CN113231069B - Maleic anhydride bulk hydrogenation succinic anhydride preparation composite efficient catalyst and preparation method thereof - Google Patents
Maleic anhydride bulk hydrogenation succinic anhydride preparation composite efficient catalyst and preparation method thereof Download PDFInfo
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- CN113231069B CN113231069B CN202110407718.2A CN202110407718A CN113231069B CN 113231069 B CN113231069 B CN 113231069B CN 202110407718 A CN202110407718 A CN 202110407718A CN 113231069 B CN113231069 B CN 113231069B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229940014800 succinic anhydride Drugs 0.000 title claims abstract description 56
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000004480 active ingredient Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000013543 active substance Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000012747 synergistic agent Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012188 paraffin wax Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 21
- 239000006184 cosolvent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- -1 cerium series rare earth inorganic compounds Chemical class 0.000 claims description 11
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- 238000004939 coking Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 60
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 150000000703 Cerium Chemical class 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- PUQSUZTXKPLAPR-KSSYENDESA-N 4-(beta-D-Glucopyranosyloxy) benzyl alcohol Natural products O([C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1)c1ccc(CO)cc1 PUQSUZTXKPLAPR-KSSYENDESA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PUQSUZTXKPLAPR-UJPOAAIJSA-N Gastrodin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C(CO)C=C1 PUQSUZTXKPLAPR-UJPOAAIJSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 229930193974 gastrodin Natural products 0.000 description 1
- PUQSUZTXKPLAPR-NZEXEKPDSA-N helicidol Natural products O([C@H]1[C@H](O)[C@H](O)[C@@H](O)[C@@H](CO)O1)c1ccc(CO)cc1 PUQSUZTXKPLAPR-NZEXEKPDSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a composite high-efficiency catalyst for preparing succinic anhydride by bulk hydrogenation of maleic anhydride and a preparation method thereof, wherein the catalyst comprises a carrier gamma-Al 2 O 3 Ni (NO) as active ingredient 3 ） 2 .6H 2 O, a composite solvent and a metal synergist, wherein the carrier gamma-Al is calculated by mass parts 2 O 3 100 parts by mass of the active ingredient Ni (NO 3 ） 2 .6H 2 The mass part of O is 25-200 parts, wherein the addition amount of the composite solvent is active ingredient Ni (NO 3 ） 2 .6H 2 0.1 to 1.8 times of the Ni molar quantity in the O, and the addition quantity of the metal synergistic agent is the active ingredient Ni (NO) 3 ） 2 .6H 2 0.1 to 2 percent of Ni mole amount in O; the preparation method comprises the following steps: mixing the prepared aqueous solution of active agent with Na 2 CO 3 And (3) dropwise adding the aqueous solution into the prepared carrier suspension solution in parallel, and reducing the catalytic precursor after reaction, aging, filtering, washing and drying in a hydrogen atmosphere and solidifying paraffin to obtain a catalyst finished product. The catalyst prepared by the process has the advantages of high activity, good selectivity, strong coking resistance and toxicity resistance, long service life and multiple times of multiplexing.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of a compound efficient catalyst for preparing succinic anhydride by bulk hydrogenation of maleic anhydride.
Background
Succinic anhydride, which is an important fine chemical raw material, is produced by maleic anhydride catalytic hydrogenation, and has a molecular formula of C 4 H 4 O 3 The molecular weight is 100.07, and the product is colorless needle-like or flake-like crystal, slightly soluble in cold water and diethyl ether, soluble in hot water and ethanol, and has a melting point of 119.6deg.C and a boiling point of 261 deg.C, and can be widely used in surfactant, pharmacy, food additive and pharmaceutical intermediate, and can be used for preparing medicines such as gastrodin, succinimide, etc. Succinic anhydride is a raw material for preparing paint, synthetic resin and dye. The coating and resin produced by the succinic anhydride have excellent performance, are used for manufacturing the coating and have flexure resistance and water resistance, are used for manufacturing polybutylene succinate (PBS) biological full-degradable plastics, are used for manufacturing high-grade coatings with excellent chromatic light and weather resistance of 1, 4-diketopyrrolopyrrole dyes (DPP dyes for short), and have been developed in recent years, and the demand for the succinic anhydride is relatively large.
The most main methods for preparing succinic anhydride at present in China are a succinic acid dehydration method and a maleic anhydride catalytic hydrogenation method. The succinic anhydride prepared by the succinic anhydride dehydration method has low yield, unstable product quality, generally 85-94% of succinic anhydride content, easy carbonization of succinic acid in the production process, difficult control of the operation process, long process flow and higher production cost. The maleic anhydride catalytic hydrogenation method is divided into a melting method and a solvent dissolution catalytic method, wherein the melting method does not need to add a solvent, so that the product is not easy to purify and environmental pollution caused by the solvent is avoided, but the catalyst system screening and the reaction condition control of the melting method are all technical difficulties of hydrogenation reaction, and the solvent dissolution catalytic method mainly refers to gas-solid-liquid three-phase catalytic reaction, and is to dissolve maleic anhydride in the solvent for catalytic hydrogenation. The succinic anhydride produced by the method has higher selectivity, is the most promising method for preparing the succinic anhydride at present, but the succinic anhydride prepared by the maleic anhydride hydrogenation is a strong exothermic reaction, the activity and the cost of the catalyst are the most critical factors influencing the yield of the succinic anhydride, and the catalyst with strong activity, low cost and small dosage is adopted as the difficulty of preparing the succinic anhydride by the maleic anhydride hydrogenation.
Chinese patent CN92103481.4 discloses a process for preparing succinic anhydride by bulk hydrogenation under maleic anhydride melting with raney nickel and skeletal nickel as catalysts, the catalyst consumption is 4-10%, the reaction temperature is 120-250 ℃, the reaction pressure is 1.5-2.0Mpa, the maleic anhydride conversion rate is 96%, the succinic anhydride selectivity is 90%, and the succinic anhydride content is 98%; the Pd-based catalyst prepared by the colloid deposition method of Chinese patent CN103007929A, a preparation method and application thereof disclose a Pd-based catalyst prepared by the colloid deposition method, a preparation method and application thereof, wherein the conversion rate of maleic anhydride is more than or equal to 99.99 percent, the selectivity of succinic acid is more than or equal to 99.99 percent, but the dosage of the Pd-based catalyst is 0.01 to 10 percent by weight of the mass of maleic anhydride in a high-pressure reaction kettle at the reaction temperature of 10 to 180 ℃ and the pressure of 0.1 to 4 MPa; chinese patent CN1453066a discloses a catalyst for preparing succinic anhydride by hydrogenating maleic anhydride, and the molar ratio of active component nickel to carrier is Ni: siO (SiO) 2 ：Al 2 O 3 =1:1.47-5.98): (0-3.3). The catalyst is used for reacting for 1 to 3 hours under the pressure of 0.5 to 3MPa and the temperature of 120 to 180 ℃, and nickel: the maleic anhydride is directly hydrogenated to generate succinic anhydride under the condition that the maleic anhydride molar ratio is 0.3-1.6:100 (the mass ratio is 0.18-0.95:100), the maleic anhydride conversion rate is 100%, and the succinic anhydride selectivity is 99.5%; in the preparation process of the succinic anhydride, the defects of large catalyst consumption, low maleic anhydride conversion rate and succinic anhydride selectivity, high hydrogenation temperature and pressure and impure product quality of Chinese patent CN92103481.4 exist; the cost of the catalyst prepared by noble metal Pd is high in China patent CN 103007929A; the catalyst prepared by the patent CN1453066A has complex gelling process, is difficult to realize industrial production, needs high-temperature roasting after the catalyst is dried, and has the addition amount of 0.77 weight percent of maleic anhydride and large nickel dosage. Therefore, the preparation method for preparing the succinic anhydride composite high-efficiency catalyst by bulk hydrogenation of maleic anhydride is objectively needed, and the preparation method is simple in production process, low in cost, high in activity, small in dosage and high in multiplexing times.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a preparation method of a compound efficient catalyst for preparing succinic anhydride by maleic anhydride bulk hydrogenation, which has the advantages of simple production process, low cost, high activity, small dosage and multiple times.
A composite efficient catalyst for preparing succinic anhydride by bulk hydrogenation of maleic anhydride comprises a carrier gamma-Al 2 O 3 Ni (NO) as active ingredient 3 ） 2 .6H 2 O, a composite solvent and a metal synergist, wherein the carrier gamma-Al is calculated by mass parts 2 O 3 100 parts by mass of the active ingredient Ni (NO 3 ） 2 .6H 2 The mass part of O is 25-200 parts, wherein the addition amount of the composite solvent is active ingredient Ni (NO 3 ） 2 .6H 2 0.1 to 1.8 times of the Ni molar quantity in the O, and the addition quantity of the metal synergistic agent is the active ingredient Ni (NO) 3 ） 2 .6H 2 0.1 to 2 percent of Ni mole amount in O.
Further, the carrier gamma-Al 2 O 3 Has a specific surface area of 140 to 350m 2 And/g, the grain diameter is 0.1-300 mu m.
Further, the composite solvent comprises a cosolvent, an adsorbent and an organic dispersing agent, wherein the cosolvent accounts for 10-30% by mass, the adsorbent accounts for 5-25% by mass, and the organic dispersing agent accounts for 50-75% by mass. Preferably, the cosolvent is one or more of methanol, ethanol and tetrahydrofuran; the adsorbent is one or more of toluene, dimethylbenzene and ethylbenzene; the organic dispersing agent is one or more of polyalcohol such as glycerol, sorbitol, ethylene glycol, 1, 4-butanediol, N-butanol and amine such as N-methyl formamide, N-dimethylformamide, N-dimethylacetamide and the like.
Further, the metal synergist is one or more of rare earth inorganic compounds such as cobalt series, lanthanide series, cerium series and the like, and potassium, barium, calcium, magnesium, manganese, copper and zinc salts.
The invention relates to a preparation method of a succinic anhydride composite efficient catalyst by maleic anhydride bulk hydrogenation, which is characterized by comprising the following steps:
(1) suspension of the carrier in solutionPreparation: 100 parts by mass of carrier gamma-Al 2 O 3 Adding the mixture into deionized water, and stirring at the temperature of 70-90 ℃ to obtain a carrier suspension solution, wherein the mass concentration of the carrier suspension solution is 5-30%;
(2) preparation of aqueous active agent solution: weighing 25-200 parts by mass of active ingredient Ni (NO) 3 ） 2 .6H 2 O, and according to the active ingredient Ni (NO 3 ） 2 .6H 2 O, sequentially weighing the mass of the composite solvent and the mass of the metal synergist, and then adding the active ingredient Ni (NO 3 ） 2 .6H 2 O, the composite solvent and the metal synergistic agent are added into deionized water at the same time, and the mixture is stirred and mixed until the mixture is dissolved to prepare an active agent aqueous solution, wherein the mass concentration of the active agent aqueous solution is 5-30%;
③Na 2 CO 3 preparation of aqueous solution: na is mixed with 2 CO 3 Adding into deionized water, stirring and mixing until dissolving to obtain Na 2 CO 3 Aqueous solution, na 2 CO 3 The mass volume concentration of the aqueous solution is 0.05-0.5 g/mL;
(5) and (3) mixing reaction and post-treatment: the aqueous solution of the active agent prepared in the step (2) and the Na prepared in the step (3) are mixed 2 CO 3 The aqueous solution is added into the reactor of the carrier suspension solution prepared in the step (1) in parallel, the reaction temperature is controlled at 70-90 ℃ and the PH value is 7-13, the reactants are subjected to standing aging after the reaction is finished, the reactants are filtered after the aging for 1-2 hours, the sediment obtained by filtering is washed to be neutral, and then the sediment is dried for 3-4 hours at the temperature of 115-120 ℃ to prepare the catalytic precursor;
(6) reduction treatment: placing the catalytic precursor obtained in the step (5) in a reduction device, maintaining the temperature at 150-550 ℃, reducing for 3-4 h in a hydrogen atmosphere to obtain a catalyst semi-finished product, solidifying the catalyst semi-finished product with paraffin, wrapping the surface of the solidified catalyst semi-finished product for protection to obtain a catalyst finished product
Compared with the prior art, the invention has the advantages that:
1. using gamma-Al of a certain range of specific surface areas 2 O 3 Carrier and certainThe active component loading in the range can optimize the active component distribution, reduce the agglomeration of the active component, ensure that the active component is more uniformly dispersed in the carrier, and improve the activity and selectivity of the catalyst due to the synergistic effect of the acid center of the carrier and the active component;
2. the cosolvent can promote the active components in the solution, so that the organic dispersing agent is fully contacted with the carrier, the adsorption position of the active components is changed, the active components and the carrier form direct bond or local interaction characteristic, and the decomposed cavity enables the catalyst to have higher surface agent, and the activity of the catalyst is improved;
3. the organic dispersing agent can improve the precipitation condition, so that the precipitate formed by the active component is highly dispersed in the carrier to finally form fine active particles, and nickel aluminum spinel which is difficult to reduce due to electron migration during high-temperature reduction of the active component and the carrier can be inhibited, and more effective active components can be easily reduced;
4. the metal synergist changes the electronic structure, ionic valence state and crystal property of the active component nickel, has strong binding force with a carrier, can effectively prevent hydrogenation coking and sintering of the catalyst, ensures high mechanical strength and high thermal stability of the catalyst, and enhances the wear resistance of the catalyst;
5. the catalyst precursor prepared by mixing and post-treatment is carbonate which is easy to decompose, and is directly reduced under the reduction condition without high-temperature roasting after being prepared and dried, so that nickel aluminate which is difficult to reduce is avoided being generated at high temperature, and the catalyst precursor can be reduced at a lower temperature;
6. the catalyst prepared by the invention can realize maleic anhydride bulk hydrogenation to prepare succinic anhydride under the condition of no solvent, the hydrogenation condition is mild, the catalyst usage amount is small, the catalyst addition amount is only 0.04-0.07wt% of maleic anhydride calculated by Ni mass, and the catalyst prepared by carrier particle size in a certain range is easy to separate from the product separation catalyst;
7. when the catalyst is used for preparing succinic anhydride by first hydrogenation of maleic anhydride, the conversion rate is 100%, the succinic anhydride selectivity is 99.96%, and the separated catalyst still has higher activity and selectivity after being reused for eight times; the method is suitable for the intermittent hydrogenation process of maleic anhydride to prepare succinic anhydride by a solvent-free method, and is also suitable for continuous hydrogenation of a bubbling bed or a slurry bed to prepare succinic anhydride;
in conclusion, the production process is simple, and the catalyst prepared by the process has the advantages of high activity, good selectivity, strong coking resistance and toxicity resistance, long service life and multiple multiplexing times, and has good industrial application prospect and is easy to popularize and use.
Detailed Description
The invention is further illustrated, but is not limited in any way, by the following examples, and any alterations or substitutions based on the teachings of the invention are within the scope of the invention.
Example 1:
the composite efficient catalyst for preparing succinic anhydride by bulk hydrogenation of maleic anhydride, which is described in the embodiment 1, is characterized by comprising a carrier gamma-Al 2 O 3 Ni (NO) as active ingredient 3 ） 2 .6H 2 O, a composite solvent and a metal synergist, wherein the carrier gamma-Al is calculated by mass parts 2 O 3 100 parts by mass of the active ingredient Ni (NO 3 ） 2 .6H 2 The mass part of O is 25 parts, wherein the addition amount of the composite solvent is active ingredient Ni (NO 3 ） 2 .6H 2 0.1 times of the Ni mole amount in O, the addition amount of the metal synergist is the active ingredient Ni (NO 3 ） 2 .6H 2 0.1% of Ni mole in O.
Further, the carrier gamma-Al 2 O 3 Has a specific surface area of 140m 2 Per gram, particle size of 0.1 μm, using gamma-Al with specific surface area in a certain range 2 O 3 The carrier can optimize the distribution of the active components, reduce the agglomeration of the active components, enable the active components to be more uniformly dispersed in the carrier, and effectively improve the activity and selectivity of the catalyst due to the synergistic effect of the acid center of the carrier and the active components.
Further, the compound solvent comprises a cosolvent, an adsorbent and an organic dispersing agent, wherein the mass percent of the cosolvent is 10%, the mass percent of the adsorbent is 25%, the mass percent of the organic dispersing agent is 65%, the cosolvent can promote active components in the solution, the organic dispersing agent is fully contacted with a carrier, the adsorption position of the active components is changed, direct bonds or local interaction characteristics are formed between the active components and the carrier, and a decomposed cavity enables the catalyst to have a higher surface agent, so that the activity of the catalyst is improved; the active agent can further enhance the activity degree of the catalyst; the organic dispersing agent can improve the precipitation condition, so that the precipitate formed by the active component is highly dispersed in the carrier to finally form fine active particles, nickel aluminum spinel which is difficult to reduce due to electron migration during high-temperature reduction of the active component and the carrier is inhibited, more effective active components are easily obtained through reduction, and preferably, the cosolvent is methanol; the adsorbent is toluene and xylene; the organic dispersant is a polyhydric alcohol such as glycerin and an amine such as N-methylformamide.
Furthermore, the metal synergist is a rare earth inorganic compound such as cobalt series, lanthanide series, cerium series and the like and potassium, changes the electronic structure, ionic valence state and crystal property of active component nickel, has strong binding force with a carrier, can effectively prevent hydrogenation coking and sintering of the catalyst, ensures high mechanical strength and high thermal stability of the catalyst, and enhances the wear resistance of the catalyst.
The preparation method of the succinic anhydride composite efficient catalyst prepared by maleic anhydride bulk hydrogenation is characterized by comprising the following steps of:
(1) preparation of the carrier solution: 100 parts by mass of carrier gamma-Al 2 O 3 Adding the suspension into deionized water, and stirring at 70 ℃ to obtain a carrier suspension solution, wherein the mass concentration of the carrier solution is 5%;
(2) preparation of aqueous active agent solution: 25 parts by mass of Ni (NO 3 ） 2 .6H 2 O, and according to the active ingredient Ni (NO 3 ） 2 .6H 2 O, sequentially weighing the mass of the composite solvent and the mass of the metal synergist, and then adding the active ingredient Ni (NO 3 ） 2 .6H 2 O, the composite solvent and the metal synergistic agent are added into deionized water simultaneouslyStirring and mixing until the active agent aqueous solution is dissolved, wherein the mass concentration of the active agent aqueous solution is 5%;
③Na 2 CO 3 preparation of aqueous solution: na is mixed with 2 CO 3 Adding into deionized water, stirring and mixing until dissolving to obtain Na 2 CO 3 Aqueous solution, na 2 CO 3 The mass volume concentration of the aqueous solution is 0.05g/mL;
(5) and (3) mixing reaction and post-treatment: the aqueous solution of the active agent prepared in the step (2) and the Na prepared in the step (3) are mixed 2 CO 3 The aqueous solution is added into a carrier suspension solution reactor prepared in the step (1) in parallel, the reaction temperature is controlled at 70 ℃, the PH value is 7.5, reactants are subjected to standing and aging after the reaction is finished, the reactants are filtered after being aged for 1h, precipitates obtained by filtering are washed to be neutral, then the precipitates are dried for 3h at 115 ℃ to prepare a catalytic precursor, the catalytic precursor prepared by the post-treatment of the compounding reaction is carbonate which is easy to decompose, after the preparation and drying, the catalytic precursor is directly reduced under the reduction condition without high-temperature roasting, the difficult-to-reduce nickel aluminate is avoided to be generated at high temperature, and the catalytic precursor can be reduced at a lower temperature;
(6) reduction treatment: and (3) placing the catalytic precursor prepared in the step (5) in a reduction device, maintaining the temperature of 150 ℃, reducing for 3 hours in a hydrogen atmosphere to obtain a semi-finished catalyst, solidifying the semi-finished catalyst by paraffin, and wrapping the semi-finished catalyst on the surface of the solidified semi-finished catalyst for protection to obtain the finished catalyst.
Example 2:
the composite efficient catalyst for preparing succinic anhydride by bulk hydrogenation of maleic anhydride, which is described in the embodiment 2, is characterized by comprising a carrier gamma-Al 2 O 3 Ni (NO) as active ingredient 3 ） 2 .6H 2 O, a composite solvent and a metal synergist, wherein the carrier gamma-Al is calculated by mass parts 2 O 3 100 parts by mass of the active ingredient Ni (NO 3 ） 2 .6H 2 The mass part of O is 100 parts, wherein the addition amount of the composite solvent is the active ingredient Ni (NO 3 ） 2 .6H 2 1 time of Ni mole amount in O, and adding amount of metal synergistAs active ingredient Ni (NO) 3 ） 2 .6H 2 1.2% of the Ni mole amount in O.
Further, the carrier gamma-Al 2 O 3 Has a specific surface area of 280m 2 Per gram, particle size of 200 μm, using gamma-Al of a certain range of specific surface area 2 O 3 The carrier can optimize the distribution of the active components, reduce the agglomeration of the active components, enable the active components to be more uniformly dispersed in the carrier, and effectively improve the activity and selectivity of the catalyst due to the synergistic effect of the acid center of the carrier and the active components.
Further, the compound solvent comprises a cosolvent, an adsorbent and an organic dispersing agent, wherein the mass percent of the cosolvent is 20%, the mass percent of the adsorbent is 25%, the mass percent of the organic dispersing agent is 55%, the cosolvent can promote active components in the solution, the organic dispersing agent is fully contacted with a carrier, the adsorption position of the active components is changed, direct bonds or local interaction characteristics are formed between the active components and the carrier, and a decomposed cavity enables the catalyst to have a higher surface agent, so that the activity of the catalyst is improved; the active agent can further enhance the activity degree of the catalyst; the organic dispersing agent can improve the precipitation condition, so that the precipitate formed by the active component is highly dispersed in the carrier to finally form fine active particles, nickel aluminum spinel which is difficult to reduce due to electron migration during high-temperature reduction of the active component and the carrier is inhibited, more effective active components are easily obtained through reduction, and preferably, the cosolvent is methanol and ethanol; the adsorbent is toluene; the organic dispersant is polyalcohol such as glycerol, sorbitol and amine such as N-methyl formamide and N, N-dimethyl formamide.
Furthermore, the metal synergist is a rare earth inorganic compound such as cobalt series, lanthanide series, cerium series and the like, and potassium and barium, and changes the electronic structure, ionic valence state and crystal property of active component nickel, has strong binding force with a carrier, can effectively prevent hydrogenation coking and sintering of the catalyst, ensures high mechanical strength and high thermal stability of the catalyst, and enhances the wear resistance of the catalyst.
The preparation method of the succinic anhydride composite efficient catalyst prepared by bulk hydrogenation of maleic anhydride, disclosed in the embodiment 2, is characterized by comprising the following steps:
(1) preparation of the carrier solution: 100 parts by mass of carrier gamma-Al 2 O 3 Adding the suspension into deionized water, and stirring at 80 ℃ to obtain a carrier suspension solution, wherein the mass concentration of the carrier solution is 20%;
(2) preparation of aqueous active agent solution: 100 parts by mass of Ni (NO 3 ） 2 .6H 2 O, and according to the active ingredient Ni (NO 3 ） 2 .6H 2 O, sequentially weighing the mass of the composite solvent and the mass of the metal synergist, and then adding the active ingredient Ni (NO 3 ） 2 .6H 2 Adding O, a composite solvent and a metal synergistic agent into deionized water simultaneously, stirring and mixing until the mixture is dissolved to obtain an active agent aqueous solution, wherein the mass concentration of the active agent aqueous solution is 25%;
③Na 2 CO 3 preparation of aqueous solution: na is mixed with 2 CO 3 Adding into deionized water, stirring and mixing until dissolving to obtain Na 2 CO 3 Aqueous solution, na 2 CO 3 The mass volume concentration of the aqueous solution is 0.3g/mL;
(5) and (3) mixing reaction and post-treatment: the aqueous solution of the active agent prepared in the step (2) and the Na prepared in the step (3) are mixed 2 CO 3 The aqueous solution is added into a carrier suspension solution reactor prepared in the step (1) in parallel, the reaction temperature is controlled at 80 ℃, the PH value is 10, reactants are subjected to standing and aging after the reaction is finished, the reactants are filtered after being aged for 1.5 hours, precipitates obtained by filtering are washed to be neutral, then the precipitates are dried at 118 ℃ for 3.5 hours, a catalytic precursor is prepared, the catalyst precursor prepared through mixing and post-treatment is carbonate which is easy to decompose, after preparation and drying, high-temperature roasting is not needed, the catalyst precursor is directly reduced under a reduction condition, difficult-to-reduce nickel aluminate is avoided from being generated at a high temperature, and the catalyst precursor can be reduced at a lower temperature;
(6) reduction treatment: and (3) placing the catalytic precursor prepared in the step (5) in a reduction device, maintaining the temperature of 400 ℃, reducing for 3.5 hours in a hydrogen atmosphere to obtain a semi-finished catalyst, solidifying the semi-finished catalyst by paraffin, and wrapping the semi-finished catalyst on the surface of the solidified semi-finished catalyst for protection to obtain the finished catalyst.
Example 3:
the embodiment of the composite efficient catalyst for preparing succinic anhydride by bulk hydrogenation of maleic anhydride is characterized by comprising a carrier gamma-Al 2 O 3 Ni (NO) as active ingredient 3 ） 2 .6H 2 O, a composite solvent and a metal synergist, wherein the carrier gamma-Al is calculated by mass parts 2 O 3 100 parts by mass of the active ingredient Ni (NO 3 ） 2 .6H 2 The mass part of O is 200 parts, wherein the addition amount of the composite solvent is active ingredient Ni (NO 3 ） 2 .6H 2 The addition amount of the metal synergist is 1.8 times of the Ni molar amount in O, and the addition amount of the metal synergist is the active ingredient Ni (NO 3 ） 2 .6H 2 2% of the Ni mole amount in O.
Further, the carrier gamma-Al 2 O 3 Is 350m 2 Per gram, particle size of 300 μm, using gamma-Al of a certain range of specific surface area 2 O 3 The carrier can optimize the distribution of the active components, reduce the agglomeration of the active components, enable the active components to be more uniformly dispersed in the carrier, and effectively improve the activity and selectivity of the catalyst due to the synergistic effect of the acid center of the carrier and the active components.
Further, the compound solvent comprises a cosolvent, an adsorbent and an organic dispersing agent, wherein the mass percent of the cosolvent is 20%, the mass percent of the adsorbent is 5%, the mass percent of the organic dispersing agent is 75%, the cosolvent can promote active components in the solution, the organic dispersing agent is fully contacted with a carrier, the adsorption position of the active components is changed, direct bonds or local interaction characteristics are formed between the active components and the carrier, and a decomposed cavity enables the catalyst to have a higher surface agent, so that the activity of the catalyst is improved; the active agent can further enhance the activity degree of the catalyst; the organic dispersing agent can improve the precipitation condition, so that the precipitate formed by the active component is highly dispersed in the carrier to finally form fine active particles, nickel aluminum spinel which is difficult to reduce due to electron migration during high-temperature reduction of the active component and the carrier is inhibited, more effective active components are easily obtained through reduction, and preferably, the cosolvent is methanol, ethanol and tetrahydrofuran; the adsorbent is toluene, dimethylbenzene and ethylbenzene; the organic dispersing agent is one or more of polyalcohol such as glycerol, sorbitol, ethylene glycol, 1, 4-butanediol, N-butanol and amine such as N-methyl formamide, N-dimethylformamide, N-dimethylacetamide and the like.
Furthermore, the metal synergistic agent is a rare earth inorganic compound such as cobalt series, lanthanide series, cerium series and the like, and potassium, barium, calcium, magnesium, manganese, copper and zinc, and the metal synergistic agent changes the electronic structure, ionic valence state and crystal property of active component nickel, has strong binding force with a carrier, can effectively prevent hydrogenation coking and sintering of the catalyst, ensures high mechanical strength and strong thermal stability of the catalyst, and enhances the wear resistance degree of the catalyst.
The preparation method of the succinic anhydride composite efficient catalyst prepared by maleic anhydride bulk hydrogenation, disclosed in the embodiment 3, is characterized by comprising the following steps:
(1) preparation of the carrier solution: 100 parts by mass of carrier gamma-Al 2 O 3 Adding the suspension into deionized water, and stirring at 90 ℃ to obtain a carrier suspension solution, wherein the mass concentration of the carrier solution is 30%;
(2) preparation of aqueous active agent solution: 200 parts by mass of Ni (NO 3 ） 2 .6H 2 O, and according to the active ingredient Ni (NO 3 ） 2 .6H 2 O, sequentially weighing the mass of the composite solvent and the mass of the metal synergist, and then adding the active ingredient Ni (NO 3 ） 2 .6H 2 Adding O, a composite solvent and a metal synergistic agent into deionized water simultaneously, stirring and mixing until the components are dissolved to prepare an active agent aqueous solution, wherein the mass concentration of the active agent aqueous solution is 30%;
③Na 2 CO 3 preparation of aqueous solution: na is mixed with 2 CO 3 Adding into deionized water, stirring and mixing until dissolving to obtain Na 2 CO 3 Aqueous solution, na 2 CO 3 Of aqueous solutionsThe mass volume concentration is 0.5g/mL;
(5) and (3) mixing and post-treatment: the aqueous solution of the active agent prepared in the step (2) and the Na prepared in the step (3) are mixed 2 CO 3 The aqueous solution is added into a reactor of the carrier suspension solution prepared in the step (1) in parallel, the reaction temperature is controlled at 90 ℃, the PH value is 7-13, reactants are subjected to standing and aging after the reaction is finished, the reactants are filtered after being aged for 2 hours, precipitates obtained by filtering are washed to be neutral, then the precipitates are dried for 4 hours at the temperature of 120 ℃ to prepare a catalytic precursor, the catalytic precursor prepared by mixing and post-treatment is carbonate which is easy to decompose, after the preparation and drying, the catalytic precursor is directly reduced under the reduction condition without high-temperature roasting, the difficult-to-reduce nickel aluminate is avoided to be generated at high temperature, and the catalytic precursor can be reduced at a lower temperature;
(6) reduction treatment: and (3) placing the catalytic precursor prepared in the step (5) in a reduction device, maintaining the temperature of 550 ℃, reducing for 4 hours in a hydrogen atmosphere to obtain a semi-finished catalyst, solidifying the semi-finished catalyst by paraffin, and wrapping the semi-finished catalyst on the surface of the solidified semi-finished catalyst for protection to obtain the finished catalyst.
In summary, the production process of the embodiment 1-3 is simple, the catalyst prepared in the embodiment 1-3 can be used for preparing succinic anhydride by bulk hydrogenation of maleic anhydride under the condition of no solvent, the hydrogenation condition is mild, the catalyst usage amount is small, the catalyst addition amount is only 0.04-0.07wt% of maleic anhydride calculated by Ni mass, and the catalyst prepared by carrier particle size in a certain range is easy to separate from the product separation catalyst; meanwhile, when the catalyst is used for preparing succinic anhydride by first hydrogenation of maleic anhydride, the conversion rate is 100%, the succinic anhydride selectivity is 99.96%, and the separated catalyst still has higher activity and selectivity after being reused for eight times; the method is not only suitable for the intermittent hydrogenation process of maleic anhydride without solvent to prepare succinic anhydride, but also suitable for continuous hydrogenation of bubbling bed or slurry bed to prepare succinic anhydride, and has better industrial application prospect.
When the catalysts prepared in the examples 1 to 3 are used for preparing succinic anhydride by bulk hydrogenation of maleic anhydride, the using method is as follows: the catalyst and maleic anhydride are fed into a closed high-pressure reaction kettle, the feeding amount of the catalyst is 0.05wt% of the mass of maleic anhydride, then the air in the high-pressure reaction kettle is replaced by nitrogen, the pressure is maintained, the leakage is tested, the nitrogen in the reaction kettle is replaced by hydrogen after the leakage is tested to be qualified, the reaction is carried out for 100-180 min under the conditions that the pressure is 0.5-3.0 MPa and the temperature is 65-160 ℃, the maleic anhydride conversion rate can reach 100%, the succinic anhydride selectivity reaches 99.96%, and after the separated catalyst is repeatedly used for eight times, the maleic anhydride conversion rate can still reach 91.5%, and the succinic anhydride selectivity reaches 99.98%. The technical parameters of the specific catalyst after eight repeated uses are shown in table 1.
TABLE 1
| Number of catalyst uses | Reaction pressure (MPa) | Reaction temperature (. Degree. C.) | Reaction time (min) | Maleic anhydride conversion (%) | Succinic anhydride selectivity (%) |
| 1 | 1.5 | 130 | 150 | 100 | 99.96 |
| 2 | 1.5 | 130 | 150 | 99.98 | 99.95 |
| 3 | 1.5 | 130 | 150 | 99.93 | 99.92 |
| 4 | 1.5 | 130 | 150 | 99.89 | 99.91 |
| 5 | 1.5 | 130 | 150 | 99.73 | 99.90 |
| 6 | 1.5 | 130 | 150 | 99.45 | 99.93 |
| 7 | 1.5 | 130 | 150 | 94.04 | 99.95 |
| 8 | 1.5 | 130 | 150 | 91.5 | 99.98 |
As can be seen from Table 1, the catalysts prepared in examples 1 to 3 have the advantages of high activity, good selectivity, strong coking resistance and toxicity resistance, long service life and multiple multiplexing times, and the catalysts still have higher activity and selectivity after being reused for eight times.
Claims (5)
1. A preparation method of a succinic anhydride composite efficient catalyst by maleic anhydride bulk hydrogenation is characterized by comprising the following steps of:
raw materials: comprising a carrier gamma-Al 2 O 3 Ni (NO) as active ingredient 3 ） 2 .6H 2 O, a composite solvent and a metal synergist, wherein the carrier gamma-Al is calculated by mass parts 2 O 3 100 parts by mass of the active ingredient Ni (NO 3 ）2 .6H 2 The mass part of O is 25-200 parts, wherein the addition amount of the composite solvent is active ingredient Ni (NO 3 ） 2 .6H 2 0.1 to 1.8 times of the Ni molar quantity in the O, and the addition quantity of the metal synergistic agent is the active ingredient Ni (NO) 3 ） 2 .6H 2 0.1 to 2 percent of Ni mole amount in O;
the composite solvent comprises a cosolvent, an adsorbent and an organic dispersing agent, wherein the cosolvent accounts for 10-30% by mass, the adsorbent accounts for 5-25% by mass, and the organic dispersing agent accounts for 50-75% by mass;
the cosolvent is one or more of methanol, ethanol and tetrahydrofuran; the adsorbent is one or more of toluene, dimethylbenzene and ethylbenzene; the organic dispersing agent is one or more of polyalcohol such as glycerol, sorbitol, ethylene glycol, 1, 4-butanediol, N-butanol and amine such as N-methyl formamide, N-dimethylformamide and N, N-dimethylacetamide;
the preparation method comprises the following steps:
(1) preparation of the carrier solution: 100 parts by mass of carrier gamma-Al 2 O 3 Adding the mixture into deionized water, and stirring at the temperature of 70-90 ℃ to obtain a carrier suspension solution, wherein the mass concentration of the carrier suspension solution is 5-30%;
(2) preparation of aqueous active agent solution: weighing 25-200 parts by mass of active ingredient Ni (NO) 3 ） 2 .6H 2 O, and according to the active ingredient Ni (NO 3 ） 2 .6H 2 O, sequentially weighing the mass of the composite solvent and the mass of the metal synergist, and then adding the active ingredient Ni (NO 3 ） 2 .6H 2 O, the composite solvent and the metal synergistic agent are added into deionized water at the same time, and the mixture is stirred and mixed until the mixture is dissolved to prepare an active agent aqueous solution, wherein the mass concentration of the active agent aqueous solution is 5-30%;
③Na 2 CO 3 preparation of aqueous solution: na is mixed with 2 CO 3 Adding into deionized water, stirring and mixing until dissolving to obtain Na 2 CO 3 Aqueous solution, na 2 CO 3 The mass volume concentration of the aqueous solution is 0.05-0.5 g/mL;
(5) and (3) mixing reaction and post-treatment: the aqueous solution of the active agent prepared in the step (2) and the Na prepared in the step (3) are mixed 2 CO 3 The aqueous solution is added into the reactor of the carrier suspension solution prepared in the step (1) in parallel, the reaction temperature is controlled at 70-90 ℃ and the pH value is 7-13, the reactant is subjected to standing aging after the reaction is finished, the reactant is filtered after the aging is carried out for 1-2 hours, the precipitate obtained by filtering is washed to be neutral, and then the precipitate is dried for 3-4 hours at the temperature of 115-120 ℃ to prepare the catalytic precursor;
(6) reduction treatment: and (3) placing the catalytic precursor prepared in the step (5) in a reduction device, maintaining the temperature of 150-550 ℃, reducing for 3-4 hours in a hydrogen atmosphere to obtain a semi-finished catalyst, solidifying the semi-finished catalyst by paraffin, and wrapping the semi-finished catalyst on the surface of the solidified semi-finished catalyst for protection to obtain the finished catalyst.
2. The preparation method of the succinic anhydride composite efficient catalyst prepared by bulk hydrogenation of maleic anhydride, which is disclosed in claim 1, is characterized in that: the carrier gamma-Al 2 O 3 Has a specific surface area of 140 to 350m 2 And/g, the grain diameter is 0.1-300 mu m.
3. The preparation method of the succinic anhydride composite efficient catalyst prepared by bulk hydrogenation of maleic anhydride, which is disclosed in claim 1, is characterized in that: the metal synergist is one or more of cobalt series, lanthanide series and cerium series rare earth inorganic compounds and potassium, barium, calcium, magnesium, manganese, copper and zinc salts.
4. A succinic anhydride composite high-efficiency catalyst prepared by bulk hydrogenation of maleic anhydride according to the method of claim 1, 2 or 3.
5. The method for preparing succinic anhydride by bulk hydrogenation of maleic anhydride by using the composite high-efficiency catalyst as claimed in claim 4, which is characterized by comprising the following steps: the catalyst and maleic anhydride are fed into a closed high-pressure reaction kettle, the feeding amount of the catalyst is 0.05wt% of the mass of maleic anhydride, then the air in the high-pressure reaction kettle is replaced by nitrogen, the pressure is maintained, the leakage is tested, the nitrogen in the kettle is replaced by hydrogen after the leakage is tested to be qualified, the reaction is carried out for 100-180 min under the conditions that the pressure is 0.5-3.0 MPa and the temperature is 65-160 ℃, the maleic anhydride conversion rate reaches 100%, the succinic anhydride selectivity reaches 99.96%, and after the separated catalyst is repeatedly used for eight times, the maleic anhydride conversion rate reaches 91.5%, and the succinic anhydride selectivity reaches 99.98%.
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