CN105536780B - A kind of preparation method of high selectivity palladium catalyst - Google Patents
A kind of preparation method of high selectivity palladium catalyst Download PDFInfo
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- CN105536780B CN105536780B CN201610084521.9A CN201610084521A CN105536780B CN 105536780 B CN105536780 B CN 105536780B CN 201610084521 A CN201610084521 A CN 201610084521A CN 105536780 B CN105536780 B CN 105536780B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 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 19
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 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 abstract description 6
- 239000000413 hydrolysate Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 17
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004821 distillation 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
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000013598 vector Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 16
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000012224 working solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- ZXAGXLDEMUNQSH-UHFFFAOYSA-N 2-ethylanthracene Chemical class C1=CC=CC2=CC3=CC(CC)=CC=C3C=C21 ZXAGXLDEMUNQSH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 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
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance 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
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 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
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-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
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010025 steaming 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
- 230000007704 transition Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is a kind of preparation method of high selectivity palladium catalyst, and step is as follows：(1) 2 EAQs are sufficiently stirred at room temperature and be dissolved in isopropanol, the quality proportioning that 2 EAQs and aluminium isopropoxide are pressed into above-mentioned solution is 1：(28.57~100) aluminium isopropoxide is added, the mixed liquor of acetic acid and water is added dropwise into above-mentioned solution, is sufficiently stirred hydrolysis at room temperature again for heating stirring after fully dissolving；(2) by above-mentioned hydrolysate at 80 DEG C aging 20h, after separation, it is scrubbed, dry successively, roasting obtain γ Al2O3Powder；(3) the above-mentioned γ Al of tetrachloro-palladium acid sodium solution incipient impregnation are used2O3Powder, then successively it is scrubbed, dry, roasting after be made the high efficiency load type palladium catalyst.The present invention has the advantages that the texture properties such as novel method, simple to operate, product specific surface area and aperture are controllable, and the catalyst of 2 prepared EAQs regulation and control has excellent selectivity and activity to anthraquinone hydrogenation reaction.
Description
Technical field
It is specifically a kind of to be used for anthraquinone production the invention belongs to the preparation of meso-porous alumina and catalytic applications
H2O2High selectivity palladium catalyst of hydrogenation process and preparation method thereof.
Background technology
H2O2It is a kind of excellent green chemical industry raw material, is widely used in the industries such as papermaking, food, environmental protection and medicine.It is given birth to
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 in laboratory stage mostly, and anthraquinone is
Industrial production H at present2O2Main flow route.The country generally uses the anthraquinone production H of palladium catalyst fixed bed at present2O2, hydrogenated
Journey is anthraquinone committed step, and the process mainly uses the catalyst of mesoporous active aluminum oxide supported precious metal palladium.Due to expensive
Metals resources are limited, expensive, how to improve noble metal service efficiency, reduce catalyst preparation cost, and improve catalyst
Activity and selectivity is always the emphasis studied.
CN104192880B discloses a kind of method for preparing high purity pseudoboehmite：Acetic acid, nitric acid, urine will be contained first
The pore creating material such as element or F127 is 1 by mass ratio:The hydrolyzate that 0.5~3 deionized water and isopropanol is prepared is added to isopropyl
In aluminium alcoholates-aqueous isopropanol, 2~8h of hydrolysis, the wherein material of deionized water and aluminium isopropoxide amount at 60~80 DEG C
The ratio between be 2~20:1, hydrolysate obtains high purity pseudoboehmite after 60~260 DEG C of dryings, drying；Prepared by this method
Boehmite product purity is high, and pore volume and specific surface area are easily controlled, and preparation process is without waste discharge, the letter of simultaneous reactions flow
Single, cost is low.Red et al. (Ding Tong, Qin Yongning, the Ma Zhi.Effect of transition metal of fourth
on the activity ofγ-Al2O3-supported Pd catalyst.Chinese Journal of Catalysis,
2002,23(3):227-230.) using the method for distribution incipient impregnation, with transition such as a certain amount of iron, cobalt, nickel, copper or zinc
The nitrate solution dipping γ-Al of metal2O3, after drying and roasting reduces nitrate, then palladium chloride solution is impregnated, most passed through afterwards
Cross drying and roasting and obtain the activated alumina catalyst that the palladium that transition metal is auxiliary agent loads；Wherein, the iron and zinc added helps
Agent is advantageous to palladium and disperseed, and improves its activity in anthraquinone hydrogenation reaction, and enhance the ability of the anti-inactivation of catalyst.Wang Rong
Et al. (Wang R, Lin C, Chen T, Lin J, Mao S.Effect of rare earth oxides on catalytic
performance of Pd/δ,θ-Al2O3for anthraquinone hydrogenation to H2O2.Chinese
Journal of Catalysis,2004,25(9):Different rare-earth oxides 711-714.) have been investigated to Pd/ δ, θ-
Al2O3The influence of catalyst performance, using dipping normal direction γ-Al2O3The upper nitrate solution for impregnating different rare earth metals, is dried
Afterwards δ, θ-Al are obtained in 960 DEG C of roastings2O3, then impregnated with tetrachloro-palladium acid sodium solution, by washing, roasting obtains rare earth metal
Modified Pd/ δ, θ-Al2O3Catalyst；It is characterized and reaction result shows that appropriate rare earth metal can suppress Al during high temperature2O3Crystal grain
Growth, increase specific surface area of catalyst, improve Pd decentralization so as to improve hydrogenation activity.
Molecular imprinting technology is to simulate the Molecular Recognization between the antibody and antigen or enzyme-to-substrate in nature
A kind of technology that the imprinted polymer to it with selection evident characteristics is prepared using template molecule as microsphere, the technology are extensive
For chromatographic isolation, chemobionics sensor, mimetic enzyme catalysis and absorption and catalytic field.CN104289202A discloses one
The method that the method for kind polymerisation in bulk prepares numb surface Sudan molecules trace sorbing material, tonyred point prepared by this method
Sub- imprinted material has specific hole, there is special recognition capability to Sudan molecules, has higher selectivity, does not adsorb it
Its coexisting substances, easily elution, technique is simple, and environment-friendly.But molecular imprinting technology anthracene is not used for also as far as we know,
Quinone method prepares H2O2The report of hydrogenation process catalyst preparation process.
The content of the invention
The technical problems to be solved by the invention are：A kind of catalyst and its system for anthraquinone slurry bed hydroprocessing is provided
Preparation Method, obtained product have high selectivity, high catalytic activity and high stability in anthraquinone hydrogenation reaction.
The present invention solves its technical problem and uses following technical scheme：
The preparation method of high selectivity palladium catalyst provided by the invention, comprises the following steps：
(1) 2- EAQs are sufficiently stirred at room temperature and be dissolved in isopropanol, 2- ethyl anthracenes are pressed into above-mentioned solution
The quality proportioning of quinone and aluminium isopropoxide is 1：(28.57~100) aluminium isopropoxide is added, hydrolysate is formed after PROCESS FOR TREATMENT；
(2) by above-mentioned hydrolysate after 80 DEG C of constant temperature aging 20h, separation, with isopropanol centrifuge washing three times, Ran Hou
80 DEG C of 6~12h of vacuum drying, desciccate obtain γ-Al through 400~700 DEG C of 3~5h of roasting2O3Powder；
(3) the above-mentioned γ-Al of tetrachloro-palladium acid sodium solution incipient impregnation are used at 60 DEG C2O3Powder 2h, with distillation water washing,
Filter into filtrate without Cl-, after filter cake is calcined into 3~5h at 80~120 DEG C of dry 2~4h, 400~500 DEG C successively, then pass through
Described palladium catalyst is made in cooling.
In the above method, described microsphere 2- EAQs, its addition is theoretical vectors γ-Al2O3The 4 of yield
~14wt%.
In above-mentioned steps (1), after adding aluminium isopropoxide into 2- EAQs and isopropyl alcohol mixture, in 72 DEG C of heating
The mol ratio for pressing aluminium isopropoxide, water and acetic acid after stirring fully dissolving into above-mentioned solution again is 1：(2~5)：0.5 is added dropwise second
The mixed solution of acid and water, is sufficiently stirred 0.5~3h at room temperature.
In above-mentioned steps (1), product is controlled by adding 2- EAQs in the preparation process of its carrier predecessor
Specific surface area and aperture texture property.
In above-mentioned steps (3), described tetrachloro-palladium acid sodium solution is 1 by mol ratio:2 palladium bichloride and sodium chloride is dissolved in steaming
Obtained in distilled water, active component Pd content is theoretical γ-Al2O30.1~0.3wt% of yield.
In the above method, aluminium isopropoxide is added into the aqueous isopropanol of 2- EAQs, is dissolved in 72 DEG C of heating stirrings
It is due to that aluminium isopropoxide and isopropanol are heated more than 70 DEG C and just dissolved each other.
Palladium catalyst prepared by the above method provided by the invention, its purposes are：The palladium catalyst is in anthraquinone preparation H2O2
Application in hydrogenation process.
Due to the application of above-mentioned technical proposal, the present invention has advantages below compared with prior art：
(1) activated alumina is prepared using aluminium isopropoxide Hydrolyze method, technological operation is simple, and product has purity height, compares table
The characteristics of area is big, it is adapted as catalyst carrier.
(2) preparation method used by, structure directing agent 2- EAQs are added before aluminium isopropoxide hydrolyzes, it is participated in
AlOOH nucleus is formed, and roasting forms γ-Al2O3When, it is embedded in γ-Al2O3The directed agents of the inside are decomposed, in γ-Al2O3In stay
Lower similar molecular engram space.Controllable γ-the Al of the method2O3Pore-size distribution and specific surface area, and improve it to directed agents
The adsorption capacity of itself, and then improve the activity and selectivity of the catalyst during anthraquinone hydrogenation.
Brief description of the drawings
Fig. 1 is Jie for being not added with 2- EAQs and adding different content 2- EAQs prepared by embodiment 1~5
Hole Pd/ γ-Al2O3The N of catalyst2Adsorption/desorption curve.
Fig. 2 is Jie for being not added with 2- EAQs and adding different content 2- EAQs prepared by embodiment 1~5
Hole Pd/ γ-Al2O3The pore size distribution curve of catalyst.
Fig. 3 is Jie for being not added with 2- EAQs and adding different content 2- EAQs prepared by embodiment 1~5
Hole Pd/ γ-Al2O3Hydrogenation efficiency curve of the catalyst in anthraquinone hydrogenation reaction.
Fig. 4 is the mesoporous Pd/ γ-Al that 2- EAQs are not added with embodiment 52O3The TEM pictures of catalyst.
Fig. 5 is the mesoporous Pd/ γ-Al for the 2- EAQs that 4wt% is added in embodiment 12O3The TEM pictures of catalyst.
Embodiment
The present invention prepares high purity pseudoboehmite using aluminium isopropoxide Hydrolyze method, and the composition by changing hydrolyzate is adjusted
The texture property such as its specific surface area and aperture is controlled, can obtain the boehmite of high specific surface area and specified pore structure.Making
Microsphere 2- EAQs are added during standby, it is uniformly distributed in boehmite body phase；Microsphere 2- ethyls
Anthraquinone is removed in follow-up boehmite roasting process, obtained γ-Al2O3Carrier has specific recognition property to anthraquinone,
Enhance H2O2Its loaded palladium catalyst of hydrogenation process improves the anthraquinone hydrogen of catalyst to the adsorptive selectivity of reactant anthraquinone
Change performance.
With reference to embodiment and accompanying drawing, the invention will be further described, and these embodiments are only preferable to the present invention
The description of embodiment, but it is not limited to the following content.
Embodiment 1：
First, 0.048g 2- EAQs (4wt%) are sufficiently stirred at room temperature and be dissolved in 45mL isopropanols.Connect
, add 4.8g aluminium isopropoxides, being stirred at 72 DEG C makes it fully dissolve.Then, be added dropwise thereto by 1.27mL water and
Mixed solution (the mol ratio water of 0.67mL peracetic acid formulations：Acetic acid=6:1) 0.5h, is sufficiently stirred at room temperature, obtains colloidal sol, by this
Colloidal sol is put into baking oven, the constant temperature aging 20h at 80 DEG C, by the gel obtained after aging isopropanol centrifuge washing 3 times；Finally
Successively γ-Al are obtained after 12h being dried in vacuo at 80 DEG C, be calcined 4h at 550 DEG C2O3。
Take above-mentioned 1.2g γ-Al2O3, it is water-soluble with being prepared by 0.0060g palladium bichlorides and 0.0040g sodium chloride at 60 DEG C
Liquid incipient impregnation 2h, with distillation water washing, filter into filtrate without Cl-, 2h is then dried at 120 DEG C in an oven, is entered
One step is calcined 4h at 450 DEG C, and most afterwards through cooling, products obtained therefrom is palladium catalyst.
The specific surface area of gained palladium catalyst is 303.4m2/ g, pore volume 0.49cm3/ g, average pore size 5.43nm.Its
Measured hydrogenation efficiency is 10.28g/L working solutions in slurry bed system is made by oneself, and selectivity is 99.33%.
Embodiment 2：
First, 0.168g2- EAQs (14wt%) are sufficiently stirred at room temperature and be dissolved in 45mL isopropanols.Connect
, add 4.8g aluminium isopropoxides, being stirred at 72 DEG C makes it fully dissolve.Then, be added dropwise thereto by 0.85mL water and
Mixed solution (the mol ratio water of 0.67mL peracetic acid formulations：Acetic acid=4:1) 1.5h, is sufficiently stirred at room temperature, obtains colloidal sol, by this
Colloidal sol is put into baking oven, the constant temperature aging 20h at 80 DEG C, by the gel obtained after aging isopropanol centrifuge washing 3 times；Finally
Successively γ-Al are obtained after 6h being dried in vacuo at 80 DEG C, be calcined 3h at 700 DEG C2O3。
Take above-mentioned 1.2g γ-Al2O3, it is water-soluble with being prepared by 0.0040g palladium bichlorides and 0.0026g sodium chloride at 60 DEG C
Liquid incipient impregnation 2h, with distillation water washing, filter into filtrate without Cl-, 4h is then dried at 80 DEG C in an oven, enters one
Step is calcined 3h at 500 DEG C, and most afterwards through cooling, products obtained therefrom is palladium catalyst.
The specific surface area of gained palladium catalyst is 236.1m2/ g, pore volume 0.61cm3/ g, average pore size 8.18nm.Its
Measured hydrogenation efficiency is 7.91g/L working solutions in slurry bed system is made by oneself, and selectivity is 95.90%.
Embodiment 3：
First, 0.108g 2- EAQs (9wt%) are sufficiently stirred at room temperature and be dissolved in 45mL isopropanols.Connect
, add 4.8g aluminium isopropoxides, being stirred at 72 DEG C makes it fully dissolve.Then, be added dropwise thereto by 2.12mL water and
Mixed solution (the mol ratio water of 0.67mL peracetic acid formulations：Acetic acid=10:1) 3h, is sufficiently stirred at room temperature, obtains colloidal sol, by this
Colloidal sol is put into baking oven, the constant temperature aging 20h at 80 DEG C, by the gel obtained after aging isopropanol centrifuge washing 3 times；Finally
Successively γ-Al are obtained after 9h being dried in vacuo at 80 DEG C, be calcined 5h at 400 DEG C2O3。
Take above-mentioned 1.2g γ-Al2O3, it is water-soluble with being prepared by 0.0020g palladium bichlorides and 0.0013g sodium chloride at 60 DEG C
Liquid incipient impregnation 2h, with distillation water washing, filter into filtrate without Cl-, 3h is then dried at 100 DEG C in an oven, is entered
One step is calcined 5h at 400 DEG C, and most afterwards through cooling, products obtained therefrom is palladium catalyst.
The specific surface area of gained palladium catalyst is 317.1m2/ g, pore volume 0.41cm3/ g, average pore size 4.35nm.Its
Measured hydrogenation efficiency is 6.23g/L working solutions in slurry bed system is made by oneself, and selectivity is 98.04%.
Embodiment 4：
First, 0.048g 2- EAQs (4wt%) are sufficiently stirred at room temperature and be dissolved in 45mL isopropanols.Connect
, add 4.8g aluminium isopropoxides, being stirred at 72 DEG C makes it fully dissolve.Then, be added dropwise thereto by 0.85mL water and
Mixed solution (the mol ratio water of 0.67mL peracetic acid formulations：Acetic acid=4:1) 2h, is sufficiently stirred at room temperature, obtains colloidal sol, this is molten
Glue is put into baking oven, the constant temperature aging 20h at 80 DEG C, by the gel obtained after aging isopropanol centrifuge washing 3 times；Finally according to
It is secondary to obtain γ-Al after 6h being dried in vacuo at 80 DEG C, be calcined 4h at 600 DEG C2O3。
Take above-mentioned 1.2g γ-Al2O3, it is water-soluble with being prepared by 0.0040g palladium bichlorides and 0.0026g sodium chloride at 60 DEG C
Liquid incipient impregnation 2h, with distillation water washing, filter into filtrate without Cl-, 4h is then dried at 80 DEG C in an oven, enters one
Step is calcined 3h at 500 DEG C, and most afterwards through cooling, products obtained therefrom is palladium catalyst.
The specific surface area of gained palladium catalyst is 294.1m2/ g, pore volume 0.46cm3/ g, average pore size 5.12nm.Its
Measured hydrogenation efficiency is 8.58g/L working solutions in slurry bed system is made by oneself, and selectivity is 99.16%.
Embodiment 5：
First, 4.8g aluminium isopropoxides are sufficiently stirred at 72 DEG C and be dissolved in 45mL isopropanols.Then, it is added dropwise thereto
By the mixed solution of 1.27mL water and 0.67mL peracetic acid formulations (mol ratio water：Acetic acid=6:1) 1.5h, is sufficiently stirred at room temperature,
Obtain colloidal sol, this colloidal sol be put into baking oven, the constant temperature aging 20h at 80 DEG C, by the gel isopropanol obtained after aging from
The heart washs 3 times；Finally obtain γ-Al after 12h being dried in vacuo at 80 DEG C, be calcined 4h at 550 DEG C successively2O3。
Take above-mentioned 1.2g γ-Al2O3, it is water-soluble with being prepared by 0.0060g palladium bichlorides and 0.0040g sodium chloride at 60 DEG C
Liquid incipient impregnation 2h, with distillation water washing, filter into filtrate without Cl-, 2h is then dried at 100 DEG C in an oven, is entered
One step is calcined 4h at 450 DEG C, and most afterwards through cooling, products obtained therefrom is palladium catalyst.
The specific surface area of gained palladium catalyst is 276.8m2/ g, pore volume 0.59cm3/ g, average pore size 6.68nm.Its
Measured hydrogenation efficiency is 7.49g/L working solutions in slurry bed system is made by oneself, and selectivity is 97.84%.
The experiment working solution that the present invention mentions is industrial working solution, and its composition is：Effective anthraquinone 2- EAQs
(EAQ) content is 77.223g/L, and the content of tetrahydrochysene -2- EAQs (THEAQ) is 100.82g/L.
The evaluation of catalytic activity：Using the miniature paste state bed reactor based on three-necked flask, after sealing reaction unit, check
Device air-tightness, and use N2Replace the air in flask.Mol ratio 3 is used before catalytic reaction:1 H2And N2Activate and urge at 60 DEG C
Agent 2h.Catalytic reaction temperature is 60 DEG C, hydrogen flow rate 75mL/min, and catalyst loading amount is 1.2g, and the dosage of working solution is
60ml, 3mL hydrogenated work liquid is taken every 30min, sample 6 end hydrogenations.
The measure of hydrogenation efficiency：After the sample 8000r/min taken is centrifuged into 3min, supernatant liquor 2mL is taken to be placed in liquid separation leakage
In bucket, 2 drop concentrated phosphoric acids (preventing that hydrogen peroxide decomposes in oxidizing process) are added, and add 20mL deionized waters, are passed through O2, flow
For 35mL/min, make reactant complete oxidation at normal temperatures and pressures, until working solution color returns to original glassy yellow (about
25min).Stopping is passed through oxygen, stands, and by lower floor's aqueous phase separation in conical flask, organic phase continues to extract 5 with deionized water
Secondary, aqueous phase is still collected in conical flask.After extraction terminates, 5mL 20% sulfuric acid solution is added into conical flask, is well mixed,
Solution colour, which is titrated to, with 0.02mol/L or so liquor potassic permanganate starts pink and 30s not untill armpit color.Write down height
The consumption volume of potassium manganate solution simultaneously calculates hydrogenation efficiency.
Selective enumeration method method：Prepare the standard liquid of 2- EAQs and tetrahydrochysene -2- EAQs, different times of dilution
Number, the standard serial solution of various concentrations gradient is prepared, makees standard curve, you can associated its chromatographic peak area with content
Come.By 1000 times of organic phase dilution in the product after original working solution and hydrogenated work liquid oxidation and pass through organic filter membrane mistake
After filter, detected on Agilent HP1100 high performance liquid chromatographs, by standard curve calculate wherein 2- EAQs and
The content of tetrahydrochysene -2- EAQs, and calculate hydrogenation selectivity.
From the specific surface area of Fig. 1, Fig. 2 and obtained palladium catalyst, pore volume and average pore size data, in aluminium isopropoxide
Pd/ γ-the Al of the controllable gained of different content 2- EAQs are added in hydrolytic process2O3Texture property, suitable 2- ethyl anthracenes
The catalyst pore-size distribution of (embodiment 1) is more concentrated under quinone addition.
From the figure 3, it may be seen that hydrogenation effect of the catalyst of addition proper content 2- EAQs in anthraquinone hydrogenation hydrogenation process
The more un-added catalyst of rate is obviously improved, and the catalyst of 4wt%2- EAQs is added in embodiment 1 than in embodiment 5
The activity for being not added with the catalyst of 2- EAQs is higher by 37.25%.
From Fig. 4 and Fig. 5, embodiment 5 does not add 2- EAQs and embodiment 1 adds 4wt% 2- EAQs
The club shaped structure particle that resulting palladium catalyst shows as a diameter of 1-2nm, length is 20-30nm, but in embodiment 1
Club shaped structure particle is more uniformly scattered, and diameter slightly reduces.
Obviously, above-described embodiment is only to be lifted by the clear explanation present invention, is not the complete restriction to embodiment.
Here embodiment can not be provided without to all embodiments, but the obvious variation thus amplified out is still in this
In the protection domain of invention.
Claims (6)
1. a kind of preparation method of high selectivity palladium catalyst, it is characterised in that comprise the following steps：
(1) 2- EAQs are sufficiently stirred at room temperature and are dissolved in isopropanol, into above-mentioned solution by 2- EAQs and
The quality proportioning of aluminium isopropoxide is 1：(28.57~100) aluminium isopropoxide is added, hydrolysate is formed after PROCESS FOR TREATMENT；
(2) by above-mentioned hydrolysate after 80 DEG C of constant temperature aging 20h, separation, then at 80 DEG C with isopropanol centrifuge washing three times
6~12h is dried in vacuo, desciccate obtains γ-Al through 400~700 DEG C of 3~5h of roasting2O3Powder；
(3) the above-mentioned γ-Al of tetrachloro-palladium acid sodium solution incipient impregnation are used at 60 DEG C2O3Powder 2h, with distillation water washing, filter
Into filtrate without Cl-, after filter cake is calcined into 3~5h at 80~120 DEG C of dry 2~4h, 400~500 DEG C successively, then through cooling
Described palladium catalyst is made.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), in the preparation process of its carrier predecessor
In by add 2- EAQs control product specific surface area and aperture texture property.
3. preparation method as claimed in claim 1, it is characterised in that described microsphere 2- EAQs, its addition are
Theoretical vectors γ-Al2O34~14wt% of yield.
4. preparation method as claimed in claim 1, it is characterised in that in step (1), mixed to 2- EAQs and isopropanol
After adding aluminium isopropoxide in solution, after 72 DEG C of heating stirrings fully dissolve again into above-mentioned solution by aluminium isopropoxide, water and second
The mol ratio of acid is 1：(2~5)：0.5 is added dropwise the mixed solution of acetic acid and water, is sufficiently stirred 0.5~3h at room temperature.
5. preparation method as claimed in claim 1, it is characterised in that in step (3), described tetrachloro-palladium acid sodium solution is by rubbing
You are than being 1:2 palladium bichloride and sodium chloride, which is dissolved in distilled water, to be obtained, and active component Pd content is theoretical γ-Al2O3Yield
0.1~0.3wt%.
6. the purposes of palladium catalyst prepared by any claim methods described in claim 1 to 5, it is characterized in that the palladium chtalyst
Agent is in anthraquinone preparation H2O2Application in hydrogenation process.
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