CN110639512A - Palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparation method thereof - Google Patents
Palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparation method thereof Download PDFInfo
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- CN110639512A CN110639512A CN201911169517.2A CN201911169517A CN110639512A CN 110639512 A CN110639512 A CN 110639512A CN 201911169517 A CN201911169517 A CN 201911169517A CN 110639512 A CN110639512 A CN 110639512A
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- palladium
- hydrogen peroxide
- aluminum
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 46
- 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 title claims abstract description 43
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 rare earth salt Chemical class 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 230000032683 aging Effects 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 19
- 239000003292 glue Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 62
- 235000002639 sodium chloride Nutrition 0.000 claims description 41
- 238000005303 weighing Methods 0.000 claims description 30
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 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 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 235000011181 potassium carbonates Nutrition 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- XPSQBNPZMNWIPV-UHFFFAOYSA-N ethenoxyperoxyethene Chemical compound C=COOOC=C XPSQBNPZMNWIPV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 2
- 239000004568 cement Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 31
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 21
- 238000005984 hydrogenation reaction Methods 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012224 working solution Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 239000010413 mother solution Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 6
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000002431 foraging effect Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/31—Density
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and particularly discloses a palladium catalyst for producing hydrogen peroxide by an anthraquinone process, which comprises a carrier and active components, wherein the carrier comprises the following raw materials: aluminum glue, urotropine aqueous solution, urea, template agent and rare earth salt. The invention also discloses a preparation method of the palladium catalyst. In order to solve the problems that the fixed bed catalyst used for the hydrogen peroxide production device by the industrial anthraquinone method is easy to remove palladium and powder and has poor comprehensive performance, the invention uniformly mixes the alumina gel with urotropine, urea, a template agent and a rare earth salt solution, then drops the mixture into an oil column for forming and aging, soaks the mixture with alkali metal salt after impurity removal to adjust the surface acidity and alkalinity, then forms a carrier through heat treatment, soaks the carrier in a palladium solution to prepare the palladium catalyst, and prepares the finished product catalyst through reduction after water washing.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a palladium catalyst for producing hydrogen peroxide by an anthraquinone process and a preparation method thereof.
Background
With the development of society and the progress of science and technology, hydrogen peroxide is widely applied to the industrial fields of medical treatment, papermaking, chemical industry, food, electronics, organic synthesis, environmental protection and the like as an important inorganic chemical product. In recent years, with the increasing awareness of ecological protection, the application of hydrogen peroxide as a green oxidant in some new chemical clean production processes is expanding, such as newly-built process devices of cyclohexanone, caprolactam, propylene oxide and the like. With some new applications of hydrogen peroxide and from the viewpoint of environmental protection, the demand of hydrogen peroxide will increase day by day, and further the yield of hydrogen peroxide is promoted to keep continuously increasing.
Among the hydrogen peroxide production methods, the anthraquinone method is the most important production method and accounts for more than 98% of the whole hydrogen peroxide production capacity. The industrial production of hydrogen peroxide by anthraquinone process mainly includes fixed bed and fluidized bed processes, the catalyst uses palladium as main active component, and more than 90% of hydrogen peroxide production devices in China adopt fixed bed processes, and mainly includes several links of hydrogenation, oxidation, extraction and post-treatment, in which the hydrogenation link is the core link of the whole process, and the palladium catalyst is the soul of the whole hydrogenation link.
However, the commercial palladium catalyst for producing hydrogen peroxide by a fixed bed in the domestic anthraquinone method mainly comprises the following components: strip, three (four) leaf grass type, teethed ball type, rolling ball type and drop ball type palladium catalysts. Wherein, the strip-shaped and three (four) leaf grass type palladium catalysts have the defects of easy breakage in production, packaging, transportation, loading and unloading, bed filling and use due to appearance reasons; the tooth-ball type palladium catalyst has a groove structure due to the appearance, the activity is higher in the initial use, but system degradation products and alumina powder are easy to accumulate in an outer groove along with the prolonging of the use time, the degradation products are difficult to remove in the regeneration after the first use period is finished, the activity is reduced quickly, and the subsequent use effect is poor; the spherical palladium catalyst (rolling sphere and dropping sphere) prepared by the rolling granulation method has the defects of high possibility of palladium and powder shedding, high shedding speed of noble metal, high activity attenuation speed, low residual value and the like in the using process due to the forming mode. Therefore, the design of a palladium catalyst for producing hydrogen peroxide by an anthraquinone method, which has good comprehensive performance and is difficult to remove palladium and powder, becomes a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a palladium catalyst for producing hydrogen peroxide by an anthraquinone process and a preparation method thereof, which are used for solving the problems in the background art and have excellent economic benefit by providing a palladium catalyst for fixed bed hydrogenation, which has high activity, high selectivity, high strength, difficult palladium and powder removal and long service life, and is used in a device for producing hydrogen peroxide by an industrial anthraquinone process.
In order to achieve the purpose, the invention provides the following technical scheme:
a palladium catalyst for producing hydrogen peroxide by an anthraquinone process comprises a carrier and an active component, wherein the active component is noble metal palladium, and the loading amount of the noble metal palladium is 0.1-1.0% of the weight of the carrier; the carrier comprises the following raw materials in parts by weight: 100 parts of aluminum glue, 10-50 parts of urotropine aqueous solution, 0-20 parts of urea, 0-20 parts of template agent and 0-5 parts of rare earth salt.
As a further scheme of the invention: the loading amount of the active component is 0.2-0.4% of the weight of the carrier, and the concentration of the urotropine aqueous solution is 30-40 wt%.
As a still further scheme of the invention: the aluminum glue is prepared from aluminum powder, hydrochloric acid and pseudo-boehmite powder according to a molar ratio of 1: 0.4-1: 0.1-1; specifically, the preparation method of the aluminum paste comprises the following steps: aluminum powder, hydrochloric acid and water are subjected to reflux reaction at the temperature of 60-100 ℃ under normal pressure for 2-10 hours, and then pseudo-boehmite powder is added to continue the reaction for 0.5-5 hours to prepare the aluminum adhesive, wherein the molar ratio of the aluminum powder to the hydrochloric acid to the pseudo-boehmite powder is 1: 0.4-1: 0.1-1, and the aluminum content in the aluminum adhesive is 5-15 wt%.
As a still further scheme of the invention: the template agent is long-chain alkane epoxy vinyl ether (C)nH2n+1EOm) Polyethylene oxide-polypropylene oxide block copolymer (EO)nPOmEOn) One or more of (a).
As a still further scheme of the invention: the rare earth salt is one or more of lanthanum nitrate, cerium nitrate and samarium nitrate.
As a still further scheme of the invention: the preparation method of the carrier comprises the steps of weighing 100 parts of aluminum adhesive, 10-50 parts of urotropine aqueous solution, 0-20 parts of urea, 0-20 parts of template agent and 0-5 parts of rare earth salt according to the parts by weight, dissolving the urea, the template agent and the rare earth salt in the urotropine aqueous solution to obtain urotropine mixed solution, cooling the aluminum adhesive and the urotropine mixed solution to 2-15 ℃ respectively, mixing uniformly, dropping the mixture into hot oil at 50-100 ℃ for forming, aging in the hot oil for 2-30 hours (the temperature is 80-150 ℃ during aging and the pressure is 0.1-0.5 MPa, aging and crystallizing under specific conditions), taking out particles from the oil after aging, washing with water and removing chlorine to obtain the carrier.
As a still further scheme of the invention: the carrier is pretreated before being loaded with active components, the pretreatment is to soak the carrier in an alkali metal salt aqueous solution with the concentration of 1-20 wt%, the mass ratio of the carrier to the alkali metal salt aqueous solution is 1:2, the soaking time is 1-5 hours, then the carrier is taken out and put into an oven to be dried for 2-24 hours at the temperature of 80-150 ℃, and the surface acidity and alkalinity of the carrier is adjusted through the soaking of the alkali metal salt aqueous solution; the pretreated alumina carrier is placed into a roasting furnace to be roasted at 800-1000 ℃, the roasting time is 2-10 hours, the diameter of the roasted carrier is 1-4 mm, and the final alumina carrier is formed by heat treatment after pretreatment.
As a still further scheme of the invention: the alkali metal salt is one or more of potassium nitrate, sodium nitrate, potassium chloride, sodium chloride, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide.
The preparation method of the palladium catalyst for producing hydrogen peroxide by the anthraquinone process comprises the following steps:
1) preparing aluminum glue: respectively weighing aluminum powder, hydrochloric acid and pseudo-boehmite powder according to the weight parts, carrying out reflux reaction on the aluminum powder, the hydrochloric acid and water at the temperature of 60-100 ℃ for 2-10 hours under normal pressure, then adding the pseudo-boehmite powder, and continuing the reaction for 0.5-5 hours to prepare the aluminum adhesive, wherein the molar ratio of the aluminum powder to the hydrochloric acid to the pseudo-boehmite powder is 1: 0.4-1: 0.1-1, wherein the aluminum content in the aluminum adhesive is 5-15 wt%;
2) molding of the catalyst carrier: dissolving urotropine in water to prepare a urotropine aqueous solution with the concentration of 30-40 wt%, and then mixing the urotropine aqueous solution with the following components in parts by weight: 30-40 wt% urotropin aqueous solution: urea: template agent: the rare earth salt is 100: 10-50: weighing the materials in a ratio of 0-20: 0-5 (weight ratio), dissolving urea, a template agent and rare earth salt in a urotropine aqueous solution to obtain a urotropine mixed solution, cooling the aluminum glue and the urotropine mixed solution to 2-15 ℃ respectively, uniformly mixing, dripping into hot oil at 50-100 ℃ for forming, aging in the hot oil for 2-30 hours (the temperature is 80-150 ℃ and the pressure is 0.1-0.5 MPa, aging and crystallizing under specific conditions), taking out the particles from the oil after aging, and washing with water to remove oil and chlorine to obtain a carrier;
3) pretreatment, drying and roasting of a catalyst carrier: weighing alkali metal salt, dissolving in water to prepare an alkali metal salt aqueous solution with the concentration of 1-20 wt%, washing the carrier obtained in the step 2), soaking in the alkali metal salt aqueous solution, wherein the mass ratio of the carrier to the alkali metal salt aqueous solution is 1:2, the soaking time is 1-5 hours, taking out the carrier, drying in a drying oven at 80-150 ℃ for 2-24 hours, roasting in a roasting oven at 800-1000 ℃ for 2-10 hours, and the diameter of the roasted carrier is 1-4 mm, so as to obtain the roasted carrier, adjusting the surface acidity and alkalinity of the carrier through soaking in the alkali metal salt aqueous solution, and performing heat treatment to form the final alumina carrier; wherein the alkali metal salt is one or more of potassium nitrate, sodium nitrate, potassium chloride, sodium chloride, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide;
4) loading of active components: immersing the roasted carrier obtained in the step 3) into a chloropalladic acid or sodium chloropalladate solution with the pH value of 3-6.5 for impregnation, wherein the volume ratio of the carrier to the chloropalladate or sodium chloropalladate solution is 1:2, the mass ratio of the carrier to palladium in the chloropalladate or sodium chloropalladate solution is 1000: 2-4, the impregnation temperature is 25-90 ℃, the impregnation time is 0.5-3 hours, then filtering out a mother solution, and carrying out reduction reaction on a palladium catalyst obtained by filtering out the mother solution to obtain a finished palladium catalyst;
specifically, the reduction may be to reduce the palladium catalyst after the mother liquor is filtered off with 0.5 to 1.5 wt% of formaldehyde solution or hydrazine hydrate solution at room temperature to 90 ℃ for 0.5 to 3 hours, then to remove chlorine by water washing, or to directly remove chlorine by water washing and then to dry and calcine the palladium catalyst at 80 to 750 ℃ in air atmosphere for 2 to 24 hours, then to reduce the palladium catalyst with hydrogen at 25 to 750 ℃ for 1 to 10 hours, and then to cool the palladium catalyst to room temperature in nitrogen atmosphere, thus obtaining the finished product palladium catalyst.
As a still further scheme of the invention: the catalyst prepared by the invention has the advantages of 0.1-1.0 wt% of palladium, 1-4 mm of particle size and 0.3-0.7 cm of bulk density3/g。
Compared with the prior art, the invention has the beneficial effects that:
the palladium catalyst for producing hydrogen peroxide by the anthraquinone process has good comprehensive performance, is not easy to remove palladium and powder, has the advantages of high strength, long service cycle, high activity, good selectivity and the like, is not easy to remove palladium and powder, and is suitable for a device for producing hydrogen peroxide by an industrial anthraquinone process; the invention prepares the alumina gel by taking aluminum powder, hydrochloric acid and pseudo-boehmite powder as main raw materials, then the alumina gel is evenly mixed with urotropine, urea, a template agent and a rare earth salt solution, the mixture is dripped into an oil column for forming and is aged and crystallized under specific conditions, then the alumina gel is washed to remove impurities and is soaked in alkali metal salt for adjusting the surface acidity and alkalinity of a carrier, then the final alumina carrier is formed by heat treatment, the carrier is soaked in a palladium solution for preparing a palladium catalyst, the palladium catalyst is reduced by formaldehyde or hydrazine hydrate solution or is reduced by hydrogen after being washed, and finally the finished catalyst is prepared, the activity, selectivity and strength of the catalyst are improved by more than 20 percent compared with commercial catalysts in the market, the longest service life of the catalyst can reach more than 10 years, the problems that the existing fixed bed catalyst used for the hydrogen peroxide production device by the industrial anthraquinone method is easy to remove palladium and powder and has poor comprehensive performance are solved, and the catalyst has wide market prospect.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1
The palladium catalyst for producing hydrogen peroxide by the anthraquinone process comprises a carrier and an active component, wherein the active component is noble metal palladium, the content of palladium in the catalyst is 0.3%, the content of lanthanum in the catalyst is 1.6%, the particle size of the catalyst is 1.8mm, the bulk density of the catalyst is 0.38g/ml, and the compressive strength of the catalyst is 51N/particle.
In this embodiment, the preparation method of the palladium catalyst for producing hydrogen peroxide by the anthraquinone process includes the following steps:
(1) preparing catalyst carrier alumina gel: respectively weighing 54g of aluminum powder, 80g of hydrochloric acid (the concentration is 36.5 percent) and 1040g of water, carrying out reflux reaction at 60 ℃ under normal pressure for 10 hours, then adding 14g of pseudo-boehmite powder, and continuing the reaction for 5 hours to prepare 1188g of alumina gel; wherein the molar ratio of the aluminum powder to the hydrochloric acid to the pseudo-boehmite powder is 1: 0.4: 0.1, the aluminum content in the glue is 5 wt%.
(2) Molding of the catalyst carrier: 150g of urotropine is weighed and dissolved in 350g of water to prepare 500g of urotropine aqueous solution with the concentration of 30wt percent, and 200g of urea and 20g of C are weighed12H25EO8And 5g of lanthanum nitrate is dissolved in the urotropine aqueous solution, the temperature is reduced to 2-15 ℃, 1000g of 5 wt% of alumina gel prepared in the step (1) is weighed and cooled to 2-15 ℃, the 5 wt% of alumina gel and the 5 wt% of alumina gel are uniformly mixed and then dripped into hot oil at 100 ℃ for forming, then the mixture is subjected to heat preservation in the hot oil at 80 ℃ and pressure maintenance at 0.1MPa for aging for 30 hours, the particles are taken out of the oil after aging is finished, and the carrier is obtained by water washing, oil removal and dechlorination.
(3) Pretreatment, drying and roasting of a catalyst carrier: dissolving potassium carbonate in water to prepare a 20 wt% alkali metal salt aqueous solution (namely, a potassium carbonate aqueous solution), washing the carrier obtained in the step 2), soaking the carrier in the potassium carbonate aqueous solution, wherein the mass ratio of the carrier to the potassium carbonate aqueous solution is 1:2, soaking for 5 hours, taking out the carrier, drying at 80 ℃ in a baking oven for 24 hours, roasting in a roasting oven at 800 ℃ for 10 hours, wherein the diameter of the roasted carrier is 1.8mm, thus obtaining the roasted carrier, regulating the surface acidity and alkalinity of the carrier through soaking in the alkali metal salt aqueous solution, and then carrying out heat treatment to form the final alumina carrier.
(4) Loading of active components: adding 2ml of concentrated hydrochloric acid into 200g of deionized water, weighing 0.52g of palladium chloride, heating and dissolving in the hydrochloric acid solution, adjusting the pH value to 3.0 by using a potassium hydroxide solution to obtain a chloropalladate solution, weighing 100g of the calcined carrier obtained in the step 3), soaking in the chloropalladate solution, quickly stirring for 20 minutes, standing for 1 hour, filtering out a mother solution, reducing the palladium catalyst with the mother solution filtered out at 70 ℃ for 1 hour by using 1 wt% of hydrazine hydrate solution, and washing with water to remove chlorine; and (3) drying the washed and dechlorinated catalyst in an air atmosphere at 130 ℃ for 24 hours, reducing the catalyst by using hydrogen at 600 ℃ for 3 hours, and cooling the catalyst to room temperature in a nitrogen atmosphere to obtain a finished product.
In this embodiment, the palladium catalyst for producing hydrogen peroxide by the anthraquinone process is applied to the preparation of noble metal catalyst products.
Example 2
The palladium catalyst for producing hydrogen peroxide by the anthraquinone process comprises a carrier and an active component, wherein the active component is noble metal palladium, the palladium content in the catalyst is 0.3%, the particle size is 2.6mm, the bulk density is 0.54g/ml, and the compressive strength is 58N/particle.
In this embodiment, the preparation method of the palladium catalyst for producing hydrogen peroxide by the anthraquinone process includes the following steps:
(1) preparing catalyst carrier alumina gel: respectively weighing 54g of aluminum powder, 200g of hydrochloric acid (the concentration is 36.5%) and 326g of water, carrying out reflux reaction at 100 ℃ under normal pressure for 2 hours, then adding 140g of pseudo-boehmite powder, and continuing the reaction for 5 hours to prepare 720g of aluminum adhesive; wherein the molar ratio of the aluminum powder to the hydrochloric acid to the pseudo-boehmite powder is 1:1:1, and the aluminum content in the glue is 15 wt%.
(2) Molding of the catalyst carrier: 100g of urotropine is weighed and dissolved in 150g of water to prepare 250g of urotropine aqueous solution with the concentration of 40wt percent, and then 10g of urea and 2g of P123 (EO) are weighed20PO70EO20) Dissolving the mixture in the urotropine aqueous solution, cooling to 2-15 ℃, weighing 500g of 15 wt% of alumina gel prepared in the step (1), cooling to 2-15 ℃, uniformly mixing the two, dripping the mixture into hot oil at 50 ℃ for forming, then preserving heat in the hot oil at 150 ℃ and maintaining pressure at 0.5MPa for aging for 2 hours, and agingAnd finally, taking the particles out of the oil, washing with water to remove oil and chlorine to obtain the carrier.
(3) Pretreatment, drying and roasting of a catalyst carrier: dissolving sodium carbonate in water to prepare a 10 wt% sodium carbonate aqueous solution, washing the carrier obtained in the step 2) with water, soaking the carrier in the sodium carbonate aqueous solution for 1 hour, wherein the mass ratio of the carrier to the sodium carbonate solution is 1: 2; and then taking out the carrier, putting the carrier into an oven for drying at 150 ℃ for 12 hours, then putting the carrier into a roasting furnace for roasting at 1000 ℃ for 2 hours to obtain a roasted carrier, wherein the diameter of the roasted carrier is 2.6 mm.
(4) Loading of active components: adding 2ml of concentrated hydrochloric acid into 200g of deionized water, then weighing 0.52g of palladium chloride, heating and dissolving the palladium chloride in the hydrochloric acid solution, adjusting the pH value to 6.5 by using a potassium hydroxide solution to obtain a chloropalladate solution, then weighing 100g of the roasted carrier obtained in the step 3), soaking the carrier in the chloropalladate solution, quickly stirring for 20 minutes, standing for 1 hour, and then filtering out a mother solution; and (3) washing the palladium catalyst after filtering the mother liquor to remove chlorine, drying the washed and dechlorinated catalyst for 5 hours in an air atmosphere at 750 ℃, reducing the catalyst for 10 hours at room temperature by using hydrogen, and cooling the catalyst to room temperature in a nitrogen atmosphere to obtain a finished product.
In this embodiment, the palladium catalyst for producing hydrogen peroxide by the anthraquinone process is applied to the preparation of noble metal catalyst products.
Example 3
The palladium catalyst for producing hydrogen peroxide by the anthraquinone process comprises a carrier and an active component, wherein the active component is noble metal palladium, the content of palladium in the catalyst is 0.3%, the content of cerium in the catalyst is 0.3%, the particle size of the catalyst is 2.0mm, the bulk density of the catalyst is 0.65g/ml, and the compressive strength of the catalyst is 75N/particle.
In this embodiment, the preparation method of the palladium catalyst for producing hydrogen peroxide by the anthraquinone process includes the following steps:
(1) preparing catalyst carrier alumina gel: respectively weighing 54g of aluminum powder, 120g of hydrochloric acid (the concentration is 36.5%) and 566g of water, carrying out reflux reaction at 100 ℃ under normal pressure for 5 hours, then adding 70g of pseudo-boehmite powder, and continuing the reaction for 3 hours to prepare 810g of aluminum adhesive; wherein the molar ratio of the aluminum powder to the hydrochloric acid to the pseudo-boehmite powder is 1: 0.6: 0.5, the aluminum content in the glue is 10 wt%.
(2) Molding of the catalyst carrier: weighing 40g of urotropin, dissolving in 60g of water to prepare 100g of urotropin aqueous solution with the concentration of 40 wt%, weighing 10g of urea and 5g of P123 (EO)20PO70EO20) And 1g of cerium nitrate is dissolved in the urotropine aqueous solution, the temperature is reduced to 2-15 ℃, 500g of 10 wt% of alumina gel prepared in the step (1) is weighed and cooled to 2-15 ℃, the 10 wt% of alumina gel and the 10 wt% of alumina gel are uniformly mixed and then dripped into hot oil at 80 ℃ for forming, then the mixture is subjected to heat preservation in the hot oil at 115 ℃ and pressure maintenance at 0.2MPa for aging for 15 hours, the particles are taken out of the oil after aging is finished, and the carrier is obtained by water washing, oil removal and dechlorination.
(3) Pretreatment, drying and roasting of a catalyst carrier: dissolving potassium bicarbonate in water to prepare a 10 wt% aqueous solution, washing the carrier obtained in the step 2) with water, soaking the carrier in the potassium bicarbonate solution for 3 hours, taking out the carrier, drying the carrier in a drying oven at 150 ℃ for 12 hours, then roasting the carrier in a roasting oven at 900 ℃ for 6 hours to obtain the roasted carrier, wherein the diameter of the roasted carrier is 2.0 mm.
(4) Loading of active components: adding 0.4g of sodium chloride into 200g of deionized water, then weighing 0.52g of palladium chloride, heating and dissolving in the solution to prepare a sodium chloropalladate solution, then weighing 100g of the roasted carrier obtained in the step 3), soaking in the sodium chloropalladate solution, quickly stirring for 20 minutes, standing for 1 hour, and then filtering out a mother solution; and (3) washing the palladium catalyst after filtering the mother liquor to remove chlorine, drying the washed and dechlorinated catalyst for 5 hours in an air atmosphere at 400 ℃, reducing the catalyst for 5 hours by using hydrogen at 350 ℃, and cooling the catalyst to room temperature in a nitrogen atmosphere to obtain a finished product.
Example 4
The same procedure as in example 1 was repeated, except that 1.6% of lanthanum was changed to 1% in comparison with example 1.
Example 5
The same procedure as in example 1 was repeated, except that 1.6% of lanthanum was 0% in comparison with example 1.
Example 6
Compared with example 1, except that the template C12H25EO8The amount of (2) was adjusted to 10g, and the rest was the same as in example 1.
Example 7
Compared with example 1, except that the template C12H25EO8The amount of (2) was adjusted to 0g, and the rest was the same as in example 1.
Comparative example 1
The commercial product is a certain commercial fixed bed catalyst A in China.
Comparative example 2
The commercial product is a certain commercial fixed bed catalyst B in China.
Comparative example 3
The palladium catalyst has palladium content of 0.3%, grain size of 1.8mm, bulk density of 0.45g/ml and compression strength of 34N/grain (less pseudo-boehmite powder, urea, lanthanum nitrate and C in the catalyst than in example 1)12H25EO8）。
The preparation method of the palladium catalyst comprises the following steps:
(1) preparing catalyst carrier alumina gel: respectively weighing 54g of aluminum powder, 80g of hydrochloric acid (the concentration is 36.5%) and 946g of water, and carrying out reflux reaction at 60 ℃ under normal pressure for 10 hours to prepare 1080g of alumina gel; wherein the molar ratio of the aluminum powder to the hydrochloric acid is 1:0.4, and the aluminum content in the glue is 5 wt%.
(2) Molding of the catalyst carrier: weighing 160g of urotropine, dissolving in 240g of water to prepare 400g of urotropine solution with the concentration of 40 wt%, cooling to 2-15 ℃, weighing 1000g of 5 wt% of alumina gel prepared in the step (1), cooling to 2-15 ℃, uniformly mixing the two, then dripping the mixture into hot oil with the temperature of 100 ℃ for forming, then preserving heat in the hot oil at the temperature of 80 ℃, maintaining the pressure at 0.1MPa for aging for 30 hours, taking out the particles from the oil after aging, and washing with water to remove oil and chlorine to obtain the carrier.
(3) Pretreatment, drying and roasting of a catalyst carrier: dissolving potassium carbonate in water to prepare a 20 wt% aqueous solution, washing the carrier obtained in the step 2) with water, soaking the carrier in the potassium carbonate solution for 5 hours, wherein the mass ratio of the carrier to the potassium carbonate solution is 1: 2; and then taking out the carrier, putting the carrier into an oven for drying at 80 ℃ for 24 hours, then putting the carrier into a roasting furnace for roasting at 800 ℃ for 10 hours to obtain a roasted carrier, wherein the diameter of the roasted carrier is 1.8 mm.
(4) Loading of active components: adding 2ml of concentrated hydrochloric acid into 200g of deionized water, then weighing 0.52g of palladium chloride, heating and dissolving the palladium chloride in the hydrochloric acid solution, adjusting the pH value to 3.0 by using a potassium hydroxide solution, then weighing 100g of roasted carrier, soaking the carrier in the palladium chloride acid solution, quickly stirring for 20 minutes, standing for 1 hour, and then filtering out a mother solution; reducing the palladium catalyst after filtering mother liquor for 1 hour at 70 ℃ by using 1 wt% hydrazine hydrate solution, and then washing with water to remove chlorine; and (3) drying the washed and dechlorinated catalyst in an air atmosphere at 130 ℃ for 24 hours, reducing the catalyst by using hydrogen at 600 ℃ for 3 hours, and cooling the catalyst to room temperature in a nitrogen atmosphere to obtain a finished product.
Comparative example 4
A palladium catalyst having a palladium content of 0.3%, a particle diameter of 1.8mm, a bulk density of 0.45g/ml and a compressive strength of 28N per particle.
The preparation method of the palladium catalyst comprises the following steps:
(1) preparing catalyst carrier alumina gel: respectively weighing 54g of aluminum powder, 80g of hydrochloric acid (the concentration is 36.5%) and 946g of water, and carrying out reflux reaction at 60 ℃ under normal pressure for 10 hours to prepare 1080g of alumina gel; wherein the molar ratio of the aluminum powder to the hydrochloric acid is 1:0.4, and the aluminum content in the glue is 5 wt%.
(2) Molding of the catalyst carrier: weighing 160g of urotropine, dissolving in 240g of water to prepare 400g of a urotropine solution with the concentration of 40 wt%, cooling to 2-15 ℃, weighing 1000g of the aluminum glue with the concentration of 5 wt% prepared in the step (1), cooling to 2-15 ℃, uniformly mixing the urotropine solution and the aluminum glue, then dripping the mixture into hot oil with the temperature of 100 ℃ for forming, then preserving heat in the hot oil at the temperature of 80 ℃, maintaining the pressure at 0.1MPa for aging for 30 hours, taking out the particles from the oil after aging is finished, and washing with water to remove oil and chlorine to obtain the carrier.
(3) Pretreatment, drying and roasting of a catalyst carrier: and (3) drying the carrier subjected to water washing, oil removal and chlorine removal in the step 2) in an oven at the temperature of 80 ℃ for 24 hours, then roasting in a roasting furnace at the temperature of 800 ℃ for 10 hours to obtain a roasted carrier, wherein the diameter of the roasted carrier is 1.8 mm.
(4) Loading of active components: adding 2ml of concentrated hydrochloric acid into 200g of deionized water, then weighing 0.52g of palladium chloride, heating and dissolving the palladium chloride in the hydrochloric acid solution, adjusting the pH value to 3.0 by using a potassium hydroxide solution to obtain a chloropalladate solution, then weighing 100g of roasted carrier, soaking the carrier in the chloropalladate solution, quickly stirring for 20 minutes, standing for 1 hour, and then filtering out a mother solution; reducing the palladium catalyst after filtering mother liquor for 1 hour at 70 ℃ by using 1 wt% hydrazine hydrate solution, and then washing with water to remove chlorine; and drying the washed and dechlorinated catalyst in an air atmosphere at 130 ℃ for 24 hours, then placing the catalyst into a roasting furnace for roasting in the air atmosphere at the roasting temperature of 600 ℃ for 3 hours, and then cooling the catalyst to room temperature in the air atmosphere to obtain a finished product.
Performance testing
The performance of the catalysts prepared in examples 1 to 7 and comparative examples 1 to 4 was evaluated, and the specific results are shown in table 1.
The catalyst performance evaluation method and terms used in the present invention are explained as follows:
hydrogenation efficiency: under the specific reaction temperature and reaction pressure and in the hydrogen atmosphere, the working solution containing a quantitative reactant (anthraquinone) is subjected to hydrogenation reaction by a quantitative catalyst within a certain time, and then the anthrahydroquinone in the hydrogenated working solution is completely oxidized, and the working solution per unit volume contains H2O2Mass number of (2), unit g/L.
Activity: the present invention uses the actually measured hydrogenation efficiency as a measure of the catalyst activity per unit of the catalyst's ability to produce hydrogen peroxide.
And (3) selectivity: under specific reaction temperature and reaction pressure, working solution containing a quantitative reactant (anthraquinone) is subjected to over hydrogenation catalysis by a quantitative catalyst within a certain time, and the ratio of the product anthrahydroquinone (effective anthrahydroquinone capable of being used for producing hydrogen peroxide and taking the actually measured hydrogenation efficiency as a measurement reference) to the anthrahydroquinone which can be generated by theoretical calculation of the working solution (the hydrogenation efficiency which can be obtained by theoretical calculation of 100 percent as the measurement reference) is the selectivity of the palladium catalyst.
Catalyst activity evaluation method: filling 5g of catalyst into a fixed bed reactor each time, measuring the hydrogenation efficiency under the conditions of 50 ℃, normal pressure and 20L/h of hydrogen flow rate, and taking the hydrogenation efficiency as the basis of activity; the working solution takes 2-B-grade anthraquinone (EAQ) as a working medium, and takes heavy aromatic hydrocarbon (AR) and trioctyl phosphate (TOP) as solvents, wherein the EAQ content is 100g/L, and AR: TOP =3:1 (volume ratio).
The selectivity evaluation method comprises the following steps: 10g of catalyst is filled in a fixed bed reactor each time, 2-B-anthraquinone in 50ml of working solution is circularly and excessively hydrogenated under the conditions of 70 ℃, normal pressure and 30L/h of hydrogen flow rate, and the hydrogenation efficiency of the working solution after excessive hydrogenation is measured after 2 hours. The ratio of the actually measured hydrogenation efficiency to the hydrogenation efficiency calculated by the working solution theory to be 100 percent is taken as a selectivity index. The working solution takes 2-grade B anthraquinone (EAQ) as a working medium and takes heavy aromatic hydrocarbon (AR) and trioctyl phosphate (TOP) as solvents, wherein the EAQ content is 60g/L, and AR: TOP =65:35 (volume ratio).
Evaluation method of compressive strength: the magnitude of the force to which the sample catalyst was subjected just before breaking was taken as the sample compressive strength. And measuring 20 grains, and taking the average value as the numerical value of the compressive strength of the sample in N/grain.
Wear rate: the measurement was carried out according to the regulation of HG/T3927-2007. The invention uses the abrasion rate as the index for judging whether the catalyst is easy to remove palladium and fall off powder.
TABLE 1 test results Table
As can be seen from the comparison of example 1 with examples 4 and 5, the selectivity of the catalyst is slightly reduced with the decrease of the lanthanum content, and the activity, the crushing strength, the bulk density and the abrasion are basically not affected; as can be seen from comparison of example 1 with examples 6 and 7, the template C was added12H25EO8The reduction of the amount, the activity and the selective crushing strength of the catalyst are both slightly reduced, and the abrasion is slightly increased, which shows that the template agent has larger influence on the internal structure of the catalyst; from examples 1, 4 and 5,6. 7 comparing with comparative example 3, it can be seen that the following components were added together with pseudo-boehmite, urea, and template C12H25EO8The loss of rare earth salt, the crushing strength, the activity and the selectivity of the catalyst are obviously reduced, and the abrasion is obviously improved; as can be seen from comparison of comparative example 3 with comparative example 4, the carrier is not pretreated by alkali metal salt, the catalyst is not activated by hydrogen, and the activity and selectivity of the catalyst are obviously reduced; it is understood from the comparison between examples 1 and 2 and comparative examples 1 and 2 that the indexes of the catalyst such as bulk density, crushing strength, activity, selectivity and abrasion are changed according to the change of the compounding ratio of the powdery aluminum, hydrochloric acid, pseudo-boehmite and the template and the change of the condition of activating the carrier by the alkali metal salt and the catalyst by hydrogen gas, but examples 1 to 3 are better than comparative examples 1 and 2 in all aspects.
The data show that the catalyst provided by the invention is added with pseudo-boehmite, urea, a template agent, rare earth salt, alkali metal and other catalytic auxiliaries for synergistic modification and is subjected to hydrogen activation treatment, compared with the existing catalyst in the market, the catalyst has the advantages of greatly improved crushing strength, activity, selectivity and the like, low abrasion, difficult palladium and powder removal, long service life and high catalyst residue value, can be used for an industrial hydrogen peroxide device, can obviously reduce the loading amount of the device catalyst and the consumption of materials such as anthraquinone, alumina and the like, and is an optimal product for the comprehensive performance of the prior fixed bed anthraquinone hydrogenation catalyst.
The invention has the beneficial effects that the invention provides a fixed bed catalyst for a device for producing hydrogen peroxide by an industrial anthraquinone process and a preparation method thereof, the invention prepares alumina gel by taking aluminum powder, hydrochloric acid and pseudo-boehmite powder as main raw materials, the pseudo-boehmite is taken as a crystal seed in the reaction to guide the whole reaction to form a specific alumina gel structure, then the alumina gel is uniformly mixed with urotropine, urea, a template agent and a rare earth salt solution, the mixture is dropped into an oil column for forming and is aged and crystallized under specific conditions, the urotropine, the urea, the template agent and the alumina gel are mutually reacted under specific aging conditions to form aluminum hydroxide with a specific pore structure in the aging process, the rare earth salt is embedded into corresponding crystal lattices in the aging process to adjust the surface acidity and alkalinity of the aluminum oxide, then the alkali metal salt is used for soaking to further adjust the surface acidity and alkalinity of a carrier after washing and impurity removal, and then the final aluminum oxide carrier is formed by heat treatment, soaking the carrier in palladium solution to prepare the palladium catalyst, washing with water, and then reducing with formaldehyde or hydrazine hydrate solution or hydrogen to finally prepare the finished catalyst. The combination of the specific pore structure, surface acidity and alkalinity and active component palladium in the finished catalyst is extremely suitable for anthraquinone hydrogenation reaction, the activity, selectivity and strength of the catalyst are improved by more than 20 percent compared with those of commercial catalysts in the market, and the longest service life of the catalyst can reach more than 10 years; moreover, the invention provides the palladium catalyst for fixed bed hydrogenation, which has high activity, high selectivity, high strength, difficult palladium removal and powder falling and long service life, the activity, the selectivity and the strength of the catalyst are improved by more than 20 percent compared with commercial catalysts in the market, and the longest service life of the catalyst can reach more than 10 years; the catalyst prepared by the invention has good comprehensive performance, is not easy to remove palladium and powder, has the advantages of high strength, long service cycle, high activity, good selectivity and the like, is a fixed bed catalyst which is most suitable for a device for producing hydrogen peroxide by an industrial anthraquinone method at present, solves the problems that the fixed bed catalyst for producing hydrogen peroxide by the industrial anthraquinone method is easy to remove palladium and powder and has poor comprehensive performance, and has wide market prospect.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. The palladium catalyst for producing hydrogen peroxide by the anthraquinone process comprises a carrier and an active component, and is characterized in that the active component is noble metal palladium, and the loading amount of the noble metal palladium is 0.1-1.0% of the weight of the carrier;
the carrier comprises the following raw materials in parts by weight: 100 parts of aluminum glue, 10-50 parts of urotropine aqueous solution, 0-20 parts of urea, 0-20 parts of template agent and 0-5 parts of rare earth salt.
2. The palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to claim 1, wherein the loading amount of the active component is 0.2-0.4% of the weight of the carrier, and the concentration of the urotropine aqueous solution is 30-40 wt%.
3. The palladium catalyst for producing hydrogen peroxide by using the anthraquinone process according to claim 2, wherein the aluminum glue is aluminum powder, hydrochloric acid and pseudo-boehmite powder, and the molar ratio of the aluminum glue to the pseudo-boehmite powder is 1: 0.4-1: 0.1-1, and the aluminum content in the aluminum adhesive is 5-15 wt%.
4. The palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to claim 3, wherein the template agent is one or more of long-chain alkane epoxy vinyl ether and polyethylene oxide-polypropylene oxide block copolymers.
5. The palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to claim 3, wherein the rare earth salt is one or more of lanthanum nitrate, cerium nitrate and samarium nitrate.
6. The palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to claim 5, wherein the preparation method of the carrier comprises the steps of weighing the aluminum colloid, the urotropine aqueous solution, the urea, the template agent and the rare earth salt according to the parts by weight, dissolving the urea, the template agent and the rare earth salt in the urotropine aqueous solution to obtain a urotropine mixed solution, cooling the aluminum colloid and the urotropine mixed solution to 2-15 ℃ respectively, mixing uniformly, dripping the mixture into hot oil of 50-100 ℃ for molding, aging the mixture in the hot oil, taking out particles after aging, washing the particles with water to remove oil and chlorine, and obtaining the carrier.
7. The palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to claim 6, wherein the carrier is subjected to pretreatment operation before loading active components, and the pretreatment is to soak the carrier in an alkali metal salt aqueous solution with a concentration of 1-20 wt% for 1-5 hours, and then take out and place in an oven for drying.
8. The palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to claim 7, wherein the alkali metal salt is one or more of potassium nitrate, sodium nitrate, potassium chloride, sodium chloride, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide.
9. A method for preparing a palladium catalyst for producing hydrogen peroxide by an anthraquinone process according to any one of claims 1 to 8, which is characterized by comprising the following steps:
1) preparing aluminum glue: respectively weighing aluminum powder, hydrochloric acid and pseudo-boehmite powder according to the weight parts, adding water into the hydrochloric acid, mixing the hydrochloric acid with the aluminum powder, carrying out reflux reaction at the temperature of 60-100 ℃ under normal pressure for 2-10 hours, adding the pseudo-boehmite powder, and continuously reacting for 0.5-5 hours to prepare the aluminum cement;
2) molding of the catalyst carrier: respectively weighing aluminum glue, a urotropine aqueous solution, urea, a template agent and rare earth salt according to the weight parts, dissolving the urea, the template agent and the rare earth salt in the urotropine aqueous solution to obtain a urotropine mixed solution, respectively cooling the aluminum glue and the urotropine mixed solution to 2-15 ℃, uniformly mixing, dripping into hot oil with the temperature of 50-100 ℃ for forming, aging in the hot oil for 2-30 hours, taking out particles from the oil after aging, washing with water to remove oil and chlorine, and obtaining a carrier;
3) pretreatment, drying and roasting of a catalyst carrier: weighing alkali metal salt, dissolving the alkali metal salt in water to prepare an alkali metal salt aqueous solution with the concentration of 1-20 wt%, washing the carrier obtained in the step 2), soaking the carrier in the alkali metal salt aqueous solution for 1-5 hours, taking out the carrier, drying the carrier in an oven, and roasting the carrier in a roasting furnace at 800-1000 ℃ for 2-10 hours to obtain a roasted carrier;
4) loading of active components: immersing the roasted carrier obtained in the step 3) into a chloropalladate or sodium chloropalladate solution with the pH value of 3-6.5 for impregnation, filtering mother liquor, and performing reduction reaction to prepare a finished product palladium catalyst; wherein the volume ratio of the carrier to the chloropalladate or sodium chloropalladate solution is 1:2, the mass ratio of the carrier to the palladium in the chloropalladate or sodium chloropalladate solution is 1000: 2-4, the dipping temperature is 25-90 ℃, and the dipping time is 0.5-3 hours.
10. The method according to claim 9, wherein in the step 2), the aging temperature is 80 to 150 ℃ and the pressure is 0.1 to 0.5 MPa.
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| CN117380183A (en) * | 2023-12-04 | 2024-01-12 | 黎明化工研究设计院有限责任公司 | Preparation method and application of supported palladium nanoparticle catalyst |
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