CN115814809B - Monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, and preparation method and application thereof - Google Patents
Monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, and preparation method and application thereof Download PDFInfo
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- maleic anhydride
- butyrolactone
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 112
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 67
- 239000006260 foam Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005253 cladding Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011701 zinc Chemical class 0.000 claims abstract description 5
- 229910052742 iron Chemical class 0.000 claims abstract description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000010924 continuous production Methods 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010606 normalization Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 5
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- -1 salt compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
Abstract
The invention discloses an integral catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, and a preparation method and application thereof, and belongs to the technical field of catalyst preparation and application. The catalyst takes foam nickel with nickel hydroxide cladding structure as a catalytic active component and a catalyst carrier, and adopts an impregnation method to load metal ion auxiliary agent to form the integral catalyst. The nickel hydroxide cladding structure is formed by aqueous ammonia hydrothermally etching the surface of foam nickel. The first auxiliary agent comprises one or two of molybdate and tungstate, and the second auxiliary agent comprises one or more of metal salts of copper, zinc and iron. The integral catalyst is filled in a fixed bed reactor and is used in the process of continuously producing gamma-butyrolactone by maleic anhydride hydrogenation. The integral catalyst of the invention has the advantages of high activity, good selectivity, low cost, long service life and the like, realizes continuous production of gamma-butyrolactone by maleic anhydride hydrogenation, ensures that the maleic anhydride conversion rate reaches more than 99.8 percent, and ensures that the gamma-butyrolactone selectivity reaches more than 98.5 percent.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application thereof, and mainly relates to an integral catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, and a preparation method and application thereof.
Background
Maleic anhydride (maleic anhydride for short) is an important organic chemical raw material, and is the third largest anhydride next to acetic anhydride and phthalic anhydride in the world at present, and the main production methods thereof are benzene oxidation method and n-butane oxidation method. In recent years, the production and development of maleic anhydride are rapid, the supply and demand of maleic anhydride market is greater than that of maleic anhydride, surplus capacity is generated, the development of downstream product market of maleic anhydride is enhanced, and the method has very important significance for the healthy development of maleic anhydride industry in China.
The gamma-butyrolactone is a downstream hydrogenation product of maleic anhydride, is also an important fine chemical product and a drug intermediate, has the characteristics of high boiling point, good solubility, strong conductivity, good stability and the like, and is widely applied to the fields of fibers, resins, petroleum processing, medicines and the like. It is also an important organic synthesis intermediate for producing N-methyl pyrrolidone, alpha-pyrrolidone, polyvinylpyrrolidone, etc. At present, the production method of gamma-butyrolactone comprises the following steps: the Reppe method, DAVYMCKEE method, allyl alcohol method, direct maleic anhydride hydrogenation method, etc. have gradually become the main method for producing gamma-butyrolactone with the increase of maleic anhydride production capacity and the decrease of price.
The direct hydrogenation method of maleic anhydride can be divided into two technological routes of gas phase hydrogenation and liquid phase hydrogenation. The gas-phase hydrogenation of maleic anhydride is a process in which maleic anhydride is heated and gasified, then mixed with hydrogen and subjected to catalytic hydrogenation under certain conditions and the action of a catalyst. The method has the advantages of high maleic anhydride conversion rate and low reaction pressure, but local hot spots are easy to generate on the surface of the catalyst in the gas phase hydrogenation process, so that reactants coke and carbon are deposited on the surface of the catalyst, and the catalyst is deactivated. And Cu-Cr catalyst is often adopted for maleic anhydride gas phase hydrogenation, and the Cr element is extremely toxic, so that environmental pollution is easy to cause in the use process. The liquid-phase hydrogenation of maleic anhydride is a process in which maleic anhydride is dissolved in an organic solvent or is melted to be liquid, and then reacts with hydrogen under the action of a catalyst at a certain temperature and under a certain pressure. The maleic anhydride liquid phase hydrogenation method has the advantages of easy separation of products, mild operation conditions and high product yield. The existing catalysts for preparing gamma-butyrolactone by maleic anhydride liquid phase hydrogenation can be roughly divided into three types: noble metal catalysts, ni-based catalysts and Cu-based catalysts, wherein the Ni-based catalysts are hot spots for research at home and abroad due to good catalyst activity and low price.
Patent CN102335611A discloses a Ni-Mo/AC catalyst which has higher maleic anhydride hydrogenation activity, the yield of target product gamma-butyrolactone is up to 97.6%, but the catalyst is prepared by adopting an isovolumetric co-impregnation method, the content of active metal nickel is up to 50%, and the catalyst cost is too high.
Patent US2772291 discloses a Ni-Cr-Co catalyst, maleic anhydride has higher conversion rate, but gamma-butyrolactone has poor selectivity, and byproducts such as tetrahydrofuran, 1, 4-butanediol and the like; patent US3312718 improves the catalyst, nickel is used as an active center, and tungstic acid is used as an auxiliary agent, so that the yield of gamma-butyrolactone is improved, but the tungstic acid is easy to run off in the reaction process, so that the stability of the catalyst is reduced.
In large-scale industrial production, the defects of the traditional powder catalyst in the aspect of heat and mass transfer are amplified, and the problems of high pressure drop, uneven distribution of reactants and heat and the like of a catalyst bed layer often occur, so that the problems of high industrial cost, low product selectivity and the like are caused. Therefore, research into monolithic catalysts has become a trend to overcome the conventional powder catalysts.
Therefore, the conventional powder catalyst for producing gamma-butyrolactone by liquid phase hydrogenation of maleic anhydride still has inconvenience and defects, and further improvement is needed. The novel monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation and the preparation method and application thereof can be created, so that the monolithic catalyst uses a three-dimensional porous structure of foam nickel as a carrier, and nickel hydroxide cladding structure sheets formed by in-situ etching are used for effectively improving the specific surface area of the carrier, increasing the specific surface area of active components, fully contacting maleic anhydride molecules to complete the reaction, improving the cis-rod conversion rate, and having important significance for replacing the traditional powder catalyst.
Disclosure of Invention
In view of the above, the invention provides an integral catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, which solves the problems of low selectivity, large bed pressure drop, poor heat transfer and the like of the traditional powder catalyst in the prior art.
In order to achieve the above object, the present invention adopts the following technical scheme:
The invention provides an integral catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, which takes foam nickel with a nickel hydroxide cladding structure as a catalytic active component and a catalyst carrier, and adopts an impregnation method to load a metal ion auxiliary agent to form the integral catalyst.
Further improved, the nickel hydroxide cladding structure of the foam nickel is formed by aqueous ammonia hydrothermally etching the surface of the foam nickel.
Further improved, the metal ion auxiliary agent comprises a first auxiliary agent and a second auxiliary agent, wherein the first auxiliary agent comprises one or two of molybdate and tungstate, the second auxiliary agent comprises one or more of copper, zinc and iron metal salts, the first auxiliary agent and the second auxiliary agent are jointly dissolved in water to form an impregnating solution, foam nickel after hot etching is impregnated, and the integral catalyst is obtained after drying and roasting.
Further improves, the adding amount of the metal elements of molybdenum and tungsten in the first auxiliary agent is 3-7wt% of the mass of the foam nickel carrier, and the adding amount of the metal elements of copper, zinc and iron in the second auxiliary agent is 1-5wt% of the mass of the foam nickel carrier.
Further improved, the appearance size of the foam nickel is 1-5mm multiplied by 1-5mm cubic flake or 1-5mm diameter circular flake with 1-5mm thickness.
As a further improvement of the invention, the invention also provides a preparation method of the monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, which comprises the following steps:
(1) Cutting foam nickel material into pieces, cleaning with deionized water, and drying;
(2) Placing the foam nickel obtained in the step (1) into an ammonia water solution for hydrothermal etching, naturally cooling to room temperature after the reaction is finished, cleaning the surface of the foam nickel by using ethanol and deionized water, and drying;
(3) And (3) dissolving the first auxiliary agent and the second auxiliary agent in deionized water to form an impregnating solution, then impregnating the thermally etched foam nickel material obtained in the step (2) by adopting an equal volume impregnation method, and drying and roasting after impregnation to obtain the integral catalyst for producing gamma-butyrolactone by hydrogenating maleic anhydride.
Further improved, the foamed nickel material in the step (1) has cubic flakes with the appearance size of 1-5mm multiplied by 1-5mm or round flakes with the diameter of 1-5mm and the thickness of 1-5mm, and the drying condition is 60-100 ℃ for 10-15h.
Further improved, the concentration of the ammonia water solution in the step (2) is 5-25 wt%, the hydrothermal etching condition is 100-160 ℃, the reaction is 5-15h, and the drying condition in the step is 60-120 ℃ and the drying condition is 4-20h.
Further improved, the soaking time in the step (3) is 2-6h, the drying condition in the step is 80-120 ℃ for 5-10h, and the roasting condition is 350-500 ℃ for 2-5h. The nickel after roasting exists in the form of NiO in an oxidized state or forms stable salt compounds with metal assistants, such as NiMoO 4 and the like.
As another improvement of the invention, the invention also provides the application of the monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation, the monolithic catalyst is filled in a fixed bed reactor and is used in the process for continuously producing gamma-butyrolactone by maleic anhydride hydrogenation, hydrogen is introduced into the monolithic catalyst for reduction after filling, so that nickel exists in a reduced metallic nickel form, and the catalytic activity is improved. The reduction conditions are as follows: the temperature is 300-400 ℃, the pressure is 1-3MPa, the hydrogen space velocity is 200-600h -1, and the reduction time is 1-3h; then 10-15 wt% maleic anhydride reaction solution is introduced to carry out maleic anhydride selective hydrogenation reaction, and the hydrogenation reaction conditions are as follows: the temperature is 160-250 ℃, the pressure is 2-4MPa, the mass airspeed of maleic anhydride is 1-3h -1, and the molar ratio of hydrogen to maleic anhydride is 20:1-40:1.
Compared with the prior art, the invention has at least the following outstanding beneficial effects:
the monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation uses the three-dimensional porous structure of foam nickel as a catalytic carrier, and carries out in-situ hot etching on the foam nickel to generate nickel hydroxide cladding structure sheets in situ, so that the specific surface area of the carrier is effectively increased, the quantity of active components is increased, the catalyst is fully contacted with maleic anhydride molecules and reacts with the maleic anhydride molecules, and the maleic anhydride conversion rate is improved. Then, a metal ion auxiliary agent is loaded by an impregnation method, so that the foam nickel is used as a carrier to provide supporting and dispersing effects for the introduced metal ions. The addition of the auxiliary agent plays a role in limiting the domain and prevents nickel particles from gathering in the reduction process; on the other hand, the auxiliary agent can improve the adsorption activation capability of the catalyst on the C=C double bond and the C=O bond of maleic anhydride molecules and improve the selectivity of gamma-butyrolactone. The integral catalyst introduces metal ions onto a regular carrier, so that the abrasion problem of the traditional powder catalyst can be solved, and the problems of high pressure drop and poor heat transfer of the powder catalyst in a reactor can be solved, so that the integral catalyst has the advantages of high activity, good selectivity, low cost, long service life and the like.
The monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation has good maleic anhydride hydrogenation activity and gamma-butyrolactone selectivity, the maleic anhydride conversion rate reaches more than 99.8%, and the gamma-butyrolactone selectivity reaches more than 98.5%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the surface of nickel foam after pretreatment in step (1) according to an embodiment of the present invention;
FIG. 2 is an SEM image of the surface of nickel foam thermally etched with ammonia water in step (2) according to the embodiment of the present invention;
FIG. 3 is an SEM image of the surface of a monolithic catalyst prepared according to one embodiment of the invention.
Detailed Description
The catalyst and the preparation method thereof according to the present invention will be further described in conjunction with specific examples to help those skilled in the art to understand the inventive concept, technical scheme more fully, accurately and deeply. It should be noted that the description of the process flow, parameters, etc. in the embodiments is exemplary and not intended to limit the scope of the invention. The test methods described in the examples below, unless otherwise specified, are all conventional; the instrument and the material are all available from commercial sources without special description, for example, the foam nickel material has a thickness of 1-5mm, an areal density of 150-600g/m 2 and an average pore diameter: 0.1-0.3mm, porosity: 80-97%.
Example 1
(1) Cutting commercially available foam nickel material into cubic particles with the size of 2mm multiplied by 2mm, cleaning the cubic particles with deionized water, and then drying the cubic particles at 70 ℃ for 15 hours;
(2) Diluting 2000ml of concentrated ammonia water into 3000ml of distilled water, uniformly mixing, placing 300g of the foam nickel material treated in the step (1) into the obtained ammonia water solution, performing hydrothermal etching at 100 ℃ for 15 hours, respectively cleaning the foam nickel with ethanol and deionized water, and drying at 100 ℃ for 6 hours;
(3) 27.6g of ammonium molybdate tetrahydrate, 27.3g of zinc nitrate hexahydrate and 200g of deionized water are weighed, heated, stirred and dissolved to form an impregnating solution, then the impregnating solution is dripped onto 300g of foam nickel, impregnated for 4 hours at room temperature, dried for 10 hours at 80 ℃, and baked for 4 hours at 400 ℃ in a muffle furnace to obtain the catalyst 1.
Fig. 1 shows an SEM image of the surface of the nickel foam treated in step (1) of the embodiment, fig. 2 shows an SEM image of the surface of the nickel foam treated in step (2) of the embodiment by electron microscopy, and fig. 3 shows an SEM image of the surface of the nickel foam treated in step (3) of the embodiment by metal ion assistant loading under different magnification, namely, a schematic structural diagram of the surface of the monolithic catalyst for producing γ -butyrolactone by hydrogenation of maleic anhydride prepared in the embodiment. As can be seen from the attached figure 1, the surface of the non-etched foam nickel is smooth, and the surface area is small; as can be clearly seen from fig. 2, the surface of the foam nickel subjected to the hydrothermal etching of ammonia water forms a coating structure for coating the nickel hydroxide sheet layer, so that the specific surface area of the foam nickel is greatly increased, and favorable conditions are provided for loading of auxiliary metal ions. It is clear from fig. 3 that the metal ion assistant is uniformly distributed on the surface of the foam nickel, so as to play a role in preventing the aggregation of nickel metal particles and improve the selectivity of gamma-butyrolactone.
The monolithic catalyst 1 prepared in the embodiment can be used in a process for continuously producing gamma-butyrolactone by maleic anhydride hydrogenation, wherein the process adopts a fixed bed reactor, and the maleic anhydride conversion rate and the gamma-butyrolactone selectivity are both measured by gas chromatography (HP-5 chromatographic column, FID detector) by adopting a peak area normalization method.
Specifically, 40g of catalyst 1 is filled in a fixed bed reactor, the catalyst 1 is firstly subjected to reduction and activation under the hydrogen atmosphere before the activity test, and the temperature is programmed to 350 ℃ at 2 ℃/min for 2 hours under the conditions that the hydrogen space velocity is 400h -1 and the pressure is 3 MPa. Then 10wt% maleic anhydride solution is introduced, diethylene glycol dimethyl ether is adopted as a solvent of the maleic anhydride solution, and the catalyst is evaluated under the conditions that the mass airspeed of maleic anhydride is 2h -1 and the molar ratio of hydrogen to maleic anhydride is 30 at 200 ℃ and 3 MPa.
After stable operation, the maleic anhydride conversion rate is 100%, and the gamma-butyrolactone selectivity is 99.2%.
Example 2
(1) Cutting commercially available foam nickel material into cubic particles with the size of 2mm multiplied by 2mm, cleaning the cubic particles with deionized water, and then drying the cubic particles at 60 ℃ for 12 hours;
(2) Weighing 1500ml of concentrated ammonia water, diluting in 3500ml of distilled water, uniformly mixing, placing 300g of the foam nickel material treated in the step (1) into the obtained ammonia water solution, performing hydrothermal etching at 160 ℃ for 5 hours, respectively cleaning the foam nickel with ethanol and deionized water, and drying at 120 ℃ for 4 hours;
(3) 38.6g of ammonium molybdate tetrahydrate, 43.4g of ferric nitrate nonahydrate are weighed, heated, stirred and dissolved in 200g of deionized water to form an impregnating solution, then the impregnating solution is dripped onto 300g of foam nickel, the foam nickel is impregnated for 6 hours at room temperature, then dried for 8 hours at 100 ℃, and baked for 3 hours at 450 ℃ in a muffle furnace to obtain the catalyst 2.
The monolithic catalyst 2 prepared in this example was used in a process for continuous production of gamma-butyrolactone by maleic anhydride hydrogenation, which uses a fixed bed reactor, and both maleic anhydride conversion and gamma-butyrolactone selectivity were measured by gas chromatography (HP-5 column, FID detector) using peak area normalization.
Specifically, 50g of catalyst 2 is filled in a fixed bed reactor, the catalyst 2 is firstly subjected to reduction and activation under the hydrogen atmosphere before the activity test, and the temperature is programmed to 400 ℃ at 2 ℃/min for 1h under the conditions that the hydrogen space velocity is 200h -1 and the pressure is 3 MPa. Then 15wt% maleic anhydride solution is introduced, tetrahydrofuran solution is adopted as solvent of the maleic anhydride solution, and the catalyst is evaluated under the conditions that the mass airspeed of maleic anhydride is 1.5h -1 and the molar ratio of hydrogen to maleic anhydride is 40 at 190 ℃ and 5 MPa.
After stable operation, the maleic anhydride conversion rate is 100%, and the gamma-butyrolactone selectivity is 98.9%.
Example 3
(1) Cutting a commercially available foam nickel material into round slices with the diameter of 4mm and the thickness of 2mm, cleaning the round slices by deionized water, and then drying the round slices at the temperature of 100 ℃ for 10 hours;
(2) Diluting 2500ml of concentrated ammonia water into 2500ml of distilled water, uniformly mixing, placing 300g of the foam nickel material treated in the step (1) into the obtained ammonia water solution, performing hydrothermal etching at 130 ℃ for 10 hours, respectively cleaning the foam nickel with ethanol and deionized water, and drying at 60 ℃ for 20 hours;
(3) 16.6g of ammonium molybdate tetrahydrate, 45.6g of copper nitrate trihydrate are weighed, heated, stirred and dissolved in 200g of deionized water to form impregnating solution, then the impregnating solution is dripped onto 300g of foam nickel, the foam nickel is impregnated for 4 hours at room temperature, then dried for 6 hours at 100 ℃, and baked for 5 hours at 350 ℃ in a muffle furnace to obtain the catalyst 3.
The monolithic catalyst 3 prepared in this example was used in a process for continuous production of gamma-butyrolactone by maleic anhydride hydrogenation, which uses a fixed bed reactor, and maleic anhydride conversion and gamma-butyrolactone selectivity were both determined by gas chromatography (HP-5 column, FID detector) using peak area normalization.
Specifically, 40g of catalyst 3 is filled in a fixed bed reactor, the catalyst 3 is firstly subjected to reduction and activation under the hydrogen atmosphere before the activity test, and the temperature is programmed to 300 ℃ at 2 ℃/min for 3 hours under the conditions that the hydrogen space velocity is 500h -1 and the pressure is 2 MPa. And then 10wt% maleic anhydride solution is introduced, the solvent of the maleic anhydride solution is ethylene glycol dimethyl ether solution, and the catalyst is evaluated under the conditions that the mass airspeed of maleic anhydride is 3h -1 and the molar ratio of hydrogen to maleic anhydride is 20 at 220 ℃ and 2 MPa.
After stable operation, the maleic anhydride conversion rate is 99.8%, and the gamma-butyrolactone selectivity is 98.5%.
Example 4
(1) Cutting a commercially available foam nickel material into round slices with the diameter of 4mm and the thickness of 2mm, cleaning the round slices by deionized water, and then drying the round slices at the temperature of 100 ℃ for 10 hours;
(2) Diluting 2000ml of concentrated ammonia water into 3000ml of distilled water, uniformly mixing, placing 300g of the foam nickel material treated in the step (1) into the obtained ammonia water solution, performing hydrothermal etching at 160 ℃ for 10 hours, respectively cleaning the foam nickel with ethanol and deionized water, and drying in a constant-temperature drying oven at 120 ℃ for 5 hours;
(3) 26.4g of ammonium molybdate tetrahydrate, 45.6g of zinc nitrate hexahydrate, heating, stirring and dissolving in 200g of deionized water to form an impregnating solution, then dripping the impregnating solution onto 300g of foam nickel, impregnating for 4 hours at room temperature, drying for 6 hours at 100 ℃, and roasting for 2 hours at 500 ℃ in a muffle furnace to obtain the catalyst 4.
The monolithic catalyst 4 prepared in this example was used in a process for continuous production of gamma-butyrolactone by maleic anhydride hydrogenation, which uses a fixed bed reactor, and both maleic anhydride conversion and gamma-butyrolactone selectivity were measured by gas chromatography (HP-5 column, FID detector) using peak area normalization.
Specifically, 30g of catalyst 4 is filled in a fixed bed reactor, the catalyst 4 is firstly subjected to reduction and activation under the hydrogen atmosphere before the activity test, and the temperature is programmed to 350 ℃ at 2 ℃/min for 2 hours under the conditions that the hydrogen space velocity is 600h -1 and the pressure is 1 MPa. Then 10wt% maleic anhydride solution is introduced, benzene solution is adopted as solvent of the maleic anhydride solution, and the catalyst is evaluated under the conditions that the mass airspeed of maleic anhydride is 1h -1 and the molar ratio of hydrogen to maleic anhydride is 30 at 210 ℃ and under the pressure of 4 MPa.
After stable operation, the maleic anhydride conversion rate is 100%, and the gamma-butyrolactone selectivity is 99.0%.
Comparative example 1
Commercially available foam nickel material was cut into 2mm×2mm cubic particles, washed with deionized water, and dried at 70 ℃ for 15 hours to obtain catalyst 5.
The monolithic catalyst 5 prepared in this example was used in a process for continuous production of gamma-butyrolactone by maleic anhydride hydrogenation, which uses a fixed bed reactor, and both maleic anhydride conversion and gamma-butyrolactone selectivity were measured by gas chromatography (HP-5 column, FID detector) using peak area normalization.
Specifically, 40g of catalyst 5 is filled in a fixed bed reactor, the catalyst 5 is firstly subjected to reduction and activation under the hydrogen atmosphere before the activity test, and the temperature is programmed to 350 ℃ at 2 ℃/min for 2 hours under the conditions that the hydrogen space velocity is 500h -1 and the pressure is 1 MPa. Then 10wt% maleic anhydride solution is introduced, diethylene glycol dimethyl ether solution is adopted as solvent of the maleic anhydride solution, and the catalyst is evaluated under the conditions that the mass airspeed of maleic anhydride is 1h -1 and the molar ratio of hydrogen to maleic anhydride is 30 at 210 ℃ and 4 MPa.
After stable operation, the maleic anhydride conversion rate is 76.3%, and the gamma-butyrolactone selectivity is 23.3%.
Comparative example 2
(1) Cutting a commercially available foam nickel material into round slices with the diameter of 4mm and the thickness of 2mm, cleaning the round slices by deionized water, and then drying the round slices at 70 ℃ for 15 hours;
(2) 27.6g of ammonium molybdate tetrahydrate, 27.3g of zinc nitrate hexahydrate and 200g of deionized water are weighed, heated, stirred and dissolved to form an impregnating solution, then the impregnating solution is dripped onto 300g of foam nickel, impregnated for 4 hours at room temperature, dried for 10 hours at 80 ℃, and baked for 4 hours at 400 ℃ in a muffle furnace to obtain the catalyst 6.
The monolithic catalyst 6 prepared in this example was used in a process for continuous production of gamma-butyrolactone by maleic anhydride hydrogenation, which uses a fixed bed reactor, and both maleic anhydride conversion and gamma-butyrolactone selectivity were measured by gas chromatography (HP-5 column, FID detector) using peak area normalization.
Specifically, 40g of catalyst 6 is filled in a fixed bed reactor, the catalyst 6 is firstly subjected to reduction and activation under the hydrogen atmosphere before the activity test, and the temperature is programmed to 300 ℃ at 2 ℃/min for 3 hours under the conditions that the hydrogen space velocity is 400h -1 and the pressure is 2 MPa. And then 10wt% maleic anhydride solution is introduced, the solvent of the maleic anhydride solution is ethylene glycol dimethyl ether solution, and the catalyst is evaluated under the conditions that the mass airspeed of maleic anhydride is 1h -1 and the molar ratio of hydrogen to maleic anhydride is 20 at 220 ℃ and 2 MPa.
After stable operation, the maleic anhydride conversion rate is 96.7%, and the gamma-butyrolactone selectivity is 68.6%.
It should be noted that, in the case of no conflict, the above-mentioned embodiments and features in the embodiments may be combined with each other; and that all other embodiments, which are intended to be within the scope of the present invention, will be readily apparent to those of ordinary skill in the art based upon the embodiments in this disclosure without undue burden.
Claims (7)
1. The monolithic catalyst for producing gamma-butyrolactone by maleic anhydride hydrogenation is characterized in that the monolithic catalyst takes foam nickel with a nickel hydroxide cladding structure as a catalytic active component and a catalyst carrier, and adopts an impregnation method to load a metal ion auxiliary agent to form the monolithic catalyst, and the nickel hydroxide cladding structure of the foam nickel is formed by aqua-thermoetching the surface of the foam nickel by ammonia water;
The metal ion auxiliary agent comprises a first auxiliary agent and a second auxiliary agent, wherein the first auxiliary agent comprises one or two of molybdate and tungstate, the second auxiliary agent comprises one or more of copper, zinc and iron metal salts, the first auxiliary agent and the second auxiliary agent are jointly dissolved in water to form an impregnating solution, foam nickel after hot etching is impregnated, and the integral catalyst is obtained after drying and roasting;
the addition amount of the metal elements of molybdenum and tungsten in the first auxiliary agent is 3-7wt% of the mass of the foam nickel carrier, and the addition amount of the metal elements of copper, zinc and iron in the second auxiliary agent is 1-5wt% of the mass of the foam nickel carrier.
2. The monolithic catalyst for the hydrogenation of maleic anhydride to gamma-butyrolactone according to claim 1, wherein the nickel foam has external dimensions of 1-5mm x 1-5mm cubic flakes or 1-5mm diameter round flakes 1-5mm thick.
3. A process for preparing a monolithic catalyst for the hydrogenation of maleic anhydride to gamma-butyrolactone according to claim 1 or 2, comprising the steps of:
(1) Cutting foam nickel material into pieces, cleaning with deionized water, and drying;
(2) Placing the foam nickel obtained in the step (1) into an ammonia water solution for hydrothermal etching, naturally cooling to room temperature after the reaction is finished, cleaning the surface of the foam nickel by using ethanol and deionized water, and drying;
(3) And (3) dissolving the first auxiliary agent and the second auxiliary agent in deionized water to form an impregnating solution, then impregnating the thermally etched foam nickel material obtained in the step (2) by adopting an equal volume impregnation method, and drying and roasting after impregnation to obtain the integral catalyst for producing gamma-butyrolactone by hydrogenating maleic anhydride.
4. The method for preparing monolithic catalyst for producing gamma-butyrolactone by hydrogenating maleic anhydride according to claim 3, wherein the foamed nickel material in step (1) has cubic flakes having an external dimension of 1-5mm x 1-5mm or round flakes having a diameter of 1-5mm and a thickness of 1-5mm, and the drying condition is 60-100 ℃ for 10-15 hours.
5. The method for preparing monolithic catalyst for producing gamma-butyrolactone by hydrogenating maleic anhydride according to claim 3, wherein the concentration of the ammonia solution in the step (2) is 5wt% -25wt%, the hydrothermal etching condition is 100-160 ℃, the reaction is 5-15h, and the drying condition in the step is 60-120 ℃ and the drying condition is 4-20h.
6. The method for preparing a monolithic catalyst for producing gamma-butyrolactone by hydrogenating maleic anhydride according to claim 3, wherein the impregnation time in the step (3) is 2 to 6 hours, the drying condition in the step is 80 to 120 ℃ for 5 to 10 hours, and the roasting condition is 350 to 500 ℃ for 2 to 5 hours.
7. The application of the monolithic catalyst for producing gamma-butyrolactone by hydrogenating maleic anhydride according to claim 1 or 2, wherein the monolithic catalyst is filled in a fixed bed reactor and is used in a process for continuously producing gamma-butyrolactone by hydrogenating maleic anhydride, hydrogen is introduced for reduction after filling the monolithic catalyst, and the reduction conditions are as follows: the temperature is 300-400 ℃, the pressure is 1-3MPa, the hydrogen space velocity is 200-600h -1, and the reduction time is 1-3h; then 10-15 wt% maleic anhydride reaction solution is introduced to carry out maleic anhydride selective hydrogenation reaction, and the hydrogenation reaction conditions are as follows: the temperature is 160-250 ℃, the pressure is 2-4MPa, the mass airspeed of maleic anhydride is 1-3h -1, and the molar ratio of hydrogen to maleic anhydride is 20:1-40:1.
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| US3169975A (en) * | 1962-06-06 | 1965-02-16 | Basf Ag | Production of saturated cyclic dicarboxylic anhydrides |
| JPS6388045A (en) * | 1986-09-30 | 1988-04-19 | Mitsubishi Petrochem Co Ltd | Hydrogenation catalyst for preparing gamma-butyrolactone |
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