CN106669856A - Anthraquinone hydrogenation monolithic catalyst with non-uniform channels and preparation method of catalyst - Google Patents
Anthraquinone hydrogenation monolithic catalyst with non-uniform channels and preparation method of catalyst Download PDFInfo
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- CN106669856A CN106669856A CN201510761764.7A CN201510761764A CN106669856A CN 106669856 A CN106669856 A CN 106669856A CN 201510761764 A CN201510761764 A CN 201510761764A CN 106669856 A CN106669856 A CN 106669856A
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- catalyst
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- anthraquinone
- integer catalyzer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 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 28
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 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 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 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 description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 239000012224 working solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- -1 hydrogen anthraquinone Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 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
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 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
- 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 1
- 239000005995 Aluminium silicate Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XAIKOVRFTSBNNU-UHFFFAOYSA-N anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 XAIKOVRFTSBNNU-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 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
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000008187 granular material Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 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
- 239000010970 precious metal Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 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
- 238000009941 weaving Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J23/42—Platinum
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an anthraquinone hydrogenation monolithic catalyst with non-uniform channels and a preparation method of the catalyst. An area ratio of an opening I to an opening II in two ends of each channel of the catalyst is 1:1.1-1:100, preferably, 1:2-1:10, and the cross section area of the channel between the opening I and the opening II is in a mode of one or combination of continuous increase or stepped increase. The preparation method comprises steps as follows: (1), a carrier in a shape of the monolithic catalyst is soaked in a solution containing active components for a certain period of time and then is taken out, dried and roasted, and an oxidation-state catalyst is obtained; (2), the obtained oxidation-state catalyst is reduced and dried under the inert atmosphere, and the anthraquinone hydrogenation monolithic catalyst with the non-uniform channels is obtained. The monolithic catalyst has the non-uniform channels and is applied to a hydrogenation process for hydrogen peroxide preparation based on an anthraquinone process, thereby guaranteeing reactivity and improving selectivity of reaction.
Description
Technical field
The invention belongs to field of catalyst preparation, more particularly to a kind of reduction-state precious metal integer catalyzer with non-homogeneous pore passage structure, is mainly used in the anthraquinone anthraquinone hydrogenation reaction for preparing hydrogen peroxide process.
Background technology
Hydrogen peroxide, also known as hydrogen peroxide, are a kind of important industrial chemicals, have industrially just been produced early in 19 middle of century, are one of main essential chemistry products in the world.With becoming more and more important for the growth of social need, especially ecological environmental protection, hydrogen peroxide becomes an important chemicals.Used as a kind of oxidant, bleach, disinfectant, polymerization initiator and cross-linking agent, it is widely used in the numerous areas such as papermaking, weaving, chemicals synthesis, military project, electronics, food processing, medicine, cosmetics, environmental conservation, metallurgy.Water and oxygen are produced after decomposing due to hydrogen peroxide, to environment non-secondary pollution, belongs to green chemical.In the production of hydrogen peroxide, countries in the world are most commonly anthraquinone.
Anthraquinone technique is anthraquinone derivative autoxidation method, and it is made into working solution with appropriate organic solvent dissolving operation material-anthraquinone alkyl derivative, in the presence of a catalyst, anthraquinone hydrogenation is reduced with hydrogen, hydrogen anthraquinone is generated, the oxidation of the latter Jing air or oxygens obtains H2O2, while hydrogen anthraquinone is oxidized to anthraquinone.Then, the H in working solution is extracted with water2O2, it is separated to obtain H2O2Aqueous solution；Can also further distill refined, obtain high concentration H2O2, raffinate Jing process after return to hydrogenation stage recycle.
Hydrogen effect is an important indicator in anthraquinone technique, and it directly determines the scale of hydrogen peroxide plant.Because anthraquinone selective hydrogenation is typical gas-liquid-solid three phase catalytic reaction process, imitate and selectivity to obtain higher hydrogen, it is necessary to can effectively control the outstanding effect between hydrogen, liquid phase reactor thing and catalyst surface.That realizes said process at present has slurry bed system and fixed bed, slurry bed system（US6306356, US5399333, CN1088885A）It is that solid catalyst particle is suspended in liquid medium, then passing to gas makes it be scattered in liquid, mix with medium, reaction focus should not be produced, but due to catalyst granules it is less, and it is more to rub between catalyst, the problems such as big catalyst attrition, catalyst and reactants separate can be caused difficult and follow-up processing procedure is affected.
For the problem for overcoming oar state bed to exist, fixed bed is also widely used in the technical process of hydrogen dioxide solution production by anthraquinone process, in fixed bed, the duct that catalyst buildup is formed is irregular, cause liquid and other skewness, channel and the short circuit of fluid are inevitably produced, here it is liquid reactants, gas and catalyst surface can not be fully contacted, causes catalyst utilization to reduce.In addition, because the pore distribution of catalyst is uneven, the velocity contrast that reactant spreads in different ducts is larger, may result in a part of reaction depth inadequate, and in addition your a part of reaction depth is excessive, the situation for causing the activity and selectivity of catalyst to reduce.
Integer catalyzer is the monolith support being made up of passage that is regular, repeating separation mutually, and catalytic active component is evenly distributed in the inner surface in duct in the form of thin layer.Compared to the irregular space piled up between other beaded catalysts, integer catalyzer has the passage of same shape and length, therefore logistics is identical by the resistance drop of bed, ensure that the distribution that logistics passes through bed is uniform, there is the identical time of staying and reaction condition in bed so as to reach logistics, simultaneously integer catalyzer has very big specific surface, ensure that what product can be quickly diffuses out, the by-product for avoiding deep reaction occurs, and improves the activity and selectivity of reaction.
A kind of preparation method of the integer catalyzer for anthraquinone hydrogenation process is disclosed in patent US6207128 of AKZO Nobel companies, the catalyst carrier adopted in patent is inactive ceramic, then apply on the surface of ceramics after being covered with silicon oxide or aluminium oxide etc., using the upper active metal component of method load of chemical plating.Above-mentioned method for preparing catalyst process is complicated, step is more, influence process factor is more, and the repeatability of catalyst preparation and production cost aspect also need to improve.
CN104368336A discloses a kind of integer catalyzer that hydrogen peroxide process is produced for amyl anthraquinone and preparation method thereof.It is that then auxiliary agent and active metal component on step load, eventually pass reduction and obtain invention catalyst using inert ceramic monolith.The catalyst has an advantage of integer catalyzer, but still has that preparation process is more, noble metal dosage is big and the low deficiency of catalyst choice.
CN104368374A discloses a kind of high dispersive integer catalyzer for hydrogen peroxide synthesis and its preparation method and application.It is, using inert ceramic monolith, then to load upper molecular sieve-oxide complex as support modification, then substep auxiliary agent and active metal component, eventually pass reduction and obtain invention catalyst.The hydrogen effect of the catalyst is improved significantly, but still has that preparation process is more, noble metal dosage is big and the low deficiency of catalyst choice.
In prior art, general integer catalyzer used is uniform pore size structure, namely in reaction, flow velocity of the reactant in duct is constant, but with the carrying out of reaction, reactant content is constantly reduced in reaction system, under conditions of same flow velocity, it is difficult to reach higher conversion level, causes that side reaction occurs because catalyst initial activity is too high when starting, conversion level is made because flow velocity is too fast not enough to the later stage, that is, the result that the activity and selectivity for reacting is reduced.
The content of the invention
For the deficiencies in the prior art, the invention discloses non-homogeneous duct integer catalyzer of a kind of anthraquinone hydrogenation and preparation method thereof, the catalyst has non-homogeneous duct, is applied to the anthraquinone hydrogenation process for preparing hydrogen peroxide, it is ensured that the selectivity of reaction is improve while catalyst reaction activity.
The non-homogeneous duct integer catalyzer of anthraquinone hydrogenation of the present invention, the area ratio of the opening I and opening II at the duct two ends of catalyst is 1：1.1~1：100, preferably 1：2~1：10, the one or both being open in duct sectional area continuous way increase or the staged increase between I and opening II is combined；Described continuous way increase can be that the continuous increase of straight line or the one or both in the continuous increase of curve are combined；The shape of opening I or opening II can be circular, oval or polygon, circular；The shape in the duct section between opening I and opening II can be one or more in circular, oval or polygon, circular；Duct section is preferably identical with the shape of opening I or opening II, and further preferred duct section, opening I are identical with opening II three's shape.
The duct mesh number of catalyst of the present invention（Refer to the number of one square inch of endoporus on the section in duct）For 50 ~ 500, preferably 100 ~ 300.
Integer catalyzer of the present invention is made up of the carrier with integer catalyzer shape and active component, one or more combination of the active component in palladium, platinum, ruthenium, rhodium and iridium, preferably palladium, active component accounts for the 0.01% ~ 5% of catalyst gross mass in terms of metal simple-substance, preferably 0.05% ~ 2%, more preferably 0.1% ~ 1%, balance of carrier.
The preparation method of the described carrier with integer catalyzer shape is prepared according to prior art, and according to the shape and size in duct mould is selected.Carrier matrix can be various refractory materials, for example Kaolin, clay, silicon oxide, zirconium oxide, magnesium oxide, Calcium Carbonate and aluminium oxide etc., preferably gama-alumina.By taking gama-alumina as an example, preparation method is as follows：Aluminum hydroxide solid elastomer powder, pore creating material, peptizer and water are sufficiently mixed into into plastic paste, extrusion is pasted placed in pressing mold into non-homogeneous multi-pore channel overall structure, through being dried with after calcination process, certain height is intercepted as monolithic catalyst support along vertical channel direction；The preparation method of the aluminum hydroxide solid elastomer powder can be aluminum sulfate method or carbonizatin method, preferably carbonizatin method.The pore creating material can be polyvinyl alcohol, white carbon black, cellulose, sesbania powder, methylcellulose, starch etc., preferably methylcellulose.The peptizer can be the material that can make mixture peptization, such as organic acid or mineral acid, preferably mineral acid, more preferably nitric acid.The hole shape and density of the mould can be designed as needed.Described drying condition is 20 ~ 200 DEG C, preferably 80 DEG C ~ 150 DEG C, 0.5 hour ~ 48 hours, preferably 1 hour ~ 12 hours；Roasting condition is 300 DEG C ~ 1000 DEG C, and preferably 400 DEG C ~ 800 DEG C, roasting time is 0.5 hour ~ 8 hours, preferably 1 hour ~ 4 hours.
The preparation method of the non-homogeneous duct integer catalyzer of anthraquinone hydrogenation of the present invention, including following content：
（1）By with impregnation process in the carrier of integer catalyzer shape solution of the immersion containing active component, through being dried with after calcination process, oxidized catalyst is obtained；
（2）By the oxidized catalyst of gained through reduction, then it is dried under inert atmosphere, obtains the non-homogeneous duct integer catalyzer of anthraquinone hydrogenation.
Step（1）The active component presoma is Palladous chloride., Palladous nitrate., chloroplatinic acid, one or more in nitric acid Asia platinum, ruthenic chloride, rhodium nitrate and iridium chloride etc., preferably Palladous chloride., the percent concentration containing active component solution（Metal simple-substance meter）Determined according to the saturated water absorption and the active metallic content of needs load and the height of carrier of carrier.
Step（1）The described impregnation process time is 0.1 hour ~ 48 hours, preferably 0.5 hour ~ 12 hours；Described baking temperature is room temperature ~ 200 DEG C, and preferably 80 DEG C ~ 150 DEG C, drying time is 0.5 hour ~ 48 hours, preferably 1 hour ~ 12 hours；Described sintering temperature is 300 DEG C ~ 1000 DEG C, and preferably 400 DEG C ~ 800 DEG C, roasting time is 0.5 hour ~ 8 hours, preferably 1 hour ~ 4 hours.
Step（2）Described reduction mode can be wet reducing, reducing agent used by wet reducing is one or more in sodium borohydride, hydrazine hydrochloride, formaldehyde, preferably formaldehyde, and reductant concentration can be in interior change in a big way according to condition difference, such as 0.1M ~ 10M, wet reducing condition is：Room temperature ~ 200 DEG C, 0.1 ~ 24 hour；In order that reduction-state catalyst is not oxidized, catalyst needs under an inert atmosphere or is dried under vacuum condition, and drying condition is room temperature ~ 200 DEG C, 0.5 ~ 48 hour.
Catalyst of the present invention is applied in the hydrogenation process of hydrogen dioxide solution production by anthraquinone process, and reaction raw materials logistics direction is along opening I to the opening II directions in catalyst duct, general process conditions：0.1 ~ 2.0MPa of hydrogen partial pressure, 10 ~ 100 DEG C of reaction temperature, 1.0 ~ 50.0h of volume space velocity-1, gas agent volume ratio 10：1~1000:1；Optimum condition is：0.2 ~ 1.0MPa of hydrogen partial pressure, 30 ~ 80 DEG C of reaction temperature, 2 ~ 20h of volume space velocity-1, gas agent volume ratio 20：1~500：1.
Catalyst of the present invention is different from the conventional straight pore passage structure of both ends open area identical rule, but using the non-homogeneous drill way layout of class, catalyst channel openings I areas are little, and catalyst bottom channel openings II areas are big, and the duct area of section being open between I and opening II constantly increases.The catalyst is applied in anthraquinone hydrogenation technique, along opening I to the opening II directions in catalyst duct, because reactant concentration is larger in fresh feed, the activity of catalyst is also higher in reaction raw materials logistics direction, when material flows through catalyst duct, under starting high-speed（Aperture area is little）Reaction, shorten the time of contact of reactant and catalytic active center, in order to avoid excessive even degraded, cracking or carbon deposit etc. the side reaction of the depth that reacts occurs, with the carrying out of reaction, reactant content is constantly reduced in reaction system, and the sectional area in duct is also continuously increased, that is, react is carried out under the continuous air speed for reducing, extend the time of contact of reactant and catalytic active center, it is ensured that the depth of reaction（The activity of catalyst）, while also improving the selectivity of reaction.
Specific embodiment
The preparation process of catalyst of the present invention is further illustrated below by embodiment, but be invention should not be deemed limited in below example.If indicated without special below, degree is weight percentage.
The performance evaluation of catalyst adopts Miniature tube type reactor, and volume is the constant temperature zone that 20 milliliters of integer catalyzer is positioned over reaction tube, and the periphery asbestos cloth filling of catalyst prevents gas and liquid from passing through.Hydrogen and working solution enter into the passage of integer catalyzer by way of cocurrent from the top of reactor（By opening I to the opening II directions in catalyst duct）Hydrogenation reaction is carried out, reaction condition is：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 ratio is 3 in the working solution for being used:1 mixed solvent, diethyl anthraquinone content wherein is 120g/L.Without specified otherwise, catalyst is evaluated using above-mentioned condition.
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 of 30w% salpeter solution be sufficiently mixed into plastic paste, paste placed into hole density for 300/square inch, be highly 10 centimetres, opening I and opening II areas ratio are 1:Extrusion is into multi-pore channel overall structure in 5 pressing mold, and through 150 DEG C of dryings 12 hours, 650 DEG C of roastings 4 hours obtained catalyst carrier；
B) it is 300 to take duct mesh number, and the area ratio of the I and opening II that is open is 1:5, the highly cellular gamma oxidation aluminium block for 10 centimetres, in being totally immersed into the aqueous solution of 0.5Mol/L Palladous chloride .s, impregnate 5 minutes under room temperature, take out the solution that after-blow goes out in duct remaining, in 120 DEG C of dryings 6 hours, 450 DEG C of roastings 2 hours, repetition is secondary, obtains oxidized catalyst;
C) by step a）The oxidized catalyst of gained, in putting into the formalin of 0.2M, is kept for 4 hours at 75 DEG C, takes out the solution that after-blow goes out in duct remaining, and in a nitrogen atmosphere 120 DEG C of dryings 6 hours, obtain catalyst, and numbering is E-1;
D) catalyst composition analysis and reactivity worth evaluation experimental are carried out, appreciation condition is it has been observed that the results are shown in Table 1.
Embodiment
2
With embodiment 1, difference is the differences such as used metal species, content, the mesh number of carrier, the area ratio of carrier duct upper and lower side opening and reducing condition to method for preparing catalyst, uses reducing agent for hydrogen, reducing condition：Hydrogen Vapor Pressure 2MPa, 300 DEG C of temperature, 4 hours, resulting catalyst numbering was respectively E-2, and actual conditions and reaction result are shown in Table 1.
Embodiment
3~7
Method for preparing catalyst is with embodiment 1, difference is the differences such as area ratio, the shape of carrier openings and the reducing condition of used metal species, content, the mesh number of carrier, carrier channel openings I and opening II, resulting catalyst numbering is respectively E-3 ~ E-7, and actual conditions and reaction result are shown in Table 1.
Comparative example
1
With embodiment 1, difference is that used catalyst carrier pore passage structure is upper and lower side aperture area identical cylindrical duct to method for preparing catalyst, obtains comparative example catalyst, and numbering is respectively C-1, and actual conditions and reaction result are shown in Table 1.
Comparative example
2
With embodiment 1, difference is the ceramic honeycomb block that used catalyst carrier is duct upper and lower side aperture area identical cylindrical duct to method for preparing catalyst, obtains comparative example catalyst, and numbering is respectively C-2, and actual conditions and reaction result are shown in Table 1.
Comparative example
3
Take the alumina globule carrier of a diameter of 2.0mm（Pore volume 0.57ml/g, specific surface area 160m2/ g, proportion 0.52g/ml）, then according to the method for embodiment 1 is impregnated with palladium chloride solution, through being dried with after roasting, upper 0.3% Metal Palladium is loaded, comparative catalyst is obtained, numbering is C-3, and actual conditions and reaction result are shown in Table 1.
The catalyst of table 1 is constituted and evaluation result.
Note： Hydrogen imitates unit：gH2O2/ L working solutions；The each section in carrier duct is regular hexagon；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 comparative catalyst for catalyst of the present invention.
Claims (10)
1. the non-homogeneous duct integer catalyzer of a kind of anthraquinone hydrogenation, it is characterised in that：The area ratio of the opening I and opening II at the duct two ends of catalyst is 1：1.1~1：100, the one or both being open in duct sectional area continuous way increase or the staged increase between I and opening II is combined.
2. according to the catalyst described in claim 1, it is characterised in that：Generally circular in shape, the oval or polygon of opening I or opening II；One or more in generally circular in shape, the oval or polygon in the duct section between opening I and opening II.
3. according to the catalyst described in claim 1 or 2, it is characterised in that：The duct mesh number of described catalyst is 50 ~ 500.
4. according to the catalyst described in claim 1 or 2, it is characterised in that：Described integer catalyzer is made up of the carrier with integer catalyzer shape and active component, one or more combination of the active component in palladium, platinum, ruthenium, rhodium and iridium, active component accounts for the 0.01% ~ 5% of catalyst gross mass, balance of carrier in terms of metal simple-substance.
5. the preparation method of the non-homogeneous duct integer catalyzer of anthraquinone hydrogenation described in a kind of claim 1 or 2, it is characterised in that including following content：（1）By with the carrier of integer catalyzer shape solution of the immersion containing active component, impregnation process, through being dried with after calcination process, obtains oxidized catalyst；（2）By the oxidized catalyst of gained through reduction, then it is dried under inert atmosphere, obtains the non-homogeneous duct integer catalyzer of anthraquinone hydrogenation.
6. in accordance with the method for claim 5, it is characterised in that：Step（1）The active component presoma is Palladous chloride., Palladous nitrate., chloroplatinic acid, one or more in nitric acid Asia platinum, ruthenic chloride, rhodium nitrate and iridium chloride.
7. in accordance with the method for claim 5, it is characterised in that：Step（1）The described impregnation process time is 0.1 hour ~ 48 hours.
8. in accordance with the method for claim 5, it is characterised in that：Step（1）Described baking temperature is room temperature ~ 200 DEG C, and drying time is 0.5 hour ~ 48 hours；Described sintering temperature is 300 DEG C ~ 1000 DEG C, and roasting time is 0.5 hour ~ 8 hours.
9. the non-homogeneous duct integer catalyzer of anthraquinone hydrogenation described in a kind of claim 1 or 2 is applied in the hydrogenation process of hydrogen dioxide solution production by anthraquinone process, it is characterised in that：Opening I to opening II direction of the reaction raw materials logistics direction along catalyst duct.
10. according to the application described in claim 9, it is characterised in that process conditions are：0.1 ~ 2.0MPa of hydrogen partial pressure, 10 ~ 100 DEG C of reaction temperature, 1.0 ~ 50.0h of volume space velocity-1, gas agent volume ratio 10：1~1000:1.
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