CN105536780A - Preparation method of high-selectivity palladium catalyst - Google Patents
Preparation method of high-selectivity palladium catalyst Download PDFInfo
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- CN105536780A CN105536780A CN201610084521.9A CN201610084521A CN105536780A CN 105536780 A CN105536780 A CN 105536780A CN 201610084521 A CN201610084521 A CN 201610084521A CN 105536780 A CN105536780 A CN 105536780A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 22
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 5
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 239000013598 vector Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 abstract 3
- 238000001354 calcination Methods 0.000 abstract 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 abstract 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 239000012224 working solution Substances 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241001191009 Gymnomyza Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002821 scintillation proximity assay Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
Abstract
The invention provides a preparation method of a high-selectivity palladium catalyst, which comprises the following steps of: (1) dissolving 2-ethyl anthraquinone in isopropanol at room temperature by sufficiently stirring, adding aluminum isopropoxide to the solution according to the mass ratio of 2-ethyl anthraquinone to aluminum isopropoxide being 1:(28.57-100), heating, sufficiently stirring for dissolving, dripping mixed liquid of acetic acid and water, and sufficiently stirring at room temperature for hydrolysis; (2) aging a hydrolysis product at 80 DEG C for 20h, separating, washing, drying and calcining to obtain gamma-Al2O3 powder; and (3) isometrically immersing the gamma-Al2O3 powder with sodium tetrachloropalladate solution, washing, drying and calcining to obtain the efficient loaded palladium catalyst. The preparation method has the advantages of novelty, simple operation, controllable specific area, pore diameter and other structure properties of the product and the like; and the prepared 2-ethyl anthraquinone regulated and controlled catalyst has good selectivity and activity on anthraquinone hydrogenation reaction.
Description
Technical field
The invention belongs to preparation and the catalytic applications of meso-porous alumina, specifically a kind of for anthraquinone production H
2o
2high selectivity palladium catalyst of hydrogenation process and preparation method thereof.
Background technology
H
2o
2be a kind of excellent green chemical industry raw material, be widely used in the industries such as papermaking, food, environmental protection and medicine.Its production method is constantly weeded out the old and bring forth the new, and hydrogen-oxygen direct synthesis technique receives much concern at present, but is mostly in laboratory stage, and anthraquinone be current industrial production H
2o
2main flow route.The H of the anthraquinone production of domestic generally employing palladium catalyst fixed bed at present
2o
2, hydrogenation process is anthraquinone committed step, and this process mainly uses the catalyst of mesoporous active aluminum oxide supported precious metal palladium.Because Precious Metals Resources is limited, expensive, how to improve noble metal service efficiency, reduce catalyst preparing cost, and improve the emphasis that catalyst activity and selectivity is research always.
CN104192880B discloses a kind of method preparing high purity pseudoboehmite: will be first that the hydrolyzate that the deionized water of 1:0.5 ~ 3 and isopropyl alcohol are prepared joins in aluminium isopropoxide-aqueous isopropanol by mass ratio containing the pore creating material such as acetic acid, nitric acid, urea or F127, hydrolysis 2 ~ 8h at 60 ~ 80 DEG C, wherein the ratio of the amount of substance of deionized water and aluminium isopropoxide is 2 ~ 20:1, hydrolysate, 60 ~ 260 DEG C of dryings, obtains high purity pseudoboehmite after drying; Boehmite product purity prepared by the method is high, and pore volume and specific area easily control, and preparation process no waste is discharged, and simultaneous reactions flow process is simple, and cost is low.The people such as Ding Tong (DingTong, QinYongning, MaZhi.Effectoftransitionmetalontheactivityof γ-Al
2o
3-supportedPdcatalyst.ChineseJournalofCatalysis, 2002,23 (3): 227-230.) method of distribution incipient impregnation is adopted, with the nitrate solution dipping γ-Al of the transition metal such as a certain amount of iron, cobalt, nickel, copper or zinc
2o
3, after drying and roasting reduces nitrate, then flood palladium chloride solution, eventually pass drying and roasting and obtain the activated alumina catalyst that transition metal is the palladium load of auxiliary agent; Wherein, the iron added and zinc auxiliary agent are conducive to palladium dispersion, improve its activity in anthraquinone hydrogenation reaction, and enhance the ability of the anti-inactivation of catalyst.The people such as Wang Rong (WangR, LinC, ChenT, LinJ, MaoS.EffectofrareearthoxidesoncatalyticperformanceofPd/ δ, θ-Al
2o
3foranthraquinonehydrogenationtoH
2o
2.ChineseJournalofCatalysis, 2004,25 (9): 711-714.) different rare-earth oxide has been investigated to Pd/ δ, θ-Al
2o
3the impact of catalyst performance, adopts infusion process to γ-Al
2o
3the nitrate solution of the different rare earth metal of upper dipping, obtains δ 960 DEG C of roastings after drying, θ-Al
2o
3, then with tetrachloro-palladium acid sodium solution dipping, through washing, roasting obtains rare-earth metal modified Pd/ δ, θ-Al
2o
3catalyst; Its characterize and reaction result shows that appropriate rare earth metal can suppress high temperature time Al
2o
3the growth of crystal grain, increases specific surface area of catalyst, improves the decentralization of Pd thus improves hydrogenation activity.
Molecular imprinting is a kind of of Molecular Recognization between antibody in simulating nature circle and antigen or enzyme-to-substrate take template molecule as the technology that microsphere prepares the imprinted polymer it to selective recognition characteristic, this technology is widely used in chromatographic isolation, chemobionics sensor, mimetic enzyme catalysis and absorption and catalytic field.A kind of method that CN104289202A discloses polymerisation in bulk prepares the method for numb surperficial Sudan molecules trace sorbing material, Sudan molecules imprinted material prepared by the method has specific hole, special recognition capability is had to Sudan molecules, have higher selective, do not adsorb other coexisting substances, easy wash-out, technique is simple, and environmental friendliness.But as far as we know, also molecular imprinting is not used for anthraquinone preparation H
2o
2the report of hydrogenation process catalyst preparation process.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of Catalysts and its preparation method for anthraquinone slurry bed system hydrogenation, and obtained product has high selectivity, high catalytic activity and high stability in anthraquinone hydrogenation reaction.
The present invention solves its technical problem and adopts following technical scheme:
The preparation method of high selectivity palladium catalyst provided by the invention, comprises the following steps:
(1) by 2-EAQ at room temperature fully stirring and dissolving in isopropyl alcohol, be 1:(28.57 ~ 100 by the quality proportioning of 2-EAQ and aluminium isopropoxide in above-mentioned solution) add aluminium isopropoxide, after PROCESS FOR TREATMENT, form hydrolysate;
(2) by said hydrolyzed product 80 DEG C of aging 20h of constant temperature, be separated after, with isopropyl alcohol centrifuge washing three times, then at 80 DEG C of vacuum drying 6 ~ 12h, desciccate obtains γ ~ Al through 400 ~ 700 DEG C of roasting 3 ~ 5h
2o
3powder;
(3) at 60 DEG C, the above-mentioned γ of tetrachloro-palladium acid sodium solution incipient impregnation-Al is used
2o
3powder 2h, with distilled water washing, in suction filtration to filtrate without Cl
-, by filter cake successively at 80 ~ 120 DEG C of drying 2 ~ 4h, at 400 ~ 500 DEG C after roasting 3 ~ 5h, then through cooling obtained described palladium catalyst.
In said method, described microsphere 2-EAQ, its content is theoretical vectors γ-Al
2o
34 ~ 14wt% of output.
In above-mentioned steps (1), add aluminium isopropoxide in 2-EAQ and isopropyl alcohol mixture after, in 72 DEG C add thermal agitation fully dissolve after be 1:(2 ~ 5 by the mol ratio of aluminium isopropoxide, water and acetic acid in above-mentioned solution again): 0.5 mixed solution dripping acetic acid and water, fully stir 0.5 ~ 3h under room temperature.
In above-mentioned steps (2), in the preparation process of its carrier predecessor and desciccate, control the texture character such as the specific area of product and aperture by adding 2-EAQ.
In above-mentioned steps (3), described tetrachloro-palladium acid sodium solution is that the palladium bichloride of 1:2 and sodium chloride are dissolved in distilled water and obtain by mol ratio, and the content of active component Pd-is theoretical γ-Al
2o
30.1 ~ 0.3wt% of output.
In said method, in the aqueous isopropanol of 2-EAQ, adding aluminium isopropoxide, is just dissolve each other because aluminium isopropoxide and isopropyl alcohol heat more than 70 DEG C 72 DEG C of heating stirring and dissolving.
Palladium catalyst prepared by said method provided by the invention, its purposes is: this palladium catalyst is at anthraquinone preparation H
2o
2application in hydrogenation process.
Due to the application of technique scheme, the present invention compared with prior art has the following advantages:
(1) adopt aluminium isopropoxide Hydrolyze method to prepare activated alumina, technological operation is simple, and product has the advantages that purity is high, specific area is large, is suitable for as catalyst carrier.
(2) preparation method adopted, adds structure directing agent 2-EAQ before aluminium isopropoxide hydrolysis, and it participates in AlOOH nucleus and is formed, and roasting forms γ-Al
2o
3time, be embedded in γ-Al
2o
3the directed agents of the inside is decomposed, at γ-Al
2o
3in leave similar molecular engram space.The method controllable γ-Al
2o
3pore-size distribution and specific area, and improve its adsorption capacity to directed agents self, and then improve the activity and selectivity of catalyst in anthraquinone hydrogenation process.
Accompanying drawing explanation
Not Fig. 1 not adding 2-EAQ and adding the mesoporous Pd/ γ-Al of different content 2-EAQ prepared by embodiment 1 ~ 5
2o
3the N of catalyst
2adsorption/desorption curve.
Not Fig. 2 not adding 2-EAQ and adding the mesoporous Pd/ γ-Al of different content 2-EAQ prepared by embodiment 1 ~ 5
2o
3the pore size distribution curve of catalyst.
Not Fig. 3 not adding 2-EAQ and adding the mesoporous Pd/ γ-Al of different content 2-EAQ prepared by embodiment 1 ~ 5
2o
3the hydrogenation efficiency curve of catalyst in anthraquinone hydrogenation reaction.
Fig. 4 is the mesoporous Pd/ γ-Al not adding 2-EAQ in embodiment 5
2o
3the TEM picture of catalyst.
Fig. 5 is the mesoporous Pd/ γ-Al of the 2-EAQ adding 4wt% in embodiment 1
2o
3the TEM picture of catalyst.
Detailed description of the invention
The present invention adopts aluminium isopropoxide Hydrolyze method to prepare high purity pseudoboehmite, and regulates and controls its texture character such as specific area and aperture by the composition changing hydrolyzate, can obtain the boehmite of high specific surface area and specified pore structure.In preparation process, add microsphere 2-EAQ, make it boehmite body mutually in be uniformly distributed; Microsphere 2-EAQ is removed in follow-up boehmite roasting process, the γ-Al obtained
2o
3carrier has specific recognition character to anthraquinone, enhances H
2o
2its loaded palladium catalyst of hydrogenation process, to the adsorptive selectivity of reactant anthraquinone, improves the anthraquinone hydrogenation performance of catalyst.
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, and these embodiments are only the descriptions to better embodiment of the present invention, but are not limited to described content below.
Embodiment 1:
First, at room temperature by 0.048g2-EAQ (4wt%) fully stirring and dissolving in 45mL isopropyl alcohol.Then, add 4.8g aluminium isopropoxide, stir at 72 DEG C and make it fully dissolve.Then, drip the mixed solution (mol ratio water: acetic acid=6:1) by 1.27mL water and 0.67mL peracetic acid formulation wherein, fully 0.5h is stirred under room temperature, obtain colloidal sol, this colloidal sol is put into baking oven, the aging 20h of constant temperature at 80 DEG C, by the gel isopropyl alcohol centrifuge washing that obtains after aging 3 times; Last successively through vacuum drying 12h at 80 DEG C, obtain γ-Al after roasting 4h at 550 DEG C
2o
3.
Get above-mentioned 1.2g γ-Al
2o
3, with the aqueous solution incipient impregnation 2h prepared by 0.0060g palladium bichloride and 0.0040g sodium chloride at 60 DEG C, with in distilled water washing, suction filtration to filtrate without Cl
-, then dry 2h at 120 DEG C, further roasting 4h at 450 DEG C in an oven, finally by cooling, products obtained therefrom is palladium catalyst.
The specific area of gained palladium catalyst is 303.4m
2/ g, pore volume are 0.49cm
3/ g, average pore size are 5.43nm.Its measured hydrogenation efficiency in self-control slurry bed system is 10.28g/L working solution, and selective is 99.33%.
Embodiment 2:
First, at room temperature by 0.168g2-EAQ (14wt%) fully stirring and dissolving in 45mL isopropyl alcohol.Then, add 4.8g aluminium isopropoxide, stir at 72 DEG C and make it fully dissolve.Then, drip the mixed solution (mol ratio water: acetic acid=4:1) by 0.85mL water and 0.67mL peracetic acid formulation wherein, fully 1.5h is stirred under room temperature, obtain colloidal sol, this colloidal sol is put into baking oven, the aging 20h of constant temperature at 80 DEG C, by the gel isopropyl alcohol centrifuge washing that obtains after aging 3 times; Last successively through vacuum drying 6h at 80 DEG C, obtain γ-Al after roasting 3h at 700 DEG C
2o
3.
Get above-mentioned 1.2g γ-Al
2o
3, with the aqueous solution incipient impregnation 2h prepared by 0.0040g palladium bichloride and 0.0026g sodium chloride at 60 DEG C, with in distilled water washing, suction filtration to filtrate without Cl
-, then dry 4h at 80 DEG C, further roasting 3h at 500 DEG C in an oven, finally by cooling, products obtained therefrom is palladium catalyst.
The specific area of gained palladium catalyst is 236.1m
2/ g, pore volume are 0.61cm
3/ g, average pore size are 8.18nm.Its measured hydrogenation efficiency in self-control slurry bed system is 7.91g/L working solution, and selective is 95.90%.
Embodiment 3:
First, at room temperature by 0.108g2-EAQ (9wt%) fully stirring and dissolving in 45mL isopropyl alcohol.Then, add 4.8g aluminium isopropoxide, stir at 72 DEG C and make it fully dissolve.Then, drip the mixed solution (mol ratio water: acetic acid=10:1) by 2.12mL water and 0.67mL peracetic acid formulation wherein, fully 3h is stirred under room temperature, obtain colloidal sol, this colloidal sol is put into baking oven, the aging 20h of constant temperature at 80 DEG C, by the gel isopropyl alcohol centrifuge washing that obtains after aging 3 times; Last successively through vacuum drying 9h at 80 DEG C, obtain γ-Al after roasting 5h at 400 DEG C
2o
3.
Get above-mentioned 1.2g γ-Al
2o
3, with the aqueous solution incipient impregnation 2h prepared by 0.0020g palladium bichloride and 0.0013g sodium chloride at 60 DEG C, with in distilled water washing, suction filtration to filtrate without Cl
-, then dry 3h at 100 DEG C, further roasting 5h at 400 DEG C in an oven, finally by cooling, products obtained therefrom is palladium catalyst.
The specific area of gained palladium catalyst is 317.1m
2/ g, pore volume are 0.41cm
3/ g, average pore size are 4.35nm.Its measured hydrogenation efficiency in self-control slurry bed system is 6.23g/L working solution, and selective is 98.04%.
Embodiment 4:
First, at room temperature by 0.048g2-EAQ (4wt%) fully stirring and dissolving in 45mL isopropyl alcohol.Then, add 4.8g aluminium isopropoxide, stir at 72 DEG C and make it fully dissolve.Then, drip the mixed solution (mol ratio water: acetic acid=4:1) by 0.85mL water and 0.67mL peracetic acid formulation wherein, fully 2h is stirred under room temperature, obtain colloidal sol, this colloidal sol is put into baking oven, the aging 20h of constant temperature at 80 DEG C, by the gel isopropyl alcohol centrifuge washing that obtains after aging 3 times; Last successively through vacuum drying 6h at 80 DEG C, obtain γ-Al after roasting 4h at 600 DEG C
2o
3.
Get above-mentioned 1.2g γ-Al
2o
3, with the aqueous solution incipient impregnation 2h prepared by 0.0040g palladium bichloride and 0.0026g sodium chloride at 60 DEG C, with in distilled water washing, suction filtration to filtrate without Cl
-, then dry 4h at 80 DEG C, further roasting 3h at 500 DEG C in an oven, finally by cooling, products obtained therefrom is palladium catalyst.
The specific area of gained palladium catalyst is 294.1m
2/ g, pore volume are 0.46cm
3/ g, average pore size are 5.12nm.Its measured hydrogenation efficiency in self-control slurry bed system is 8.58g/L working solution, and selective is 99.16%.
Embodiment 5:
First, at 72 DEG C by abundant for 4.8g aluminium isopropoxide stirring and dissolving in 45mL isopropyl alcohol.Then, drip the mixed solution (mol ratio water: acetic acid=6:1) by 1.27mL water and 0.67mL peracetic acid formulation wherein, fully 1.5h is stirred under room temperature, obtain colloidal sol, this colloidal sol is put into baking oven, the aging 20h of constant temperature at 80 DEG C, by the gel isopropyl alcohol centrifuge washing that obtains after aging 3 times; Last successively through vacuum drying 12h at 80 DEG C, obtain γ-Al after roasting 4h at 550 DEG C
2o
3.
Get above-mentioned 1.2g γ-Al
2o
3, with the aqueous solution incipient impregnation 2h prepared by 0.0060g palladium bichloride and 0.0040g sodium chloride at 60 DEG C, with in distilled water washing, suction filtration to filtrate without Cl
-, then dry 2h at 100 DEG C, further roasting 4h at 450 DEG C in an oven, finally by cooling, products obtained therefrom is palladium catalyst.
The specific area of gained palladium catalyst is 276.8m
2/ g, pore volume are 0.59cm
3/ g, average pore size are 6.68nm.Its measured hydrogenation efficiency in self-control slurry bed system is 7.49g/L working solution, and selective is 97.84%.
The experiment working solution that the present invention mentions is industrial working solution, and its composition is: the content of effective anthraquinone 2-EAQ (EAQ) is 77.223g/L, and the content of tetrahydrochysene-2-EAQ (THEAQ) is 100.82g/L.
The evaluation of catalytic activity: adopt the miniature paste state bed reactor based on there-necked flask, after sealed reaction device, testing fixture air-tightness, and use N
2air in displacement flask.With the H of mol ratio 3:1 before catalytic reaction
2and N
2activating catalyst 2h at 60 DEG C.Catalytic reaction temperature is 60 DEG C, hydrogen flow rate 75mL/min, and catalyst loading amount is 1.2g, and the consumption of working solution is 60ml, gets 3mL hydrogenated work liquid every 30min, samples 6 times and terminates hydrogenation.
The mensuration of hydrogenation efficiency: by after the centrifugal 3min of sample 8000r/min that gets, get supernatant liquor 2mL and be placed in separatory funnel, add 2 SPAs (preventing peroxide decomposition in oxidizing process), and add 20mL deionized water, pass into O
2, flow is 35mL/min, makes reactant complete oxidation at normal temperatures and pressures, until working solution color turns back to original glassy yellow (about 25min).Stop passing into oxygen, leave standstill, lower layer of water be separated in conical flask, organic phase continuation deionized water extracts 5 times, and aqueous phase is still collected in conical flask.After extraction terminates, in conical flask, add the sulfuric acid solution of 5mL20%, mix, be titrated to solution colour with the liquor potassic permanganate of about 0.02mol/L and start pink and 30s not till armpit look.Write down the consumption volume of liquor potassic permanganate and calculate hydrogenation efficiency.
Selective enumeration method method: the standard liquid of preparation 2-EAQ and tetrahydrochysene-2-EAQ, dilution different multiples, the standard serial solution of preparation variable concentrations gradient, makes calibration curve, its chromatographic peak area and content can be associated.Organic phase in product after original working solution and hydrogenated work liquid oxidation is diluted 1000 times and by after organic membrane filtration, AgilentHP1100 high performance liquid chromatograph detects, calculated the content of wherein 2-EAQ and tetrahydrochysene-2-EAQ by calibration curve, and calculate hydrogenation selectivity.
From the specific area of Fig. 1, Fig. 2 and the palladium catalyst that obtains, pore volume and average aperture number according to, in aluminium isopropoxide hydrolytic process, add the Pd/ γ-Al of different content 2-EAQ controllable gained
2o
3texture character, under suitable 2-EAQ addition, the catalyst pore-size distribution of (embodiment 1) is more concentrated.
As shown in Figure 3, the more un-added catalyst of the hydrogenation efficiency of catalyst in anthraquinone hydrogenation hydrogenation process adding proper content 2-EAQ has obvious lifting, and the catalyst adding 4wt%2-EAQ in embodiment 1 exceeds 37.25% than the activity of the catalyst not adding 2-EAQ in embodiment 5.
From Fig. 4 and Fig. 5, embodiment 5 is not added the palladium catalyst that 2-EAQ that 2-EAQ and embodiment 1 add 4wt% obtains and is all shown as the club shaped structure particle that diameter is 1-2nm, length is 20-30nm, but the club shaped structure particle dispersion in embodiment 1 obtains more even, and diameter slightly reduces.
Obviously, above-described embodiment is lifted by clearly demonstrating the present invention, is not the restriction completely to embodiment.Here cannot also without the need to providing embodiment to all embodiments, but thus the apparent variation of amplifying out be still in protection scope of the present invention.
Claims (6)
1. a preparation method for high selectivity palladium catalyst, is characterized in that comprising the following steps:
(1) by 2-EAQ at room temperature fully stirring and dissolving in isopropyl alcohol, be 1:(28.57 ~ 100 by the quality proportioning of 2-EAQ and aluminium isopropoxide in above-mentioned solution) add aluminium isopropoxide, after PROCESS FOR TREATMENT, form hydrolysate;
(2) by said hydrolyzed product 80 DEG C of aging 20h of constant temperature, be separated after, with isopropyl alcohol centrifuge washing three times, then at 80 DEG C of vacuum drying 6 ~ 12h, desciccate obtains γ ~ Al through 400 ~ 700 DEG C of roasting 3 ~ 5h
2o
3powder;
(3) at 60 DEG C, the above-mentioned γ of tetrachloro-palladium acid sodium solution incipient impregnation-Al is used
2o
3powder 2h, with distilled water washing, in suction filtration to filtrate without Cl
-, by filter cake successively at 80 ~ 120 DEG C of drying 2 ~ 4h, at 400 ~ 500 DEG C after roasting 3 ~ 5h, then through cooling obtained described palladium catalyst.
2. preparation method as claimed in claim 1, is characterized in that in step (2), in the preparation process of its carrier predecessor and desciccate, control the texture character such as the specific area of product and aperture by adding 2-EAQ.
3. preparation method as claimed in claim 1, it is characterized in that described microsphere 2-EAQ, its content is theoretical vectors γ-Al
2o
34 ~ 14wt% of output.
4. preparation method as claimed in claim 1, it is characterized in that in step (1), add aluminium isopropoxide in 2-EAQ and isopropyl alcohol mixture after, in 72 DEG C add thermal agitation fully dissolve after be 1:(2 ~ 5 by the mol ratio of aluminium isopropoxide, water and acetic acid in above-mentioned solution again): 0.5 mixed solution dripping acetic acid and water, fully stir 0.5 ~ 3h under room temperature.
5. preparation method as claimed in claim 1, is characterized in that in step (3), and described tetrachloro-palladium acid sodium solution is that the palladium bichloride of 1:2 and sodium chloride are dissolved in distilled water and obtain by mol ratio, and the content of active component Pd-is theoretical γ-Al
2o
30.1 ~ 0.3wt% of output.
6. the purposes of palladium catalyst prepared by method described in arbitrary claim in claim 1 to 5, is characterized in that this palladium catalyst is at anthraquinone preparation H
2o
2application in hydrogenation process.
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| CN110479254A (en) * | 2019-09-12 | 2019-11-22 | 中触媒新材料股份有限公司 | A kind of method for preparing catalyst of anthraquinone hydrogenation |
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