CN106040314A - Preparation and application of coating catalyst using ionic liquid as binder - Google Patents

Preparation and application of coating catalyst using ionic liquid as binder Download PDF

Info

Publication number
CN106040314A
CN106040314A CN201610413058.8A CN201610413058A CN106040314A CN 106040314 A CN106040314 A CN 106040314A CN 201610413058 A CN201610413058 A CN 201610413058A CN 106040314 A CN106040314 A CN 106040314A
Authority
CN
China
Prior art keywords
ionic liquid
coated catalysts
catalyst
preparation
binding agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610413058.8A
Other languages
Chinese (zh)
Other versions
CN106040314B (en
Inventor
闫瑞
闫瑞一
吕兆坡
郭伟
王亚男
白银鸽
钱建国
王蕾
张锁江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201610413058.8A priority Critical patent/CN106040314B/en
Publication of CN106040314A publication Critical patent/CN106040314A/en
Application granted granted Critical
Publication of CN106040314B publication Critical patent/CN106040314B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J23/85—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
    • B01J23/70—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
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten 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
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/64—Pore diameter
    • B01J35/653—500-1000 nm
    • 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
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method of producing a coating catalyst and application thereof. The method of producing the coating catalyst comprises: applying catalyst powder with an active component to an inertial support under the action of ionic liquid, wherein the outer active component of the coating catalyst contains molybdenum oxide, bismuth oxide and other oxides, the inner active component is an inertial support such as aluminum oxide and silicon oxide. During preparation of the catalyst, it is possible to disperse the catalyst powder and ionic liquid jointly (or separately) in ethanol and is sprayed (simultaneously) to an inertial spherical support so as to obtain the coating catalyst. The catalyst forms pores of special distribution after being treated via drying and calcining and the like, has high mechanical strength, and has good reacting performance during acrolein production by propylene oxidation, (methyl) acrylic acid by (methyl) acrolein oxidation and methacrylaldehyde production by isobutylene.

Description

The preparation of a kind of coated catalysts using ionic liquid as binding agent and application
Technical field
The present invention relates to preparation and the application thereof of a kind of coated catalysts with ionic liquid as binding agent, belong to catalyst Preparation and application field.
Background technology
α, β unsaturated aldehyde is prepared in the selective oxidation of alkene and unsaturated acids is the important chemical process in commercial production, its In typical course of reaction have propylene oxidative synthesis acrylic aldehyde, acrolein oxidation acrylic acid synthesizing, isobutylene oxidation synthesizing methyl Acrylic aldehyde and methylacrolein oxidative synthesis methacrylic acid.At present, it is many that catalyst that such reaction uses is mainly molybdenum, bismuth system Component composite metal catalyst and heteropolyacid catalyst, wherein multicomponent O composite metallic oxide catalyst has propylene oxidative synthesis The Mo-Bi-Fe-Co-O catalyst of acrylic aldehyde, the Mo-V-Cu-O catalyst of acrolein oxidation acrylic acid synthesizing and isobutylene oxidation The Mo-Bi-Cs-Fe-O catalyst of synthesizing methyl acrylic aldehyde, heteropolyacid catalyst is methylacrolein oxidative synthesis metering system The Mo-P-V-Cu-O catalyst of acid.At present owing to the specific surface area of such catalyst is more relatively low, difficult forming and active component profit Low by rate, cause its industry to amplify more difficulty.
Patent documentation CN104649875A, CN103769148A, CN104549353A are by using extrusion or compression molding Mode improve the mechanical strength of catalyst, but catalyst activity component utilization rate is relatively low；Patent documentation CN101088608A carries Go out and combine by co-precipitation, ultrasound wave and three kinds of methods of microwave, be prepared for the preferable molybdenum-bismuth-antimony composite oxides of dispersion effect Catalyst, but the active component utilization rate of molding rear catalyst and mechanical strength are the most relatively low.
Patent documentation CN101980781A proposes to add in the catalyst the Organic substance of easy burning-off, by removing when roasting These Organic substances reach the purpose of pore-creating, to improve the pore volume of catalyst.But it is short, alive to there is the life-span in the catalyst of the disclosure report The shortcoming such as property component utilization rate is low.
Patent documentation CN104437476A proposes the method that nebulization prepares catalyst, and it is active that it utilizes aerosol apparatus to contain The solution even application of component is in inert carrier surface, thus improves dispersion and the utilization ratio of catalyst activity component, reaches To the effect of raising catalyst reaction performance, but the active component utilization rate of catalyst is relatively low.
Patent documentation CN104525242A proposes the preparation method of molecular sieve integral type catalyst, and it utilizes painting method It is prepared for molecular sieve coating catalyst, improves the utilization rate of catalyst, but catalyst easily peels off, bad mechanical strength；Patent literary composition Offer CN0185995.8 proposition binding agent by the catalyst coated coated catalysts for preparing on a inert carrier, but this bonding operation Complicated, it is desirable to high, and the catalytic mechanical intensity prepared is relatively low.
Patent documentation CN104801351A utilizes spraying method to prepare coated catalysts, adds macromolecule in preparation process Organic compound, as binding agent, improves the mechanical strength of catalyst and the utilization rate of active component, but its high score used Sub-organic compound molecule amount width, carburizing temperature scope is big, causes coated catalysts selectivity pore-creating difficulty, and at roasting process Middle meeting has remained, and impacts the performance of catalyst；It addition, this macromolecular organic compound is the most anti-with catalyst pulp Should, spraying equipment is required higher, operation complexity.
Compared with macromolecular organic compound, ionic liquid there is physical dimension and the adjustable advantage of chemical property, During preparing coated catalysts with it for binding agent, select the ionic liquid of different structure size, will in roasting process It completely removes and obtains required aperture and pore-size distribution selectively；It addition, according to the change of different catalysts slurry Learning character selects suitable ionic liquid to mix, and uses single fluid spraying, simplifies spraying operation step.Therefore, with ion Liquid prepares, as binding agent, the preparation method that coated catalysts is a kind of great prospect.
Summary of the invention
An object of the present invention is optionally to obtain aperture and pore-size distribution, proposes a kind of with ionic liquid for bonding The preparation method of the coated catalysts of agent.The method selects the ionic liquid of different structure as binding agent, uses spraying legal system Standby coated catalysts, removes after uniform temperature roasting and is entrained in the ionic liquid in outer layer active component, it is thus achieved that different holes Footpath and pore-size distribution, selectively regulate the pore structure of catalyst, and the active component utilization rate and the machinery that improve catalyst are strong Degree.
The two of the purpose of the present invention are the preparation processes simplifying coated catalysts, propose a kind of by catalyst powder and ion Liquid solution mixes, and uses single fluid operational approach to spray, it is thus achieved that low cost, the coated catalysts of favorable reproducibility.
The three of the purpose of the present invention are to provide the purposes of above-mentioned coated catalysts, and this catalyst is used for propylene oxidative synthesis Have excellent when acrylic aldehyde, isobutylene oxidation synthesizing methyl acrylic aldehyde and (methyl) acrolein oxidation synthesis (methyl) acrylic acid Conversion ratio and selectivity.
For reaching object above, the present invention adopts the following technical scheme that
The preparation method of a kind of coated catalysts, comprises the following steps:
A required dissolving metal salts under certain condition, is mixed and added into precipitant by (), obtain catalyst pulp, and The most aging standby.
B the suspension obtained by () drying process (a) under certain condition, obtains required catalyst powder.
C a certain amount of ionic liquid is disperseed in ethanol by (), obtain ionic liquid solution.
D catalyst powder that operation (b) is obtained by () join operation (c) the ionic liquid solution obtained in, To catalyst and the mixed slurry of ionic liquid.
E the mixed slurry obtained in operation (d) is sprayed to, on sphere inert carrier, obtain coated catalysts by ().
F () is placed under uniform temperature is dried obtaining coated catalysts in operation (e).
G the dried catalyst obtained in operation (f) is placed in roasting under certain condition in tube furnace by ().
The compound of each element used in operation (a) need to be dissolved in water, and remaining is without particular restriction, it is possible to use its nitric acid Salt, chloride, acetate etc., the preferably nitrate of metallic element.
The precipitant used in operation (a) is chosen but is not limited to ammonium molybdate, ammonium metavanadate, potassium hydroxide, sodium hydroxide etc., According to the precipitant that different selecting response is optimum.
The drying means used in operation (b), can use pneumatic spray drying, centrifugal spray drying, even evaporate Be dried, sucking filtration is dried, the present invention preferred pneumatic spray drying method, and during spray drying, inlet temperature is 120～240 DEG C, Outlet temperature is 70～160 DEG C.
The particle size range being dried gained catalyst powder in operation (b) controls in 0.1～20 μm, preferably scope to be 2～15 μ m。
Catalyst powder used in operation (d) is 200～10:1 with the mass ratio of operation (c) ionic liquid, preferably 100～50:1, the ionic liquid cognition of too low ratio makes the stickiness of catalyst powder reduce, and is unfavorable for the knot of catalyst and carrier Close, cross a high proportion of ionic liquid and know from experience and the coating in roasting process is easily burst apart cave in, and the cost of catalyst can be increased.
In order to make the catalyst powder in operation (d) preferably disperse, catalyst powder and the quality of ethanol in operation (c) Ratio is 4～0.3:1, preferably 2～0.5:1, and should control water content≤10wt% in ethanol, preferably water content≤5wt%.
Spray gun used in operation (e) is import anticorrosion spray gun, and spraying operation uses single fluid spray pattern.
Spraying equipment used in operation (e) is the small-sized seed-coating machine of test-type, uses blowing hot wind mode to heat, heating temperature Degree is 30～90 DEG C, preferably 50～80 DEG C, and too high temperature can cause coated catalysts to burst apart and uneven, too low temperature Reducing spraying rate, rate of catalyst loss increases, coated catalysts lack of homogeneity.
The drying mode used in operation (f), can be selected for forced air drying, vacuum drying and microwave drying, preferably air blast dry Dry and vacuum drying；Baking temperature is 40～110 DEG C, preferably 60～90 DEG C, and drying time is 2～18 hours, and preferably 4～15 is little Time.
Operation (h) uses the dried catalyst of mode roasting of baking inphases: first paragraph be under inert atmosphere 200～ 550 DEG C of roastings 1～8 hours, sintering temperature preferably 300～450 DEG C, roasting time preferably 2～4 hours；Second segment is oxidisability 240～550 DEG C of roastings 2～10 hours under atmosphere, sintering temperature preferably 300～500 DEG C, roasting time preferably 3～8 hours.
Sphere inert carrier of the present invention mainly includes aluminium oxide, pelelith, molecular sieve, red pottery stone etc., preferably oxygen Changing aluminum and red pottery stone, Carrier diameters is 1～6mm, and water absorption rate is 10～40wt%.
In the present invention, the outer layer active component of obtained coated catalysts and the mass ratio of ball type carrier are 2～0.1: 1, preferably 1.3～0.2:1.
Heretofore described noble gas is optional but is not limited to nitrogen, argon, helium, preferably nitrogen；Described oxidation Property atmosphere refers to the such as oxygen of the gas containing oxidizing substance, or pure oxygen, and preferably oxygen concentration is the gas of 10～30% Mixture, such as air etc..
Dry run of the present invention is primarily to the ethanol removed in coated catalysts；First paragraph roasting process Main Function is the interaction between fortifying catalytic agent powder body and ionic liquid, makes the ionic liquid contacted with catalyst powder Decompose, form certain pore structure, but do not destroy the structure of catalyst；The Main Function of second segment roasting process is oxidation point Solve catalyst, it is thus achieved that required active sites.
Coated catalysts obtained by the present invention can be applicable to propylene oxidative synthesis acrylic aldehyde, acrolein oxidation synthesizing propylene Acid, isobutylene oxidation synthesizing methyl acrylic aldehyde and the reaction system of methylacrolein oxidative synthesis methacrylic acid.Raw material propylene, Acrylic aldehyde, isobutene. or methylacrolein and air or the admixture of gas containing a certain amount of oxygen preheated after, be passed through equipped with The fixed bed reactors of catalyst are carried out purpose product is synthesized.Admixture of gas containing a certain amount of oxygen used, its Oxygen content is 10～50%, and remaining component can be the mixture of one or more noble gases such as nitrogen, helium, argon.
Coated catalysts of the present invention is for propylene oxidative synthesis acrylic aldehyde, acrolein oxidation acrylic acid synthesizing, different The reaction condition of butylene oxidation synthesizing methyl acrylic aldehyde and methylacrolein oxidative synthesis methacrylic acid is shown in example.
Detailed description of the invention
With embodiment, the present invention is described below, but the scope of the present invention should not be limited by the examples.
Catalyst load percentage is defined as follows:
W (catalyst) %=[(quality-carrier quality of coated catalysts)/carrier quality] × 100%
Embodiment 1
The preparation of (a) propylene oxidative synthesis acrylic aldehyde catalyst
Measure 1000mL deionized water, add 1000.0g ammonium molybdate, be placed in 70 DEG C of stirred in water bath and dissolve, treat that it is complete Add 2.9g potassium nitrate and 5.5g cesium nitrate after dissolving, add the Ludox that 573.9g concentration is 40wt%, obtain material A； Measure 150mL deionized water, add 396.9g nine water ferric nitrate, be placed in 70 DEG C of stirred in water bath and dissolve, after it is completely dissolved, Being separately added into 229.0g five water bismuth nitrate again, 480.8g cobalt nitrate hexahydrate, 452.1g six water nickel nitrate, 150.5g concentration are The manganese nitrate aqueous solution of 50wt%, 19.6g nitrate trihydrate lanthanum, and 41.7g antimony oxide, stirring obtains material B；By material B Join under fast stirring in material A, form catalyst pulp, and stir at 65 DEG C aging 2 hours, obtain required catalysis Agent slurry.
Weigh a certain amount of above-mentioned catalyst suspension, this solution is placed on pneumatic spray drying device and carries out spray dried Dry, compressed air flow velocity is 10L/min, and the inlet temperature of spray dryer is 180～200 DEG C, and outlet temperature is 123～128 DEG C, charging pump speed is 450～500mL/h, obtains required catalyst powder, and its mean diameter is 8.0 μm.
Take 3.0g 1-butyl-3-Methylimidazole. acetate to be dissolved in the ethanol that 300g water content is 5wt% and obtain slurry (being designated as slurry A), takes 200g catalyst powder and is dispersed in slurry A, obtain slurry B, and the slurry B obtained is sprayed to seed-coating machine On the alumina balls of the 100g a diameter of 2～3mm of middle progressive rolling movement, in spraying process, the design temperature of seed-coating machine is 70 DEG C, whole Individual intermittent spray process time-consuming 45min altogether, obtains coated catalysts.
The coated catalysts of gained is placed in 80 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, stops 4 hours under 500 DEG C of air atmospheres, finally gives coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: its catalyst load percentage is 28%, abrasion Index is 2.1%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 76% of total pore volume, aperture is 50 ～the pore volume shared by the hole of 500nm accounts for the 42% of total pore volume.
The reaction of (b) propylene oxidative synthesis acrylic aldehyde
Being filled in the fixed bed reactors that internal diameter is 12mm by coated catalysts obtained by 1.2g, catalyst is the most equal The quartz sand of the particle diameters such as filling, with air: propylene: steam=73:10:17 (mol ratio) is as raw material, and air speed is 1200h-1, pressure Power (absolute pressure) be 0.05MPa be reaction condition, at 375 DEG C react 4 hours.
Propylene conversion is defined as follows:
X (propylene) %=[1-(amount of the material of the propylene of the amount/supply of the material of unreacted propylene)] × 100%
Acrylic aldehyde selectivity of product is defined as follows:
S (acrylic aldehyde) %=[amount of the material of the acrylic aldehyde of generation/(amount of the material of the propylene of supply-unreacted third The amount of the material of alkene)] × 100%
Through gas chromatogram on-line analysis and calculate, experimental result be propylene conversion ratio 95.6%, the selectivity of acrylic aldehyde 87.2%.
Embodiment 2
Except changing the 1-butyl-3-Methylimidazole. acetate in embodiment 1 into 1-hexyl-3-Methylimidazole. caproate, Other are prepared the most as described in Example 1, obtain coated catalysts.The load percentage of its catalyst is 31%, and abrasion refers to Number test result is 3.4%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 78% of total pore volume, hole Footpath is that the pore volume shared by the hole of 50～500nm accounts for the 45% of total pore volume.
Carry out the reaction of propylene oxidative synthesis acrylic aldehyde according to method same as in Example 1, at 375 DEG C, react 4 little Time, through gas chromatogram on-line analysis and calculate, experimental result is the conversion ratio 91.1% of propylene, the selectivity of acrylic aldehyde 89.8%.
Embodiment 3
The preparation of (a) acrolein oxidation synthesizing propylene acid catalyst
Measure 500mL deionized water, add 500.0g tetra-water ammonium heptamolybdate, be placed in 70 DEG C of stirred in water bath and dissolve, obtain Solution A；Measure 250mL deionized water, add 129.0g ammonium metavanadate, be placed in 70 DEG C of stirred in water bath and dissolve, obtain solution B； Measure 100mL deionized water, add 52.1g antimony oxide, it is placed in 70 DEG C of stirred in water bath and dissolves, after it is completely dissolved Adding 171.0g nitrate trihydrate copper, 60.0g strontium nitrate and 63.5g ammonium tungstate, stirring and dissolving obtains solution C；Measure 20mL go from Sub-water, adds 9.5g Strong oxdiative potassium, is placed in stirring and dissolving under room temperature, and joining 322.0g concentration after it is completely dissolved is In the Ludox of 40wt%, stirring at normal temperature obtains material D after 15 minutes；Material D is joined in solution A, treats its mix homogeneously After again solution B is added, mix homogeneously, add solution C, stirring forms catalyst suspension.
Weigh a certain amount of above-mentioned catalyst suspension, this solution is placed on pneumatic spray drying device and carries out spray dried Dry, compressed air flow velocity is 10L/min, and the inlet temperature of spray dryer is 170～185 DEG C, and outlet temperature is 93～95 DEG C, Charging pump speed is 500～550mL/h, obtains required catalyst powder, and its mean diameter is 10.0 μm.
Take 3.6g 1-ethyl-3-methylimidazole acetate to be dissolved in the ethanol that 400g water content is 5wt% and obtain slurry (being designated as slurry A), takes 300g catalyst powder and is dispersed in slurry A, obtain slurry B, and the slurry B obtained is sprayed to seed-coating machine On the red pottery stone bead of the 100g a diameter of 3～4mm of middle progressive rolling movement, in spraying process, the design temperature of seed-coating machine is 70 DEG C, Whole intermittent spray process time-consuming 35min altogether, obtains coated catalysts.
The coated catalysts of gained is placed in 80 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, stops 6 hours under 430 DEG C of air atmospheres, finally gives coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: its catalyst load percentage is 38%, abrasion Index is 2.1%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 74% of total pore volume, aperture is 50 ～the pore volume shared by the hole of 500nm accounts for the 39% of total pore volume.
The reaction of (b) acrolein oxidation acrylic acid synthesizing
Being filled in the fixed bed reactors that internal diameter is 12mm by coated catalysts obtained by 1.2g, catalyst is the most equal The quartz sand of the particle diameters such as filling, with air: acrylic aldehyde: steam=36:24:40 (mol ratio) is as raw material, and air speed is 1200h-1, Pressure (absolute pressure) be 0.02MPa be reaction condition, at 280 DEG C react 4 hours.
Product gas chromatogram on-line analysis.
Acrolein conversion rate is defined as follows:
X (acrylic aldehyde) %=[1-(amount of the material of the acrylic aldehyde of the amount/supply of the material of unreacted acrylic aldehyde)] × 100%
Acrylic acid product is optionally defined as follows:
S (acrylic acid)=[amount of acrylic acid material of generation/(amount of the material of the acrylic aldehyde of supply-unreacted third The amount of the material of olefine aldehydr)] × 100%
Through gas chromatogram on-line analysis and calculate, experimental result be acrylic aldehyde conversion ratio 94.8%, acrylic acid selection Property 98.5%.
Embodiment 4
Prepare O composite metallic oxide catalyst powder body with reference to embodiment 3, then use following steps to prepare coating catalysis Agent: take 3.6g tetrapropyl ammonium acetate and be dissolved in the ethanol that 300g water content is 5wt% and obtain slurry (being designated as slurry A), take 300g catalyst powder is dispersed in slurry A, obtains slurry B, and the slurry B obtained is sprayed to progressive rolling movement in seed-coating machine On the red pottery stone bead of 150g a diameter of 3～4mm, in spraying process, the design temperature of seed-coating machine is 60 DEG C, whole intermittent spray Process time-consuming 30min altogether, obtains coated catalysts.
The coated catalysts of gained is placed in 80 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, stops 6 hours under 430 DEG C of air atmospheres, finally gives coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: its catalyst load percentage is 40%, abrasion Index is 3.3%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 81% of total pore volume, aperture is 50 ～the pore volume shared by the hole of 500nm accounts for the 46% of total pore volume.
Carry out the reaction of acrolein oxidation acrylic acid synthesizing according to method same as in Example 3, at 280 DEG C, react 4 Hour, through gas chromatogram on-line analysis and calculate, experimental result is the conversion ratio 98.6% of acrylic aldehyde, acrylic acid selectivity 97.0%.
Embodiment 5
The preparation of (a) isobutene. gaseous oxidation synthesizing methyl acrylic aldehyde catalyst
Measure 3000mL deionized water, add 270.0g ammonium molybdate, be placed in 50 DEG C of stirred in water bath and dissolve, obtain solution A； 292.5g cobalt nitrate, 4.5g potassium nitrate, 4.5g cesium nitrate, 45.0g is added in the aqueous solution of nitric acid that 300mL concentration is 15wt% Ferric nitrate, 90.0g bismuth nitrate and 22.5g cerous nitrate, obtain solution B；Solution B is added dropwise to the solution A under 50 DEG C of stirrings In, after being added dropwise to complete, it being added dropwise over ammonia, regulation pH is to stir at 3.0,50 DEG C aging 8 hours, obtains catalyst suspension.
Weigh a certain amount of above-mentioned catalyst suspension, this solution is placed on pneumatic spray drying device and carries out spray dried Dry, compressed air flow velocity is 8L/min, and the inlet temperature of spray dryer is 220～230 DEG C, and outlet temperature is 135～145 DEG C, charging pump speed is 450～500mL/h, and the mean diameter obtaining catalyst powder is 12 μm.
Take 2.5g tetrapropyl ammonium acetate to be dissolved in the ethanol that 300g water content is 5wt% and obtain slurry (being designated as slurry A), Take 150g catalyst powder to be dispersed in slurry A, obtain slurry B, the slurry B obtained is sprayed to progressive rolling movement in seed-coating machine On the alumina balls of 100g a diameter of 1～2mm, in spraying process, the design temperature of seed-coating machine is 60 DEG C, whole intermittent spray mistake Journey time-consuming 40min altogether, obtains coated catalysts.
The coated catalysts of gained is placed in 70 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, stops 5 hours under 400 DEG C of air atmospheres.Finally give coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: its catalyst load percentage is 35%, abrasion Index is 2.6%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 82% of total pore volume, aperture is 50 ～the pore volume shared by the hole of 500nm accounts for the 49% of total pore volume.
The reaction of (b) isobutylene oxidation synthesizing methyl acrylic aldehyde
Being filled in the fixed bed reactors that internal diameter is 12mm by coated catalysts obtained by 0.6mL, catalyst is upper and lower All quartz sand of the particle diameter such as filling, with air: isobutene .=25:1 (mol ratio) is as raw material, air speed is 9000h-1, pressure is (definitely Pressure) be 0.15MPa be reaction condition, respectively 320 DEG C, react 2 hours at 380 DEG C.
Product gas chromatogram on-line analysis.
The conversion ratio of isobutene. is defined as follows:
X (isobutene .) %=[1-(amount of the material of the isobutene. of the amount/supply of the material of unreacted isobutene .)] × 100%
The selectivity of methylacrolein is defined as follows:
S (methylacrolein) %=[amount of the material of the methylacrolein of generation/(amount of the material of the isobutene. of supply- The amount of the material of unreacted isobutene .)] × 100%
Record isobutene. and be respectively 67.6%, 89.8% at the conversion ratio of 320 DEG C and 380 DEG C, the selection of methylacrolein Property is respectively 77.3%, 75.0%.At 380 DEG C, successive reaction is after 10 hours, and the conversion ratio recording isobutene. is 88.1%, first The selectivity of base acrylic aldehyde is 74.6%.
Embodiment 6
Prepare O composite metallic oxide catalyst powder body with reference to embodiment 5, then use following steps to prepare coating catalysis Agent: take 2.5g tetraethyl ammonium acetate and be dissolved in the ethanol that 300g water content is 15wt% and obtain slurry (being designated as slurry A), take 150g catalyst powder is dispersed in slurry A, obtains slurry B, and the slurry B obtained is sprayed to progressive rolling movement in seed-coating machine On the alumina balls of 100g a diameter of 1～2mm, in spraying process, the design temperature of seed-coating machine is 30 DEG C, whole intermittent spray mistake In journey, seed-coating machine fused glass inside is more serious, and time-consuming 70min, obtains coated catalysts altogether.
The coated catalysts of gained is placed in 70 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, stops 5 hours under 400 DEG C of air atmospheres.Finally give coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: its catalyst load percentage is 16%, abrasion Index is 7.6%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 76% of total pore volume, aperture is 50 ～the pore volume shared by the hole of 500nm accounts for the 33% of total pore volume.
Carry out the reaction of isobutylene oxidation synthesizing methyl acrylic aldehyde according to method same as in Example 5,320 DEG C, 380 Reacting 2 hours at DEG C, the conversion ratio recording isobutene. is respectively 41.3%, 65.8%, and the selectivity of methylacrolein is respectively 69.8%, 74.0%.At 380 DEG C, successive reaction is after 10 hours, and the conversion ratio recording isobutene. is 61.1%, methylacrolein Selectivity be 71.6%.
Embodiment 7
The preparation of (a) methylacrolein oxidative synthesis metering system acid catalyst
Measure 4000mL deionized water, add 490.5g molybdenum trioxide, 18.2g vanadic anhydride, 9.0g tellurium dioxide, 5.4g Uranous oxide, 43.6g mass concentration be 85% phosphoric acid, 24.7g mass concentration be the arsenic acid of 80%, be placed in the water of 98 DEG C Bath is stirred at reflux 1 hour, adds 3.6g cupric phosphate, 2.0g Cu-lyt. and 13.6g copper nitrate, continue return stirring 10 little Time after to navy blue catalyst precursor solution.
Weigh a certain amount of above-mentioned catalyst solution, this solution is placed on pneumatic spray drying device and carries out spray dried Dry, compressed air flow velocity is 8L/min, and the inlet temperature of spray dryer is 130～145 DEG C, and outlet temperature is 73～80 DEG C, Charging pump speed is 450～500mL/h, and the mean diameter obtaining catalyst powder is 4 μm.
Take 4.2g 1-butyl-3-Methylimidazole. acetate to be dissolved in the ethanol that 400g water content is 5wt% and obtain slurry (being designated as slurry A), takes 300g catalyst powder and is dispersed in slurry A, obtain slurry B, and the slurry B obtained is sprayed to seed-coating machine On the alumina balls of the 150g a diameter of 1～2mm of middle progressive rolling movement, in spraying process, the design temperature of seed-coating machine is 60 DEG C, whole Individual intermittent spray process time-consuming 30min altogether, obtains coated catalysts.
The coated catalysts of gained is placed in 75 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 2 hours under 370 DEG C of nitrogen atmospheres, stops 5 hours under 330 DEG C of air atmospheres.Finally give coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: the load percentage of its catalyst is 42%, mill Damaging index is 1.0%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 77% of total pore volume, aperture is Pore volume shared by the hole of 50～500nm accounts for the 41% of total pore volume.
The reaction of (b) isobutene. gaseous oxidation synthesizing methyl acrylic aldehyde
Being filled in the fixed bed reactors that internal diameter is 12mm by coated catalysts obtained by 1.2mL, catalyst is upper and lower All quartz sand of the particle diameter such as filling, with methylacrolein: oxygen: water: nitrogen=5:9:20:90 (mol ratio) as raw material, air speed For 1100h-1, pressure (absolute pressure) be 0.15MPa be reaction condition, at 300 DEG C react 2 hours.
Product n-heptanol absorbs and uses gas chromatographic analysis.
The conversion ratio of methylacrolein is defined as follows:
[1-be (methylacrolein of the amount/supply of the material of unreacted methylacrolein for X (methylacrolein) %= The amount of material)] × 100%
The selectivity of methacrylic acid is defined as follows:
S (methacrylic acid) %=[amount of the material of the methacrylic acid of generation/(material of the methylacrolein of supply The amount of material of amount-unreacted methylacrolein)] × 100%
The conversion ratio recording methylacrolein is 80.6%, and the selectivity of methacrylic acid is respectively 81.1%.
Embodiment 8
Prepare heteropolyacid catalyst powder body with reference to embodiment 7, then use following steps to prepare coated catalysts: to take 5.0g Tetraethyl ammonium acetate is dissolved in the ethanol that 400g water content is 5wt% and obtains slurry (being designated as slurry A), takes 250g catalyst powder Body is dispersed in slurry A, obtains slurry B, the slurry B obtained is sprayed in seed-coating machine the 120g of progressive rolling movement a diameter of 1～ On the alumina balls of 2mm, in spraying process, the design temperature of seed-coating machine is 70 DEG C, and whole intermittent spray process is the most time-consuming 40min, obtains coated catalysts.
The coated catalysts of gained is placed in 75 DEG C dry 5 hours in air dry oven.Again dried catalyst is entered Row roasting, stops 2 hours under 370 DEG C of nitrogen atmospheres, stops 5 hours under 330 DEG C of air atmospheres.Finally give coating catalysis Agent.
Coated catalysts after above-mentioned roasting is carried out Analysis of Physical: the load percentage of its catalyst is 53%, mill Damaging index is 1.1%；Outer layer active component mesoporous be 20～1000nm hole contained by pore volume account for the 84% of total pore volume, aperture is Pore volume shared by the hole of 50～500nm accounts for the 48% of total pore volume.
The reaction of methylacrolein oxidative synthesis methacrylic acid is carried out, at 300 DEG C according to method same as in Example 7 Lower reaction 2 hours, the conversion ratio recording methylacrolein is 89.7%, and the selectivity of methacrylic acid is 86.8%.
Being illustrated by above-described embodiment, the preparation method of this coated catalysts is simple, use variety classes and chain length from Sub-liquid, as binding agent, can selectively obtain required aperture and pore-size distribution, and prepared catalyst has higher resistance to Mill performance, mechanical strength, and this coated catalysts prepares acrylic aldehyde in propylene oxidation, (methyl) acrolein oxidation prepares (first Base) acrylic acid tool and isobutylene oxidation have good reactivity when preparing methylacrolein.

Claims (11)

1. the preparation method of the coated catalysts with ionic liquid as binding agent, it is characterised in that the method is with ionic liquid Body, as binding agent, combines by being co-precipitated, being spray-dried and spray three kinds of methods, obtains the easy modulation of pore structure, machinery by force Degree height, uniformity height good, active and the coated catalysts of good stability.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 1, it is characterised in that Described coated catalysts includes outer layer active component and sphere inert carrier.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 2, it is characterised in that The outer layer active component of described coated catalysts and the mass ratio of sphere inert carrier are 2～0.1:1.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 2, it is characterised in that The outer layer active component of described coated catalysts is preferably but not limited to Fe, Bi, Co, Ni, Cs, Ce, La, Zr, Sb, Sr, W, Sn, K Deng one or two or more element.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 2, it is characterised in that The sphere inert carrier of described coated catalysts is aluminium oxide, pelelith, molecular sieve or red pottery stone, Carrier diameters be 1～ 6mm。
6. according to the preparation method of the coated catalysts with ionic liquid as binding agent in claim 1, it is characterised in that institute The spray dryer inlet temperature stating spray drying process is 120～240 DEG C, and outlet temperature is 70～160 DEG C.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 1, it is characterised in that Described ionic liquid selects ion liquid of quaternaries or glyoxaline ion liquid.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 7, it is characterised in that Described ion liquid of quaternaries formula is [NRaRbRcRd] Z, glyoxaline ion liquid formula is [CnMim] Y, wherein a, b, C, d value 1-4, n value 3-8；Anion Z and Y choose organic acid anions.
The preparation method of the coated catalysts with ionic liquid as binding agent the most according to claim 1, it is characterised in that Described spraying operation uses single fluid spray pattern, and spraying temperature is 30～90 DEG C.
10., according to the preparation method of the coated catalysts with ionic liquid as binding agent described in claim 9, its feature exists The catalyst powder of component described in ethanol, water, ionic liquid and claim 3 is comprised in, described single fluid composition；Wherein, The concentration of ionic liquid is 0.5～5wt%, and water content is≤10wt%.
11. according to the preparation method of the coated catalysts with ionic liquid as binding agent described in claim 1, and its feature exists Prepare acrylic aldehyde in, described coated catalysts for propylene oxidation, isobutylene oxidation prepares reaction and the (first of methylacrolein Base) acrolein oxidation prepares (methyl) acrylic acid.
CN201610413058.8A 2016-06-13 2016-06-13 The preparation and application of a kind of coated catalysts using ionic liquid as binder Active CN106040314B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610413058.8A CN106040314B (en) 2016-06-13 2016-06-13 The preparation and application of a kind of coated catalysts using ionic liquid as binder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610413058.8A CN106040314B (en) 2016-06-13 2016-06-13 The preparation and application of a kind of coated catalysts using ionic liquid as binder

Publications (2)

Publication Number Publication Date
CN106040314A true CN106040314A (en) 2016-10-26
CN106040314B CN106040314B (en) 2018-09-18

Family

ID=57171270

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610413058.8A Active CN106040314B (en) 2016-06-13 2016-06-13 The preparation and application of a kind of coated catalysts using ionic liquid as binder

Country Status (1)

Country Link
CN (1) CN106040314B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110560079A (en) * 2019-07-31 2019-12-13 浙江新和成股份有限公司 Catalyst for preparing acrylic acid or acrolein and preparation method thereof
CN110743558A (en) * 2019-08-16 2020-02-04 中国科学院过程工程研究所 Preparation method and application of eggshell type composite metal catalyst
CN111403805A (en) * 2020-04-28 2020-07-10 深圳先进技术研究院 Composite solid electrolyte, preparation method thereof and lithium ion battery
CN106902873B (en) * 2017-03-24 2020-12-22 河南大学 Arsenic vanadium oxygen cluster based polyacid ionic liquid and preparation method and application thereof
CN112547082A (en) * 2019-09-25 2021-03-26 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof
CN114054100A (en) * 2020-08-06 2022-02-18 中国科学院过程工程研究所 Preparation and application of doped composite oxide catalyst
CN114887627A (en) * 2022-05-14 2022-08-12 中海油天津化工研究设计院有限公司 Preparation method of coating catalyst for preparing acrylic acid by acrolein oxidation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012034839A1 (en) * 2010-09-17 2012-03-22 Jbach Gmbh Method for catalytically producing formic acid
CN102553624A (en) * 2012-01-05 2012-07-11 中国科学院过程工程研究所 Preparation method of catalyst for synthesizing methacrylic acid
US20130244867A1 (en) * 2009-05-19 2013-09-19 Bayer Materialscience Ag Catalyst for producing n-substituted carbamates, and the preparation and application of the same
CN104801351A (en) * 2015-04-01 2015-07-29 万华化学集团股份有限公司 Preparation method of coating catalyst and coating catalyst prepared by using method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130244867A1 (en) * 2009-05-19 2013-09-19 Bayer Materialscience Ag Catalyst for producing n-substituted carbamates, and the preparation and application of the same
WO2012034839A1 (en) * 2010-09-17 2012-03-22 Jbach Gmbh Method for catalytically producing formic acid
CN102553624A (en) * 2012-01-05 2012-07-11 中国科学院过程工程研究所 Preparation method of catalyst for synthesizing methacrylic acid
CN104801351A (en) * 2015-04-01 2015-07-29 万华化学集团股份有限公司 Preparation method of coating catalyst and coating catalyst prepared by using method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106902873B (en) * 2017-03-24 2020-12-22 河南大学 Arsenic vanadium oxygen cluster based polyacid ionic liquid and preparation method and application thereof
CN110560079A (en) * 2019-07-31 2019-12-13 浙江新和成股份有限公司 Catalyst for preparing acrylic acid or acrolein and preparation method thereof
CN110560079B (en) * 2019-07-31 2022-01-25 浙江新和成股份有限公司 Catalyst for preparing acrylic acid or acrolein and preparation method thereof
CN110743558A (en) * 2019-08-16 2020-02-04 中国科学院过程工程研究所 Preparation method and application of eggshell type composite metal catalyst
CN112547082A (en) * 2019-09-25 2021-03-26 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof
CN112547082B (en) * 2019-09-25 2023-08-29 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof
CN111403805A (en) * 2020-04-28 2020-07-10 深圳先进技术研究院 Composite solid electrolyte, preparation method thereof and lithium ion battery
CN114054100A (en) * 2020-08-06 2022-02-18 中国科学院过程工程研究所 Preparation and application of doped composite oxide catalyst
CN114054100B (en) * 2020-08-06 2023-01-10 中国科学院过程工程研究所 Preparation and application of doped composite oxide catalyst
CN114887627A (en) * 2022-05-14 2022-08-12 中海油天津化工研究设计院有限公司 Preparation method of coating catalyst for preparing acrylic acid by acrolein oxidation
CN114887627B (en) * 2022-05-14 2023-12-12 中海油天津化工研究设计院有限公司 Preparation method of coating catalyst for preparing acrylic acid by acrolein oxidation

Also Published As

Publication number Publication date
CN106040314B (en) 2018-09-18

Similar Documents

Publication Publication Date Title
CN106040314A (en) Preparation and application of coating catalyst using ionic liquid as binder
JP5458088B2 (en) Method for producing nanocrystalline bismuth-molybdenum mixed oxide
JP3834087B2 (en) Method for producing catalyst, outer shell catalyst, method for producing acrylic acid, acrolein and methacrolein, and method for catalytic gas phase oxidation
US8008227B2 (en) Mixed oxide catalysts for the catalytic gas-phase oxidation of olefins and processes for producing them
JP2011518659A (en) Shell catalyst containing multi-metal oxides containing molybdenum, bismuth and iron
US20040147393A1 (en) Preparation of a multimetal oxide composition
US8716523B2 (en) Catalyst for use in production of methacrylic acid and method for manufacturing the same
KR20040045496A (en) Method for Producing Ammoxidation Catalyst
EP1138385A1 (en) Catalyst
JP4204327B2 (en) Method for producing acrylic acid by vapor phase oxidation of propene with heterogeneous catalyst using molecular oxygen in reaction zone
CN104437581B (en) Catalyst for acrylic acid synthesis and preparation method of catalyst
US6762148B2 (en) Catalyst process of making
CN104661745A (en) Composite oxide catalyst, method for producing same, and method for producing unsaturated nitrile
US20120283088A1 (en) Mixed Oxide Catalysts Made of Hollow Shapes
JP2013169482A (en) Catalyst for producing acrylonitrile, method of producing the same, and method of producing acrylonitrile using the same
JP4119748B2 (en) Method for producing an annular shell catalyst and use of the catalyst for producing acrolein
JP2011516256A (en) Shell catalyst containing molybdenum-containing multimetallic oxide
JP2008212779A (en) Method for producing molybdenum-, bismuth-, iron-, and silica-containing composite oxide catalyst
CN105921154B (en) A kind of preparation method of more metal composite oxide catalysts and its catalyst of preparation and application thereof
JP2016531739A (en) High performance polyoxometalate catalyst and method for producing the same
US11007506B2 (en) Method for preparing mixed metal oxide catalysts containing molybdenum and bismuth
TWI417138B (en) Oxide catalyst, process for producing acrylic acid and process for producing water-absorbent resin
JP4255542B2 (en) Method for producing acrolein oxidation catalyst
CN106732634A (en) One kind is used to produce the catalyst and preparation method of unsaturated aldehyde (acid)
CN106582677B (en) A kind of preparation method and its usage of more metal composite oxide catalysts

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant