CN106669665B - The integral catalyzer and preparation method thereof of hydrogen dioxide solution production by anthraquinone process process - Google Patents
The integral catalyzer and preparation method thereof of hydrogen dioxide solution production by anthraquinone process process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 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 29
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 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 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000012224 working solution Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- -1 hydrogen anthraquinone Chemical class 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PLVLWMLQCINABX-UHFFFAOYSA-N 1,2-diethylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3C(=O)C2=C1 PLVLWMLQCINABX-UHFFFAOYSA-N 0.000 description 1
- INPHIYULSHLAHR-UHFFFAOYSA-N 1-pentylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCC INPHIYULSHLAHR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 238000009941 weaving 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
- B01J23/54—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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- 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
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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 discloses a kind of integral catalyzers and preparation method thereof of hydrogen dioxide solution production by anthraquinone process process, catalyst includes catalyst carrier, auxiliary agent and active metal component, catalyst carrier is honeycomb gama-alumina, active metal component distribution, which has the property that, is divided into A along integral catalyzer duct direction, two regions B, a-quadrant loads auxiliary agent and active metal component, B area supported active metals component, the active metal component is selected from palladium, platinum, ruthenium, the combination of one or more of rhodium and iridium, in terms of metal simple-substance, it accounts for the 0.01% ~ 5% of catalyst gross mass, the auxiliary agent is selected from zinc, sodium, potassium, with the combination of one or more of magnesium, account for the 0.01% ~ 2% of catalyst gross mass.Preparation method: distinguishing load active component for the A of catalyst carrier, B area, and then dry and roasting obtains product.The catalyst is for having higher active, selective and lower production cost in the hydrogenation process of hydrogen dioxide solution production by anthraquinone process.
Description
Technical field
The present invention relates to a kind of integral catalyzers and preparation method thereof of hydrogen dioxide solution production by anthraquinone process process.
Background technique
Hydrogen peroxide also known as hydrogen peroxide are a kind of important industrial chemicals, industrially just have early in 19 middle of century
Production, is one of main essential chemistry product in the world.Increasingly with the growth of social demand, especially ecological environmental protection
Important, hydrogen peroxide becomes an important chemicals.As a kind of oxidant, bleaching agent, disinfectant, polymerization initiator and
Crosslinking agent, it is widely used in papermaking, weaving, chemicals synthesis, military project, electronics, food processing, medicine, cosmetics, environment guarantor
The numerous areas such as shield, metallurgy.Water and oxygen are generated after decomposing due to hydrogen peroxide, it is without secondary pollution to environment, belong to greenization
Product.In the production of hydrogen peroxide, the most commonly used is anthraquinone for countries in the world.
Anthraquinone technique is anthraquinone derivative autoxidation method, it dissolves operation material-anthraquinone with organic solvent appropriate
Alkyl derivative is made into working solution, in the presence of a catalyst, is restored anthraquinone hydrogenation with hydrogen, generates hydrogen anthraquinone, Hou Zhejing
Air or oxygen oxidation, obtains H2O2, while hydrogen anthraquinone is oxidized to anthraquinone.Then, with the H in water extraction working solution2O2, through dividing
From obtaining H2O2Aqueous solution；Purification can be also further distilled, high concentration H is obtained2O2, raffinate returns to after processing hydrogenates rank
Section is recycled.
Hydrogen effect is an important indicator in anthraquinone technique, it directly determines the scale of hydrogen peroxide plant.Due to anthraquinone
Selective hydrogenation is typical gas-liquid-solid three phase catalytic reaction process, in order to obtain higher hydrogen effect and selectivity, it is necessary to
The outstanding effect between hydrogen, liquid phase reactor object and catalyst surface can effectively be controlled.Having for the above process is realized at present
Slurry bed system and fixed bed, slurry bed system (US6306356, US5399333, CN1088885A) are that solid catalyst particle is suspended in liquid
In body medium, then passing to gas is scattered in it in liquid, mixes with medium, should not generate reaction hot spot, but due to
Catalyst granules is smaller, and it is more to rub between catalyst, and it is difficult to will lead to big catalyst attrition, catalyst and reactants separate
The problems such as with subsequent treatment process is influenced.
In order to overcome the problems, such as that paddle-bed exists, fixed bed is also widely used in the technique mistake of hydrogen dioxide solution production by anthraquinone process
Journey, in fixed bed, the duct that catalyst buildup is formed is irregular, causes liquid and others to be unevenly distributed, unavoidably
Generation fluid channel and short circuit, here it is liquid reactants, gas and catalyst surfaces to come into full contact with, and causes to urge
Agent utilization rate reduces.In addition, the pore distribution due to catalyst is uneven, the speed that reactant is spread in different ducts
Difference is larger, and it is inadequate to will lead to a part of reaction depth, and in addition your a part of reaction depth is excessive, causes the work of catalyst
Property and selectivity reduce the case where.
Integral catalyzer be by it is regular, repeat the monolith support that the channel that is mutually mutually separated constitutes, catalytic active component with
The form of thin layer is evenly distributed in the inner surface in duct.It is irregular empty compared to made of being accumulated between other beaded catalysts
Gap, integral catalyzer has the channel of same shape and length, therefore logistics is identical by the resistance drop of bed, ensure that object
Stream by the distribution of bed be uniformly, to reach logistics residence time having the same and reaction condition in bed,
Integral catalyzer has very big specific surface simultaneously, ensure that product cracking can diffuse out, avoids deep reaction
By-product occur, improve the activity and selectivity of reaction.
A kind of preparation method of integral catalyzer for anthraquinone hydrogenation process is disclosed in US6207128, in patent
The catalyst carrier of use is inactive ceramic, is then applied on the surface of ceramics after being covered with silica or aluminium oxide etc., using change
The method for learning plating loads upper active metal component.Above-mentioned method for preparing catalyst process is complicated, step is more, influence process factor
It is more, it also needs to improve in terms of the repeatability and production cost of catalyst preparation.
CN104368336 discloses a kind of integral catalyzer and its preparation that hydrogen peroxide process is produced for amyl anthraquinone
Method.It is using inert ceramic monolith, then auxiliary agent and active metal component on step load, are finally sent out by reduction
Bright catalyst.The catalyst has the advantage of integral catalyzer, but still that there are preparation steps is more, noble metal dosage greatly and is urged
The selectively low deficiency of agent.
CN104368374 disclose a kind of high dispersive integral catalyzer and preparation method thereof for hydrogen peroxide synthesis and
Using.It is then to load upper molecular sieve-oxide compound using inert ceramic monolith and helped as support modification, then step by step
Agent and active metal component finally obtain invention catalyst by reduction.The hydrogen effect of the catalyst is improved significantly, but still
It is mostly low etc. insufficient with catalyst choice there are preparation step.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of hydrogen dioxide solution production by anthraquinone process process integral catalyzer and
Preparation method, the catalyst are used in the hydrogenation process of hydrogen dioxide solution production by anthraquinone process, with higher active, selectivity and more
Low production cost.
The integral catalyzer of hydrogen dioxide solution production by anthraquinone process process of the invention, including catalyst carrier, auxiliary agent and activity
Metal component, catalyst carrier are honeycomb gama-alumina, and active metal component distribution has the property that urges along monoblock type
Agent duct direction is divided into two regions A, B, and a-quadrant loads auxiliary agent and active metal component, B area supported active metals group
Point, the active metal component is the combination selected from one or more of palladium, platinum, ruthenium, rhodium and iridium, more preferably palladium, with gold
Belong to simple substance meter, account for the 0.01% ~ 5% of catalyst gross mass, preferably 0.05% ~ 2%, the auxiliary agent be selected from zinc, sodium, potassium and
The combination of one or more of magnesium, preferably potassium account for the 0.01% ~ 2% of catalyst gross mass, preferably 0.05% ~ 1%.
The height ratio in two regions A, B of integral catalyzer of the present invention can according to the requirement of reaction and into
Row is adjusted, height the ratio generally 1:10 ~ 10:1, preferably 2:5 ~ 5:2 of A, B area.
The duct mesh number of catalyst of the present invention is 50 ~ 500 mesh, and preferably 100 ~ 400 mesh, the shape in duct section can
Think round, ellipse or polygon, circular.The honeycomb gamma-aluminium oxide carrier the preparation method is as follows: by hydrogen
Aluminum oxide dry glue powder, pore creating material, peptizing agent and water are sufficiently mixed into plastic paste, paste placed into pressing mold extrusion at
Multi-pore channel overall structure intercepts certain height formula catalyst as a whole along vertical channel after dry and calcination process
Carrier；The preparation method of the aluminum hydroxide solid elastomer powder can be aluminum sulfate method or carbonizatin method, preferably carbonizatin method.It is described to make
Hole agent can be polyvinyl alcohol, carbon black, cellulose, sesbania powder, methylcellulose, starch etc., preferably methylcellulose.It is described
Peptizing agent can be the substance that can make mixture peptization, such as organic acid or inorganic acid, preferably inorganic acid, more preferably
Nitric acid.The hole shape and density of the grinding tool can according to need to design.The drying condition is 20 ~ 200 DEG C, preferably
80 ~ 150 DEG C, 0.5 ~ 48 hour, preferably 1 ~ 12 hour；Roasting condition is 300 ~ 1000 DEG C, preferably 400 ~ 800 DEG C, is roasted
Time is 0.5 ~ 8 hour, preferably 1 ~ 4 hour.
The preparation method of the integral catalyzer of hydrogen dioxide solution production by anthraquinone process process of the invention, including following content:
A) honeycomb gamma-aluminium oxide carrier is totally immersed into impregnation in the solution containing active metal component, impregnated
After by dry and calcination process；
B) it by step a) treated catalyst carrier, is immersed along the solution containing auxiliary agent along duct direction part, dipping
Processing obtains product after dry and calcination process；The part that wherein load has auxiliary agent is integral catalyzer a-quadrant, remaining
Lower part is divided into integral catalyzer B area.
Noble metal active component solution described in step a) can be palladium chloride solution, platinum acid chloride solution, chlorination ruthenium solution, nitre
One or more of sour rhodium solution etc., preferably palladium chloride solution, concentration are adjusted as needed, generally 0.1 ~ 5M；
Compounding agent solution described in step b) be the aqueous solution containing auxiliary agent soluble compound, as sodium hydroxide solution, potassium hydroxide solution,
Potassium nitrate solution, zinc nitrate, magnesium nitrate solution etc., preferably potassium nitrate solution, concentration are adjusted as needed, generally
0.1~5M。
The immersion time described in step a) is 0.1 minute ~ 2 hours, preferably 0.5 minute ~ 1 hour；Described in step b)
The immersion time be 0.1 minute ~ 2 hours, preferably 0.5 minute ~ 1 hour.
The drying temperature of step a) is room temperature ~ 200 DEG C, and preferably 80 ~ 150 DEG C, drying time is 0.5 ~ 48 hour, preferably
It is 1 ~ 12 hour；Maturing temperature be 300 ~ 1000 DEG C, preferably 400 ~ 800 DEG C, calcining time be 0.5 ~ 8 hour, preferably 1 ~ 4
Hour.
The drying condition of step b) is room temperature ~ 200 DEG C, and preferably 80 ~ 150 DEG C, drying time is 0.5 ~ 48 hour, preferably
It is 1 ~ 12 hour；Maturing temperature be 300 ~ 1000 DEG C, preferably 400 ~ 800 DEG C, calcining time be 0.5 ~ 8 hour, preferably 1 ~ 4
Hour.
Catalyst of the present invention is applied to the technical process of hydrogen dioxide solution production by anthraquinone process, and there is catalysis in the logistics direction of reaction raw materials
Agent a-quadrant is to catalyst B area, general process conditions are as follows: 0.1 ~ 2.0MPa of hydrogen partial pressure, 10 ~ 100 DEG C of reaction temperature, and body
Product 1.0 ~ 50.0h of air speed-1, gas agent volume ratio 10:1 ~ 1000:1；Optimum condition are as follows: 0.2 ~ 1.0MPa of hydrogen partial pressure, reaction temperature
30 ~ 80 DEG C, 2 ~ 20h of volume space velocity-1, gas agent volume ratio 20:1 ~ 500:1.Wherein working solution is hydrogen dioxide solution production by anthraquinone process technique
In common working solution, generally anthraquinone is dissolved in the mixture formed in heavy aromatics and trioctyl phosphate, heavy aromatics and phosphoric acid
The volume ratio of three monooctyl esters is 5:1 ~ 1:1, and the concentration of anthraquinone is 80 ~ 150g/L in working solution.The heavy aromatics is selected from carbon atom
One of aromatic hydrocarbons that number is 8 ~ 11 is a variety of, wherein C9And/or C10The volume of aromatic hydrocarbons accounts for 95% of heavy aromatics or more.
Currently, there are two types of catalyst used in during the hydrogenation process of hydrogen dioxide solution production by anthraquinone process is general: one is
Common spherical shape or bar shaped catalyst, will appear that pressure drop of column is excessively high, and reactant is easily accessible catalysis in use
Cause to degrade in agent duct seriously, many deficiencies such as catalyst caused by bullion content is high is at high cost；Another is no work
Property ceramics integral carriers, upper aluminium oxide is then loaded, then load noble metal, due between ceramic surface and aluminium oxide and metal
Active force it is very weak, be easy to fall off in use, there are also be exactly with single noble metal, it is not only at high cost, but also reaction
Selectivity decline, leads to the deficiencies of feed degradation is serious in reaction process.
The present inventor is not under the premise of changing hydrogenation process, by the way that catalyst is divided into two regions, creatively will
Hydrogenation merges in two regions A, B of catalyst.Auxiliary agent and noble metal active component are contained in a-quadrant, and B area contains only expensive
Metal active constituent and do not contain auxiliary agent, a-quadrant provide have suitable activity and highly selective reactive moieties, and B area provide
More high activity reactive moieties.Since reactant concentration is higher in fresh feed, such as directly with higher catalytic activity central contact,
Deep reaction may occur and generate side reaction, such as dissolution or the degradation of anthraquinone or carbon deposit etc., when there is the anti-of part
It after answering object to react, then is contacted with the noble metal region of catalyst lower part high activity and deep hydrogenation occurs, both ensure that in this way
The activity of reaction, while the selectivity of the reaction also improved.
Specific embodiment
Further illustrate the preparation process of catalyst of the present invention below by embodiment, but it is not considered that the present invention only office
It is limited in embodiment below.Below if indicated without special, degree is weight percentage.
The performance evaluation of catalyst uses Miniature tube type reactor, and volume is that 20 milliliters of integral catalyzer is placed in instead
Should pipe constant temperature zone, catalyst periphery asbestos cloth filling prevent gas and liquid from passing through.Feed procatalyst with hydrogen also
Original, gas agent volume ratio are 300, and temperature is 320 DEG C, are restored 4 hours.Then hydrogen and working solution are by way of cocurrent from reaction
The channel that the top of device enters integral catalyzer carries out hydrogenation reaction, reaction condition are as follows: pressure 0.3MPa, 65 DEG C of temperature,
Working solution volume air speed 10h-1, hydrogen to oil volume ratio 10；Solvent is heavy aromatics and trioctyl phosphate volume in used working solution
Than the mixed solvent for 3:1, diethyl anthraquinone is 120g/L in content wherein.There is no specified otherwise, catalyst is all made of
The condition stated is evaluated.
Embodiment 1
A) by 5000 grams of aluminum hydroxide solid elastomer powder (butt 73.6w%), 100 grams of methylcellulose, 4300 grams of water and 500 grams
The nitric acid solution of 30w% is sufficiently mixed into plastic paste, and pasting placed into hole density is extrusion in 300 press mold at more
Duct overall structure, 12 hours dry by 150 DEG C, 650 DEG C roast 4 hours, intercept 10 centimetres high along duct vertical direction
Sample is as carrier；
B) taking duct mesh number is 300, is highly 10 centimetres of honeycomb gamma oxidation aluminium block, is totally immersed into 0.5Mol/L
It in the aqueous solution of palladium chloride, impregnates 5 minutes at room temperature, takes out after-blow and go out solution remaining in duct, it is 6 hours dry at 120 DEG C,
450 DEG C roast 2 hours, and repetition is secondary, obtain catalyst precarsor A of the present invention；
C) the catalyst precarsor A for taking step a) to prepare, is immersed in 2Mol/L nitric acid for 4 cm height part of one end (area A)
It in the aqueous solution of potassium, impregnates 5 minutes at room temperature, takes out after-blow and go out solution remaining in duct, it is 6 hours dry at 120 DEG C, 500
DEG C roasting 2 hours, obtain the integral catalyzer of the present invention containing potassium, number E-1 carries out catalyst composition analysis and reactivity
Energy evaluation experimental, evaluation condition is it has been observed that the results are shown in Table 1.
Embodiment 2 ~ 7
Each embodiment method for preparing catalyst is with embodiment 1, the difference is that used metal species, content, containing
The differences such as the height (A, B area ratio) of auxiliary agent, the mesh number of carrier, obtained catalyst number is respectively E-2 ~ E-7, specifically
Condition and reaction result are shown in Table 1.
Comparative example 1 ~ 3
Method for preparing catalyst is with embodiment 1, the difference is that the used carrier of comparative example 1 is to prepare with embodiment 1,
Carrier used in comparative example 2 and comparative example 3 is that bulk ceramics block, metal species, content, height of impregnating metal etc. are different,
Wherein the active metal component of 2 integral catalyzer of comparative example dipping all contains palladium and potassium, and comparative example 1 and comparative example 3 are whole
The all palladiums of active metal of body formula catalyst dipping, and auxiliary agent potassium is free of, COMPARATIVE CATALYST EXAMPLE's catalyst of the present invention is obtained, is compiled
Number be respectively C-1, C-2 and C-3, actual conditions and reaction result are shown in Table 1.
Comparative example 4
Taking the alumina globule carrier that 100 grams of diameters are 2.0mm, (hole holds 0.57ml/g, specific surface area 160m2/ g, specific gravity
0.52g/ml), it is saturated dipping with the palladium chloride solution containing 0.3 gram of palladium, then 6 hours dry at 120 DEG C, 500 DEG C of roastings 2 are small
When, comparative catalyst, number C-4 are obtained, actual conditions and reaction result are shown in Table 1.
1 catalyst of table composition and evaluation result.
Note:Hydrogen imitates unit: gH2O2/ L working solution；Carrier is ceramic honeycomb block.
From the results shown in Table 1, in the reaction of production hydrogen peroxide, hydrogenation efficiency is apparently higher than catalyst of the present invention
Comparative catalyst.
Claims (10)
1. a kind of integral catalyzer of hydrogen dioxide solution production by anthraquinone process process, it is characterised in that: including catalyst carrier, auxiliary agent and
Active metal component, catalyst carrier are honeycomb gama-alumina, and active metal component distribution has the property that along entirety
Formula catalyst duct direction is divided into two regions A, B, and a-quadrant loads auxiliary agent and active metal component, B area supported active metals
Component, the active metal component is the combination selected from one or more of palladium, platinum, ruthenium, rhodium and iridium, in terms of metal simple-substance,
The 0.01% ~ 5% of catalyst gross mass is accounted for, the auxiliary agent is the combination selected from one or more of zinc, sodium, potassium and magnesium, accounts for and urges
The 0.01% ~ 2% of agent gross mass.
2. catalyst described in accordance with the claim 1, it is characterised in that: two regions A, B of the integral catalyzer
Height ratio is 1:10 ~ 10:1.
3. catalyst described in accordance with the claim 1, it is characterised in that: the duct mesh number of the catalyst is 50 ~ 500 mesh；
The shape in duct section is round, ellipse or polygon.
4. a kind of system of the integral catalyzer of hydrogen dioxide solution production by anthraquinone process process described in claim 1 ~ 3 any claim
Preparation Method, including following content:
A) honeycomb gamma-aluminium oxide carrier is totally immersed into impregnation in the solution containing active metal component, dipping terminates
Afterwards by dry and calcination process；
B) it by step a) treated catalyst carrier, is immersed along the solution containing auxiliary agent along duct direction part, impregnation,
After dry and calcination process, product is obtained；The part that wherein load has auxiliary agent is integral catalyzer a-quadrant, remaining portion
It is divided into integral catalyzer B area.
5. according to the method for claim 4, it is characterised in that: noble metal active component solution described in step a) is palladium chloride
One or more of solution, platinum acid chloride solution, chlorination ruthenium solution or rhodium nitrate solution；Compounding agent solution described in step b) is hydrogen-oxygen
Change one or more of sodium solution, potassium hydroxide solution, potassium nitrate solution, magnesium nitrate solution or zinc nitrate solution.
6. according to the method for claim 4, it is characterised in that: the immersion time described in step a) is 0.1 minute ~ 2 small
When；The immersion time described in step b) is 0.1 minute ~ 2 hours.
7. according to the method for claim 4, it is characterised in that: the drying temperature of step a) is room temperature ~ 200 DEG C, when dry
Between 0.5 ~ 48 hour；Maturing temperature is 300 ~ 1000 DEG C, and calcining time is 0.5 ~ 8 hour.
8. according to the method for claim 4, it is characterised in that: the drying condition of step b) is room temperature ~ 200 DEG C, when dry
Between 0.5 ~ 48 hour；Maturing temperature is 300 ~ 1000 DEG C, and calcining time is 0.5 ~ 8 hour.
9. catalyst described in a kind of claim 1 ~ 3 any claim is in the technical process of hydrogen dioxide solution production by anthraquinone process
Using, it is characterised in that: the logistics direction of reaction raw materials is by catalyst a-quadrant to catalyst B area.
10. applying according to claim 9, it is characterised in that: process conditions are as follows: 0.1 ~ 2.0MPa of hydrogen partial pressure, reaction
10 ~ 100 DEG C of temperature, 1.0 ~ 50.0h of volume space velocity-1, gas agent volume ratio 10:1 ~ 1000:1.
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| CN109806892A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of integral catalyzer and application in hydrogen peroxide is directly synthesized in hydrogen and oxygen |
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| CN108057438A (en) * | 2017-09-06 | 2018-05-22 | 贵研工业催化剂（云南）有限公司 | It is a kind of to prepare ruthenium catalyst of hydrogen peroxide and preparation method thereof for anthraquinone hydrogenation |
| CN109806861B (en) * | 2017-11-20 | 2020-06-23 | 中国科学院大连化学物理研究所 | Preparation of nano-sandwich structure noble metal catalyst and application of nano-sandwich structure noble metal catalyst in hydrogen and oxygen direct synthesis of hydrogen peroxide |
| CN111686721A (en) * | 2019-03-12 | 2020-09-22 | 山西潞安矿业(集团)有限责任公司 | Palladium ruthenium alloy catalyst and preparation method and application thereof |
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