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CN103772178B - Method for preparing unsaturated acid from unsaturated aldehyde - Google Patents

Method for preparing unsaturated acid from unsaturated aldehyde Download PDF

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Publication number
CN103772178B
CN103772178B CN201210404852.8A CN201210404852A CN103772178B CN 103772178 B CN103772178 B CN 103772178B CN 201210404852 A CN201210404852 A CN 201210404852A CN 103772178 B CN103772178 B CN 103772178B
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catalyst
catalyzer
layer
internal layer
concentration
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CN103772178A (en
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王学丽
景志刚
谢元
颉伟
常晓昕
胡晓丽
蒋满俐
葛汉青
刘肖飞
李平智
蔡小霞
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Petrochina Co Ltd
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    • 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
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • 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
    • B01J23/888—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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • 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)

Abstract

The invention relates to a method for preparing unsaturated acid from unsaturated aldehyde, which adopts a fixed bed reactor, wherein the reactor is divided into S parts from a reaction raw material inlet to a reaction raw material outlet1Segment and S2Segment, S1The section is filled with Mo-V series double-layer catalyst with the concentration of the inner layer higher than that of the outer layer, S2The stage reactor contains a catalyst having a double-layer structure, the catalyst having a double-layer structure and having main compositions represented by general formulae and (ii) from the inner layer to the outer layer of the catalyst, respectively. MoaVbNicCudMeSigOx（ⅰ），Moa′VbNic′Cud′SrfWhMiNjSikOy(ii), the process can produce acrylic acid stably for a long period.

Description

A kind of unsaturated aldehyde prepares the method for unsaturated acid
Technical field
The present invention relates to a kind of method that unsaturated aldehyde prepares unsaturated acid, especially acrylic acid is prepared in acrolein selectivity oxidation.
Background technology
Current industrial main employing propylene two-step oxidation style prepares vinylformic acid, and first propylene catalytic gas phase oxidation generates propenal, and propenal is reoxidised into vinylformic acid.Acrolein oxidation reaction is strong exothermal reaction, focus can be produced in beds, the heat gathered instantaneously is constantly accumulated, to the loss of catalyst activity component be caused, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause the formation aggravating by product because of over oxidation reaction, even cause uncontrolled reaction, make sintering of catalyst.
The appearance of " progress of oxidative synthesis acrylic acid process and catalyzer " (petrochemical complex, the 39th volume the 7th phase in 2010) social focus also can make catalyst damage evil, shortens the work-ing life of catalyzer.For 80,000 tons/year of acroleic acid devices, propylene oxidation is prepared in acrolein reaction device needs more than 2.5 ten thousand tubulation, and acrolein oxidation is prepared in vinylformic acid reactor also needs more than 2.5 ten thousand tubulation, loads propenal, acrylic acid catalyst more than 100 ton altogether.More than 50000 reaction tubes, the filling of catalyzer ensures that not filling sky has certain difficulty, if because focus is crossed high catalyst and sintered very soon, again change agent more in a short time, it is huge for can envisioning its financial loss; In addition, carry out under cryogenic as much as possible for propenal, acrylic acid production, because reaction needed salt bath heating, it maintains the energy consumption of producing also is huge spending; Due to the generation of focus, require high temperature resistant to reaction tubes tubing, for up to ten thousand reaction tubess, tubing expense is exactly the very large cost of item.Therefore, if effectively suppress the generation of beds focus, huge economic benefit can be brought to large-scale commercial production.
Industrial propenal or methacrolein oxidation prepare the reaction unit mainly many reaction tubess of corresponding unsaturated aldehyde, ensureing that catalyzer is not sintered, under the prerequisite of long service life, improve selectivity and object product yield as far as possible, conservation, even if if feed stock conversion, vinylformic acid yield improve 0.1 ~ 0.5 percentage point, the amount of the product obtained increases with the level of hundreds of ~ thousands of tons of, and its economic benefit is also very considerable.
At present, there is multiple method can reduce or avoid gathering and peroxidation of focus, can from the viewpoint of the improvement two of the improvement of reaction unit and catalyzer.In catalyzer, as: Japanese Patent Laid-Open 04-217932 propose a kind of suppress focus appearance or focus on the method for hot polymerization collection, namely by the multiple catalyzer with different possessive volume of preparation, and from the mode that unstripped gas inlet side reduces to outlet side catalyzer possessive volume, fill reaction tubes successively, but the possessive volume of catalyzer is by the restriction of reaction tube diameter, and it is also very difficult multiple catalysts to be filled into reaction tubes.US200421442A is mixed into heat resistanceheat resistant point in the catalyst and forms catalyzer and inert substance with by catalyst dilution, and the method for tubulose made by catalyzer by Japanese Patent Publication 36739/1987.Further, the catalyst loading that unstripped gas ingress reduces by active ingredient.CN01121191.1 provides one to prepare acrylic acid, and namely by the gas of tube-shell type fixed bed reactor catalytic gas phase oxidation containing propenal, the method effectively inhibits the generation of focus and prepared vinylformic acid with high yield.The feature of described method is each reaction tubes to be axially divided at least three conversion zones along it, with packed catalyst first conversion zone near gas inlet higher than the catalyst activity of filling adjacent second conversion zone, and with the packed catalyst conversion zone subsequently of different activities level, catalyst activity is raised continuously to pneumatic outlet side from the second conversion zone.This catalyst reaction temperatures is higher, and substantially more than 240 DEG C, hot(test)-spot temperature is more than 300 DEG C.CN200510007929.8 provides the acrylic acid catalyzer of a kind of catalyzing propone aldehyde gaseous oxidation system, described catalyzer comprises molybdenum and vanadium, also comprise at least one volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyzer can reduce the temperature of hot spot, and the reduction of the reaction efficiency of suppression thermal destruction.Specific practice is, comprise by making the volatility toxic component of specified quantitative and originally had in highly active catalyzer, catalytic activity declines momently, can reduce the temperature of hot spot.CN97104224.1 is loaded in after on carrier by catalytic active component being divided, and calcine the catalyzer of load sharing to suppress the generation of focus, the median size of catalyzer is 4 ~ 16mm, and the median size of carrier is 3 ~ 12mm, and calcining temperature is 500 ~ 600 DEG C.US2009415167A discloses a kind of method of producing unsaturated aldehyde and unsaturated acid, two or more catalyst layer is loaded in reactor, each catalyst layer by different holes density and or aperture size the shaping packed catalyst of catalytic active component, particular table area from reactor inlet to outlet catalytic active component increase gradually with control punch density and or aperture size, and then inhibited reaction focus.Even if under CN200410007263.1 provides a kind of condition forming focus, activity, selectivity, life-span are all excellent, demonstrate the catalyzer of stability for a long time, and use the method for producing acrylic acid of this catalyzer.Said catalyzer is following general formula (1) Mo av bw ccu da eb fc go xrepresent.A is at least one selected from cobalt, nickel, iron, lead, bismuth, and B is at least one selected from antimony, niobium, tin, and C is at least one selected from silicon, aluminium, titanium, zirconium.This catalyzer can not effectively suppress being emerged of beds focus.Under higher hot-spot conditions, reaction unit requires to have superpower resistance to elevated temperatures, and reaction later separation, to absorb process operations expense also very high.CN200410048021.7 discloses a kind of O composite metallic oxide catalyst, and catalyzer is by 1. molybdenum, vanadium, copper main active component and 2. requisite at least by stable component and the 3. composite oxides that form of nickel, iron, silicon, aluminium, basic metal, alkaline-earth metal of antimony and titanium.2. and be 3. wherein can composite oxides that within the scope of 120 DEG C to 900 DEG C prepared by roasting.This catalyzer shows the permanent stability under high reactivity and good selectivity.CN201010180103.2 discloses a kind of multilayer composite metal oxide catalyst, and the composition of this O composite metallic oxide catalyst can by formula M o abi bni ccs dcu eti fa gb hc io jrepresent, described O composite metallic oxide catalyst has multilayered structure, reduces successively from internal layer parent to each concentration of element of skin, even if catalyzer initial reaction activity is very high, this catalyzer effectively can reduce single tube reactor localized heat and gather, and suppresses being emerged of focus.This catalyzer mainly controls the focus produced because catalyzer initial activity is high, but selectivity and the yield of object product have much room for improvement, and under the mixed airflow such as propylene, water vapour long period Scouring Condition, catalyst surface active component has part to run off, and affects catalyst activity and stability.CN201010180184.6 provides a kind of three layers of multi-metal-oxide catalyst and preparation method thereof, this catalyzer contains Multimetal oxide as active ingredient, this catalyzer is applicable to propylene or corresponding unsaturated aldehyde is produced in selective isobutene oxidation, the organism due to unstripped gas middle and high concentration effectively can be suppressed to contact with the catalyzer initial stage form higher focus and generate a large amount of by products, improve catalyst selectivity.These three layers of catalyzer are easy to come off through long-term operation skin, increase catalyst bed layer resistance, thus cause activity decrease.And the selectivity of this catalyzer object product and yield also have much room for improvement.
All there is a problem in the method that above-mentioned suppression focus produces, the catalyzer be filled in reaction tubes is diluted from the inlet to the outlet all in a variety of manners, both after having made catalyst runs some cycles, activity decrease also can not change thinning ratio, catalyzer also cannot reoffer higher activity, not only load, dismantle, be separated, reclaim catalyzer and make troubles, and the reactive behavior of catalyzer can be reduced, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.
CN102039143A discloses the preparation method that a kind of acrolein oxidation prepares acrylic acid catalyzer, a) preparation method of composite oxide coating: be dispersed in water/organic phase mixed system by the water-soluble metal salt containing Mo, V, W, Cu, Sb composition in 30-100 DEG C; Organic solvent and water weight ratio is kept to be 5 ~ 50%; Reaction generates composite oxides presoma slurries; Catalyst activity component is obtained again through distillation, oven dry, roasting; B) the main component of above-mentioned active ingredient, be selected from Mo, V, Cu, W, Sb wherein one or more; Wherein active ingredient following formula represents: Mo av bcu cw dsb eo f, in formula, a ~ f represents the atomic ratio of each element, and as a=12, b=0 ~ 10, c=0 ~ 6, d=0 ~ 10, e=0 ~ 0.5, f is the value meeting other element oxide states.This catalyzer adopts the mixed system preparation of water and lower alcohol, catalyzer has higher specific surface area and special microtexture, there is comparatively high-ratio surface and difficult drop-off, and bearing capacity can reach 50% and more than, solve shorter problem in application type catalyzer work-ing life.
CN1647854 discloses a kind of catalyzer of selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid, and the composition general formula of this catalyzer is: x (Mo 12p ak bsb ccu das ea fd gq ho imO j)/yZ, Z is carrier dilution thermal conducting agent; Mo, P, K, Sb, Cu and As are respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic; A represents at least one element in tungsten W, vanadium V, niobium Nb, iron Fe and plumbous Pb; D represents at least one element in boron, gallium Ga, indium In, germanium Ge and silicon Si; Q represents at least one element in rubidium Rb, caesium Cs and thallium Tl, and this invention improves the activity and selectivity of catalyzer on the one hand by adding Sb, Cu and As; On the other hand by adding MoO 3improve the thermostability of catalyzer, heat conductivility and physical strength with carrier heat conduction thinner, effectively inhibit activities component heteropolyacid salt decomposition and reduce beds hot(test)-spot temperature, avoid the loss of Mo and As, extending catalyst work-ing life.Similar also has CN101579631, CN101850259ACN101850259A.CN101274279 discloses a kind of oxide catalyst, Mo 12v gw hcu ie jf kg lh mo y(3) (wherein Mo is molybdenum, and V is vanadium, and W is tungsten, Cu is copper, and E is at least the element being selected from cobalt, nickel, iron, lead and bismuth, and F is at least the element being selected from antimony, niobium and tin, G is at least the element being selected from silicon, aluminium, titanium and zirconium, and H is selected from alkali-metal element, and O is oxygen; G, h, i, j, k, l, m and y are the corresponding atomic ratios of V, W, Cu, E, F, G, H and O, it is respectively 2≤g≤15,0≤h≤10,0 < i≤6,0≤j≤30,0≤k≤6,0≤l≤60,0≤m≤6, and y is the numerical value determined by the oxidation state of respective element).This invention in order to solve to cause due to the appearance of catalyzer focus its active or selectivity due to sintering etc. significantly reduced problem.This invention is such technical solution problem, the catalyzer loaded in reactor has specific particle size distribution, space between granules of catalyst can by evenly and expand, the appearance of the extra high temperature spot in local (focus) in catalyst layer can be suppressed and do not reduce propenal or acrylic acid output, and propenal or vinylformic acid can be obtained long-term and stably.This catalyst particle size relative standard deviation is 0.02 ~ 0.20.Because industrial propenal, acrylic acid production loaded catalyst are larger; want that the particle size relative standard deviation ensureing catalyzer is 0.02 ~ 0.20; the large-scale production of catalyzer can be restricted undoubtedly, can because of the irregularity of catalyst size as useless agent process in possible production process.And tons of catalyzer, screening particle size relative standard deviation is that the work of 0.02-0.20 is also wasted time and energy very much.
CN200980112659.3 discloses a kind of coated catalysts comprising following component: (a) carrier, b () comprises molybdenum oxide or forms the first layer of precursor compound of molybdenum oxide, (c) comprises the second layer of the poly-metal deoxide containing molybdenum and other metal of at least one.The molybdenum oxide of preferred the first layer is MoO 3, the poly-metal deoxide of the second layer is the poly-metal deoxide that general formula I I represents: Mo 12bi acr bx 1 cfe dx 2 ex 3 fo y.This catalyzer is the application type catalyzer comprising carrier.Goal of the invention suppresses heterogeneously catalysed partial gas phase oxidation propenal to be acrylic acid coated catalysts inactivation, has the inactivation performance of improvement.This invention is not clearly recorded catalyzer and is used for catalyzing propone oxidation acrolein, acrylic acid reactivity worth evaluating data, such as transformation efficiency, selectivity, yield etc.CN1121441 discloses a kind of for by propenal or carry out oxidizing reaction containing the gas of acrolein gas and a kind of molecule-containing keto in vapour phase and produce acrylic acid catalyzer, this catalyzer comprises (A) a kind of composite oxides, there is molybdenum and vanadium as base stock, and be suitable for by vapor phase catalytic oxidation propenal to produce vinylformic acid, (B) solid peracid, its strength of acid (Ho) is not more than-11.93 (Ho≤-11.93).This invention adopts molybdenum vanadium type composite oxides to combine with the solid acid that a kind of strength of acid is no more than-11.93, improves the low temperature high activity of catalyzer.CN200610073671.6 discloses a kind of carrier of gas-phase oxidation catalyst, and described carrier comprises its strength of acid (H 0) meet inequality :-5.6≤H 0the solid acid of≤1.5; A kind of gas-phase oxidation catalyst, it comprises carrier above and comprises molybdenum and the vanadium composite oxides as basal component, and described composite oxides are carried on described carrier; Vinylformic acid is prepared by the catalytic gas phase oxidation of propenal and molecular oxygen.Prepare a method for carrier above, described method comprises the strength of acid (H by regulating the calcining temperature in the preparation being contained in the solid acid in carrier to control solid acid 0), to meet inequality :-5.6≤H 0≤ 1.5.CN200510059468.9 discloses a kind of vinylformic acid catalyst for producing, it is characterized in that, the oxide compound of the metallic element composition represented at following formula M oaVbWcCudOx (1) and/or composite oxides are must in the vinylformic acid catalyst for producing of catalyst component, need to control the face side that tungsten is this catalyzer partially, and/or copper is the core side of this catalyzer partially, to improve catalyst activity.Tungsten is the face side of this catalyzer partially, and/or copper is that the core side of this catalyzer is difficult to accurately control partially.
In addition, under the high temperature conditions, in catalyzer, part active ingredient molybdenum loses from catalyst surface because of distillation.The mixed airflows such as propenal, air (oxygen), nitrogen and water vapour wash away the loss of active component that also can make in catalyzer.For suppressing the loss of molybdenum distillation to cause active decay, CN1121504, by mixing copper component and having the zirconium of specified particle diameter and specific surface area and/or titanium and/or cerium, can suppress dissipation effect and the over reduction of molybdenum composition; CN1445020 adds the effect that a small amount of tellurium plays stable free molybdic oxide and copper molybdate crystalline structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is with molybdenum, vanadium, copper, tungsten and/or niobium for main ingredient, and the composite oxides formed with other element or its hopcalite form the loss that catalyzer suppresses molybdenum.
CN1328988 provides one to prepare acrylic acid, and namely by the gas of tube-shell type fixed bed reactor catalytic gas phase oxidation containing propenal, the method effectively inhibits the generation of focus and prepared vinylformic acid with high yield.The feature of described method is each reaction tubes to be axially divided at least three conversion zones along it, with packed catalyst first conversion zone near gas inlet higher than the catalyst activity of filling adjacent second conversion zone, and with the packed catalyst conversion zone subsequently of different activities level, catalyst activity is raised continuously to pneumatic outlet side from the second conversion zone.This invention needs preparation to have multiple catalyzer of different catalytically active level, and by the packed catalyst second of in lowest activity level conversion zone.With the conversion zone of packed catalyst then the second conversion zone, activity level is made to increase continuously from the second conversion zone.This invention " activity " refers to the performance that catalyzer transforms propenal.Therefore the catalyzer showing the conversion of higher (or lower) propenal is called the catalyzer with higher (or lower) activity.This invention is prepared the multiple method with the catalyzer of different activities level and is comprised: (1) regulates kind and/or the quantity of catalytic active component, (2) what regulate catalyzer occupies volume, (3) when adopting loaded catalyst, regulate the charge capacity of catalytic active component, (4) regulate the maturing temperature during catalyst preparing.
CN1343192 relates to one and propenal gas phase catalyst is oxidized to acrylic acid, wherein initial action gaseous mixture is catalyst fixed bed by one, wherein load >=150l (the s.t.p.)/lh of propenal in initial action gaseous mixture, catalyst fixed bed setting is in two spatially in reaction zone A, B in succession, and the temperature of reaction zone B is higher than the temperature of reaction zone A.Wherein the temperature of reaction zone A is 230-270 DEG C, and the temperature of reaction zone B is 250-300 DEG C, at least exceeds 5 DEG C than the temperature of reaction zone A simultaneously.This invention meets the requirement of load mainly through the temperature controlling reaction zone A, B, and technological operation is loaded down with trivial details, and process cost is high.Heterogeneously catalysed partial gas phase oxidation of propylene is formed acrylic acid by the open one of CN101384538.According to described method, initial action mixture comprises cyclopropane as impurity, and vinylformic acid by separating by Crystallization Separation mode after be converted to condensation mutually from product gas mixture.CN1874984 mono-kind is prepared the method for unsaturated aldehyde in shell-tube type reactor by alkene by fixed-bed catalytic partial oxidation reaction, described reactor comprises the reaction zone of preparing unsaturated aldehyde, this reaction zone comprises two-layer or multilayer Catalytic Layer, each Catalytic Layer is all filled with the shaped catalyst product as secondary particle, secondary particle wherein in each Catalytic Layer is formed by the primary particle with varigrained catalytic active component, and the granularity controlling the primary particle of described catalytic active component reduces to reactor outlet from reactor inlet to make this granularity.This invention is hot issue in order to control catalyzer, the catalyst pellets sublayering filling that this catalyzer adopts particle size to vary in size to suppress focus.Namely the focus with top temperature is preferably included by the Catalytic Layer that the shaped catalyst product with maximum primary size of particles is filled.The preferred 10-150 micron of Primary particle size of shaped catalyst product.
Under CN1283604 provides the condition existed containing the oxide catalyst of Mo-Bi-Fe compound, propenal and acrylic acid is produced by vapor phase propylene oxide, described packed catalyst is in multitubular reactor of fixed bed, and the method can generate propenal and vinylformic acid with high stable yield in long-time.The method is characterized in that and configure in each tubular reactor of two or more reaction zone vertically, each district's filling different catalysts, namely fill out Bi and/or Fe content catalyzer from gas inlet end to gas outlet end and reduce with the ratio of Mo content.
Heterogeneously catalysed partial gas phase oxidation of propylene is formed acrylic acid by the open one of CN101384538.According to described method, initial action mixture comprises cyclopropane as impurity, and vinylformic acid by separating by Crystallization Separation mode after be converted to condensation mutually from product gas mixture.
The invention provides a kind of method that unsaturated aldehyde prepares unsaturated acid, more specifically, provide a kind of acrolein selectivity to be oxidized acrylic acid processed, react under low temperature, high-load condition, and improve selectivity and the yield of object product as far as possible, to obtain larger economic benefit.
Summary of the invention
The object of this invention is to provide a kind of method that unsaturated aldehyde prepares unsaturated acid, especially propenal or Methylacrylaldehyde selective oxidation produce the method for corresponding unsaturated acid.Vinylformic acid is prepared in the oxidation of particularly suitable acrolein selectivity.
Unsaturated aldehyde prepares a method for unsaturated acid, adopts fixed-bed reactor, and reactor is along reaction raw materials entrance to outlet point S 1section and S 2section, S 1section is equipped with the Mo-V system double-layer catalyst (catalyzer as CN201110265250.4) of internal layer concentration higher than outer concentration, S 2reactor is in-built has bilayer structure catalyzer (I) for section, and this catalyzer (I) has bilayer structure, mainly forms respectively by general formula (I) and (II) expression from catalyst inner layer to skin.
Mo aV bNi cCu dM eSi gO x（ⅰ），Mo a′V b′Ni c′Cu d′Sr fW hM iN jSi kO y（ⅱ）
Wherein: Mo is molybdenum, V is alum, and Ni is nickel, and Cu is copper, and Sr is strontium, and W is tungsten, and Si is silicon, and silicon is the carrier added in catalyzer, and M is at least one element be selected from calcium, titanium, zirconium; N is selected from least one element in boron, rubidium, lanthanum; O is oxygen; A, b, c, d, e, a ', b ', c ', d ', f, g, h, i, j, k represent each Elements Atom ratio respectively, wherein a, a ' is a number of 12-14, one number of b, b ' be 0.2-5, one number of c, c ' be 0.5-4, one number of d, d ' be 1-5, e is a number of 0.05-3, f is a number of 0.1-2.5, g is a number of 5-40, h is a number of 0.05-3, and i is a number of 0.05-3, and j is a number of 0.05-3, k is a number of 0.2-30, and x, y are the numerical value determined by the oxygen of each oxide compound.
Acrylic acid is prepared in a kind of acrolein selectivity oxidation, the processing condition of oxidizing reaction are not limited especially, as following processing condition can be adopted: reaction raw materials propenal, water, oxygen enter reactor after preheater more than 160 DEG C preheatings, salt bath heating, salt temperature 240 ~ 260 DEG C, preferably 240 ~ 250 DEG C; Air speed 800 ~ 2200h -1, preferably 800 ~ 1800h -1, feed composition: propenal 8 ~ 12 volume %, water vapour 11 ~ 17%, oxygen 9 ~ 17 volume %, nitrogen 60 ~ 71 volume %; The present invention loads the Mo-V system double-layer catalyst of internal layer concentration higher than outer concentration along feed(raw material)inlet end to exit end beds ingress to the scope between 1/3 or ingress to 1/2 place, as the catalyzer of CN201110265250.4, the filling scope of catalyzer is not strictly limited, 1/3 of beds can be less than, also can unnecessary 1/3.The filling of residual catalyst bed mainly forms the catalyzer (I) represented by general formula (I) and (II) respectively.Used catalyst active ingredient of the present invention not easily runs off, and water repelling property is good, effectively improves object selectivity of product and yield.
Used catalyst of the present invention has multilayer structure, and outer double-layer structure namely, internal layer catalyst main ingredient is less than outer main ingredient, and in molar content, catalyst outer layer each component concentration concentration ratio internal layer parent is high.The concentration difference of ectonexine can adjust a, b, c, d, e, a ', b ', c ', d ', the Numerical Implementation such as f, g, h, i, j, k, the numerical value as a, b, c, d, e, g is less than the value of corresponding a ', b ', c ', d ', i, k.Or the materials such as different amount silicon-dioxide, aluminum oxide, silicon carbide are added at ectonexine.
The multilayer structure catalyzer that the present invention is used, concentration difference can be achieved by adding the materials such as different amount silicon-dioxide, aluminum oxide, silicon carbide at ectonexine, that is, one or more molar concentration rate internal layer parent in outer silicon-dioxide, aluminum oxide or silicon carbide is low, in molar content, outer each constituent content is higher by 0.1 ~ 30% than this constituent content of internal layer, and preferably 0.1 ~ 18%, more preferably 0.5 ~ 12%.The present invention has bilayer structure, and internal layer also can be called internal layer parent.
Acrolein selectivity oxidation vinylformic acid processed is because temperature of reaction is substantially more than 270 DEG C, and long period is under such pyroreaction condition, and the active ingredient molybdenum in catalyzer is easy to run off because of distillation.N in catalyzer of the present invention preferably lanthanum, lanthanum and molybdenum, nickel, copper, antimony etc. can form stable crystal phase structure, as Cu 2la, LaNi 5, Cu 2la, Cu 5la etc., be conducive to suppressing part active ingredient molybdenum to lose from catalyst surface because of distillation, before and after catalyst reaction, active ingredient molybdenum content is substantially constant, delays active deterioration rate, and catalyst stability is good.Lanthanum and molybdenum, vanadium ratio are suitable, and in logical formula I, N is lanthanum, and i is a number of 0.1 ~ 3.5, and molybdenum is competed in the add membership and vanadium and nickel of too much lanthanum, and such as too much lanthanum adds may affect active phase VMo 3o 11to MoO 3crystallization is shifted, and affects catalyst activity.The preferred lanthanum nitrate in lanthanum source of the present invention.Outer main composition is represented by general formula (II): Mo a 'v b 'ni c 'cu d 'sr fw hm ila jsi ko y(II).
The double-layer catalyst that the present invention uses adopts common preparation method, prepares as adopted following step.
1) by relate to containing Mo, V, Ni, Cu and M compound dissolution and mix, form internal layer parent slurries after carrying out co-precipitation, then add the materials such as silicon-dioxide, aluminum oxide, silicon carbide one or more, drying, shaping, roasting obtains catalyst inner layer parent;
2) outer layer catalyst is prepared according to the method for Kaolinite Preparation of Catalyst internal layer parent, add one or more of the materials such as silicon-dioxide, aluminum oxide, silicon carbide in outer layer catalyst preparation process, make each concentration of element in outer layer catalyst higher than the concentration of this element of internal layer;
3) outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
Used catalyst internal layer parent of the present invention after shaping and skin all need roasting 3 ~ 10h at 300 ~ 550 DEG C after application, compare not the catalyzer of respectively roasting, repeatedly roasting can improve activity and the stability of catalyzer.Ectonexine maturing temperature is preferably identical.Can be open roasting also can be enclosed roasting, calcination atmosphere can be the rare gas elementes such as helium, nitrogen, argon gas.Catalyst layer too thick roasting time easily chap, in order to avoid be full of cracks preferably 55 ~ 120 DEG C of oven dry after application, and then roasting.The outer layer catalyst thickness being coated on internal layer parent is 0.1 ~ 2.0mm, preferably 0.1 ~ 1.5mm.
The compound of each component of used catalyst of the present invention can use the nitrate, ammonium salt, vitriol, oxide compound, oxyhydroxide, muriate, acetate etc. of each element.As ammonium molybdate, nickelous nitrate, strontium nitrate, ammonium paratungstate, nitrocalcite, lanthanum nitrate, zirconium nitrate, ventilation breather, cupric nitrate, boric acid, titanium oxide, rubidium nitrate, zirconium white etc.
After used catalyst internal layer parent slurries of the present invention are dried, the forming methods such as extrusion moulding, granulating and forming, compression molding are usually preferably adopted to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Used catalyst of the present invention preferably uses binding agent when applying, and ectonexine catalyzer is bondd more firm.Under internal layer parent is in rolling condition, sprays binding agent infiltrates surface, then spray the outer layer catalyst powder prepared, also internal layer parent can be put into the outer layer catalyst slurries prepared and carry out rolling coating.Binding agent is selected from one or more in water, alcohols or ethers.Alcohols is as ethanol, propyl alcohol, butanols; Ethers is as ether and butyl ether.
Each layer surface preferably uneven, surface irregularity of used catalyst of the present invention, is conducive to coating, bonds more firm between ectonexine.
The present invention, in order to improve intensity, the efflorescence degree of catalyzer, can to add in glass fibre, graphite, pottery or various whisker one or more in above-mentioned outer layer catalyst.
Used catalyst of the present invention can directly use, and also can be carried on inert support and use.Involved inert support can be the mixture of one or more of aluminum oxide, silicon-dioxide, silicon carbide etc.
Because catalyzer initial reaction activity is very high, so be easy to produce focus or produce heat built-up on fixed bed single tube reactor bed, catalyzer is easy to sintering, and this is very serious concerning loss suitability for industrialized production propenal vinylformic acid.Pass into a certain amount of water vapour in raw material, because specific heat of water is large, a large amount of reaction heat can be taken away, but water vapour input greatly often makes catalyst member active ingredient solution-off and makes activity decrease.Therefore catalyzer is needed to have good water repelling property.The present invention preferably uses two kinds to have double-deck multi-metal-oxide catalyst, at propenal Way in, scope before beds between 1/3 place or front 1/2 place uses internal layer concentration higher than the catalyzer of outer concentration, as the catalyzer of CN201110265250.4, the filling scope of catalyzer is not strictly limited, 1/3 of beds can be less than, also can unnecessary 1/3.Because the active component concentration of catalyst external surface is low, so corresponding activity is also low, therefore effectively can suppress being emerged of focus and gathering of heat, reduce the growing amount of by product (as hydrocarbon), improve the selectivity of object product.Use internal layer concentration lower than the catalyzer of outer concentration at residual catalyst bed, acrolein concentrations opposite inlet is lower, and catalyst activity is high, is more conducive to improving acrylic acid selectivity and yield.And catalyst structure is stablized, and active ingredient not easily runs off.Like this, under high-speed reaction conditions, two kinds have double-deck catalyzer layering filling, reaction bed temperature distribution is more reasonable, (bed temperature declines affects selectivity of catalyst and yield to avoid the reaction bed temperature close to exit end to decline soon, be unfavorable for the steady running of catalyzer long period), catalyzer has good water repelling property, improves selectivity and the yield of object product.
Acrolein selectivity oxidation of the present invention acrylic acid processed, catalyst segments is loaded, and feed(raw material)inlet section is equipped with the Mo-V system double-layer catalyst of internal layer concentration higher than outer concentration, suppresses focus; Remainder bed filling internal layer concentration, lower than the Mo-V system double-layer catalyst of outer concentration, is avoided the reaction bed temperature close to exit end to decline fast, is conducive to improving object product yield and highly selective, long period stably can produces vinylformic acid.
Embodiment
Illustrate that acrylic acid is prepared in acrolein selectivity oxidation with specific embodiment below, but scope of the present invention is not limited to these embodiments.The analytical procedure of product composition adopts this area universal method.
Embodiment 1:
Catalyst preparing
Under agitation condition, take 173.7 grams of ammonium molybdates, ammonium meta-vanadate 12.5 grams, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 21.4 grams of ammonium paratungstates, 28.6 grams of cupric nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active ingredient slurries (a).0.7 gram of titanium dioxide and 89.1 grams of silicon-dioxide are added in active ingredient slurries (a), 80 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating, with 160 DEG C of thermal treatments 3 hours in nitrogen, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion molding, dry rear 450 DEG C of roastings 5 hours for 110 DEG C, obtained catalyst Precursors, this catalyst inner layer parent mainly consists of: Mo 12v 1.3ni 1cu 1.5ti 0.1si 18.1o x(I).
Under agitation condition, get 202.7 grams of ammonium molybdates, ammonium meta-vanadate 21.1 grams, be dissolved in (water temperature more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 4.3 grams of ammonium paratungstates, 49.6 grams of cupric nitrates, 50.1 grams of nickelous nitrates, 2.1 grams of strontium nitrates, 56 grams of lanthanum nitrates are dissolved in (water temperature more than 65 DEG C) in 1000ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain active ingredient slurries (a), 22.1 grams of silicon-dioxide, 1.3 grams of titanium dioxide are added in active ingredient slurries (a), 85 DEG C of strong stirrings carry out the drying of coprecipitation reaction post-heating, with 160 DEG C of thermal treatments 3 hours in nitrogen, 500 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grinding, sieve.This catalyst outer layer mainly consists of: Mo 14v 2.2ni 2.1cu 2.6 'sr 0.1w 0.2ti 0.2la 2.1si 4.5o y(II).
Catalyst inner layer parent is placed in round bottom container, ethanolic soln is sprayed to catalyst Precursors under container rotation condition, stop operating under the condition of fully wetting catalyst inner layer parent, put it into rapidly another rotate be placed with in the round bottom container of outer layer catalyst powder, apply, coat-thickness is at 1.0 ~ 2.0mm, and namely gained catalyzer 105 DEG C obtains catalyzer 1 in 5 hours through 500 DEG C of roastings after drying.Outer field each constituent content is higher by 0.4% ~ 14.7% than this constituent content of internal layer.
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads 12ml CN201110265250.4 catalyzer 3(S along feedstock direction reactor bed 1section), the above-mentioned catalyzer 1 of 23ml or comparative catalyst 1 or 2(S 2section), salt bath heating, salt temperature 245 DEG C.From above-mentioned reaction tubes ingress with air speed 1000h -1enter the mixed gas of propenal 8 volume %, oxygen 12 volume %, water vapour 15 volume %, nitrogen 65 volume %.Mixed gas.24 hours beds S are reacted under the low temperature of 245 DEG C 2section hot localised points temperature 272 DEG C, acrolein conversion rate is 99.1%, acrylic acid selectivity 90.6%, vinylformic acid yield 89.2%.Adopt two kinds of double-layer catalyst segmentation fillings, compare a kind of catalyzer of filling separately, reaction bed temperature calibration is more reasonable, improves object selectivity of product and yield.Comparative example 1,2 selectivity relative mistake, vinylformic acid yield is low.After the oxidizing reaction 1000h of embodiment 1, bed S 2section hot localised points temperature is 270 DEG C ~ 272 DEG C, and acrolein conversion rate is 99.1%, acrylic acid selectivity 90.5%, vinylformic acid yield 89.1%.Catalyst activity component molybdenum etc. not easily runs off, and stable performance, has good water repelling property, and acrolein selectivity oxidizing reaction long period is stably carried out.
Comparative example 1:
With the internal layer parent of catalyzer 1 for comparative catalyst 1, banded extruder extrusion molding is the hollow columnar particle of φ 5 × 5mm, and acrolein selectivity oxidizing reaction is with embodiment 1.React 24 hours S 2section hot localised points temperature 274 DEG C, acrolein conversion rate is 98.5%, acrylic acid selectivity 88.0%, vinylformic acid yield 85.6%.
Comparative example 2:
With the skin of catalyzer 1 for comparative catalyst 2, banded extruder extrusion molding is the hollow columnar particle of φ 5 × 5mm, and acrolein selectivity oxidizing reaction is with embodiment 1.React 24 hours S 2section hot localised points temperature 276 DEG C, acrolein conversion rate is 98.9%, acrylic acid selectivity 87.2%, vinylformic acid yield 85.1%.
Embodiment 2:
The preparation of catalyzer 2
With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, internal layer adds 108.7 grams of silicon-dioxide and 1.2 grams of aluminum oxide, and through banded extruder extruding, rolling is a granulated into the ball shape that diameter is 2mm, and skin adds 11.3 grams of silicon-dioxide.Coat-thickness, at 0.5 ~ 2.0mm, namely obtains catalyzer 2 in 4.5 hours through 500 DEG C of roastings.Catalyzer 2 internal layer parent mainly consists of: Mo 12v 2ni 1.8cu 1ca 0.1si 22.1o x, skin mainly consists of: Mo 13v 4.8ni 3.8cu 2.2sr 0.5w 3ca 0.3rb 0.1si 2.3o y(II).
Outer field each constituent content is higher by 0.3% ~ 12.5% than this constituent content of internal layer.
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads 15ml CN201110265250.4 catalyzer 3(S along feedstock direction reactor bed 1section), the above-mentioned catalyzer (S of 20ml 2section), salt bath heating, salt temperature 250 DEG C.From above-mentioned reaction tubes ingress with air speed 1750h -1enter the mixed gas of propenal 9 volume %, oxygen 13 volume %, water vapour 16 volume %, nitrogen 62 volume %.React 24 hours beds S 2section hot localised points temperature 278 DEG C, acrolein conversion rate is 99.2%, acrylic acid selectivity 91.0%, vinylformic acid yield 89.3%.Adopt two kinds of double-layer catalyst segmentation fillings, compare a kind of catalyzer of filling separately, reaction bed temperature calibration is more reasonable, improves object selectivity of product and yield.
Embodiment 3:
With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, internal layer adds 57.5 grams of silicon-dioxide and 3.6 grams of graphite, and be the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion molding, skin adds 28.5 grams of silicon-dioxide.Coat-thickness, at 0.1 ~ 1.5mm, namely obtains catalyzer 3 in 6 hours through 400 DEG C of roastings.Catalyzer 3 internal layer parent mainly consists of: Mo 12v 0.5ni 2cu 2zr 1.5si 22o x(I); Skin mainly consists of: Mo 14v 2.8ni 4cu 4.8sr 2w 1zr 2.5b 0.1la 1.1si 3.7o y(II).
Outer field each constituent content is higher by 0.3% ~ 8.9% than this constituent content of internal layer.
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads 17ml CN201110265250.4 catalyzer 3(S along feedstock direction reactor bed 1section), the above-mentioned catalyzer of 28ml or comparative example catalyzer (S 2section), salt bath heating, salt temperature 243 DEG C.From above-mentioned reaction tubes ingress with air speed 1450h -1enter the mixed gas of propenal 10 volume %, oxygen 14 volume %, water vapour 15 volume %, nitrogen 61 volume %.React 24 hours, beds S 2section hot localised points temperature 270 DEG C, acrolein conversion rate is 99.2%, acrylic acid selectivity 90.8%, vinylformic acid yield 89.3%.Adopt two kinds of double-layer catalyst segmentation fillings, compare a kind of catalyzer of filling separately, reaction bed temperature calibration is more reasonable, improves object selectivity of product and yield.Comparative example 3 selectivity relative mistake, vinylformic acid yield is low.After embodiment 3 oxidizing reaction 1000h, bed S 2section hot localised points temperature is 268 ~ 270 DEG C, and acrolein conversion rate is 99.1%, acrylic acid selectivity 90.6%, vinylformic acid yield 89.3%.Catalyst activity component molybdenum etc. not easily runs off, and stable performance, has good water repelling property, and acrolein selectivity oxidizing reaction long period is stably carried out.
Comparative example 3:
Independent filling CN201110265250.4 embodiment 3 catalyzer, acrolein selectivity oxidizing reaction is with embodiment 3.React 24 hours S 2section hot localised points temperature 267 DEG C, acrolein conversion rate is 98.3%, acrylic acid selectivity 87.8%, vinylformic acid yield 85.7%.
Embodiment 4:
With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, internal layer adds 77.7 grams of silicon-dioxide and 2 grams of silicon carbide, then through banded extruder extruding, rolling is a granulated into the ball shape that diameter is 2mm, skin adds 6.9 grams of silicon-dioxide.Coat-thickness, at 0.5 ~ 2.0mm, namely obtains catalyzer 4 in 5 hours through 480 DEG C of roastings.Catalyzer 4 internal layer parent mainly consists of: Mo 12v 1.6ni 0.5cu 0.8ti 0.3si 15.8o x(I), skin mainly consists of: Mo 13v 3.8ni 2.5cu 3sr 1w 2ti 0.7rb 0.1la 0.5si 1.4o y(II).
Outer field each constituent content is higher by 0.4% ~ 8.6% than this constituent content of internal layer.
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads 12ml CN201110265250.4 catalyzer 3(S along feedstock direction reactor bed 1section), the above-mentioned catalyzer (S of 23ml 2section), salt bath heating, salt temperature 253 DEG C.From above-mentioned reaction tubes ingress with air speed 2200h -1enter the mixed gas of propenal 11 volume %, oxygen 14 volume %, water vapour 15 volume %, nitrogen 60 volume %.React 24 hours, beds S 2section hot localised points temperature 281 DEG C, acrolein conversion rate is 99.3%, acrylic acid selectivity 91.3%, vinylformic acid yield 89.5%.
Embodiment 5:
Independent loading catalyst 4, acrolein selectivity oxidizing reaction is with embodiment 4.React 24 hours S 2section hot localised points temperature 276 DEG C, acrolein conversion rate is 98.8%, acrylic acid selectivity 88.4%, vinylformic acid yield 86.1%.

Claims (11)

1. unsaturated aldehyde prepares a method for unsaturated acid, adopts fixed-bed reactor, it is characterized in that reactor is along reaction raw materials entrance to outlet point S 1section and S 2section, S 1section is equipped with the Mo-V system double-layer catalyst of internal layer concentration higher than outer concentration, S 2reactor is in-built has bilayer structure catalyzer (I) for section, and this catalyzer (I) has bilayer structure, mainly forms respectively by general formula (I) and (II) expression from catalyst inner layer to skin:
Mo aV bNi cCu dM eSi gO x(ⅰ)，Mo a′V b′Ni c′Cu d′Sr fW hM iN jSi kO y(ⅱ)
Wherein: silicon is the carrier added in catalyzer, M is at least one element be selected from calcium, titanium, zirconium, N is selected from least one element in boron, rubidium, lanthanum, O is oxygen, a, b, c, d, e, a ', b ', c ', d ', f, g, h, i, j, k represents each Elements Atom ratio respectively, wherein a, a ' is a number of 12-14, b, b ' is a number of 0.2-5, c, c ' is a number of 0.5-4, d, d ' is a number of 1-5, e is a number of 0.05-3, f is a number of 0.1-2.5, g is a number of 5-40, h is a number of 0.05-3, i is a number of 0.05-3, j is a number of 0.05-3, k is a number of 0.2-30, x, y is the numerical value determined by the oxygen of each oxide compound, adding different amount silicon-dioxide at ectonexine makes catalyzer there is gradient difference from inside to exterior active combination of components substrate concentration, in molar content, the constituent content of outer active ingredient is higher by 0.1 ~ 30% than this constituent content of internal layer parent.
2. method according to claim 1, is characterized in that described method is applied to acrolein selectivity oxidation and prepares vinylformic acid.
3. method according to claim 2, it is characterized in that loading the catalyzer of internal layer concentration higher than the Mo-V system double-layer catalyst of outer concentration along feed(raw material)inlet end to exit end beds ingress to the scope between 1/3 place or ingress to 1/2 place, the filling of residual catalyst bed mainly forms the double-layer catalyst (I) represented by general formula (I) and (II) respectively.
4. method according to claim 3, is characterized in that the processing condition of oxidizing reaction are: reaction raw materials propenal, water, oxygen enter reactor, salt bath heating after preheater more than 160 DEG C preheatings, salt temperature 240 ~ 260 DEG C, air speed 800 ~ 2200h -1, feed composition: propenal 8 ~ 12 volume %, water vapour 11 ~ 17%, oxygen 9 ~ 17 volume %, nitrogen 60 ~ 71 volume %.
5. method according to claim 4, is characterized in that salt temperature 240 ~ 250 DEG C, air speed 800 ~ 1800h -1.
6. method according to claim 1, is characterized in that the constituent content of used catalyst (I) outer active ingredient is higher by 0.1 ~ 18% than this constituent content of internal layer parent.
7. method according to claim 1, is characterized in that the constituent content of used catalyst (I) outer active ingredient is higher by 0.5 ~ 12% than this constituent content of internal layer parent.
8. method according to claim 1, it is characterized in that in used catalyst (I), N is lanthanum, i is a number of 0.1 ~ 3.
9. method according to claim 8, is characterized in that lanthanum source is lanthanum nitrate.
10. the method according to any one of claim 1,6,7,8,9, it is characterized in that the preparation method of used catalyst comprises the steps: 1) compound dissolution related to containing Mo, V, Ni, Cu and M is mixed, internal layer parent slurries are formed after carrying out co-precipitation, add silicon-dioxide again, drying, shaping, roasting obtains catalyst inner layer parent; 2) prepare outer layer catalyst according to the method for Kaolinite Preparation of Catalyst internal layer parent, in outer layer catalyst preparation process, add silicon-dioxide, make the concentration of element of active ingredient in outer layer catalyst higher than the concentration of this element of internal layer; 3) outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
11. methods according to claim 10, is characterized in that the shaping rear and skin roasting 3 ~ 10h at 300 ~ 550 DEG C after application of used catalyst internal layer parent.
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Publication number Priority date Publication date Assignee Title
CN1524615A (en) * 2003-02-27 2004-09-01 ��ʽ�����ձ���ý Composite-oxide catalyst and process for production of acrylic acid using said catalyst
CN101507927A (en) * 2009-02-10 2009-08-19 上海华谊丙烯酸有限公司 Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process
CN102039141A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Catalyst for preparing unsaturated acid from unsaturated aldehyde by oxidization and preparation method of catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524615A (en) * 2003-02-27 2004-09-01 ��ʽ�����ձ���ý Composite-oxide catalyst and process for production of acrylic acid using said catalyst
CN101507927A (en) * 2009-02-10 2009-08-19 上海华谊丙烯酸有限公司 Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process
CN102039141A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Catalyst for preparing unsaturated acid from unsaturated aldehyde by oxidization and preparation method of catalyst

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