CN106669854B - A kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation and preparation method thereof - Google Patents
A kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 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 31
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 210000003850 cellular structure Anatomy 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012224 working solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 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 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- -1 hydrogen anthraquinone Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid 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
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 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
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 206010013786 Dry skin Diseases 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
- 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
- 239000010425 asbestos Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 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
- 230000005484 gravity Effects 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
- 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
- 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
- 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
- 238000000746 purification Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002689 soil 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
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses non-homogeneous duct subregion monolithic catalysts of a kind of anthraquinone hydrogenation and preparation method thereof, it is made of monolithic catalyst support and active component, one of wherein the cellular structure of catalyst and Active components distribution have the property that the area ratio of the opening I at the duct both ends of catalyst and the II that is open are 1:1.1 ~ 1:100, the duct sectional area continous way being open between I and the II that is open increases or staged increases or a combination of both；The catalyst is divided into A, the area B Liang Ge along the duct direction of opening I to opening II, and the height along duct direction in the area A, B is than being generally 1:10 ~ 10:1, and wherein the area A active component is Pd-B, and the area B active component is Ni-W；The preparation method is as follows: the carrier with catalyst shape is taken to impregnate Pd-B and Ni-W active component respectively, then through dry and roasting, catalyst prod is obtained.There is the catalyst non-homogeneous duct the selectivity of reaction is improved while ensure that catalyst reaction activity applied to the anthraquinone hydrogenation process for preparing hydrogen peroxide.
Description
Technical field
The invention belongs to field of catalyst preparation, are integrally catalyzed more particularly to a kind of non-homogeneous duct subregion of anthraquinone hydrogenation
Agent.
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.
Monolithic catalyst is the monolith support being made of channel that is regular, repeating mutually to be mutually separated, and catalytic active component is with thin
The form of 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, monolithic catalyst has the channel of same shape and length, therefore logistics is identical by the resistance drop of bed, ensure that logistics
Distribution by bed is uniform, to reach logistics residence time having the same and reaction condition in bed, together
When monolithic catalyst have very big specific surface, ensure that product cracking can diffuse out, avoid the pair of deep reaction
Product occurs, and improves the activity and selectivity of reaction.
A kind of monolithic catalyst for anthraquinone hydrogenation process is disclosed in AKZO Nobel house journal US6207128
Preparation method, the catalyst carrier used in patent is inactive ceramic, then applies on the surface of ceramics and is covered with silica or oxygen
After changing aluminium etc., upper active metal component is loaded using the method for chemical plating.Above-mentioned method for preparing catalyst process complexity, step
More, influence process factor is more, also needs to improve in terms of the repeatability and production cost of catalyst preparation.
CN104368336 discloses a kind of monolithic catalyst and its preparation side 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 invented by reduction
Catalyst.The catalyst has the advantage of monolithic catalyst, but still that there are preparation steps is more, noble metal dosage greatly and catalyst
The low deficiency of selectivity.
CN104368374 discloses a kind of high dispersive monolithic catalyst and preparation method thereof for hydrogen peroxide synthesis and answers
With.It is then upper molecular sieve-oxide compound is loaded as support modification, then substep auxiliary agent using inert ceramic monolith
And active metal component, finally invention catalyst is obtained by reduction.The hydrogen effect of the catalyst is improved significantly, but still deposits
Preparation step is more, noble metal dosage is big low with catalyst choice etc. insufficient.
General monolithic catalyst used is uniform pore size structure, that is, in reaction, reactant is in duct
Flow velocity be constant, but with the progress of reaction, reactant content is constantly reduced in reaction system, the condition of same flow velocity
Under, it is difficult to reach higher conversion level, leads to that side reaction occurs because catalyst initial activity is too high when starting, to the later period
Keep conversion level inadequate because flow velocity is too fast, that is, the result that the activity and selectivity reacted reduces.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation and its
There is non-homogeneous duct ensure that catalyst applied to the anthraquinone hydrogenation process for preparing hydrogen peroxide for preparation method, the catalyst
The selectivity of reaction is improved while reactivity.
The non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation of the invention is grouped by monolithic catalyst support and active group
At wherein the cellular structure of catalyst and Active components distribution have the property that the opening I at the duct both ends of catalyst and open
The area ratio of mouth II is 1:1.1 ~ 1:100, preferably 1:2 ~ 1:10, and the duct sectional area continous way being open between I and the II that is open increases
One of big or staged increase or a combination of both；The continous way increases can continuously enlarge for straight line or curve is continuous
One of increase or a combination of both；The shape of opening I or the II that is open can be round, ellipse or polygon, circular；
The shape in the duct section being open between I and the II that is open can be one or more of round, oval or polygon, preferably
It is round；Duct section is preferably identical as opening I or the opening shape of II, further preferred duct section, opening I and opening II tri-
Person's shape is identical；The catalyst is divided into A, the area B Liang Ge along the duct direction of opening I to opening II, the area A, B along duct side
To height than be generally 1:10 ~ 10:1, preferably 2:5 ~ 5:2；Wherein the area A active component is Pd-B, and the area B active component is
Ni-W；In terms of metal simple-substance, shared mass percent is 0.1% ~ 3%, preferably 0.2 ~ 2 to Ni in the catalyst；W is in the catalyst
Shared mass percent is 0.1% ~ 3%, preferably 0.2 ~ 2；Shared mass percent is 0.1% ~ 3% to Pd in the catalyst, preferably
It is 0.2 ~ 1；Shared mass percent is 0.1% ~ 3%, preferably 0.2% ~ 1% to B in the catalyst, and surplus is monolithic catalyst load
Body.
The subregion of monolithic catalyst support of the present invention is equal with catalyst, i.e., the area A, B of catalyst is whole
The area A, B of catalyst carrier.
The duct mesh number of catalyst of the present invention (refers to the number of one square inch of inner hole on the section perpendicular to duct
Mesh) it is 50 ~ 500, preferably 100 ~ 300.
The preparation method of carrier of the present invention with monolithic catalyst shape is prepared according to the prior art, root
Stamper mould is selected according to the shape and size in duct.Carrier matrix can be a variety of refractory materials, such as kaolin, viscous
Soil, silica, zirconium oxide, magnesia, 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, peptizing agent and water being sufficiently mixed into plastic paste, pasted placed into
Into pressing mold, extrusion is at non-homogeneous multi-pore channel overall structure, after dry and calcination process, along vertical channel direction interception one
Fixed height catalyst carrier as a whole；The preparation method of the aluminum hydroxide solid elastomer powder can be aluminum sulfate method or carbonization
Method, preferably carbonizatin method.The pore creating material can be polyvinyl alcohol, carbon black, cellulose, sesbania powder, methylcellulose, starch
Deng preferably methylcellulose.The 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 mold can according to need to design.Described
Drying condition be 20 ~ 200 DEG C, preferably 80 ~ 150 DEG C, 0.5 hour ~ 48 hours, preferably 1 ~ 12 hour；Maturing temperature is 300
~ 1000 DEG C, preferably 400 ~ 800 DEG C, calcining time are 0.5 ~ 8 hour, preferably 1 ~ 4 hour.
The preparation method of the non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation of the invention, including following content:
A) area B of the carrier with monolithic catalyst shape (i.e. the area B of monolithic catalyst) is immersed and contains the molten of Ni and W
Impregnation in liquid obtains catalyst precarsor A by dry and calcination process；
B) area A of the carrier with monolithic catalyst shape (i.e. the area A of monolithic catalyst) is immersed and contains the molten of Pd and B
Impregnation in liquid obtains the non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation by dry and calcination process.
It is the aqueous solution of the salt dissolved with Ni and W, such as nickel nitrate and metatungstic acid containing Ni and W solution described in step a)
Ammonium etc., the active metallic content and load that percent concentration (metal simple-substance meter) is loaded according to the saturated water absorption and needs of carrier
The height of body determines that load can complete with a step, can also complete step by step, and a preferably step is completed.
Solution containing Pd and B described in step b) is the aqueous solution of the salt containing Pd and B, for example, palladium chloride and boric acid it is molten
Liquid, the active metallic content and carrier that percent concentration (metal simple-substance meter) is loaded according to the saturated water absorption and needs of carrier
Height determine that load can complete with a step, can also complete step by step, a preferably step is completed.
The impregnation time that step a) is stated is 0.1 minute ~ 2 hours, preferably 0.5 minute ~ 1 hour.
The impregnation time described in step b) is 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 temperature 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 in the hydrogenation process of hydrogen dioxide solution production by anthraquinone process, reaction raw materials logistics direction edge
The extremely opening direction II the opening I in catalyst duct, general process conditions are as follows: 0.1 ~ 2.0MPa of hydrogen partial pressure, reaction temperature 10
~ 100 DEG C, 1.0 ~ 50.0h of volume space velocity-1, gas agent volume ratio 10:1 ~ 1000:1；Optimum condition are as follows: hydrogen partial pressure 0.2 ~
1.0MPa, 30 ~ 80 DEG C of reaction temperature, 2 ~ 20h of volume space velocity-1, gas agent volume ratio 20:1 ~ 500:1.Wherein working solution is anthraquinone
Common working solution in hydrogen peroxide process is produced, generally anthraquinone is dissolved in the mixing formed in heavy aromatics and trioctyl phosphate
The volume ratio of object, heavy aromatics and trioctyl phosphate is 5:1 ~ 1:1, and the concentration of anthraquinone is 80 ~ 150g/L in working solution.The weight
Aromatic hydrocarbons is selected from one of aromatic hydrocarbons that carbon atom number is 8 ~ 11 or a variety of, wherein C9And/or C10The volume of aromatic hydrocarbons accounts for heavy aromatics
95% or more.
Catalyst of the present invention is different from the conventional identical straight cellular structure of rule of both ends open area, but uses class non-
Uniform drill way layout, catalyst channel openings I area is small, and catalyst bottom channel openings II area is big, opening I and opening II it
Between duct area of section constantly increase.The catalyst is applied in anthraquinone hydrogenation technique, and reaction raw materials logistics direction is along catalysis
The opening I in agent duct is to the opening direction II, since reactant concentration is larger in fresh feed, in order to avoid caused by deep reaction
The reaction such as degradation, it is preferred from the opening I high speed (high-speed) in the lesser aperture of catalyst enter in duct with high activity noble metal
Activated centre contact, with the expansion of channel diameter, fluid linear velocity is slower and slower, and apparent back-mixing occurs, and makes to react
The object long period contacts with the general base metal active sites of activity, equally ensure that the depth of reaction, while avoiding secondary anti-
It should occur, the selectivity of reaction can be significantly improved, also considerably reduce the production cost of catalyst.
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 the monolithic catalyst that volume is 20 milliliters (put by microstome
It is placed in the constant temperature zone of reaction tube below), the periphery asbestos cloth filling of catalyst prevents gas and liquid from passing through.Before charging
Catalyst hydrogen reducing, gas agent volume ratio are 300, and temperature is 420 DEG C, are restored 6 hours.Then hydrogen and working solution are by simultaneously
The channel (opening I to the opening direction II) that the mode of stream enters monolithic catalyst from the lower part of reactor 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；Used working solution
The mixed solvent that middle solvent is heavy aromatics and trioctyl phosphate volume ratio is 3:1, diethyl anthraquinone are 120g/ in content wherein
L.There is no specified otherwise, catalyst is all made of above-mentioned condition and 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 300/square inch, height
It is 10 centimetres, top and bottom open area ratio is that extrusion is at multi-pore channel overall structure in the pressing mold of 1:5, by 150 DEG C of dryings
12 hours, 650 DEG C roasted 4 hours, obtained catalyst carrier；
B) taking duct mesh number is 300, and the area ratio of channel openings II and opening I are 5:1, is highly 10 centimetres of honeycomb
Opening 4 cm height part of the one end II (area B) is immersed in 2Mol/L nickel nitrate and 1Mol/L metatungstic acid by shape gamma oxidation aluminium block
It in the aqueous solution of ammonium, 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, in triplicate, obtain nickeliferous monolithic catalyst support, number E-1S;
The 6 cm height parts (area A) of the one end I that is open are immersed in 0.5Mol/ by the E-1S carrier for c) taking step a) to prepare
It in the aqueous solution of L palladium chloride and 0.3Mol/L boric acid, impregnates 5 minutes at room temperature, takes out after-blow and go out solution remaining in duct,
120 DEG C drying 6 hours, 450 DEG C roast 2 hours, repeat it is secondary, obtain the monolithic catalyst of complex function of the present invention, number is
E-1;
D) catalyst composition analysis and reactivity worth evaluation experimental are carried out, 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 active metal component content, impregnating metal
Height, the mesh number of carrier and the cross sectional shape in carrier duct etc. it is different, obtained catalyst number is respectively E-2 ~ E-7,
Actual conditions and reaction result are shown in Table 1.
Comparative example 1
Method for preparing catalyst is with embodiment 1, the difference is that catalyst not subregion, i.e., Metal Distribution is equal on catalyst
Even, comparative example catalyst is obtained, number is respectively C-1, and actual conditions and reaction result are shown in Table 1
Comparative example 2
Method for preparing catalyst is with embodiment 1, the difference is that used catalyst carrier cellular structure is upper and lower
The identical cylindrical duct of end opening area obtains comparative example catalyst, and number is respectively C-2, and actual conditions and reaction result are shown in
Table 1.
Comparative example 3
Method for preparing catalyst is with embodiment 1, the difference is that used catalyst carrier is that duct upper and lower side is opened
The ceramic honeycomb block of the identical cylindrical duct of open area, obtains comparative example catalyst, and number is respectively C-3, actual conditions and
Reaction result is shown in Table 1.
Comparative example 4
Removing the alumina globule carrier that diameter is 2.0mm, (hole holds 0.57ml/g, specific surface area 160m2/ g, specific gravity 0.52g/
Ml), then impregnated according to the method for embodiment 1 with palladium chloride solution, after drying and roasting, load upper 0.3% Metal Palladium,
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:The area catalyst B and the area A (top and the bottom) are highly than (total height containing metal part, centimetre)；The area B metal
Content, (Ni+W) %；The area A tenor, (Pd+B) %；Hydrogen imitates unit: gH2O2/ L working solution；Each section in carrier duct
It 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 catalyst of the present invention
Comparative catalyst.
Claims (9)
1. a kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation, the catalyst is by monolithic catalyst support and active component
Composition, it is characterised in that: the cellular structure and Active components distribution of catalyst have the property that the duct both ends of catalyst
Be open I and be open II area ratio be 1:1.1 ~ 1:100, be open I and be open II between duct sectional area continous way increase or
One of staged increase or a combination of both；The catalyst is divided into A, B two along the duct direction of opening I to opening II
Area, the height ratio along duct direction in the area A, B are 1:10 ~ 10:1, and wherein the area A active component is Pd-B, and the area B active component is
Ni-W；Metal simple-substance meter, shared mass percent is 0.1% ~ 3%, W shared mass percent in the catalyst to Ni in the catalyst
For 0.1% ~ 3%, Pd, shared mass percent is that shared mass percent is 0.1% to 0.1% ~ 3%, B in the catalyst in the catalyst
~ 3%, surplus is monolithic catalyst support.
2. catalyst described in accordance with the claim 1, it is characterised in that: the shape of opening I or the II that is open be round, ellipse or
Polygon；The shape in the duct section being open between I and the II that is open is one or more of round, ellipse or polygon.
3. catalyst described in accordance with the claim 1, it is characterised in that: the duct mesh number of the catalyst is 50 ~ 500.
4. a kind of preparation method of the non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation described in claim 1, feature exist
In including following content: a) immersing in the area B of the carrier with monolithic catalyst shape in the solution containing Ni and W at dipping
Reason obtains catalyst precarsor A by dry and calcination process；B) area A of the carrier with monolithic catalyst shape is immersed and is contained
There is impregnation in the solution of Pd and B, by dry and calcination process, obtains the non-homogeneous duct subregion of anthraquinone hydrogenation and be integrally catalyzed
Agent.
5. according to the method for claim 4, it is characterised in that: the impregnation time described in step a) is 0.1 minute
~ 2 hours；The impregnation time described in step b) is 0.1 minute ~ 2 hours.
6. 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 be 0.5 ~ 48 hour；Maturing temperature is 300 ~ 1000 DEG C, and calcining time is 0.5 ~ 8 hour.
7. according to the method for claim 4, it is characterised in that: the drying temperature of step b) is room temperature ~ 200 DEG C, when dry
Between be 0.5 ~ 48 hour；Maturing temperature is 300 ~ 1000 DEG C, and calcining time is 0.5 ~ 8 hour.
8. a kind of non-homogeneous duct subregion monolithic catalyst of anthraquinone hydrogenation described in claim 1 is in hydrogen dioxide solution production by anthraquinone process
Application in hydrogenation process, it is characterised in that: opening I extremely opening II side of the reaction raw materials logistics direction along catalyst duct
To.
9. applying according to claim 8, it is characterised in that process conditions are as follows: 0.1 ~ 2.0MPa of hydrogen partial pressure, reaction temperature
10 ~ 100 DEG C of degree, 1.0 ~ 50.0h of volume space velocity-1, gas agent volume ratio 10:1 ~ 1000:1.
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| CN103769093A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst and preparation method thereof |
| CN104549246A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Palladium-based hydrogenation catalyst and application of palladium-based hydrogenation catalyst to anthraquinone hydrogenation |
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| CN1424145A (en) * | 2002-12-25 | 2003-06-18 | 天津大学 | Carrier style palladium amorphous alloy catalyst for hydrogenation of anthraquinone |
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