CN116020471A - Supported catalyst, its preparation method and application, and the method for producing succinic anhydride by hydrogenation of maleic anhydride - Google Patents
Supported catalyst, its preparation method and application, and the method for producing succinic anhydride by hydrogenation of maleic anhydride Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229940014800 succinic anhydride Drugs 0.000 title claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 60
- 239000002243 precursor Substances 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 35
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 claims description 29
- 239000012018 catalyst precursor Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- OUROFEZRKYXSAX-UHFFFAOYSA-N cerium(3+) zirconium(4+) dinitrate Chemical compound [N+](=O)([O-])[O-].[Zr+4].[N+](=O)([O-])[O-].[Ce+3] OUROFEZRKYXSAX-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- -1 agriculture Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
本发明涉及催化剂技术领域，具体地，涉及一种负载型催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法，所述负载型催化剂包括载体以及负载在所述载体上的活性组分，所述活性组分含有Ni元素、Ce元素和Zr元素，所述载体含有Al2O3；所述负载型催化剂中，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为8‑40重量％，Ce元素的含量为1‑8重量％，所述Zr元素的含量为1‑5重量％，所述载体的含量为60‑90重量％。本发明的催化剂具有高的催化活性和丁二酸酐选择性，且制备工艺简单，能够应用于连续的大规模生产。The present invention relates to the technical field of catalysts, in particular, to a supported catalyst, its preparation method and application, and a method for producing succinic anhydride by hydrogenation of maleic anhydride. The supported catalyst includes a carrier and an active catalyst loaded on the carrier. Component, the active component contains Ni element, Ce element and Zr element, and the support contains Al 2 O 3 ; in the supported catalyst, based on the total weight of the supported catalyst, it is calculated in terms of oxide , the content of the Ni element is 8-40% by weight, the content of the Ce element is 1-8% by weight, the content of the Zr element is 1-5% by weight, and the content of the carrier is 60-90% by weight. The catalyst of the invention has high catalytic activity and selectivity of succinic anhydride, and the preparation process is simple, and can be applied to continuous large-scale production.
Description
技术领域technical field
本发明涉及催化剂技术领域，具体地，涉及一种负载型催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法。The invention relates to the technical field of catalysts, in particular to a supported catalyst, a preparation method and application thereof, and a method for preparing succinic anhydride by hydrogenating maleic anhydride.
背景技术Background technique
丁二酸酐，又名琥珀酸酐，是一种重要的有机合成中间体和精细化工原料，被广泛地应用于食品、表面活性剂、涂料、医药、农业、塑料等领域。由于其独特的分子结构，丁二酸酐可以发生水解、醇解、酯化、卤化等反应，伴随着我国农药、医药和石油化工等行业的发展，对丁二酸酐的需求量在逐年增加，特别是高纯度的丁二酸酐，对外依存度较高。Succinic anhydride, also known as succinic anhydride, is an important organic synthesis intermediate and fine chemical raw material, and is widely used in food, surfactant, paint, medicine, agriculture, plastics and other fields. Due to its unique molecular structure, succinic anhydride can undergo hydrolysis, alcoholysis, esterification, halogenation and other reactions. With the development of my country's pesticide, pharmaceutical and petrochemical industries, the demand for succinic anhydride is increasing year by year, especially It is high-purity succinic anhydride with high external dependence.
目前，工业上采用的丁二酸酐的生产方法有：生物发酵法、丁二酸脱水法和顺酐催化加氢法。其中，生物发酵法虽然环境友好，但该方法生产成本高、产品收率低，很难满足工业生产的需要；丁二酸脱水法技术门槛较低，但生产规模小，产品品质较低，难以满足高纯度丁二酸酐原料市场的供应；顺酐加氢法具有工艺流程简单、操作方便、设备利用率高、运行成本低以及产品纯度高的优点，是目前最为高效的生产丁二酸酐的工艺。At present, the production methods of succinic anhydride used in industry include: biological fermentation method, succinic acid dehydration method and maleic anhydride catalytic hydrogenation method. Among them, although the biological fermentation method is environmentally friendly, the method has high production cost and low product yield, and it is difficult to meet the needs of industrial production; the technical threshold of the succinic acid dehydration method is low, but the production scale is small and the product quality is low, which is difficult To meet the supply of high-purity succinic anhydride raw material market; maleic anhydride hydrogenation method has the advantages of simple process flow, convenient operation, high equipment utilization rate, low operating cost and high product purity, and is currently the most efficient process for producing succinic anhydride .
顺酐分子具有一个C＝C键以及两个C＝O键，在一定催化条件下，对C＝C键的选择性加氢可以合成丁二酸酐；继续对其中一个C＝O键加氢，可以合成γ-丁内酯；接着对另一个C＝O键加氢，则可合成四氢呋喃。由此可见，深度加氢会降低丁二酸酐的选择性，如何控制加氢反应在C＝C键加氢阶段是顺酐加氢制备丁二酸酐最主要的问题，需要寻找合适的催化剂来提高丁二酸酐的选择性。The maleic anhydride molecule has a C=C bond and two C=O bonds. Under certain catalytic conditions, the selective hydrogenation of the C=C bond can synthesize succinic anhydride; continue to hydrogenate one of the C=O bonds, γ-butyrolactone can be synthesized; followed by hydrogenation of another C=O bond, tetrahydrofuran can be synthesized. It can be seen that deep hydrogenation will reduce the selectivity of succinic anhydride, how to control the hydrogenation reaction in the C=C bond hydrogenation stage is the most important problem of maleic anhydride hydrogenation to prepare succinic anhydride, and it is necessary to find a suitable catalyst to improve Selectivity of succinic anhydride.
US5770744公开了一种用于催化顺酐加氢制备丁二酸酐的催化剂及连续生产丁二酸酐的方法，该工艺条件中，反应条件较为苛刻，反应压力高达38MPa，需要对反应器的设置和材质有特殊要求，限制了其的大规模应用。US5770744 discloses a catalyst for catalyzing the hydrogenation of maleic anhydride to prepare succinic anhydride and a method for continuous production of succinic anhydride. In the process conditions, the reaction conditions are relatively harsh, and the reaction pressure is as high as 38MPa. There are special requirements, which limit its large-scale application.
US1541210和EP0691335公开的方法中，均选择了贵金属Pd作为活性组分制备催化剂，虽然加氢选择性较高，但贵金属的用量占到了催化剂总重量的3.0-10.0重量％，大大增加了生产成本，难以实现工业化。In the methods disclosed in US1541210 and EP0691335, the noble metal Pd is selected as the active component to prepare the catalyst. Although the hydrogenation selectivity is high, the amount of the noble metal accounts for 3.0-10.0% by weight of the total weight of the catalyst, which greatly increases the production cost. Difficult to achieve industrialization.
CN107597159A公开了一种碳化硅负载Ni的顺酐加氢制备丁二酸酐的催化剂的制备方法及其应用，该催化剂虽然活性及选择性都较高，但制备工艺较为复杂，并且只能用于间歇式合成反应用，无法应用于连续的大规模生产。CN107597159A discloses a preparation method and application of a catalyst for preparing succinic anhydride by maleic anhydride hydrogenation supported by Ni on silicon carbide. Although the catalyst has high activity and selectivity, the preparation process is relatively complicated and can only be used in intermittent Formula synthesis reaction, can not be applied to continuous large-scale production.
综上可知，现有的催化剂的活性和丁二酸酐选择性较低，且催化剂成本高、工艺流程复杂，无法应用于连续的大规模工业化生产。In summary, the existing catalysts have low activity and succinic anhydride selectivity, high catalyst cost and complex process flow, and cannot be applied to continuous large-scale industrial production.
发明内容Contents of the invention
本发明的目的是为了克服现有技术中存在的催化剂的活性和丁二酸酐选择性低，且催化剂成本高、工艺流程复杂，无法应用于连续的大规模生产的问题，提供一种负载型催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法，该负载型催化剂具有较高的催化活性，且制备方法简单，成本较低，能够应用于连续的大规模工业化生产。The purpose of the present invention is to provide a supported catalyst in order to overcome the problems in the prior art that the activity of the catalyst and the selectivity of succinic anhydride are low, the cost of the catalyst is high, the process flow is complicated, and it cannot be applied to continuous large-scale production The preparation method and application thereof and the method for preparing succinic anhydride by hydrogenation of maleic anhydride, the supported catalyst has high catalytic activity, simple preparation method and low cost, and can be applied to continuous large-scale industrial production.
为了实现上述目的，本发明第一方面提供一种负载型催化剂，其特征在于，所述负载型催化剂包括载体以及负载在所述载体上的活性组分，所述活性组分含有Ni元素、Ce元素和Zr元素，所述载体含有Al2O3；In order to achieve the above object, the first aspect of the present invention provides a supported catalyst, characterized in that the supported catalyst includes a carrier and an active component loaded on the carrier, and the active component contains Ni element, Ce element and Zr element, the carrier contains Al 2 O 3 ;
所述负载型催化剂中，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为8-40重量％，Ce元素的含量为1-8重量％，所述Zr元素的含量为1-5重量％，所述载体的含量为60-90重量％。In the supported catalyst, based on the total weight of the supported catalyst, the content of the Ni element is 8-40% by weight, and the content of the Ce element is 1-8% by weight. The content of the Zr element is 1-5% by weight, and the content of the carrier is 60-90% by weight.
本发明第二方面提供一种负载型催化剂的制备方法，其特征在于，所述方法包括以下步骤：The second aspect of the present invention provides a method for preparing a supported catalyst, characterized in that the method comprises the following steps:
(1)将含Ni前体化合物和载体的前体化合物进行第一混合，得到第一混合液；所述载体的前体化合物含有Al2O3；(1) first mixing the precursor compound containing Ni and the precursor compound of the carrier to obtain the first mixed solution; the precursor compound of the carrier contains Al 2 O 3 ;
(2)将所述第一混合液依次进行老化和第一干燥，得到负载型催化剂前驱体；(2) aging and first drying the first mixed solution in sequence to obtain a supported catalyst precursor;
(3)将所述负载型催化剂前驱体与含Ce前体化合物、含Zr前体化合物进行第一接触反应，得到基体催化剂；(3) carrying out the first contact reaction between the supported catalyst precursor and the Ce-containing precursor compound and the Zr-containing precursor compound to obtain a matrix catalyst;
(4)将所述基体催化剂进行第二干燥，然后焙烧和成型，得到负载型催化剂；(4) Carrying out the second drying of the base catalyst, then calcining and molding to obtain a supported catalyst;
其中，所述含Ni前体化合物、含Ce前体化合物、含Zr化合物和载体的用量使得制备得到的催化剂，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为8-40重量％，Ce元素的含量为1-8重量％，所述Zr元素的含量为1-5重量％，所述载体的含量为60-90重量％。Wherein, the amount of the Ni-containing precursor compound, the Ce-containing precursor compound, the Zr-containing compound and the support makes the prepared catalyst, based on the total weight of the supported catalyst, in terms of oxides, the Ni element The content of the Zr element is 8-40% by weight, the content of the Ce element is 1-8% by weight, the content of the Zr element is 1-5% by weight, and the content of the carrier is 60-90% by weight.
本发明第三方面提供一种由上述方法制备得到的负载型催化剂。The third aspect of the present invention provides a supported catalyst prepared by the above method.
本发明第四方面提供一种上述负载型催化剂和/或所述的负载型催化剂的制备方法在顺酐加氢制丁二酸酐中的应用。The fourth aspect of the present invention provides an application of the above-mentioned supported catalyst and/or the preparation method of the supported catalyst in hydrogenation of maleic anhydride to succinic anhydride.
本发明第五方面提供一种顺酐加氢制丁二酸酐的方法，其特征在于，该方法包括：在活化催化剂存在下，氢气和顺酐进行第二接触反应，得到所述丁二酸酐；The fifth aspect of the present invention provides a method for preparing succinic anhydride by hydrogenating maleic anhydride, which is characterized in that the method comprises: in the presence of an activated catalyst, hydrogen and maleic anhydride are subjected to a second contact reaction to obtain the succinic anhydride;
其中，所述活化催化剂为上述负载型催化剂经包含氢气的气体进行还原活化得到；Wherein, the activated catalyst is obtained by reducing and activating the above-mentioned supported catalyst through a gas containing hydrogen;
所述还原活化的条件包括：温度为350-450℃，时间为1-8h。The conditions for the reductive activation include: the temperature is 350-450°C, and the time is 1-8h.
通过上述技术方案，本发明提供的负载型催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法获得以下有益的效果：Through the above technical scheme, the supported catalyst provided by the invention and its preparation method and application and the method for hydrogenating maleic anhydride to succinic anhydride obtain the following beneficial effects:
本发明提供的负载型催化剂具有较高的活性和选择性。The supported catalyst provided by the invention has higher activity and selectivity.
进一步地，由本发明提供的方法制备得到的催化剂能够用于反应温度较低(不高于140℃)的顺酐连续加氢制丁二酸酐反应中，具有较高的催化活性和选择性。Furthermore, the catalyst prepared by the method provided by the invention can be used in the continuous hydrogenation of maleic anhydride to succinic anhydride at a relatively low reaction temperature (not higher than 140° C.), and has higher catalytic activity and selectivity.
进一步地，本发明提供的一种顺酐加氢制丁二酸酐的方法，催化反应温度低，反应压力较低，小于3MPa，且能够连续加氢制备丁二酸酐，节约了能耗，简化了生产操作流程，降低了生产操作费用。Further, the method for preparing succinic anhydride by hydrogenation of maleic anhydride provided by the present invention has low catalytic reaction temperature, low reaction pressure, less than 3MPa, and can be continuously hydrogenated to prepare succinic anhydride, which saves energy consumption and simplifies The production operation process reduces the production operation cost.
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明第一方面提供一种负载型催化剂，其特征在于，所述负载型催化剂包括载体以及负载在所述载体上的活性组分，所述活性组分含有Ni元素、Ce元素和Zr元素，所述载体含有Al2O3；The first aspect of the present invention provides a supported catalyst, characterized in that the supported catalyst includes a carrier and an active component loaded on the carrier, the active component contains Ni element, Ce element and Zr element, The carrier contains Al 2 O 3 ;
所述负载型催化剂中，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为8-40重量％，Ce元素的含量为1-8重量％，所述Zr元素的含量为1-5重量％，所述载体的含量为60-90重量％。In the supported catalyst, based on the total weight of the supported catalyst, the content of the Ni element is 8-40% by weight, and the content of the Ce element is 1-8% by weight. The content of the Zr element is 1-5% by weight, and the content of the carrier is 60-90% by weight.
本发明中，所述负载型催化剂满足上述范围时，具有较高的催化活性和选择性。In the present invention, when the supported catalyst satisfies the above range, it has higher catalytic activity and selectivity.
根据本发明，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为11-25重量％，所述Ce元素的含量为3-6重量％，所述Zr元素的含量为1-3重量％，所述载体的含量为70-85重量％。According to the present invention, based on the total weight of the supported catalyst, the content of the Ni element is 11-25% by weight, the content of the Ce element is 3-6% by weight, and the Zr The content of the element is 1-3% by weight, and the content of the carrier is 70-85% by weight.
本发明第二方面提供一种负载型催化剂的制备方法，其特征在于，所述方法包括以下步骤：The second aspect of the present invention provides a method for preparing a supported catalyst, characterized in that the method comprises the following steps:
(1)将含Ni前体化合物和载体的前体化合物进行第一混合，得到第一混合液；所述载体的前体化合物含有Al2O3；(1) first mixing the precursor compound containing Ni and the precursor compound of the carrier to obtain the first mixed solution; the precursor compound of the carrier contains Al 2 O 3 ;
(2)将所述第一混合液依次进行老化和第一干燥，得到负载型催化剂前驱体；(2) aging and first drying the first mixed solution in sequence to obtain a supported catalyst precursor;
(3)将所述负载型催化剂前驱体与含Ce前体化合物、含Zr前体化合物进行第一接触反应，得到基体催化剂；(3) carrying out the first contact reaction between the supported catalyst precursor and the Ce-containing precursor compound and the Zr-containing precursor compound to obtain a matrix catalyst;
(4)将所述基体催化剂进行第二干燥，然后焙烧和成型，得到负载型催化剂；(4) Carrying out the second drying of the base catalyst, then calcining and molding to obtain a supported catalyst;
其中，所述含Ni前体化合物、含Ce前体化合物、含Zr化合物和载体的用量使得制备得到的催化剂，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为8-40重量％，Ce元素的含量为1-8重量％，所述Zr元素的含量为1-5重量％，所述载体的含量为60-90重量％。Wherein, the amount of the Ni-containing precursor compound, the Ce-containing precursor compound, the Zr-containing compound and the support makes the prepared catalyst, based on the total weight of the supported catalyst, in terms of oxides, the Ni element The content of the Zr element is 8-40% by weight, the content of the Ce element is 1-8% by weight, the content of the Zr element is 1-5% by weight, and the content of the carrier is 60-90% by weight.
本发明中，利用上述方法制备的负载型催化剂能够使催化活性和丁二酸酐选择性更高，且制备工艺简单。In the present invention, the supported catalyst prepared by the above method can make the catalytic activity and succinic anhydride selectivity higher, and the preparation process is simple.
本发明中，步骤(1)中，对所述第一混合的具体条件没有特别限制，只要使得所述含Ni前体化合物与载体的前体化合物能够充分均匀混合即可。In the present invention, in step (1), the specific conditions for the first mixing are not particularly limited, as long as the Ni-containing precursor compound and the carrier precursor compound can be fully and uniformly mixed.
根据本发明，所述含Ni前体化合物、含Ce前体化合物、含Zr化合物和载体的用量使得制备得到的催化剂，以所述负载型催化剂的总重量为基准，以氧化物计，所述Ni元素的含量为11-25重量％，所述Ce元素的含量为3-6重量％，所述Zr元素的含量为1-3重量％，所述载体的含量为70-85重量％。According to the present invention, the amount of the Ni-containing precursor compound, the Ce-containing precursor compound, the Zr-containing compound and the support makes the prepared catalyst, based on the total weight of the supported catalyst, in terms of oxides, the The content of the Ni element is 11-25% by weight, the content of the Ce element is 3-6% by weight, the content of the Zr element is 1-3% by weight, and the content of the carrier is 70-85% by weight.
本发明中，所述含Ni前体化合物、含Ce前体化合物、含Zr前体化合物和载体的用量使得制备得到的催化剂具有更高的催化活性和选择性。In the present invention, the amount of the Ni-containing precursor compound, Ce-containing precursor compound, Zr-containing precursor compound and carrier makes the prepared catalyst have higher catalytic activity and selectivity.
根据本发明，所述含Ni前体化合物为镍氨络合物溶液。According to the present invention, the Ni-containing precursor compound is a nickel ammonia complex solution.
进一步地，所述含Ce前体化合物选自硝酸铈、硫酸铈、氯化铈和醋酸铈中的至少一种。Further, the Ce-containing precursor compound is selected from at least one of cerium nitrate, cerium sulfate, cerium chloride and cerium acetate.
进一步地，所述含Zr锆前体化合物选自硝酸锆、硫酸锆、氯化锆和醋酸锆中的至少一种。Further, the Zr-containing zirconium precursor compound is selected from at least one of zirconium nitrate, zirconium sulfate, zirconium chloride and zirconium acetate.
进一步地，所述载体的前体化合物选自铝溶胶。Further, the precursor compound of the carrier is selected from aluminum sol.
进一步地，所述含Ce前体化合物和所述含Zr前体化合物分别以溶液的形式存在。Further, the Ce-containing precursor compound and the Zr-containing precursor compound exist in the form of solutions respectively.
进一步地，所述含Ni前体化合物、载体前体化合物、含Ce前体化合物和含Zr前体化合物分别优选为镍氨络合物溶液、铝溶胶、硝酸铈和硝酸锆，制备得到的催化剂具有更加优异的催化活性和选择性。Further, the Ni-containing precursor compound, the carrier precursor compound, the Ce-containing precursor compound and the Zr-containing precursor compound are respectively preferably nickel ammonium complex solution, aluminum sol, cerium nitrate and zirconium nitrate, and the prepared catalyst It has more excellent catalytic activity and selectivity.
本发明中，所述铝溶胶中Al2O3的含量为10-40重量％。In the present invention, the content of Al 2 O 3 in the aluminum sol is 10-40% by weight.
本发明中，所述含Ce前体化合物溶液中含Ce前体化合物含量为1-10重量％。In the present invention, the content of the Ce-containing precursor compound in the Ce-containing precursor compound solution is 1-10% by weight.
本发明中，所述含Zr前体化合物溶液中含Zr前体化合物含量为1-10重量％。In the present invention, the content of the Zr-containing precursor compound in the Zr-containing precursor compound solution is 1-10% by weight.
根据本发明，该方法还包括利用以下步骤合成所述镍氨络合物溶液：在第一溶剂和氨水的存在下，将镍盐和络合剂进行第二混合，得到镍氨络合物溶液。According to the present invention, the method also includes synthesizing the nickel ammonia complex solution by using the following steps: in the presence of the first solvent and ammonia water, nickel salt and complexing agent are mixed for the second time to obtain the nickel ammonia complex solution .
进一步地，所述镍盐和所述络合剂的用量摩尔比为1:0.5-2。Further, the molar ratio of the nickel salt to the complexing agent is 1:0.5-2.
本发明中，所述第一溶剂选自水，优选为去离子水和/或蒸馏水，所述第一溶剂的用量使得制备得到的镍氨络合物溶液的浓度为0.5-2mol/L。In the present invention, the first solvent is selected from water, preferably deionized water and/or distilled water, and the amount of the first solvent is such that the concentration of the prepared nickel ammonia complex solution is 0.5-2 mol/L.
根据本发明，所述镍盐选自硝酸镍、硫酸镍、氯化镍、碱式碳酸镍和醋酸镍中的至少一种。According to the present invention, the nickel salt is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, basic nickel carbonate and nickel acetate.
进一步地，所述络合剂选自一乙醇胺、二乙醇胺、三乙醇胺和乙二胺四乙酸中的至少一种。Further, the complexing agent is selected from at least one of monoethanolamine, diethanolamine, triethanolamine and ethylenediaminetetraacetic acid.
根据本发明，所述第二混合的条件包括：温度为40-90℃，搅拌时间为1-10h。According to the present invention, the conditions for the second mixing include: the temperature is 40-90° C., and the stirring time is 1-10 h.
进一步地，所述第二混合的条件还包括调节所述镍氨络合物的pH值为9-12。Further, the second mixing condition also includes adjusting the pH value of the nickel ammonium complex to 9-12.
本发明中，所述镍氨络合物溶液采用一步法合成：In the present invention, the nickel ammonia complex solution is synthesized in one step:
在第一溶剂和氨水存在下，将镍盐和络合剂进行混合，调节溶液的pH值为9-12，在40-90℃搅拌至所有固体溶解，一步法得到所述镍氨络合物溶液，所述硝酸镍与所述络合剂的用量摩尔比为1:0.5-2。In the presence of the first solvent and ammonia water, mix nickel salt and complexing agent, adjust the pH value of the solution to 9-12, stir at 40-90°C until all solids are dissolved, and obtain the nickel ammonia complex in one step solution, the molar ratio of the nickel nitrate to the complexing agent is 1:0.5-2.
本发明中，所述镍盐、络合剂和前述镍盐、络合剂的可选范围相同，在此不再赘述。In the present invention, the optional ranges of the nickel salt and the complexing agent are the same as those of the aforementioned nickel salt and the complexing agent, and will not be repeated here.
根据本发明，步骤(2)中，所述老化的条件包括：温度为40-90℃，时间为12-36h。According to the present invention, in step (2), the aging conditions include: the temperature is 40-90°C, and the time is 12-36h.
根据本发明，步骤(3)中，所述第一接触反应的条件包括：将含Ce前体化合物和含Zr前体化合物与所述负载型催化剂前驱体进行饱和浸渍和/或喷渍。According to the present invention, in step (3), the conditions of the first contact reaction include: saturated impregnation and/or spraying of the Ce-containing precursor compound and the Zr-containing precursor compound and the supported catalyst precursor.
本发明中，所述含Ce前体化合物和含Zr前体化合物和前述含Ce前体化合物和含Zr前体化合物的可选范围和浓度相同，在此不再赘述。In the present invention, the optional ranges and concentrations of the Ce-containing precursor compound and Zr-containing precursor compound are the same as the aforementioned Ce-containing precursor compound and Zr-containing precursor compound, and will not be repeated here.
本发明中，所述第一接触反应利用饱和浸渍和/或喷渍能够使得负载型催化剂制备工艺更为简单。In the present invention, the first contact reaction utilizes saturated impregnation and/or spray impregnation to make the preparation process of the supported catalyst simpler.
根据本发明，步骤(4)中，所述焙烧的条件包括：温度为350-500℃，时间为2-6h。According to the present invention, in step (4), the roasting conditions include: the temperature is 350-500°C, and the time is 2-6h.
根据本发明，步骤(4)中，对所述负载型催化剂成型的方式及形状没有特别限制，可以利用本领域任意常规的成型方式将所述负载型催化剂成型，例如压力压片或挤压成条。According to the present invention, in step (4), there is no particular limitation on the molding method and shape of the supported catalyst, and any conventional molding method in the art can be used to shape the supported catalyst, such as pressure pressing or extrusion into strip.
根据本发明，所述第一干燥和所述第二干燥的条件各自独立地包括：温度为100-120℃，时间为10-20h。According to the present invention, the conditions of the first drying and the second drying each independently include: a temperature of 100-120° C., and a time of 10-20 hours.
本发明中，将含有载体的前体化合物铝溶胶与镍氨络合物溶液进行混合，经过老化和干燥，能够得到高分散活性的催化剂前驱体，由该催化剂前驱体制备得到的负载型催化剂具有更高的催化活性及丁二酸酐选择性。In the present invention, the precursor compound aluminum sol containing the carrier is mixed with the nickel ammonia complex solution, and after aging and drying, a catalyst precursor with high dispersion activity can be obtained, and the supported catalyst prepared by the catalyst precursor has Higher catalytic activity and succinic anhydride selectivity.
根据本发明的一种优选的实施方式：According to a preferred embodiment of the present invention:
(1)在第一溶剂去离子水和氨水的存在下，将碱式碳酸镍、乙二胺四乙酸进行第二混合，在制备过程中通入氨气，调节溶液pH值为9-11，在40-90℃下搅拌至所有固体溶解，得到镍氨络合物溶液；(1) In the presence of the first solvent deionized water and ammonia water, basic nickel carbonate and ethylenediaminetetraacetic acid are mixed for the second time, ammonia gas is introduced during the preparation process, and the pH value of the solution is adjusted to 9-11, Stir at 40-90°C until all solids are dissolved to obtain a nickel ammonia complex solution;
(2)将所述镍氨络合物溶液和铝溶胶进行第一混合，得到第一混合液；(2) first mixing the nickel ammonia complex solution and the aluminum sol to obtain the first mixed solution;
(3)将所述第一混合液在40-90℃老化12-36h后，再在100-120℃下进行第一干燥10-20h，得到负载型催化剂前驱体；(3) Aging the first mixed solution at 40-90°C for 12-36h, and then performing first drying at 100-120°C for 10-20h to obtain a supported catalyst precursor;
(4)将硝酸铈溶液和硝酸锆溶液对所述负载型催化剂前驱体进行饱和浸渍和/或喷渍，得到基体催化剂；(4) Carrying out saturated impregnation and/or spray impregnation on the supported catalyst precursor with cerium nitrate solution and zirconium nitrate solution to obtain matrix catalyst;
(5)将所述基体催化剂在350-500℃焙烧2-6h后成型，得到负载型催化剂。(5) The base catalyst is calcined at 350-500° C. for 2-6 hours, and then shaped to obtain a supported catalyst.
本发明第三方面提供一种由上述方法制备得到的负载型催化剂。The third aspect of the present invention provides a supported catalyst prepared by the above method.
本发明中，利用上述制备方法得到的负载型催化剂有更高的催化活性和选择性，更有利于应用到大规模工业化生产中。In the present invention, the supported catalyst obtained by the above-mentioned preparation method has higher catalytic activity and selectivity, and is more favorable to be applied in large-scale industrial production.
本发明第四方面提供一种上述负载型催化剂和/或所述的负载型催化剂的制备方法在顺酐加氢制丁二酸酐中的应用。The fourth aspect of the present invention provides an application of the above-mentioned supported catalyst and/or the preparation method of the supported catalyst in hydrogenation of maleic anhydride to succinic anhydride.
本发明中，所述利用所述方法制备的负载型催化剂在顺酐加氢制丁二酸酐中的应用中，催化反应温度和反应压力较低，进一步节约能耗。In the present invention, when the supported catalyst prepared by the method is used in the hydrogenation of maleic anhydride to produce succinic anhydride, the catalytic reaction temperature and reaction pressure are relatively low, further saving energy consumption.
本发明第五方面提供一种顺酐加氢制丁二酸酐的方法，其特征在于，该方法包括：在活化催化剂存在下，氢气和顺酐进行第二接触反应，得到所述丁二酸酐；The fifth aspect of the present invention provides a method for preparing succinic anhydride by hydrogenating maleic anhydride, which is characterized in that the method comprises: in the presence of an activated catalyst, hydrogen and maleic anhydride are subjected to a second contact reaction to obtain the succinic anhydride;
其中，所述活化催化剂为上述负载型催化剂采用包含氢气的气体进行还原活化得到；Wherein, the activated catalyst is obtained by reducing and activating the above-mentioned supported catalyst using a gas containing hydrogen;
所述还原活化的条件包括：温度为350-450℃，时间为1-8h。The conditions for the reductive activation include: the temperature is 350-450°C, and the time is 1-8h.
进一步地，所述包含氢气的气体中氢气的含量为5-100体积％。Further, the hydrogen content in the hydrogen-containing gas is 5-100% by volume.
本发明中，所述包含氢气的气体为氢气或者氢气和氮气的混合气。In the present invention, the gas containing hydrogen is hydrogen or a mixture of hydrogen and nitrogen.
本发明中，对所述负载型催化剂的还原活化的环境没有限制，只要能够进行活化即可，例如可以在固定床反应器中还原活化，气体空速为10-40h-1。In the present invention, there is no limitation on the environment for the reduction activation of the supported catalyst, as long as the activation can be performed, for example, the reduction activation can be performed in a fixed bed reactor with a gas space velocity of 10-40 h -1 .
根据本发明，所述第二接触反应的条件包括：温度为60-150℃，压力为1-3MPa。According to the present invention, the conditions of the second contact reaction include: a temperature of 60-150° C. and a pressure of 1-3 MPa.
进一步地，所述氢气和所述顺酐的用量摩尔比为10-30：1。Further, the molar ratio of hydrogen to maleic anhydride is 10-30:1.
根据本发明，所述顺酐以顺酐溶液形式存在，且所述顺酐溶液的浓度为10-30重量％。According to the present invention, the maleic anhydride exists in the form of a maleic anhydride solution, and the concentration of the maleic anhydride solution is 10-30% by weight.
根据本发明，所述顺酐溶液中含有第二溶剂，所述第二溶剂为四氢呋喃、γ-丁内酯、环己烷和1，4-二氧六环中的至少一种。According to the present invention, the maleic anhydride solution contains a second solvent, and the second solvent is at least one of tetrahydrofuran, γ-butyrolactone, cyclohexane and 1,4-dioxane.
进一步地，所述顺酐的液时空速为0.1-0.5h-1。Further, the liquid hourly space velocity of the maleic anhydride is 0.1-0.5h -1 .
本发明中，对所述顺酐加氢制丁二酸酐的方法所采用的设备没有限制，只要能实现发生所述反应即可，例如可以在固定床反应器中进行。In the present invention, there is no limitation on the equipment used in the method of hydrogenating maleic anhydride to succinic anhydride, as long as the reaction can be realized, for example, it can be carried out in a fixed bed reactor.
根据本发明的一种优选的实施方式：According to a preferred embodiment of the present invention:
(a)在不锈钢固定床反应器内，将上述负载型催化剂在350-450℃温度下用氮气和氢气的混合物(混合物中氢气含量为5-100体积％，氢气空速为10-40h-1)还原1-8h进行活化，得到活化催化剂；(a) In a stainless steel fixed-bed reactor, the above-mentioned supported catalyst is used at a temperature of 350-450° C. with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture is 5-100 volume %, and the hydrogen space velocity is 10-40h -1 ) is activated by reducing for 1-8h to obtain an activated catalyst;
(b)在所述活化催化剂存在下，将氢气和顺酐溶液(溶剂选自四氢呋喃、γ-丁内酯、环己烷和1，4-二氧六环中至少一种，顺酐溶液浓度为10-30重量％)，在60-150℃，压力1-3MPa，顺酐的液时空速为0.1-0.5h-1下进行第二接触反应，氢气和顺酐的用量摩尔比10-30：1；(b) In the presence of the activated catalyst, hydrogen and maleic anhydride solution (solvent is selected from at least one of tetrahydrofuran, γ-butyrolactone, cyclohexane and 1,4-dioxane, the maleic anhydride solution concentration is 10-30% by weight), at 60-150°C, pressure 1-3MPa, liquid hourly space velocity of maleic anhydride is 0.1-0.5h -1 for the second contact reaction, the molar ratio of hydrogen and maleic anhydride is 10-30:1 ;
(c)将步骤(b)反应后的产物经冷凝得到液体产品，通过气相色谱分析液体产品中各组分的含量。其中，所述顺酐转化率和所述丁二酸酐的选择性通过以下公式计算得到：(c) condensing the reacted product in step (b) to obtain a liquid product, and analyzing the contents of each component in the liquid product by gas chromatography. Wherein, the selectivity of described maleic anhydride conversion rate and described succinic anhydride is calculated by following formula:
顺酐转化率＝(Mo-Ma)/Mo×100％Maleic anhydride conversion=(Mo-Ma)/Mo×100%
丁二酸酐的选择性＝Mi/(Mo-Ma)×100％Selectivity of succinic anhydride=Mi/(Mo-Ma)×100%
其中，Mo—原料顺酐的物质的量，mol；Wherein, Mo—the amount of substance of raw material maleic anhydride, mol;
Ma—反应后顺酐剩余的物质的量，mol；Ma—the amount of the remaining material of maleic anhydride after the reaction, mol;
Mi—反应后生成的丁二酸酐的物质的量，mol。Mi—the amount of succinic anhydride generated after the reaction, mol.
以下将通过实例对本发明进行详细描述。The present invention will be described in detail below by way of examples.
本发明中所用压力均为绝对压力。All pressures used in the present invention are absolute pressures.
以下使用的铝溶胶中Al2O3的含量为20重量％。The content of Al 2 O 3 in the aluminum sol used below was 20% by weight.
在没有特别说明的情况下，以下各实施例和对比例中所用原料均为市售品。Unless otherwise specified, the raw materials used in the following examples and comparative examples are commercially available.
以下制备例和对比制备例中，所述负载型催化剂组成及其含量通过XRF测试获得。In the following preparation examples and comparative preparation examples, the composition and content of the supported catalyst were obtained through XRF testing.
以下制备例用于说明本发明的负载型催化剂及其制备方法。The following preparation examples are used to illustrate the supported catalyst of the present invention and its preparation method.
制备例1Preparation Example 1
(1)称取125.69g碱式碳酸镍(其中以元素计的镍含量为45重量％)、97.65g乙二胺四乙酸、1250g去离子水以及115g的25重量％氨水混合，并通入氨气，调节溶液pH值为10.5，在45℃下搅拌至所有固体溶解，得到镍氨络合物溶液(其中镍氨络合物浓度为0.7mol/L)；(1) 125.69g basic nickel carbonate (wherein the nickel content in terms of elements is 45% by weight), 97.65g ethylenediaminetetraacetic acid, 1250g deionized water and 115g of 25% by weight ammonia water are mixed, and pass into ammonia gas, adjust the pH value of the solution to 10.5, and stir at 45°C until all solids are dissolved to obtain a nickel ammonia complex solution (wherein the nickel ammonia complex concentration is 0.7mol/L);
(2)称取1520g的铝溶胶与步骤(1)得到的镍氨络合物溶液进行混合，得到混合液；(2) The aluminum sol of 1520g is mixed with the nickel ammonia complex solution that step (1) obtains, obtains mixed solution;
(3)在搅拌下，将所述混合液在60℃下老化14h，再经120℃干燥12h，得到负载型催化剂前驱体；(3) aging the mixed solution at 60° C. for 14 hours under stirring, and then drying at 120° C. for 12 hours to obtain a supported catalyst precursor;
(4)将含有40.36g Ce(NO3)3·6H2O和18.97g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液，饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) The cerium nitrate-zirconium nitrate mixed solution containing 40.36g Ce(NO 3 ) 3 6H 2 O and 18.97g Zr(NO 3 ) 4 5H 2 O was saturated and impregnated with the supported catalyst precursor to obtain base catalyst;
(5)将所述基体催化剂在115℃干燥12h，然后在400℃焙烧4h，成型得到负载型催化剂S1。(5) The base catalyst was dried at 115° C. for 12 hours, and then calcined at 400° C. for 4 hours to obtain a supported catalyst S1.
以所述负载型催化剂S1的总重量为基准，所述负载型催化剂S1中含有：18重量％的NiO、76重量％的Al2O3、4重量％的CeO2和2重量％的ZrO2。Based on the total weight of the supported catalyst S1, the supported catalyst S1 contains: 18% by weight of NiO, 76% by weight of Al 2 O 3 , 4% by weight of CeO 2 and 2% by weight of ZrO 2 .
制备例2Preparation example 2
(1)称取76.81g碱式碳酸镍(其中以元素计的镍含量为45重量％)、59.67g乙二胺四乙酸、760g去离子水以及70g的25重量％氨水混合，并通入氨气，调节溶液pH值为10.5，在45℃下搅拌至所有固体溶解，得到镍氨络合物溶液(其中镍氨络合物浓度为0.7mol/L)；(1) 76.81g basic nickel carbonate (wherein the nickel content in terms of elements is 45% by weight), 59.67g ethylenediaminetetraacetic acid, 760g deionized water and 70g of 25% by weight of ammonia are mixed, and pass into ammonia gas, adjust the pH value of the solution to 10.5, and stir at 45°C until all solids are dissolved to obtain a nickel ammonia complex solution (wherein the nickel ammonia complex concentration is 0.7mol/L);
(2)称取1700g的铝溶胶与步骤(1)得到的镍氨络合物溶液进行混合，得到混合液；(2) The aluminum sol of 1700g is mixed with the nickel ammonia complex solution obtained in step (1), to obtain a mixed solution;
(3)在搅拌下，将所述混合液在60℃下老化14h，再120℃干燥12h，得到负载型催化剂前驱体；(3) aging the mixed solution at 60° C. for 14 hours under stirring, and then drying at 120° C. for 12 hours to obtain a supported catalyst precursor;
(4)将含有30.27g Ce(NO3)3·6H2O和9.49g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液，饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) The cerium nitrate-zirconium nitrate mixed solution containing 30.27g Ce(NO 3 ) 3 6H 2 O and 9.49g Zr(NO 3 ) 4 5H 2 O was saturated and impregnated with the supported catalyst precursor to obtain base catalyst;
(5)将所述基体催化剂在115℃干燥12h，然后在400℃焙烧4h，成型得到负载型催化剂S2。(5) The base catalyst was dried at 115° C. for 12 hours, and then calcined at 400° C. for 4 hours to form a supported catalyst S2.
以所述负载型催化剂S2的总重量为基准，所述负载型催化剂S2中含有：11重量％的NiO、85重量％的Al2O3、3重量％的CeO2和1重量％的ZrO2。Based on the total weight of the supported catalyst S2, the supported catalyst S2 contains: 11% by weight of NiO, 85% by weight of Al2O3 , 3 % by weight of CeO2 and 1% by weight of ZrO2 .
制备例3Preparation example 3
(1)称取153.62g碱式碳酸镍(其中以元素计的镍含量为45重量％)、119.34g乙二胺四乙酸、1550g去离子水以及140g的25重量％氨水混合，并通入氨气，调节溶液pH值为10.5，在45℃下搅拌至所有固体溶解，得到镍氨络合物溶液(其中镍氨络合物浓度为0.7mol/L)；(1) Take by weighing 153.62g basic nickel carbonate (wherein the nickel content in terms of elements is 45% by weight), 119.34g ethylenediaminetetraacetic acid, 1550g deionized water and 140g of 25% by weight of ammonia are mixed, and pass into ammonia gas, adjust the pH value of the solution to 10.5, and stir at 45°C until all solids are dissolved to obtain a nickel ammonia complex solution (wherein the nickel ammonia complex concentration is 0.7mol/L);
(2)称取1400g的铝溶胶与步骤(1)得到的镍氨络合物溶液进行混合，得到混合液；(2) The aluminum sol of 1400g is mixed with the nickel ammonium complex solution obtained in step (1) to obtain a mixed solution;
(3)在搅拌下，将所述混合液在60℃下老化14h，再120℃干燥12h，得到负载型催化剂前驱体；(3) aging the mixed solution at 60° C. for 14 hours under stirring, and then drying at 120° C. for 12 hours to obtain a supported catalyst precursor;
(4)将含有50.46g Ce(NO3)3·6H2O和28.46g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液，饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) The cerium nitrate-zirconium nitrate mixed solution containing 50.46g Ce(NO 3 ) 3 6H 2 O and 28.46g Zr(NO 3 ) 4 5H 2 O was saturated and impregnated with the supported catalyst precursor to obtain base catalyst;
(5)将所述基体催化剂在115℃干燥12h，然后在400℃焙烧4h，成型得到负载型催化剂S3。(5) The base catalyst was dried at 115° C. for 12 hours, and then calcined at 400° C. for 4 hours to form a supported catalyst S3.
以所述负载型催化剂S3的总重量为基准，所述负载型催化剂S3中含有：22重量％的NiO、70重量％的Al2O3、5重量％的CeO2和3重量％的ZrO2。Based on the total weight of the supported catalyst S3, the supported catalyst S3 contains: 22% by weight of NiO, 70% by weight of Al2O3 , 5% by weight of CeO2 and 3% by weight of ZrO2 .
制备例4Preparation Example 4
(1)称取264.67g的Ni(NO3)3·6H2O与800g去离子水混合，得到硝酸镍溶液；(1) Weigh 264.67g of Ni(NO 3 ) 3 6H 2 O and mix it with 800g of deionized water to obtain nickel nitrate solution;
(2)称取1560g的铝溶胶与步骤(1)得到的所述硝酸镍溶液混合均匀，得到混合液；(2) the aluminum sol that takes 1560g is mixed with the described nickel nitrate solution that step (1) obtains, obtains mixed liquor;
(3)在搅拌下，将所述混合液在60℃下老化14h，再经120℃干燥12h，得到负载型催化剂前驱体；(3) aging the mixed solution at 60° C. for 14 hours under stirring, and then drying at 120° C. for 12 hours to obtain a supported catalyst precursor;
(4)将含有30.27g的Ce(NO3)3·6H2O和18.97g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) Saturatedly impregnate the supported catalyst precursor with a mixed solution of cerium nitrate-zirconium nitrate containing 30.27g Ce(NO 3 ) 3 6H 2 O and 18.97g Zr(NO 3 ) 4 5H 2 O, to obtain base catalyst;
(5)将所述基体催化剂在115℃干燥12h，然后在400℃焙烧4h，成型，得到负载型催化剂CS4。(5) The base catalyst was dried at 115° C. for 12 hours, then calcined at 400° C. for 4 hours, and shaped to obtain a supported catalyst CS4.
以所述负载型催化剂S4的总重量为基准，所述负载型催化剂S4中含有：17重量％的NiO、78重量％的Al2O3、3重量％的CeO2和2重量％的ZrO2。Based on the total weight of the supported catalyst S4, the supported catalyst S4 contains: 17% by weight of NiO, 78% by weight of Al2O3 , 3 % by weight of CeO2 and 2% by weight of ZrO2 .
制备例5Preparation Example 5
(1)称取75.73g醋酸镍(其中以元素计的镍含量为45重量％)、125.17g乙二胺四乙酸、1000g去离子水以及115g的25重量％氨水混合，并通入氨气，调节溶液pH值为10.5，在60℃下搅拌至所有固体溶解，得到镍氨络合物溶液(其中镍氨络合物浓度同制备例1)；(1) take by weighing 75.73g nickel acetate (wherein the nickel content in terms of elements is 45% by weight), 125.17g ethylenediaminetetraacetic acid, 1000g deionized water and 115g of 25% by weight of ammonia are mixed, and feed ammonia, Adjust the pH value of the solution to 10.5, and stir at 60° C. until all solids are dissolved to obtain a nickel ammonia complex solution (wherein the concentration of the nickel ammonia complex is the same as in Preparation Example 1);
(2)称取1780g的铝溶胶与步骤(1)得到的镍氨络合物溶液进行混合，得到混合液；(2) The aluminum sol of 1780g is mixed with the nickel ammonia complex solution that step (1) obtains, obtains mixed solution;
(3)在搅拌下，将所述混合液在80℃下老化12h，再110℃干燥18h，得到负载型催化剂前驱体；(3) aging the mixed solution at 80° C. for 12 hours under stirring, and then drying at 110° C. for 18 hours to obtain a supported catalyst precursor;
(4)将含有20.18g Ce(NO3)3·6H2O和9.49g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液，饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) The cerium nitrate-zirconium nitrate mixed solution containing 20.18g Ce(NO 3 ) 3 6H 2 O and 9.49g Zr(NO 3 ) 4 5H 2 O was saturated and impregnated with the supported catalyst precursor to obtain base catalyst;
(5)将所述基体催化剂在110℃干燥8h，然后在450℃焙烧3h，成型得到负载型催化剂S5。(5) The base catalyst was dried at 110° C. for 8 hours, and then calcined at 450° C. for 3 hours to obtain a supported catalyst S5.
以所述负载型催化剂S5的总重量为基准，所述负载型催化剂S5中含有：8重量％的NiO、89重量％的Al2O3、2重量％的CeO2和1重量％的ZrO2。Based on the total weight of the supported catalyst S5 , the supported catalyst S5 contains: 8% by weight of NiO, 89% by weight of Al2O3 , 2% by weight of CeO2 and 1% by weight of ZrO2 .
对比制备例1Comparative Preparation Example 1
采用实施例1的方法制备催化剂，不同的是，本对比例中不进行步骤(4)的硝酸铈和硝酸锆浸渍步骤，而是直接将步骤(3)得到的催化剂前驱体直接进行步骤(5)，制备得到催化剂S4。Adopt the method for embodiment 1 to prepare catalyst, difference is, do not carry out step (4) cerium nitrate and zirconium nitrate impregnation step in this comparative example, but directly carry out step (5) directly to the catalyst precursor that step (3) obtains ), prepare catalyst S4.
以所述催化剂CS1的总重量为基准，所述催化剂CS1中含有：18重量％的NiO、82重量％的Al2O3。Based on the total weight of the catalyst CS1, the catalyst CS1 contains: 18% by weight of NiO and 82% by weight of Al 2 O 3 .
对比制备例2Comparative Preparation Example 2
(1)称取55.86g碱式碳酸镍(其中以元素计的镍含量为45重量％)、32.54g乙二胺四乙酸、550g去离子水以及50g的25重量％氨水混合，并通入氨气，调节溶液pH值为10.5，在45℃下搅拌至所有固体溶解，得到镍氨络合物溶液(其中镍氨络合物浓度为0.7mol/L)；(1) 55.86g basic nickel carbonate (wherein the nickel content in terms of elements is 45% by weight), 32.54g ethylenediaminetetraacetic acid, 550g deionized water and 50g of 25% by weight of ammonia are mixed, and pass into ammonia gas, adjust the pH value of the solution to 10.5, and stir at 45°C until all solids are dissolved to obtain a nickel ammonia complex solution (wherein the nickel ammonia complex concentration is 0.7mol/L);
(2)称取1860g的铝溶胶与步骤(1)得到的镍氨络合物溶液进行混合，得到混合液；(2) The aluminum sol of 1860g is mixed with the nickel ammonia complex solution that step (1) obtains, obtains mixed solution;
(3)在搅拌下，将所述混合液在60℃下老化14h，再120℃干燥12h，得到负载型催化剂前驱体；(3) aging the mixed solution at 60° C. for 14 hours under stirring, and then drying at 120° C. for 12 hours to obtain a supported catalyst precursor;
(4)将含有5.05g Ce(NO3)3·6H2O和4.74g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) Saturatedly impregnate the supported catalyst precursor with a cerium nitrate-zirconium nitrate mixed solution containing 5.05g Ce(NO 3 ) 3 6H 2 O and 4.74g Zr(NO 3 ) 4 5H 2 O to obtain a matrix catalyst;
(5)将所述基体催化剂在115℃干燥12h，然后在400℃焙烧4h，成型得到负载型催化剂CS2。(5) The base catalyst was dried at 115° C. for 12 hours, and then calcined at 400° C. for 4 hours to obtain a supported catalyst CS2.
以所述负载型催化剂CS2的总重量为基准，所述负载型催化剂CS2中含有：6重量％的NiO、93重量％的Al2O3、0.5重量％的CeO2和0.5重量％的ZrO2。Based on the total weight of the supported catalyst CS2 , the supported catalyst CS2 contains: 6% by weight of NiO, 93% by weight of Al2O3 , 0.5% by weight of CeO2 and 0.5% by weight of ZrO2 .
对比制备例3Comparative Preparation Example 3
采用实施例1的方法制备催化剂，不同的是，本对比例步骤(4)中仅采用硝酸铈溶液(浓度同制备例1)进行饱和浸渍，制备得到负载型催化剂CS3。The catalyst was prepared by the method of Example 1, except that in step (4) of this comparative example, only cerium nitrate solution (same concentration as in Preparation Example 1) was used for saturated impregnation to prepare the supported catalyst CS3.
以所述负载型催化剂CS3的总重量为基准，所述负载型催化剂CS3中含有：18重量％的NiO、78重量％的Al2O3、4重量％的CeO2。Based on the total weight of the supported catalyst CS3, the supported catalyst CS3 contains: 18% by weight of NiO, 78% by weight of Al 2 O 3 , and 4% by weight of CeO 2 .
对比制备例4Comparative Preparation Example 4
采用实施例5的方法制备催化剂，不同的是，本对比例中不进行步骤(2)的老化和第一干燥步骤和步骤(3)中的浸渍步骤，而是直接将步骤(1)得到的催化剂前驱体直接与含Ce前体化合物、含Zr前体化合物进行第一接触反应，得到基体催化剂后进行干燥和焙烧成型，制备得到催化剂CS4。Adopt the method for embodiment 5 to prepare catalyst, difference is, do not carry out the aging of step (2) and the impregnation step in the first drying step and step (3) in this comparative example, but directly step (1) obtains The catalyst precursor is directly subjected to the first contact reaction with the Ce-containing precursor compound and the Zr-containing precursor compound to obtain the matrix catalyst, and then drying and calcining are carried out to prepare the catalyst CS4.
以所述催化剂CS4的总重量为基准，所述催化剂CS4中含有：7重量％的NiO、89重量％的Al2O3、3重量％的CeO2和1重量％的ZrO2。Based on the total weight of the catalyst CS4, the catalyst CS4 contains: 7% by weight of NiO, 89% by weight of Al 2 O 3 , 3% by weight of CeO 2 and 1% by weight of ZrO 2 .
对比制备例5Comparative Preparation Example 5
(1)称取75.73g醋酸镍(其中以元素计的镍含量为45重量％)、125.17g乙二胺四乙酸、1000g去离子水以及115g的25重量％氨水混合，并通入氨气，调节溶液pH值为10.5，在45℃下搅拌至所有固体溶解，得到镍氨络合物溶液(其中镍氨络合物浓度为0.7mol/L)；(1) take by weighing 75.73g nickel acetate (wherein the nickel content in terms of elements is 45% by weight), 125.17g ethylenediaminetetraacetic acid, 1000g deionized water and 115g of 25% by weight of ammonia are mixed, and feed ammonia, Adjust the pH value of the solution to 10.5, and stir at 45° C. until all solids are dissolved to obtain a nickel ammonia complex solution (wherein the nickel ammonia complex concentration is 0.7 mol/L);
(2)称取1780g的铝溶胶与步骤(1)得到的镍氨络合物溶液进行混合，得到混合液；(2) The aluminum sol of 1780g is mixed with the nickel ammonia complex solution that step (1) obtains, obtains mixed solution;
(3)在搅拌下，将所述混合液在60℃下老化14h，再120℃干燥12h，然后400℃焙烧4h，得到负载型催化剂前驱体；(3) Under stirring, aging the mixed solution at 60°C for 14h, then drying at 120°C for 12h, and then roasting at 400°C for 4h to obtain a supported catalyst precursor;
(4)将含有20.18g Ce(NO3)3·6H2O和9.49g Zr(NO3)4·5H2O的硝酸铈-硝酸锆混合溶液(其中Ce(NO3)3·6H2O和Zr(NO3)4·5H2O浓度同制备例1)饱和浸渍所述负载型催化剂前驱体，得到基体催化剂；(4) Mix cerium nitrate-zirconium nitrate solution containing 20.18g Ce(NO 3 ) 3 ·6H 2 O and 9.49g Zr(NO 3 ) 4 ·5H 2 O (where Ce(NO 3 ) 3 ·6H 2 O and Zr(NO 3 ) 4 5H 2 O concentration are the same as in Preparation Example 1) saturated impregnation of the supported catalyst precursor to obtain a matrix catalyst;
(5)将所述基体催化剂在115℃干燥12h，成型得到负载型催化剂CS5。(5) The base catalyst was dried at 115° C. for 12 hours, and shaped to obtain a supported catalyst CS5.
以所述催化剂CS5的总重量为基准，所述催化剂CS5中含有：7重量％的NiO、90重量％的Al2O3、2重量％的CeO2和1重量％的ZrO2。Based on the total weight of the catalyst CS5, the catalyst CS5 contains: 7% by weight of NiO, 90% by weight of Al 2 O 3 , 2% by weight of CeO 2 and 1% by weight of ZrO 2 .
以下实施例用于说明本发明的负载型催化剂的应用和顺酐加氢制丁二酸酐的方法。The following examples are used to illustrate the application of the supported catalyst of the present invention and the method for producing succinic anhydride by hydrogenation of maleic anhydride.
实施例1Example 1
将制备例1得到的催化剂通过以下方法进行活性评价：The catalyst that preparation example 1 obtains carries out active evaluation by following method:
(a)在不锈钢固定床反应器内，将以上制备例1制备得到的负载型催化剂在400℃温度下用氮气和氢气的混合物(混合物中氢气含量为100体积％，氢气空速为0.3h-1)还原6h进行活化，得到活化催化剂；(a) In a stainless steel fixed-bed reactor, use the supported catalyst prepared in the above preparation example 1 with a mixture of nitrogen and hydrogen at a temperature of 400°C (the hydrogen content in the mixture is 100% by volume, and the hydrogen space velocity is 0.3h- 1 ) Reducing for 6h to activate to obtain an activated catalyst;
(b)在所述活化催化剂存在下，将氢气和顺酐溶液(溶剂为γ-丁内酯，顺酐溶液浓度为20重量％)，在90℃，压力2.5MPa，顺酐的液时空速为0.2h-1下进行接触反应，氢气和顺酐的用量摩尔比15：1；(b) In the presence of the activated catalyst, hydrogen and maleic anhydride solution (solvent is gamma-butyrolactone, maleic anhydride solution concentration is 20% by weight), at 90°C, pressure 2.5MPa, the liquid hourly space velocity of maleic anhydride is The contact reaction is carried out under 0.2h -1 , and the molar ratio of hydrogen and maleic anhydride is 15:1;
(c)将步骤(b)反应后的产物经冷凝得到液体产品，通过气相色谱分析液体产品中各组分的含量，通过下述公式计算得到顺酐的转化率和丁二酸酐的选择性，具体结果见表1。(c) the product after the reaction of step (b) is condensed to obtain a liquid product, and the content of each component in the liquid product is analyzed by gas chromatography, and the conversion rate of maleic anhydride and the selectivity of succinic anhydride are calculated by the following formula, The specific results are shown in Table 1.
其中，所述顺酐转化率和所述丁二酸酐的选择性通过以下公式计算得到：Wherein, the selectivity of described maleic anhydride conversion rate and described succinic anhydride is calculated by following formula:
顺酐转化率＝(Mo-Ma)/Mo×100％Maleic anhydride conversion=(Mo-Ma)/Mo×100%
丁二酸酐的选择性＝Mi/(Mo-Ma)×100％Selectivity of succinic anhydride=Mi/(Mo-Ma)×100%
其中，Mo—原料顺酐的物质的量，mol；Wherein, Mo—the amount of substance of raw material maleic anhydride, mol;
Ma—反应后顺酐剩余的物质的量，mol；Ma—the amount of the remaining material of maleic anhydride after the reaction, mol;
Mi—反应后生成的丁二酸酐的物质的量，mol。Mi—the amount of succinic anhydride generated after the reaction, mol.
实施例2-5Example 2-5
按照实施例1的方法进行，不同的是，分别采用制备例2-5制得的负载型催化剂代替上述制备例1制得的负载型催化剂，其他与实施例1相同。顺酐的转化率和丁二酸酐的选择性，具体结果见表1。According to the method of Example 1, the difference is that the supported catalysts prepared in Preparation Examples 2-5 are used instead of the supported catalysts prepared in Preparation Example 1 above, and the others are the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1 for specific results.
实施例6Example 6
按照实施例1的方法进行，不同的是，步骤(b)中溶剂为1,4-二氧六环，顺酐溶液浓度为15重量％)，在70℃，压力1.5MPa，顺酐的液时空速为0.4h-1下进行接触反应，氢气和顺酐的用量摩尔比20：1，其他与实施例1相同。顺酐的转化率和丁二酸酐的选择性，具体结果见表1。According to the method of Example 1, the difference is that the solvent in step (b) is 1,4-dioxane, and the concentration of the maleic anhydride solution is 15% by weight), at 70°C, the pressure is 1.5MPa, the liquid of maleic anhydride The contact reaction was carried out at an hourly space velocity of 0.4h -1 , the molar ratio of hydrogen to maleic anhydride was 20:1, and the others were the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride, the specific results are shown in Table 1.
对比例1-5Comparative example 1-5
按照实施例1的方法进行，不同的是，分别采用对比制备例1-5制备的催化剂或负载型催化剂代替上述制备例1制得的负载型催化剂，其他与实施例1相同。顺酐的转化率和丁二酸酐的选择性，具体结果见表1。Proceed according to the method of Example 1, except that the catalyst or supported catalyst prepared in Comparative Preparation Examples 1-5 was used to replace the supported catalyst prepared in Preparation Example 1 above, and the others were the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1 for specific results.
表1Table 1
通过表1的结果可以看出，本发明提供的负载型催化剂具有较高的催化活性和选择性。It can be seen from the results in Table 1 that the supported catalyst provided by the present invention has higher catalytic activity and selectivity.
本发明提供的方法通过分别以镍氨络合物和铝溶胶为氧化镍、氧化铝、氧化铈和氧化锆的前体化合物，制备得到的负载型催化剂具有更优异的催化活性和丁二酸酐选择性。The method provided by the invention uses nickel ammonium complex and aluminum sol as precursor compounds of nickel oxide, aluminum oxide, cerium oxide and zirconium oxide respectively, and the supported catalyst prepared has more excellent catalytic activity and succinic anhydride selection sex.
由本发明提供的方法制备得到的负载型催化剂能够用于顺酐连续加氢制丁二酸酐，催化反应温度较低，进一步节约了能耗。The supported catalyst prepared by the method provided by the invention can be used for the continuous hydrogenation of maleic anhydride to produce succinic anhydride, the catalytic reaction temperature is relatively low, and energy consumption is further saved.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
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