CN106861702A - It is a kind of that the catalyst and its preparation method and application for being directly synthesized succinic acid are mutually hydrogenated with for cis-butenedioic anhydride water - Google Patents
It is a kind of that the catalyst and its preparation method and application for being directly synthesized succinic acid are mutually hydrogenated with for cis-butenedioic anhydride water Download PDFInfo
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- CN106861702A CN106861702A CN201710109984.0A CN201710109984A CN106861702A CN 106861702 A CN106861702 A CN 106861702A CN 201710109984 A CN201710109984 A CN 201710109984A CN 106861702 A CN106861702 A CN 106861702A
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- catalyst
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- succinic acid
- butenedioic anhydride
- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001384 succinic acid Substances 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 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 2
- 238000005245 sintering Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 12
- 239000010931 gold Substances 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229940014800 succinic anhydride Drugs 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004631 polybutylene succinate Substances 0.000 description 4
- 229920002961 polybutylene succinate Polymers 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- -1 poly butylene succinate Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 229910002645 Ni-Rh Inorganic materials 0.000 description 1
- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 150000001887 cortisones Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
- C07C51/087—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides by hydrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
It is a kind of be mutually hydrogenated with for cis-butenedioic anhydride water be directly synthesized succinic acid catalyst be carbon coating ambrose alloy Cu Ni/Al2O3@C catalysts, wherein carbon content are 1 7wt%, and nickel content is 10 17wt%, and copper content is 2 8wt%, and remaining is Al2O3.Catalyst of the invention has high activity, high selectivity, good stability, long lifespan, prepares simple advantage.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to one kind is directly synthesized fourth two for being catalyzed cis-butenedioic anhydride aqueous solution hydrogenation
Catalyst of acid and its preparation method and application.
Research background
Succinic acid can be used as excellent performance sensitising agent, and the important intermediate of pigment, such as dimethyl succinate are a kind of important
Light stabilizer (be used for vinyl house), and diisopropyl ester amber acid synthetic dyestuff process does not almost pollute, and produces pigment (vapour
Car metallic paint) have the advantages that degree of staining is high, bright in colour, weather resistance is high.Main application fields are broadly divided into five classes:The
One class is surfactant, cleaning agent, additive and foaming agent;Equations of The Second Kind is in food processing, as acid;3rd class
It is to be produced as medicine intermediate, can be used to produce sulfa drug, Va, B6, hemostatic and cortisone derivative;4th class is ion
Corrosion and spot corrosion in chelating agent, such as electroplating industry;5th class is most promising field, and it is biodegradable modeling
The primary raw material of material poly butylene succinate (PBS).Poly butylene succinate (PBS) is a kind of new excellent performance
Biological degradation plastics, compared with traditional biodegradable plastics, with fusing point it is high, heat resistance is good, mechanical performance is excellent,
The advantage of relative low price (being the 1/3 of existing biodegradable plastic).
The production method of succinic acid mainly has:Biological fermentation process, electrochemical reducing and cis-butenedioic anhydride catalytic hydrogenation method.Wherein,
Cis-butenedioic anhydride catalytic hydrogenation method has the advantages that technological process is simple and convenient to operate, operating cost is low, high income, good product quality, quilt
It is considered most potential succinic acid production method, the study hotspot as recent domestic.
Maleic anhydride hydrogenation synthesizing succinic acid can be divided into has solvent with solvent-free two kinds of process routes.Solvent-free maleic anhydride hydrogenation refers to
In the presence of a catalyst, directly with hydrogen there is hydrogenation reaction generation succinic anhydride in the cis-butenedioic anhydride of molten state.Patent CN
92100554.7 and CN 92103481.4 is disclosed under a kind of condition of no solvent, using Raney's nickel catalyst to molten condition
The method that maleic anhydride hydrogenation prepares succinic anhydride.Catalyst is fed intake with cis-butenedioic anhydride with certain proportion, hydrogen in kettle is kept in hydrogenation process
Atmospheric pressure is constant, using the method separating catalyst and product of heat filtering at the end of reaction.Using the method, succinic anhydride is most
High yield can reach 90% and 96%.Because maleic anhydride hydrogenation synthesizing succinic acid acid anhydride is strong exothermal reaction (Δ H=-128KJ/
Mol), the reaction heat for being produced in hydrogenation process easily makes reactant/product polycondensation for carbon species high, is covered in catalyst table
Face is present in final products, influences the yield and purity of target product succinic anhydride.Subsequently with respect to the research of maleic anhydride hydrogenation
Carry out in organic solvent more.Such as CN1453066A, CN 101891718A, CN 101502802B, CN 102311332B, CN
The patents such as 102229587B use in tetrahydrofuran, toluene, 1,4- dioxane, acetone or gamma-butyrolacton one or two with
Upper is catalysis maleic anhydride hydrogenation synthesizing succinic acid acid anhydride in the presence of solvent catalyst.By gained reaction solution through rectifying (or crystallization dry
It is dry), hydrolysis, crystallization, succinic acid is obtained after drying.
If electing the solvent of maleic anhydride hydrogenation as water, the use of organic solvent is on the one hand avoided, can significantly reduced organic
Solvent uses the harm of environmental pollution;On the other hand, it is, along acid, hydrogenation synthesis to be selected through C=C keys that cis-butenedioic anhydride meets water electrode facile hydrolysis
It is succinic acid, succinic acid is more difficult to be hydrogenated to deep hydrogenation product compared with succinic anhydride, can improve target product succinic acid
Yield;Furthermore, gained reaction solution crystallisation by cooling obtains final product succinic acid after drying, and reaction process step is greatly reduced, and improves
Economical in reaction.Have the advantages that operating process is simple, energy consumption is low, environmental benefit good.The B of Chinese patent CN 101844976 with
One or more in the cis-butenedioic anhydride aqueous solution, the fumaric acid aqueous solution or aqueous maleic acid are raw material, in silica, titanium dioxide
Carry out on Ni, Pd-Co, Pt-Fe, Ni-Ir, Ni-Rh, Ni-Ru catalyst of zirconium, activated carbon, titanium oxide or carborundum load and add
Hydrogen is reacted, and has obtained the aqueous solution of succinic acid, and succinic acid product is obtained after crystallisation by cooling, drying.The method adopts water as molten
Agent, it is, along acid, active component to be rushed from carrier surface along acid strong, the easily corrosion catalyst carrier of acid that cis-butenedioic anhydride meets water electrode facile hydrolysis
Brush down, reduce the service life of catalyst.There is a problem of that catalyst activity component is easily lost in during long time running.Patent
The B of CN 102417445 then with the aqueous solution of maleate as raw material it is hydrogenated after obtain the succinate aqueous solution, will obtain fourth
Diacid is acidified, separate after obtain succinic acid.Corrosion of the strong acid reaction solution to catalyst is this method reduce, but be increased
Follow-up acidification step, reaction process complex steps.
The content of the invention
For above technical problem, it is an object of the invention to provide a kind of high activity, high selectivity, good stability, life-span
Long, preparation is simply to cis-butenedioic anhydride water and is mutually hydrogenated with catalyst for being directly synthesized succinic acid and its preparation method and application.
The catalyst that the present invention is provided is a kind of Cu-Ni/Al of carbon coating ambrose alloy2O3@C catalysts, wherein carbon content are 1-
7wt%, nickel content is 10-17wt%, and copper content is 2-8wt%, and remaining is Al2O3。
The preparation method of catalyst of the present invention, comprises the following steps:
(1) mantoquita and nickel salt are weighed, nickel content 0.05-0.2gml is configured to respectively-1, copper content 0.01-0.1gml-1Solution;
(2) Al is taken2O3Carrier, in 400-800 DEG C of constant temperature calcining treatment 3-6h, is cooled to room temperature standby;
(3) after the nickel salt solution in step (1) is mixed with copper salt solution, the step of handling well (2) is added under agitation
Al2O3Carrier, adds the urea of 1-5 times of nickel and copper mole sum, and gained reaction solution is placed in into 70-100 under agitation
DEG C reaction 1-3h;
(4) after filtering out the filtrate of step (3) reaction solution, 2-6h is dried within the temperature range of 80-200 DEG C, then
1-50h is calcined within the temperature range of 250-550 DEG C, catalyst precarsor is obtained;
(5) the catalyst precarsor incipient impregnation for obtaining step (4) is water-soluble in the sucrose that concentration is 0.1-0.37g/ml
Liquid, 2-6h is dried after standing 20-120min at room temperature at 80-140 DEG C;In N22-6h, drop are calcined under atmosphere in 400-600 DEG C
Lead to H after to room temperature23~50h is reduced at 350-450 DEG C;N used2And H2Air speed is 300-600h-1。
Nickel salt refers to the one kind in nickel nitrate, nickel chloride or nickel sulfate in the step (1);Mantoquita refers to copper nitrate, chlorine
Change the one kind in copper or copper sulphate.
Drying temperature in the step (4) is preferably 80-150 DEG C, and sintering temperature is preferably 400-550 DEG C.
Catalyst of the present invention is applied to fixed bed or autoclave reactor, and reaction raw materials are mass concentration fractions for 8~
The cis-butenedioic anhydride aqueous solution of 30wt%, 60-140 DEG C of reaction temperature, 2~6MPa of Hydrogen Vapor Pressure.
In the fixed bed reactors, liquid air speed is 1-6h-1。
0.01~0.05g of catalyst amount (catalyst)/g (cis-butenedioic anhydride) in the autoclave reactor, the reaction time 1~
6h。
Under the above-described reaction conditions, conversion rate of maleic anhydride >=99.3%, succinic acid is selectively 100%.
Compared with prior art, advantages of the present invention and effect:
(1) catalyst of the invention is a kind of catalyst with carbon coating structure, and carbon is hydrophobic material, only reactant
Can enter catalytic inner with activated centre effect generation succinic acid along the duct of carbon along acid.And reaction dissolvent water then cannot pass through
Carbon-coating is contacted with catalyst activity centre or carrier, it is to avoid acidic aqueous solution washing away and Al to active component2O3The corruption of carrier
Erosion, significantly improves the stability in use of catalyst.
(2) catalyst of the invention is directly synthesized succinic acid suitable for cis-butenedioic anhydride aqueous solution hydrogenation, on the one hand avoids organic
The use of solvent, can significantly reduce the harm that organic solvent uses environmental pollution;On the other hand, cis-butenedioic anhydride is direct in aqueous
Through hydrolyzing hydrogenation reaction synthesizing succinic acid, succinic acid will be obtained final product after the cooling of gained reaction solution, crystallization, drying, greatly reduced
Reaction process step, improves economical in reaction.
Specific embodiment
Embodiment 1
Weigh 59.45g Ni (NO3)2·6H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to nickel is
0.12g/mL;Weigh 11.40g Cu (NO3)2·3H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to copper is
0.03g/mL.Above-mentioned nickel salt is mixed with copper salt solution, the Al after adding 82g to process 3h through 500 DEG C of constant temperature under agitation2O3Carry
Body, is subsequently adding 30.19g urea.Above-mentioned reaction solution is placed under agitation 2h is reacted in 80 DEG C of oil baths, react mistake after terminating
Filter, 3h is dried by gained catalyst precarsor in 120 DEG C, is then calcined 3h in 450 DEG C.Catalyst precarsor after roasting is isometric
The aqueous sucrose solution of 0.2g/mL is impregnated, 3h is dried after 120 DEG C 120min is stored at room temperature, then in the nitrogen of 400mL/min
3h is calcined in 450 DEG C in stream, 450mL/min hydrogen is passed through after being down to room temperature, 10h is reduced in 350 DEG C.Gained catalyst is labeled as
A.C, Ni, Cu, Al in the catalyst2O3Weight/mass percentage composition about be respectively 3wt%, 12wt%, 3wt%, 82wt%.
Embodiment 2
Weigh 74.32g Ni (NO3)2·6H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to nickel is
0.15g/mL;Weigh 10.73g CuCl2·2H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to copper is 0.04g/
mL.Above-mentioned nickel salt is mixed with copper salt solution, the Al after adding 74g to process 2h through 700 DEG C of constant temperature under agitation2O3Carrier, then
Add 28.67g urea.Above-mentioned reaction solution is placed under agitation 3h is reacted in 90 DEG C of oil baths, reaction is filtered after terminating, by institute
Obtain catalyst precarsor and dry 3h in 150 DEG C, be then calcined 10h in 550 DEG C.By the catalyst precarsor incipient impregnation after roasting
The aqueous sucrose solution of 0.37g/mL, dries 5h, then in the nitrogen stream of 500mL/min 120min is stored at room temperature after 140 DEG C
In in 550 DEG C be calcined 5h, 450mL/min hydrogen is passed through after being down to room temperature, in 400 DEG C of reductase 12 0h.Gained catalyst is labeled as B.
C, Ni, Cu, Al in the catalyst2O3Weight/mass percentage composition about be respectively 7wt%, 15wt%, 4wt%, 74wt%.
Embodiment 3
Weigh 67.18g NiSO4·6H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to nickel is 0.15g/
mL;Weigh 12.56g CuSO4The 100mL aqueous solution is configured to, the concentration that this GOLD FROM PLATING SOLUTION belongs to copper is 0.05g/mL.By above-mentioned sulphur
Sour nickel mixes with copper-bath, the Al after adding 75g to process 4h through 600 DEG C of constant temperature under agitation2O3Carrier, is subsequently adding
80.22g urea.Above-mentioned reaction solution is placed under agitation 3h is reacted in 70 DEG C of oil baths, reaction is filtered after terminating, and gained is urged
Agent precursor dries 5h in 200 DEG C, is then calcined 50h in 250 DEG C.By the catalyst precarsor incipient impregnation 0.3g/ after roasting
The aqueous sucrose solution of mL, dries 5h, then in 450 in the nitrogen stream of 400mL/min 100min is stored at room temperature after 140 DEG C
DEG C roasting 3h, 400mL/min hydrogen is passed through after being down to room temperature, in 400 DEG C of reductase 12 0h.Gained catalyst is labeled as C.The catalysis
C, Ni, Cu, Al in agent2O3Weight/mass percentage composition about be respectively 5wt%, 15wt%, 5wt%, 75wt%.
Embodiment 4
Weigh 68.85g NiCl2·6H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to nickel is 0.17g/
mL;Weigh 30.41g Cu (NO3)2·3H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to copper is 0.08g/mL.
Above-mentioned nickel salt is mixed with copper salt solution, the Al after adding 68g to process 6h through 400 DEG C of constant temperature under agitation2O3Carrier, Ran Houjia
Enter 24.94g urea.Above-mentioned reaction solution is placed under agitation 1h is reacted in 100 DEG C of oil baths, reaction is filtered after terminating, by institute
Obtain catalyst precarsor and dry 6h in 80 DEG C, be then calcined 50h in 350 DEG C.By the catalyst precarsor incipient impregnation after roasting
The aqueous sucrose solution of 0.37g/mL, dries 5h, then in the nitrogen stream of 500mL/min 20min is stored at room temperature after 140 DEG C
5h is calcined in 550 DEG C, 450mL/min hydrogen is passed through after being down to room temperature, in 400 DEG C of reductase 12 0h.Gained catalyst is labeled as D.Should
C, Ni, Cu, Al in catalyst2O3Weight/mass percentage composition about be respectively 7wt%, 17wt%, 8wt%, 68wt%.
Embodiment 5
Weigh 48.60gNiCl2·6H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to nickel is 0.12g/mL;
Weigh 16.10g CuCl2·2H2O is made the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to copper is 0.06g/mL.By above-mentioned chlorine
Change nickel to mix with copper chloride solution, the Al after adding 79g to process 5h through 500 DEG C of constant temperature under agitation2O3Carrier, is subsequently adding
89.64g urea.Above-mentioned reaction solution is placed under agitation 2h is reacted in 90 DEG C of oil baths, reaction is filtered after terminating, and gained is urged
Agent precursor dries 3h in 180 DEG C, is then calcined 8h in 500 DEG C.By the catalyst precarsor incipient impregnation 0.2g/mL after roasting
Aqueous sucrose solution, 5h is dried after 120 DEG C 120min is stored at room temperature, then in 450 DEG C in the nitrogen stream of 500mL/min
Roasting 3h, is passed through 500mL/min hydrogen, in 450 DEG C of reductase 12 2h after being down to room temperature.Gained catalyst is labeled as E.The catalyst
Middle C, Ni, Cu, Al2O3Weight/mass percentage composition about be respectively 3wt%, 12wt%, 6wt%, 79wt%.
Embodiment 6
Weigh 44.78g NiSO4·6H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to nickel is 0.10g/
mL;Weigh 5.37g CuCl2·2H2O is configured to the 100mL aqueous solution, and the concentration that this GOLD FROM PLATING SOLUTION belongs to copper is 0.02g/mL.Will be upper
State nickel salt to mix with copper salt solution, the Al after adding 87g to process 2h through 400 DEG C of constant temperature under agitation2O3Carrier, is subsequently adding
12.11g urea.Above-mentioned reaction solution is placed under agitation 3h is reacted in 90 DEG C of oil baths, reaction is filtered after terminating, and gained is urged
Agent precursor dries 6h in 80 DEG C, is then calcined 1h in 550 DEG C.By the catalyst precarsor incipient impregnation 0.1g/mL after roasting
Aqueous sucrose solution, 5h is dried after 120 DEG C 20min is stored at room temperature, then in 550 DEG C in the nitrogen stream of 600mL/min
Roasting 5h, is passed through 550mL/min hydrogen, in 350 DEG C of reductase 12 0h after being down to room temperature.Gained catalyst is labeled as F.The catalyst
Middle C, Ni, Cu, Al2O3Weight/mass percentage composition about be respectively 1wt%, 10wt%, 2wt%, 87wt%.
Embodiment 7
Above-mentioned catalyst is applied to fixed bed or autoclave reactor, reaction raw materials be cis-butenedioic anhydride mass fraction be 8~
The aqueous solution of 30wt%, 60-140 DEG C of reaction temperature, 2~6MPa of Hydrogen Vapor Pressure.Wherein liquid air speed is in fixed bed reactors
1-6h-1, 0.01~0.05g of catalyst amount (catalyst)/g (cis-butenedioic anhydride), 2~6h of reaction time in autoclave reactor.Upper
State under reaction condition, conversion rate of maleic anhydride >=99.3%, succinic acid is selectively 100%.
Each catalyst reaction condition of table 1 and result
Claims (8)
1. it is a kind of that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water, it is characterised in that catalyst is a kind of carbon coating
The Cu-Ni/Al of ambrose alloy2O3@C catalysts, wherein carbon content are 1-7wt%, and nickel content is 10-17wt%, and copper content is 2-
8wt%, remaining is Al2O3。
2. a kind of preparation method that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 1,
It is characterized in that comprising the following steps:
(1) mantoquita and nickel salt are weighed, nickel content 0.05-0.2gml is configured to respectively-1, copper content 0.01-0.1gml-1It is molten
Liquid;
(2) Al is taken2O3Carrier, in 400-800 DEG C of constant temperature calcining treatment 3-6h, is cooled to room temperature standby;
(3) after the nickel salt solution in step (1) is mixed with copper salt solution, the step of handling well (2) is added under agitation
Al2O3Carrier, adds the urea of 1-5 times of nickel and copper mole sum, and gained reaction solution is placed in into 70-100 DEG C under agitation
Reaction 1-3h;
(4) after filtering out the filtrate of step (3) reaction solution, 2-6h is dried within the temperature range of 80-200 DEG C, then in 250-550
1-50h is calcined within the temperature range of DEG C, catalyst precarsor is obtained;
(5) the catalyst precarsor incipient impregnation for obtaining step (4) in concentration for 0.1-0.37g/ml aqueous sucrose solution,
After standing 20-120min at room temperature 2-6h is dried at 80-140 DEG C;In N22-6h is calcined in 400-600 DEG C under atmosphere, room is down to
Wen Houtong H23~50h is reduced at 350-450 DEG C;N used2And H2Air speed is 300-600h-1。
3. a kind of preparation method that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 2,
It is characterized in that nickel salt is the one kind in nickel nitrate, nickel chloride or nickel sulfate in the step (1).
4. a kind of preparation method that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 2,
It is characterized in that mantoquita is the one kind in copper nitrate, copper chloride or copper sulphate in the step (1).
5. a kind of preparation method that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 2,
It is characterized in that the drying temperature in the step (4) is 80-150 DEG C.
6. a kind of preparation method that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 2,
It is characterized in that the sintering temperature in the step (4) is 400-550 DEG C.
7. a kind of application that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 1, it is special
It is that catalyst is used for fixed bed to levy, and reaction raw materials are the cis-butenedioic anhydride aqueous solution that mass concentration fraction is 8~30wt%, reaction temperature
60-140 DEG C, 2~6MPa of Hydrogen Vapor Pressure, liquid air speed is 1-6h-1。
8. a kind of application that the catalyst for being directly synthesized succinic acid is mutually hydrogenated with for cis-butenedioic anhydride water as claimed in claim 1, it is special
It is that catalyst is used for autoclave reactor to levy, and reaction raw materials are the cis-butenedioic anhydride aqueous solution that mass concentration fraction is 8~30wt%, instead
Answer 60-140 DEG C of temperature, 2~6MPa of Hydrogen Vapor Pressure, 0.01~0.05g of catalyst amount (catalyst)/g (cis-butenedioic anhydride), reaction time
1~6h.
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