tungsten lamp 2 The surface temperature reached about 70 ℃. Drop-wise adding 25ml of the prepared aqueous lithium nitrate solution to SiO 2 On the surface, the volume of the solution added dropwise was about 0.3ml for each time, and SiO was to be obtained 2 After the surface is completely dried, siO 2 The carrier is evenly stirred, then the next dripping is carried out, and the operation is circulated until the dripping of the lithium nitrate aqueous solution is completed. Drying the impregnated catalyst at 110deg.C for 12 hr, and calcining at 500deg.C for 3 hr to obtain Li 2 O/SiO 2 . 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110℃for 12 hours and then calcined at 300℃for 3 hours. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co, ni and Li are prepared after cooling 2 The O loadings were 20wt.%,5wt.% and 5wt.% Co-Ni-Li, respectively 2 O/SiO 2 A catalyst sample.
Example 7
Weigh 4g SiO with analytical balance 2 The support was placed in an evaporation dish. 1.48g of magnesium nitrate is added into a volumetric flask, 25ml of distilled water is added to prepare magnesium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. SiO was adjusted by placing the crucible under a 375W tungsten lamp 2 The surface temperature reached about 70 ℃. Drop-wise adding 25ml of the prepared magnesium nitrate aqueous solution to SiO 2 On the surface, the volume of the solution added dropwise was about 0.3ml for each time, and SiO was to be obtained 2 After the surface is completely dried, siO 2 The carrier is evenly stirred, then the next dripping is carried out, and the operation is circulated until the dripping of the magnesium nitrate aqueous solution is completed. Drying the impregnated catalyst at 110 ℃ for 12 hours, and then roasting at 500 ℃ for 3 hours to obtain MgO/SiO 2 . 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. Drying the twice impregnated catalyst at 110 ℃ for 12 hours, and thenAnd then roasting for 3 hours at 300 ℃. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co-Ni-MgO/SiO with the loading of 20 wt%, 5 wt% and 10 wt% of Co, ni and MgO are prepared after cooling 2 A catalyst sample.
Example 8
Weigh 4g SiO with analytical balance 2 The support was placed in an evaporation dish. 1.68g of tetrawater and calcium nitrate are added into a volumetric flask, 25ml of distilled water is added to prepare a calcium nitrate aqueous solution, and ultrasonic vibration is carried out for 30min. SiO was adjusted by placing the crucible under a 375W tungsten lamp 2 The surface temperature reached about 70 ℃. Drop-wise adding 25ml of the prepared aqueous solution of calcium nitrate to SiO 2 On the surface, the volume of the solution added dropwise was about 0.3ml for each time, and SiO was to be obtained 2 After the surface is completely dried, siO 2 The carrier is evenly stirred, then the next dripping is carried out, and the operation is circulated until the dripping of the calcium nitrate water solution is completed. Drying the impregnated catalyst at 110 ℃ for 12 hours, and then roasting at 500 ℃ for 3 hours to obtain CaO/SiO 2 . 3.20g of cobalt nitrate hexahydrate and 0.99g of nickel nitrate hexahydrate are added into a volumetric flask, 25ml of distilled water is added to prepare a mixed solution of cobalt nitrate and nickel nitrate for secondary impregnation, and ultrasonic vibration is carried out for 30min. The secondary impregnation was carried out in the same manner as in comparative example 2. The twice impregnated catalyst was dried at 110℃for 12 hours and then calcined at 300℃for 3 hours. Before the reaction, the catalyst is reduced for 1h under the condition of 400 ℃ and hydrogen atmosphere, and Co-Ni-CaO/SiO with the loading of 20 wt%, 5 wt% and 10 wt% of Co, ni and CaO respectively is prepared after cooling 2 A catalyst sample.
Reaction examples
Comparative example 3
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in comparative example 1 were charged into a reaction vessel having a volume of 25ml, and reacted at 200℃under a hydrogen pressure of 5MPa for 12 hours. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. The reaction results are shown in Table 1, and under the reaction conditions, the conversion of succinic acid was 98.8%, and the selectivity and yield of 1, 4-butanediol were 35.3% and 34.8%, respectively. As shown in table 1.
Comparative example 4
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in comparative example 2 were charged into a reaction vessel having a volume of 25ml, and reacted at 180℃under a hydrogen pressure of 5MPa for 12 hours. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 91.6%, and the selectivity and yield of 1, 4-butanediol were 42.6% and 39.0%, respectively. As shown in table 1.
Example 9
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in example 1 were charged into a reaction vessel having a volume of 25ml and reacted at 180℃under a hydrogen pressure of 5MPa for 8 hours. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 78.8%, and the selectivity and yield of 1, 4-butanediol were 72.5% and 57.1%, respectively. As shown in table 1.
Example 10
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 1g of the catalyst prepared in example 2 were charged into a reaction vessel having a volume of 25ml and reacted at 180℃under a hydrogen pressure of 5MPa for 8 hours. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 72.5%, and the selectivity and yield of 1, 4-butanediol were 52.4% and 38.0%, respectively. As shown in table 1.
Example 11
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 3 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 88.9%, and the selectivity and yield of 1, 4-butanediol were 96.5% and 85.8%, respectively. The reaction time was prolonged to 8 hours, the conversion of succinic acid was 99.8%, and the selectivity and yield of 1, 4-butanediol were 96.1% and 94.2%, respectively. As shown in table 1.
Example 12
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 4 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 82.3%, and the selectivity and yield of 1, 4-butanediol were 90.4% and 74.4%, respectively. As shown in table 1.
Example 13
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 5 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 83.0%, and the selectivity and yield of 1, 4-butanediol were 93.5% and 77.6%, respectively. As shown in table 1.
Example 14
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 6 were charged into a reaction vessel having a volume of 25ml and reacted for 4 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 62.6%, and the selectivity and yield of 1, 4-butanediol were 78.2% and 49.0%, respectively. As shown in table 1.
Example 15
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 7 were charged into a reaction vessel having a volume of 25ml and reacted at 180℃under a hydrogen pressure of 5MPa for 8 hours. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 75.3%, and the selectivity and yield of 1, 4-butanediol were 58.2% and 43.8%, respectively. As shown in table 1.
Example 16
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 8 were charged into a reaction vessel having a volume of 25ml and reacted for 8 hours at 180℃under a hydrogen pressure of 5 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under this reaction condition, the conversion of succinic acid was 69.4%, and the selectivity and yield of 1, 4-butanediol were 49.1% and 34.1%, respectively. As shown in table 1.
Example 17
20g of 1, 4-dioxane solution having a succinic acid concentration of 5wt.% and 0.5g of the catalyst prepared in example 3 were charged into a reaction vessel having a volume of 25ml and reacted for 6 hours at 160℃under a hydrogen pressure of 7 MPa. After the reaction, separating the catalyst from the reaction liquid by centrifugation and suction filtration, quantitatively analyzing the reaction liquid by a gas chromatograph, and obtaining the conversion rate of succinic acid and the selectivity of each product by calculation. Under the reaction conditions, the conversion of succinic acid was 96.2%, and the selectivity and yield of 1, 4-butanediol were 98.8% and 95.0%, respectively. As shown in table 1.
TABLE 1
The foregoing has outlined rather broadly the more detailed description of embodiments of the invention, wherein the principles and embodiments of the invention are explained in detail using specific examples, the above examples being provided solely to facilitate the understanding of the method and core concepts of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. A catalyst is characterized in that the expression formula of the catalyst is Co-X-M/SiO 2 Wherein SiO is 2 And X is selected from one or two of Cu, ni, fe, zn, mn, mo, V or Cr metal elements, and M is selected from one of alkali metal oxide and alkaline earth metal oxide.
2. A catalyst according to claim 1, wherein in the catalyst, siO 2 The content of the carrier is 60-89wt.%, the content of Co component is 5-30wt.%, the content of X component is 1-15wt.%, and the content of M component is 5-20wt.%.
3. A catalyst according to claim 1, wherein M is selected from Li 2 O, mgO or CaO.
4. A method for preparing a catalyst according to claim 1, comprising:
step one: impregnating SiO with a metal solution of an alkali metal or alkaline earth metal 2 In the carrier, M/SiO is obtained after drying and calcining 2 A catalyst;
step two: impregnating the mixed metal solution of Co and metal component X into the M/SiO prepared in the step one according to the method of the step one 2 In the middle, through the dryDrying, calcining and reducing to obtain the catalyst Co-X-M/SiO 2。
5. The method for preparing a catalyst according to claim 4, wherein the impregnating in the first step is specifically: dropwise and uniformly dripping a metal solution of alkali metal or alkaline earth metal into SiO 2 Evaporating solution at 65-75deg.C under tungsten lamp irradiation to obtain SiO 2 Stirring SiO after drying 2 Until the mixture is uniform, the next dripping is carried out, and the process is repeated until the metal solution is exhausted.
6. The method for preparing a catalyst according to claim 4, wherein the calcination temperature in the first step is 200-800 ℃ and the calcination time is 1-6 hours, and the calcination temperature in the second step is 200-600 ℃ and the calcination time is 1-6 hours.
7. The method for preparing a catalyst according to claim 4, wherein the reduction temperature in the second step is 200-600 ℃ and the reduction time is 0.5-4h.
8. Use of the catalyst of claim 1 in the preparation of 1, 4-butanediol by hydrogenation of succinic acid.
9. The use of the catalyst according to claim 8 for preparing 1, 4-butanediol by hydrogenating succinic acid, wherein the method for preparing 1, 4-butanediol by hydrogenating succinic acid comprises the following steps:
by H 2 Succinic acid hydrogenation reaction is carried out for a hydrogen source, and reduced Co-X-M/SiO is carried out 2 Adding the catalyst, succinic acid and the solvent into a reaction kettle to react to prepare the 1, 4-butanediol.
10. The use of the catalyst according to claim 9 for preparing 1, 4-butanediol by hydrogenating succinic acid, wherein the reaction temperature is 140-200 ℃, the hydrogen pressure is 3-10MPa, and the reaction time is 1-28h.
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