CN109529862A - A kind of nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation - Google Patents
A kind of nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation Download PDFInfo
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- CN109529862A CN109529862A CN201811430276.8A CN201811430276A CN109529862A CN 109529862 A CN109529862 A CN 109529862A CN 201811430276 A CN201811430276 A CN 201811430276A CN 109529862 A CN109529862 A CN 109529862A
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- methacrylaldehyde
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- -1 Molybdenum compound ammonium molybdate Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000005078 molybdenum compound Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229930182817 methionine Natural products 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical class [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical class C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- 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—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of nano-hollow microspherical catalysts to prepare the application in methacrylaldehyde, nano-hollow microspherical catalyst, including active constituent and carrier in propylene oxidation, and carrier is nano titania tiny balloon, and the weight of carrier is the 10% ~ 45% of catalyst weight.The present invention is because nano titania tiny balloon has high-specific surface area and hollow structure, therefore the catalyst after loading can obtain biggish specific surface area, catalytic inner has more pore structures simultaneously, and reaction causes the catalyst of carbon distribution that can more effectively remove carbon remover by calcining for a long time, by catalyst active component and this it is carrier loaded after roast available finished catalyst again, finished catalyst specific surface area is 40 ~ 100 m2/g.The catalyst is applied in the industrial production that propylene oxidation prepares methacrylaldehyde, prepares methacrylaldehyde with high catalytic activity and catalytic life for propylene oxidation.
Description
Technical field
This patent is related to the preparation method that a kind of propylene oxidation prepares methacrylaldehyde catalyst, belongs to the preparation of catalyst and answers
Use field.Prepared catalyst prepares the research of methacrylaldehyde for propylene oxidation.
Background technique
Methacrylaldehyde is the primary raw material for synthesizing the costly substance of diversified economy, the selective oxidation of alkene in modern chemical industry
Preparation a, b unsaturated aldehyde and unsaturated acids are important chemical process.Main production purposes can be used to close methacrylaldehyde at present
At methionine and other Propenal derivatives, methionine is widely used in the feed product of aquaculture animal, to animal synthetic proteins
Matter has great role, and the market demand of methionine still has larger notch at present；Methacrylaldehyde passes through reaction synthesis 1,3-PD
Elastic fibrous material ptt well can also be synthesized by reacting with terephthalic acid (TPA), therefore can bring very big economic benefit.
Current catalyst most common on the market is Mo-Bi series catalysts, passes through the transition metal member such as addition Fe, Co, Ni
The alkali metal elements such as element, Na, K improve the catalytic performance of catalyst with the catalytic active component of rugged catalyst.
Prepared by the report that methacrylaldehyde has numerous patents for propylene oxidation, mentions and adopting in Chinese patent CN101402044A
The catalytic effect of catalyst is improved with the physical mixed of different activities ingredient；Chinese patent ZL201210412591 uses molybdenum bismuth
Series catalysts, methacrylaldehyde one-way yield reach 75% or more；Chinese patent CN103739467A is improved by molybdenum bismuth series catalysts,
Methacrylaldehyde and acrylic acid yield reach 92% or more.The ratio and carrier that the present invention passes through change active component and inert carrier
Constituent achievees the purpose that improve catalyst activity.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of nano-hollow microspherical catalyst and its preparations
Method, with the application for preparing methacrylaldehyde for propylene oxidation.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of nano-hollow microspherical catalyst, including active constituent and carrier,
The active constituent group becomes Mo12BiaFebCocNidTieXfYgZhOx；
Wherein, at least one of X K, Mn, Mg, Na, V, Cr, Al；
Y is at least one of Te, Sn, Pb, Pt, Sr；
Z is at least one of Sb, Cs, As, Se；
The value range of a is 0.3~6.5,
The value range of b is 0.5~5.0,
The value range of c is 1.0~12.0,
The value range of d is 0.05~10.0,
The value range of e is 0.1~10.0,
The value range of f is 0.01~0.5,
The value range of g is 0.01~0.3；
The value range of h is 0.01~0.2,
X is the oxygen atomicity for meeting catalyst each element chemical valence,
It is characterized in that, the carrier is nano titania tiny balloon, the quality of carrier is catalyst quality
10%~45%.
In above-mentioned nano-hollow microspherical catalyst, the diameter of the nano titania tiny balloon is 150-
350nm, specific surface area 100-300m2/g。
The preparation method of above-mentioned nano-hollow microspherical catalyst includes following steps:
(1) nano titania tiny balloon is taken, is put into the deionized water solution of the compound dissolved with molybdenum element, is surpassed
Sound stir process make its be uniformly mixed obtain slurry A；
(2) compound containing bismuth, iron, cobalt element is taken to be dissolved into water and obtain B；
(3) it takes X, Y, Z compound to be dissolved in deionized water, obtains C；
(4) C is slowly added to be sufficiently stirred to obtain D in B, then D is added in A and obtains mixed catalyst slurry
Material；
(5) catalyst pulp that above-mentioned steps obtain is uniformly mixed it in certain degree Celsius of stirring certain time, simultaneously
PH is adjusted with ammonium hydroxide；
(6) catalyst pulp after stirring removes moisture removal in certain temperature drying, and with molding machine extrusion molding catalyst
Particle, and calcine a period of time.
In above-mentioned preparation method, the addition manner of molybdenum element described in step (1) is molybdenum compound ammonium molybdate.
In above-mentioned preparation method, bismuth in step (2), iron, cobalt element addition manner be respectively bismuth nitrate, nitric acid
Iron, cobalt nitrate.
In above-mentioned preparation method, the temperature of step (5) described stirring is 60~80 DEG C, and mixing time is 0.5~2h,
Adjusting pH is 5~6.4.
In above-mentioned preparation method, drying temperature is 100~130 DEG C in step (6)；The size of extrusion molding catalyst
It is highly the central column particle of 3.5~5mm for 3~5mm of outer diameter, 1~1.5mm of internal diameter；Calcination temperature is 480~520 DEG C, is forged
The burning time is 2~3h.
Above-mentioned nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation.
The method for preparing methacrylaldehyde using above-mentioned nano-hollow microspherical catalyst, include the following steps: with propylene, air,
For vapor as raw material, the volume ratio of propylene and air is 1:7~1:10, and the volume ratio of propylene and vapor is 1:1.2~1:
2, reaction temperature is 330~380 DEG C, and reaction pressure is normal pressure, and reaction velocity is 600~1500h-1, in the above conditions, raw material
It is contacted with nano-hollow microspherical catalyst, generates methacrylaldehyde.
Compared with prior art, the invention has the following beneficial effects:
The present invention is because nano titania tiny balloon has high-specific surface area and hollow structure, urging after load
Agent can obtain biggish specific surface area, while catalytic inner has more pore structures, and reaction causes to accumulate for a long time
The catalyst of carbon can more effectively remove carbon remover by calcining, by catalyst active component and this it is carrier loaded after roast again can
To obtain finished catalyst, finished catalyst specific surface area is 40~100m2/g.The catalyst is applied in propylene oxidation preparation third
In the industrial production of olefine aldehydr, prepared by methacrylaldehyde with high catalytic activity and catalytic life for propylene oxidation.
Specific embodiment
Embodiment 1:
Weigh 500 grams of (NH4)6Mo7O24·4H2O, which is added in 1000 grams 60 degrees Celsius of warm water, sufficiently to be dissolved, and is added
225 grams of nano titania tiny balloon stirs to form material A.
By 140 grams of Bi (NO3)3·5H2O is sufficiently dissolved into 120 grams of 60 degrees Celsius of hot water, adds 200 grams of Fe
(NO3)3·9H2O, 247.5 grams of Co (NO3)2·6H2O, 225 grams of Ni (NO3)2·6H2O is sufficiently stirred dissolution and forms material B.
By 1.5 grams of KNO3It is dissolved in 5 grams of 60 DEG C of warm water and obtains C.
C is added in B and obtains D.By D be slowly added dropwise into A and at a temperature of 75 DEG C stirring ammonium hydroxide 80mL be added adjust
PH to 6 aging 90 minutes, is subsequently placed in drying removal most of moisture in 110 degrees Celsius of baking ovens, is then squeezed with extrusion shaping machine
Compact dimensions are outer diameter 4mm, internal diameter 1.2mm out, are highly the central column particle of 4mm, are subsequently placed under 500 degrees Celsius of Muffle furnace
Roasting 180 minutes.
Embodiment 2~6:
By adding different elements or changing each element ratio, synthesize difference according to the identical method of embodiment 1
Catalyst, the constituent and evaluation result of the catalyst of synthesis table 2 below and table 3 are listed.
Because it is smaller that this evaluates fixed bed single tube caliber used, therefore preformed catalyst is carried out simple crushing, crosses and screen
The about 8 big small catalyst particles of mesh are taken, fixed bed evaluation condition is as follows:
1. fixed bed single tube reactor, internal diameter 9mm, catalyst filling length 300mm.
2. reaction pressure is normal pressure.
3. reaction temperature is 360 degrees Celsius.
4. raw material ratio is propylene: air: vapor=1:8:1.5
5. reaction velocity is 600h-1。
6. 1000 hours a length of when reaction.
Product after reaction obtains data using gas-chromatography FID on-line analysis by the online sample introduction of six-way valve.
The conversion ratio of propylene and the selectivity of product are calculated using normalization method
Ai=1 × fr × Cn × A ' i
Selecti%=Ai/ ∑ Ai × 100%
Conv C3H6%=∑ Ai/ (∑ Ai+AC3H6in products)
Yield Yield i%=Selecti × Conv C3H6× 100%
Wherein, Ai is the relative quantity of product i；A ' i is the peak area that gas-chromatography obtains product i；Fr is using propylene as base
Quasi- correction factor；Cn is the nitrogenous number of reactant or product.
The correction factor of Cucumber can be obtained by pertinent literature:
Table 1: correction factor of the different products relative to propylene
| Substance | C2H6 | C3H8 | CH3CHO | CH3COOH | CH2CHCHO | ACR |
| fr | 3 | 2 | 5.42 | 4.54 | 2.7 | 5.32 |
Table 2
Table 3
Claims (8)
1. a kind of nano-hollow microspherical catalyst, including active constituent and carrier,
The active constituent group becomes Mo12BiaFebCocNidTieXfYgZhOx；
Wherein, at least one of X K, Mn, Mg, Na, V, Cr, Al；
Y is at least one of Te, Sn, Pb, Pt, Sr；
Z is at least one of Sb, Cs, As, Se；
The value range of a is 0.3 ~ 6.5,
The value range of b is 0.5 ~ 5.0,
The value range of c is 1.0 ~ 12.0,
The value range of d is 0.05 ~ 10.0,
The value range of e is 0.1 ~ 10.0,
The value range of f is 0.01 ~ 0.5,
The value range of g is 0.01 ~ 0.3；
The value range of h is 0.01 ~ 0.2,
X is the oxygen atomicity for meeting catalyst each element chemical valence,
It is characterized in that, the carrier is nano titania tiny balloon, the quality of carrier be catalyst quality 10% ~
45%。
2. nano-hollow microspherical catalyst according to claim 1, which is characterized in that the nano titania is hollow micro-
The diameter of ball is 150-350nm, specific surface area 100-300m2/g。
3. the preparation method of nano-hollow microspherical catalyst described in claim 1, it is characterised in that include following steps:
(1) nano titania tiny balloon is taken, is put into the deionized water solution of the compound dissolved with molybdenum element, ultrasound is stirred
Mix processing make its be uniformly mixed obtain slurry A；
(2) compound containing bismuth, iron, cobalt element is taken to be dissolved into water and obtain B；
(3) it takes X, Y, Z compound to be dissolved in deionized water, obtains C；
(4) C is slowly added to be sufficiently stirred to obtain D in B, then D is added in A and obtains mixed catalyst pulp；
(5) catalyst pulp that above-mentioned steps obtain is uniformly mixed it in certain degree Celsius of stirring certain time, while using ammonia
Water adjusts pH；
(6) catalyst pulp after stirring removes moisture removal in certain temperature drying, and with molding machine extrusion molding catalyst granules,
And calcine a period of time.
4. preparation method according to claim 3, which is characterized in that the addition manner of molybdenum element described in step (1) is
Molybdenum compound ammonium molybdate.
5. preparation method according to claim 3, which is characterized in that the addition manner of bismuth, iron, cobalt element in step (2)
Respectively bismuth nitrate, ferric nitrate, cobalt nitrate.
6. preparation method according to claim 3, which is characterized in that the temperature of step (5) described stirring is 60 ~ 80 DEG C,
Mixing time is 0.5 ~ 2h, and adjusting pH is 5 ~ 6.4.
7. preparation method according to claim 3, which is characterized in that drying temperature is 100 ~ 130 DEG C in step (6)；It squeezes
The size of preformed catalyst is 3 ~ 5mm of outer diameter, 1 ~ 1.5mm of internal diameter out, is highly the central column particle of 3.5 ~ 5mm；Calcination temperature
It is 480 ~ 520 DEG C, calcination time is 2 ~ 3h.
8. nano-hollow microspherical catalyst described in claim 1 prepares the application in methacrylaldehyde in propylene oxidation.
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