CN103772173B - A kind of preparation method of acrylic aldehyde - Google Patents

A kind of preparation method of acrylic aldehyde Download PDF

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CN103772173B
CN103772173B CN201210405100.3A CN201210405100A CN103772173B CN 103772173 B CN103772173 B CN 103772173B CN 201210405100 A CN201210405100 A CN 201210405100A CN 103772173 B CN103772173 B CN 103772173B
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catalyst
outer layer
conversion zone
layer
reactor
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CN103772173A (en
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王学丽
刘肖飞
常晓昕
颉伟
胡晓丽
谢元
葛汉青
蒋满俐
南洋
景志刚
李自夏
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China Petroleum and Natural Gas Co Ltd
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    • 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
    • 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

Abstract

The preparation method that the present invention relates to a kind of acrylic aldehyde, adopt fixed bed reactors, it is characterized in that reactor at least divides two conversion zones along reaction raw materials entrance to outlet, close to first section of conversion zone of reactor feedstocks entrance equipped with internal layer concentration higher than the Mo-Bi system double-layer catalyst of outer layer concentration, latter end conversion zone close to reactor outlet is built-in has double-decker catalyst (I), mainly comprises and is (i) represented with () by formula respectively: Mo from catalyst inner layer to outer layeraBibFecCoeSigAhOx(i), Moa��Bib��Fec��Nid��Coe��WfAh��BiSijOy(). The preparation method process conditions of acrylic aldehyde of the present invention relax, and purpose product yield and selectivity are high.

Description

A kind of preparation method of acrylic aldehyde
Technical field
The preparation method that the present invention relates to a kind of acrylic aldehyde, aoxidizes acrolein, acrylic acid more particularly, to Propylene Selectivity.
Background technology
Propylene gas phase catalytic oxidation reaction prepares acrylic aldehyde, acrylic acid is strong exothermal reaction, in reactor, moment assembles substantial amounts of reaction heat, form hot localised points, if reaction heat can not be removed timely and effectively, the heat that moment is gathered constantly is accumulated, and will cause the loss of catalyst activity component, comes 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, thus reducing acrylic aldehyde and acrylic acid yield. Even cause runaway reaction, make sintering of catalyst.
The appearance of " progress of oxidative synthesis acrylic acid process and catalyst " (petrochemical industry, the 39th volume the 7th phase in 2010) social focus also can make catalyst damage evil, shortens the service life of catalyst. For 80,000 tons/year of acroleic acid devices, prepared by propylene oxidation need more than 25000 tubulation in acrolein reaction device, and acrolein oxidation is prepared and is also required to more than 25000 tubulation in acrylic acid reactor, loads acrylic aldehyde, acrylic acid catalyst more than 100 ton altogether. More than 50000 reaction tube, the filling of catalyst ensures that not filling sky has certain difficulty, crosses high catalyst if as focus and quickly sinters, again changes agent in a short time again, it is possible to it is huge for envisioning its economic loss; It addition, carry out under cryogenic as much as possible for acrylic aldehyde, acrylic acid production, because reaction needed salt bath heating, it maintains the energy resource consumption produced also is huge spending; Due to the generation of focus, requiring high temperature resistant to reaction tube tubing, for up to ten thousand reaction tubes, tubing expense is exactly the cost payout that item is very big. Therefore, if effectively suppressing the generation of beds focus, large-scale industrial production can be brought huge economic benefit.
Industrial propylene or isobutylene oxidation prepare corresponding unsaturated aldehyde, the reaction unit of acid is mainly many reaction tubes, ensure catalyst be not sintered, under the premise of long service life, improve selectivity and purpose product yield as far as possible, save the raw materials such as propylene, even if if feed stock conversion, acrylic aldehyde, acrylic 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 peroxidization of focus, as: Japanese Patent Laid-Open 04-217932 proposes the method for the hot polymerization collection on a kind of appearance suppressing focus or focus, namely by preparing the multiple catalyst with different possessive volume, and from the mode that unstripped gas inlet side reduces to outlet side catalyst possessive volume, it is sequentially filled reaction tube, but the possessive volume of catalyst is by the restriction of reaction tube diameter, and it is also highly difficult that multiple catalysts is filled into reaction tube. CN1210511A prepares and multiple have the catalyst-loaded of different activities and arrange catalyst layer in reaction tube, above-mentioned several catalyst-loaded according to the order arrangement uprised from the entrance of unstripped gas to outlet activity. Also the method having other, such as inert substance and catalyst mix, reduce the activity of catalyst, it is loaded into reactor inlet place, Japanese Unexamined Patent Publication 10614/1972 is mixed into heat resistanceheat resistant point in the catalyst and forms catalyst and inert substance with by catalyst dilution, and the method for tubulose made by catalyst by Japanese Patent Publication 36739/1987. Further, the Catalyst packing that unstrpped gas porch reduces by active component. CN01111960.8 uses fixed bed shell and tube reactor, in the presence of a catalyst, prepared acrylic aldehyde and acrylic acid by propylene gas phase catalytic oxidation reaction, the method can suppress producing or hot polymerization collection on focus of focus in reaction zone effectively, this catalyst consist of MoaWbBicFedAeBfCgDhEiOx, wherein Mo, W, Bi, Fe, A, B, C, D, E and O and a, b, c, d, e, f, g, h, i and x implication as used in the description. The method is characterized by preparing the multiple catalysts with above-mentioned composition, but kind and/or the quantity of the temperature that (��) possessive volume, (��) calcine and/or (��) alkali metal are different, and press the mode that catalyst activity increases to outlet from unstripped gas entrance, catalyst is sequentially filled to reaction zone. When CN00122609.6 provides the oxide catalyst existed containing Mo-Bi-Fe compound, acrylic aldehyde and acrylic acid is produced by vapor phase propylene oxide, described catalyst is filled in multitubular reactor of fixed bed, and the method can generate acrylic aldehyde and acrylic acid in for a long time with high stable yield. The method is characterized in that in each tubular reactor configuring two or more reaction zone vertically, each district's filling different catalysts, namely from gas access end to gas outlet end, in filled out catalyst, the ratio of Bi and/or Fe content and Mo content reduces. CN1672790A provides a kind of catalysis acrylic acid catalyst of acrylic aldehyde gaseous oxidation system, described catalyst 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 catalyst can reduce the temperature of hot spot, and suppresses the reduction of the reaction efficiency of thermal degradation. Specific practice is, by making the volatility toxic component of specified quantitative comprise and originally having in highly active catalyst, catalysis activity declines momently, it is possible to reduce the temperature of hot spot. CN1165055A by by catalytic active component load sharing on carrier after, calcine the catalyst of load sharing to suppress the generation of focus, the mean diameter of catalyst is 4��16mm, and the mean diameter of carrier is 3��12mm, and calcining heat is 500��600 DEG C. CN1314331A provides a kind of catalyst containing Mo-W-Bi-Fe, this catalyst passes through the mode changing the kind of possessive volume calcining heat and/or alkali metal and/or quantity and increasing to outlet side from the inlet side of unstripped gas according to catalyst activity, is sequentially filled reaction zone with described multiple types catalyst.Catalyst is at least divided into two-layer in the axial direction of the reaction tube, and this catalyst is the multiple types catalyst with different activities level, it is possible to by change calcining heat and/or wherein the kind of alkali metal and/or quantity and obtain. Hot polymerization collection in the appearance of focus or focus is effectively suppressed. JP200982239A discloses the catalyst of a kind of gas phase oxidation for Hydrocarbon such as 3C or 4C, composition Mo (a) Bi (b) Co (c) Ni (d) Fe (e) X (f) Y'(g of this catalyst) Z (h) Q (i) Si (j) O (k) or Mo (12)-V (a') X'(b') Cu (c') Y " (d') Sb (e') Z'(f') Si (g') C (h') O (i'). X is selected from sodium, potassium, rubidium, caesium or thallium, and Y' is selected from boron, phosphorus, arsenic or tungsten; Z is selected from magnesium, calcium, zinc, cerium; Y is " selected from magnesium, calcium, barium, zinc or strontium; Z' chosen from Fe, cobalt, nickel, bismuth or aluminum.
The method that above-mentioned suppression focus produces all has a problem that, the catalyst being filled in reaction tube is all diluted from the inlet to the outlet in a variety of manners, both after having made catalyst runs some cycles, activity decrease also can not change thinner ratio, catalyst also cannot reoffer higher activity, not only filling, dismounting, separation, recovery catalyst make troubles, and the reactivity of catalyst can be reduced, especially industrial long-term operation catalyst activity reduction faster, affects catalyst life.
The open a kind of oxide catalyst of CN101274279, it is represented by following formula (2): Mo12BiaFebAcBdCeDfOx(2) this invention in order to solve to cause due to the appearance of catalyst focus its activity or selectivity due to sintering etc. significantly reduced problem. This invention is so to solve technical problem, the catalyst loaded in reactor has specific particle size distribution, space between catalyst granules can by uniformly and expand, the appearance of the extra high temperature spot in local (focus) in catalyst layer can be suppressed not reduce acrylic aldehyde or acrylic acid yield, and acrylic aldehyde or acrylic acid can be obtained long-term and stably. This catalyst particle size relative standard deviation is 0.02-0.20. Owing to industrial acrylic aldehyde, acrylic acid production loaded catalyst are bigger; want that the particle size relative standard deviation ensureing catalyst is 0.02-0.20; the large-scale production of catalyst can be restricted undoubtedly, it is possible to production process can process as useless agent because of the irregular of catalyst size. And tons of catalyst, screening particle size relative standard deviation is the work also very time-consuming effort of 0.02-0.20.
The open a kind of multilayer composite metal oxide catalyst of CN201010180103.2, the composition of this O composite metallic oxide catalyst can by formula M oaBibNicCsdCueTifAgBhCiOjRepresenting, wherein: Mo is molybdenum, Bi is bismuth, and Ni is nickel, and Cs is caesium, and Cu is copper, and Ti is titanium, and A is chosen from least one element in arsenic, tellurium, manganese, cerium, niobium, zirconium, rubidium, cadmium and germanium; B is chosen from least one element in cobalt, boron, strontium, tantalum, alkali and alkaline earth metal ions; C is chosen from least one element in vanadium, stannum, gallium, zinc, ferrum, tungsten and antimony; O is oxygen, described O composite metallic oxide catalyst has multiple structure, and from internal layer parent to outer layer, each concentration of element reduces successively, even if catalyst initial reaction activity is significantly high, this catalyst can effectively reduce single tube reactor localized heat and gather, it is suppressed that being emerged of focus. This catalyst mainly controls the focus produced owing to catalyst initial activity is high, but the selectivity of purpose product and yield have much room for improvement, and under the mixed airflow long period Scouring Condition such as propylene, steam, catalyst surface active component has part to run off, and affects catalyst activity and stability.CN201010180184.6 provides a kind of three layers multi-metal-oxide catalyst and preparation method thereof, this catalyst contains Multimetal oxide as active component, this catalyst is applicable to propylene or selective isobutene oxidation produces corresponding unsaturated aldehyde, can effectively suppress, owing to the Organic substance of unstripped gas middle and high concentration contacts the higher focus of formation with the catalyst initial stage and generates substantial amounts of by-product, to improve catalyst selectivity. This catalyst preparation process is complicated, and three layers catalyst is prone to come off through long-term operation outer layer, increases catalyst bed layer resistance, thus causing activity decrease. And the selectivity of this catalyst purpose product and yield also have much room for improvement.
CN200980112659.3 discloses a kind of coating catalyst that the present invention relates to and comprise following components: (a) carrier, b () comprises the ground floor of the precursor compound of molybdenum oxide or formation molybdenum oxide, (c) comprises the second layer containing molybdenum and the poly-metal deoxide of other metal at least one. The molybdenum oxide of preferred ground floor is MoO3, the poly-metal deoxide of the second layer is the formula II poly-metal deoxide represented: Mo12BiaCrbX1 cFedX2 eX3 fOy. This catalyst is the application type catalyst including carrier. Goal of the invention is suppression heterogeneously catalysed partial gas phase oxidation acrylic aldehyde is acrylic acid coating catalysqt deactivation, has the inactivation performance of improvement. This invention is not expressly recited catalyst for catalysis propylene oxidation acrolein, acrylic acid reactivity worth evaluating data, for instance conversion ratio, selectivity, yield etc. The preparation method that CN200710106391.5 discloses a kind of composite oxide catalysts, wherein this catalyst is the catalyst containing molybdenum and the olefin oxidation of bismuth, it is characterized in that, its specific surface area is at 5��25m2/ g, its pore volume are in the scope of 0.2��0.7cc/g, and in the distribution of its fine pore, there is following distribution: fine pore (diameter) the pore volume shared by the pore of 0.03��0.1 ��m be 30% in total pore volume or more than 30%, be 20% in total pore volume or more than 20% in the pore volume shared by the pore of 0.1��1 ��m, and the pore diameter proportion less than 0.03 ��m is 10% or less than 10%, this composite oxide catalysts is represented by below general formula (1): MoaBibCocNidFeeXfYgZhSiiOj(1) in formula, X is from by magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce), the at least one element selected in the group of samarium (Sm) and halogen composition, Y is from by sodium (Na), potassium (K), rubidium (Rb), the at least one element selected in the group that caesium (Cs) and thallium (Tl) form, Z is from by boron (B), phosphorus (P), the at least one element selected in the group that arsenic (As) and tungsten (W) form, additionally, a��j represents the atomic ratio of each element, a=12, b=0.5��7, c=0��10, d=0��10, wherein c+d=1��10, e=0.05��3, f=0��2, g=0.04��2, h=0��3, i=5��48, additionally, j is the numerical value of the state of oxidation of the element meeting other. this invention needs pyrolytic silicon dioxide, and catalyst component disperses together with silicon, controls specific surface area of catalyst, pore volume, fine pore distribution, improves conversion ratio and selectivity etc. the height of beds hot localised points temperature is not mentioned in this invention. ingredient requirement is high, and complicated process of preparation, catalytic component is relatively more, and the distribution of specific surface area, pore volume, fine pore is difficult to effectively control, poor repeatability.
CN101579631 mono-kind for low-carbon alkene vapor phase catalytic oxidation prepare unsaturated aldehyde reaction containing Mo, Bi, Fe, the preparation method of the catalyst of Co composite oxides, this invention is to cause that catalytic component is uneven for what exist in prior art because of catalyst precursor different solubility, so that catalyst performance is deteriorated, and catalyst high conversion and high selectivity, the problem that high stability can not get both, the method mainly adds dilution thermal conducting agent when shaping of catalyst, catalyst dilution thermal conducting agent is selected from SiC, elemental silicon powder, the complex of one or more in graphite and carbon fiber.Similar also has CN1647854, CN101850259A. CN101850259A discloses the preparation method that under a kind of high-speed, propylene oxidation prepares the catalyst of acrylic aldehyde, and this catalyst is based on Mo-Bi-Fe-Co metal composite oxide, and formula is; MoaBibFecCodXeYfZgOh, this catalyst has selected the dilution thermal conducting agent with excellent heat conductivity performance to be incorporated in catalyst, and dilution thermal conducting agent is silica flour, solves the rendezvous problem of focus under high-speed, makes catalyst have selectivity excellent. This invention improves selectivity of catalyst mainly by adding dilution thermal conducting agent silica flour in catalyst preparation process. Silica flour is relatively common in prepared by acrylic aldehyde acrylic acid catalyst.
JP5293389A discloses a kind of PROPENE IN GAS PHASE OXIDATION and prepares the acrylic acid catalyst of acrylic aldehyde, and the composition of catalyst can have formula to represent MoaBibFecAdXeYfZgSigOi. A is at least one element in cobalt and nickel, X is at least one element in Mg, Zn, Mn, Ca, Cr, Nb, Ag, Ba, Sn, Ta or Pb, Y is selected from P, B, S, Se, Te, Ce, W, Sb or Ti, and Z is chosen from Li, Na, K, Rb, Cs or Ti at least one element. Adding organic polymer in catalyst, this catalyst has loose structure (0.01��10 micron) and is prone to gas-phase reaction. When CN1283604 provides the oxide catalyst existed containing Mo-Bi-Fe compound, acrylic aldehyde and acrylic acid is produced by vapor phase propylene oxide, described catalyst is filled in multitubular reactor of fixed bed, and the method can generate acrylic aldehyde and acrylic acid in for a long time with high stable yield. The method is characterized in that in each tubular reactor configuring two or more reaction zone vertically, each district's filling different catalysts, namely from gas access end to gas outlet end, in filled out catalyst, the ratio of Bi and/or Fe content and Mo content reduces.
It addition, under the high temperature conditions, in catalyst, part active component molybdenum loses from catalyst surface because of distillation. The mixed airflows such as acrylic aldehyde, air (oxygen), nitrogen and steam wash away the loss of active component that also can make in catalyst. For suppressing the loss of molybdenum distillation to cause the decay of activity, CN1121504 is by the zirconium mixing copper component and have specified particle diameter and specific surface area and/or titanium and/or cerium, it is possible to suppress dissipation effect and the over reduction of molybdenum composition; CN1445020 adds a small amount of tellurium and plays the effect of stably free molybdenum trioxide and copper molybdate crystal structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is with molybdenum, vanadium, copper, tungsten and/or niobium for key component, and the composite oxides constituted with other element or its hopcalite composition catalyst suppress the loss of molybdenum.
CN1874984 mono-kind reacts the method being prepared unsaturated aldehyde by alkene in shell-tube type reactor by fixed-bed catalytic partial oxidation, described reactor includes the reaction zone preparing unsaturated aldehyde, this reaction zone comprises two-layer or multilamellar Catalytic Layer, each Catalytic Layer is all filled with the shaped catalyst product as secondary, wherein the secondary in each Catalytic Layer is formed by the primary particle with varigrained catalytic active component, and controls the granularity of the primary particle of described catalytic active component so that this granularity reduces from reactor inlet to reactor outlet. This catalyst adopts the catalyst pellets sublayering filling that particle size varies in size to suppress focus.Namely the Catalytic Layer filled with the shaped catalyst product with maximum primary particle size preferably includes the focus with maximum temperature. The preferred 10-150 micron of Primary particle size of shaped catalyst product.
Propylene Selectivity is aoxidized, first has to select the oxidation catalyst of function admirable, secondly also to react under gentle operating condition, to adapt to industrial high-speed, high selective requirement. Accordingly, it would be desirable to develop the Propylene Selectivity oxidation technology that a kind of reaction condition relaxes, improve selectivity and the yield of purpose product as far as possible, to obtain bigger economic benefit.
Summary of the invention
The preparation method that the present invention relates to a kind of acrylic aldehyde, aoxidizes acrolein, acrylic acid more particularly, to Propylene Selectivity.
A kind of preparation method of acrylic aldehyde, adopt fixed bed reactors, reactor at least divides two conversion zones along reaction raw materials entrance to outlet, close to first section of conversion zone of reactor feedstocks entrance equipped with internal layer concentration higher than the Mo-Bi system double-layer catalyst (catalyst such as CN201010180103.2) of outer layer concentration, latter end conversion zone close to reactor outlet is built-in has double-decker catalyst (I), mainly comprises and (i) represented with () by formula respectively from catalyst inner layer to outer layer.
MoaBibFecCoeSigAhOx(i)
Moa��Bib��Fec��Nid��Coe��WfAh��BiSijOy()
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is ferrum, and Co is cobalt, and Ni is nickel, and W is tungsten, and Si is silicon, and silicon is the carrier added in catalyst, and A is chosen from least one element in zinc, titanium, magnesium; B is chosen from least one element in stannum, chromium, rubidium, lanthanum; O is oxygen; A, b, c, e, a ', b ', c ', d ', e ', f, g, h, h ', i, j represent each Elements Atom ratio respectively, and wherein a, a ' are numbers of 12-14, and b, b ' are numbers of 0.5-6, it is preferable that 1.0-5; C, c ' are numbers of 0.2-4, it is preferable that 0.2-3; D ' is a number of 0.2-5, it is preferable that 0.5-4; E, e ' are numbers of 0.2-5, it is preferable that 0.5-4, f are numbers of 0.1-3.5, g is a number of 0.1-40, and h, h ' are numbers of 0.1-5, and i is a number of 0.1-3.5, j is a number of 0.5-30, and x, y are the numerical value determined by the oxygen of each oxide. Catalyst activity component not easily runs off, and water repelling property is good, and the selectivity of purpose product and yield are high.
The preparation method of a kind of acrylic aldehyde, adopts fixed bed reactors, and reactor divides F along reaction raw materials entrance to outlet1Conversion zone and F2Conversion zone, F1Section is higher than the Mo-Bi system double-layer catalyst of outer layer concentration, (catalyst such as CN201010180103.2), F equipped with internal layer concentration2Reactor is built-in has double-deck catalyst of the present invention (I) for section. Such as, the catalyst of CN201010180103.2 is loaded to port of export beds porch to 1/3 place or porch to the scope between 1/2 place along feed(raw material)inlet end, internal layer concentration of the present invention is not strictly limited higher than the filling scope of the Mo-Bi system double-layer catalyst of outer layer concentration, can less than the 1/3 of beds, it is also possible to unnecessary 1/3. F2In section reactor, filling mainly comprises the catalyst of the present invention (I) (i) represented by formula with ().
The preparation method of a kind of acrylic aldehyde, reactor divides F along reaction raw materials entrance to outlet1Conversion zone, F2Conversion zone and F3Conversion zone, F1Conversion zone is higher than the Mo-Bi system double-layer catalyst of outer layer concentration, (catalyst such as CN201010180103.2), F equipped with internal layer concentration3Conversion zone reactor is built-in to be had and mainly comprises by formula (i) and () double-decker catalyst (I) of representing.F2Conversion zone is equipped with F1Section (is F1Conversion zone) and F3Section (is F3Conversion zone) mixed catalyst of two-stage catalytic agent. F1Conversion zone length is less than the 1/3, F of total reactor length2Conversion zone length is less than the 1/3, F of total reactor length3Conversion zone length is less than the 1/2 of total reactor length. F2The ratio of conversion zone mixed catalyst meets following condition: Wherein, internal layer concentration is lower than the Mo-Bi system double-layer catalyst volume (V of outer layer concentration2), internal layer concentration is higher than the Mo-Bi system double-layer catalyst volume (V of outer layer concentration1).
A kind of preparation method of acrylic aldehyde, the process conditions of oxidation reaction are not limited especially, as adopted following process conditions: adopt fixing sheet pipe reactor; Entering reactor, salt bath heating after the preheated device of reaction raw materials propylene, water, air more than 160 DEG C preheating, reaction process condition is: salt temperature 300��340 DEG C, it is preferable that 305��330 DEG C; Air speed 800��2100h-1, it is preferable that 800��1800h-1, feed composition: propylene 8��14 volume %, air 70��73 volume %, steam 15��18%.
Used catalyst has interior outer double-layer structure, i.e. multilayer structure, and internal layer catalyst key component is less than outer layer key component, and in molar content, catalyst outer layer each constituent content concentration is higher than internal layer parent. The concentration difference of ectonexine can adjust the Numerical Implementation such as a, b, c, e, a ', b ', c ', e ', g, h, h ', j, as a, b, c, e, g, h numerical value less than corresponding a ', b ', c ', e ', h ', j value. Or the materials such as not commensurability silicon dioxide, aluminium oxide, carborundum are added at ectonexine.
Catalyst used by the present invention is double-decker, and catalyst exists gradient difference from inside to exterior active combination of components substrate concentration, for instance can by being achieved concentration difference at materials such as ectonexine addition not commensurability silicon dioxide, aluminium oxide, carborundums. In molar content, each constituent content of outer layer is higher by 0.1%��25% than this constituent content of internal layer parent, it is preferable that 0.1%��15%, and more preferably 0.5%��12%.
Used catalyst of the present invention is preferably added to active component lanthanum, and lanthanum and bismuth, cobalt, stannum can form stable crystal phase structure, such as BiLa, BiLa2��Co3La2��LaNi5, LaSn etc., the good dispersion of molybdenum, thus suppressing part active component molybdenum to lose from catalyst surface because of distillation, active component molybdenum not easily runs off, before and after catalyst reaction, active component molybdenum content is basically unchanged, and delays activity deterioration rate, catalyst activity and good stability. With molybdenum, cobalt ratio suitably, in logical formula I, B is lanthanum to lanthanum, and i is a number of 0.1��3.5, and the membership that adds of too much lanthanum competes molybdenum with bismuth, cobalt and ferrum, affects catalyst activity. The preferred sodium stannate of Xi Yuan of the present invention, stannous chloride.
Used catalyst of the present invention adopts common preparation method, as following step can be adopted to prepare.
1) will containing A in Mo, Bi, Fe, the compound of Co and logical formula IhThe each elemental constituent compound dissolution related to and mix homogeneously, carry out being formed after co-precipitation internal layer parent serosity, slurry production process add one or more in silicon dioxide, aluminium oxide or carborundum, dries, molding, roasting obtains catalyst inner layer parent;
2) outer layer catalyst is prepared according to the method for preparation catalyst inner layer parent, outer layer preparation process controls one or more the addition in silicon dioxide, aluminium oxide or carborundum so that in outer layer catalyst, each concentration of element is higher than the concentration of this element of adjacent inner layer;
3) outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after fired, obtains finished catalyst.
Used catalyst internal layer parent of the present invention after shaping and outer layer be required at 400��580 DEG C roasting 3��10h after application, compare the catalyst not distinguishing roasting, repeatedly roasting can improve activity and the stability of catalyst. Can be open roasting can also being enclosed roasting, calcination atmosphere can be the noble gases such as helium, nitrogen, argon.
Easily chap during catalyst layer too thick roasting, in order to avoid be full of cracks preferably 55��125 DEG C of drying, then roasting more after application. The outer layer catalyst thickness being coated on internal layer parent is 0.1��2.0mm, it is preferable that 0.2��1.5mm.
The compound of each component of used catalyst of the present invention can use the nitrate of each element, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate etc., such as Lanthanum (III) nitrate, magnesium nitrate, ammonium chromate, rubidium nitrate, zinc nitrate, titanium dioxide, sodium stannate etc.
After used catalyst internal layer parent serosity of the present invention is dried, it is usually preferred to adopt the forming method such as extrusion molding, granulating and forming, compression molding to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., it is preferred to hollow circuit cylinder or spherical.
Catalyst used by the present invention is preferably used binding agent when being coated, and makes ectonexine catalyst bonding more firm. Spray binding agent infiltration surface when internal layer parent is in rolling, then spray the outer layer catalyst powder prepared, it is also possible to internal layer parent is put into and the outer layer catalyst serosity prepared carries out roll coating. One or more in water, alcohols or ethers of binding agent. Alcohols such as ethanol, propanol, butanol; Ethers such as ether and butyl ether.
Each layer surface preferably uneven, rough surface of used catalyst of the present invention, is conducive to coating, bonds between layers more firm.
The present invention is in order to improve the intensity of catalyst, efflorescence degree, it is possible to add in glass fibre, graphite, ceramic or various whisker one or more in above-mentioned outer layer catalyst.
Used catalyst of the present invention has double-decker, and internal layer can also be called internal layer parent. The object of the invention product refers mainly to acrylic aldehyde, acrylic acid.
Owing to catalyst initial reaction activity is significantly high, so being easy to produce focus or produce heat localization on fixing sheet pipe reactor bed, catalyst is easy to sintering, and the loss of industrialized production acrylic aldehyde acrylic acid is very serious by this. Raw material passes into a certain amount of steam, owing to specific heat of water is big, it is possible to take away a large amount of reaction heat, but steam input greatly often makes catalyst member active component solution-off make activity decrease, it is therefore desirable to catalyst has good water repelling property. Most preferably the present invention is used two kinds and there is double-deck multi-metal-oxide catalyst, at acrylic aldehyde Way in, first use the internal layer concentration catalyst (catalyst such as CN201010180103.2) higher than outer layer concentration, owing to the active component concentration of catalyst external surface is low, so corresponding activity is also low, therefore can effectively suppress being emerged of focus and gathering of heat, reduce the growing amount of by-product (such as hydrocarbon), improve the selectivity of purpose product. Use internal layer concentration lower than the catalyst of outer layer concentration or point three sections of fillings at residual catalyst bed, the mixture of two kinds of catalyst is used between two kinds of catalyst, density of propylene opposite inlet is lower, and catalyst activity is high, is more beneficial for improving the acrylic acid selectivity of acrylic aldehyde and yield. And, catalyst structure is stable, and active component not easily runs off. So, under high-speed reaction condition, two kinds have the layering filling of double-deck catalyst, reaction bed temperature distribution is more reasonable, avoid proximity to the reaction bed temperature of the port of export and decline that fast (bed temperature declines affects selectivity of catalyst and yield, it is unfavorable for catalyst long period steady running), catalyst has good water repelling property, improves selectivity and the yield of purpose product.
Detailed description of the invention
With specific embodiment, the method that Propylene Selectivity aoxidizes is described below, but the scope of the present invention is not limited to these embodiments.Following example adopt propylene be propylene content >=99.6%(volume fraction) high concentration propylene. The analysis method of product composition adopts method generally in the art.
Embodiment 1:
The preparation of catalyst 1
Under agitation, take 186.4 grams of ammonium molybdates and be dissolved in 1000ml pure water (water temperature more than 65 DEG C), obtain serosity (1), then take 20.5 grams of cobalt nitrates, 4.9 grams of magnesium nitrates, 35.6 grams of ferric nitrates are dissolved in 1000ml pure water (water temperature more than 65 DEG C), it is sufficiently stirred for mix homogeneously, obtains serosity (2). Take 85.4 grams of bismuth nitrate again, be dissolved under agitation in dust technology, obtain serosity (3). Then, serosity (1) mixes with serosity (2), obtains serosity (4), is then added in serosity (4) by serosity (3), obtains active component serosity (a).
Active component serosity (a) adds 84 grams of silicon dioxide powders, 80 DEG C of strong stirrings carry out coprecipitation reaction post-heating and dry, with 160 DEG C of heat treatments 3 hours in nitrogen, then extrude through banded extruder, rolling is a granulated into the ball shape that diameter is 2.5mm, dry rear 500 DEG C of roastings 6 hours for 105 DEG C, preparing catalyst Precursors, this catalyst inner layer parent mainly comprises as Mo12Bi2Fe1Co0.8Si15.9Mg0.3Ox(i).
Under agitation, take 217.5 grams of ammonium molybdates and be dissolved in 1000ml pure water (water temperature more than 65 DEG C), obtain serosity (1), then take 56.3 grams of cobalt nitrates, 43.5 grams of nickel nitrates, 88.9 grams of ferric nitrates, 9.8 grams of magnesium nitrates, 23 grams of ammonium paratungstates, 42.9 grams of Lanthanum (III) nitrates are dissolved in 500ml pure water (water temperature more than 65 DEG C), it is sufficiently stirred for mix homogeneously, obtains serosity (2). Take 170.8 grams of bismuth nitrate again, be dissolved under agitation in dust technology, obtain serosity (3). Then, serosity (1) mixes with serosity (2), obtains serosity (4), is then added in serosity (4) by serosity (3), obtains active component serosity (a).
Active component serosity (a) and 7.9 grams of silicon dioxide powders are carried out coprecipitation reaction post-heating dry, with 150 DEG C of heat treatments 3 hours in nitrogen, then 500 DEG C of roastings 4 hours, size-reduced, grind, sieving processes to obtain catalyst outer layer powder, outer layer mainly comprises as Mo14Bi4Fe2.5Ni1.7Co2.2W1.0Mg0.6La1.5Si1.5Oy(). The individual constituent content of outer layer is higher by 1.1%��10.8% than this constituent content of internal layer.
Prepare catalyst 1
The catalyst inner layer parent of preparation is placed in round bottom container, alcoholic solution is sprayed to catalyst Precursors when container rotation, stop operating when abundant moistening catalyst inner layer parent, put it into rapidly in the round bottom container of the outer layer catalyst powder being placed with of another rotation, it is coated, coating layer thickness is at 0.5��1.5mm, and namely gained catalyst 120 DEG C obtains catalyst 1 in 4 hours through 500 DEG C of roastings after drying.
Fixing sheet pipe reactor internal diameter 25mm, inside sets thermocouple, along reactor feedstocks gas Way in load 12mlCN201010180103.2 embodiment 4 catalyst (F1Section), the above-mentioned catalyst of 18ml or comparative example catalyst (F2Section), enter reactor after the preheated device of reaction raw materials propylene, water, air 160 DEG C preheating, salt bath heating, oxidation reaction process conditions are: salt bath heating temperature 312 DEG C. Tube inlet sentences air speed 1600h from the reactions above-1Import the mixing gas of propylene 11 volume %, air 71 volume %, steam 18 volume %. Oxidation reaction 24 hours, F2Section hot localised points temperature 364 DEG C, propylene conversion 99.1%, acrolein selectivity 88.9%, acrylic aldehyde yield 81.5%, acrolein+acrylic acid yield 92.1%.After the oxidation reaction 1000h of embodiment 1, F2Section hot localised points temperature 362��365 DEG C, bed F3Section hot localised points temperature is 362 DEG C��365 DEG C, and propylene conversion is 99.0%, acrolein selectivity 88.6%, acrylic aldehyde yield 81.4%, acrolein+acrylic acid yield 92.3%. Catalyst activity component molybdenum etc. not easily runs off, and stable performance has good water repelling property, and Propylene Selectivity oxidation reaction long period stably carries out.
Comparative example 1:
With the internal layer of catalyst 1 for comparative catalyst 1, making the ball that diameter is 4mm, oxidation reaction condition is with embodiment 1. F2Section hot localised points temperature 361 DEG C, propylene conversion 98.8%, acrolein selectivity 85.0%, acrylic aldehyde yield 77.1%, acrolein+acrylic acid yield 88.2%.
Comparative example 2:
With the outer layer of catalyst 1 for comparative catalyst 2, making the ball that diameter is 4mm, oxidation reaction condition is with embodiment 1. F2Section hot localised points temperature 368 DEG C, propylene conversion 98.8%, acrolein selectivity 83.2%, acrylic aldehyde yield 75.5%, acrolein+acrylic acid yield 87.3%.
Embodiment 2:
The preparation of catalyst 2
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, and internal layer adds 137.2 grams of silicon dioxide and 2.3 grams of aluminium oxidies, are a granulated into, through banded extruder extruding, rolling, the ball shape that diameter is 2mm, and outer layer adds 13.6 grams of silicon dioxide. Coating layer thickness, at 0.5��2.0mm, namely obtains catalyst 2 in 3 hours through 550 DEG C of roastings. Catalyst 2 internal layer parent mainly comprises as Mo13Bi0.5Fe0.3Co1.3Si20.4Ti0.5Ox(i), outer layer mainly comprises as Mo14Bi1.2Fe1.2Ni4.5Co3.1W0.3Zn1.1Ti1.2Sn0.3Si3.1Oy().
The individual constituent content of outer layer is higher by 1%��15% than this constituent content of internal layer.
12mlCN201010180103. catalyst 6(F is loaded along feedstock direction reactor bed1Section), the above-mentioned catalyst (F of 20ml3Section), at F1With F3It is provided with F between section2Section, F2Section mixes than 1:2 by same volume with catalyst 2 equipped with mixture 13ml, the CN201010180103.2 catalyst 6 of above two catalyst, salt bath heating, salt temperature 315 DEG C. Tube inlet sentences air speed 1850h from the reactions above-1Enter the mixing gas of propylene 13 volume %, air 70 volume %, steam 17 volume %. React 24 hours beds F2Section hot localised points temperature 359 DEG C, F3Section hot localised points temperature 364 DEG C, propylene conversion is 99.3%, acrolein selectivity 88.7%, acrylic aldehyde yield 81.2%, acrolein+acrylic acid yield 91.2%. Reaction bed temperature calibration is more reasonable, improves purpose selectivity of product and yield. After the oxidation reaction 1000h of embodiment 2, beds F2Section hot localised points temperature 357��359 DEG C, bed F3Section hot localised points temperature is 363 DEG C��365 DEG C, and propylene conversion is 99.1%, acrolein selectivity 88.8%, acrylic aldehyde yield 81.3%, acrolein+acrylic acid yield 91.3%. Catalyst activity component molybdenum etc. not easily runs off, and stable performance has good water repelling property, and Propylene Selectivity oxidation reaction long period stably carries out.
Embodiment 3:
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, and internal layer adds 154.5 grams of silicon dioxide and 2.2 grams of carborundums, and through the extruded hollow columnar granule for �� 5 �� 5mm of banded extruder, outer layer adds 13.6 grams of silicon dioxide. Coating layer thickness, at 0.1��1.5mm, namely obtains catalyst 3 in 8 hours through 400 DEG C of roastings. Catalyst 3 internal layer parent mainly comprises as Mo12Bi2.3Fe2Co0.3Si24.8Zn0.6Ox(i), outer layer mainly comprises as Mo14Bi6Fe3Ni0.6Co1.6W3Zn1.5Cr0.1Rb0.2Si4.1Oy().
The individual constituent content of outer layer is higher by 0.3%��12.4% than this constituent content of internal layer.
14mlCN201010180103.2 catalyst 5(F is loaded along feedstock direction reactor bed1Section), the above-mentioned catalyst (F of 20ml3Section), at F1With F3It is provided with F between section2Section, F2Section mixes than 2:3 by same volume with catalyst 3 equipped with mixture 11ml, the CN201010180103.2 catalyst 5 of above two catalyst, salt bath heating, salt temperature 308 DEG C. Tube inlet sentences air speed 850h from the reactions above-1Enter the mixing gas of propylene 10 volume %, air 72 volume %, steam 18 volume %. React 24 hours beds F2Section hot localised points temperature 355 DEG C, F3Section hot localised points temperature 359 DEG C, propylene conversion is 99.0%, acrolein selectivity 88.4%, acrylic aldehyde yield 80.7%, acrolein+acrylic acid yield 91.5%. Reaction bed temperature calibration is more reasonable, improves purpose selectivity of product and yield. After the oxidation reaction 1000h of embodiment 3, beds F2Section hot localised points temperature 354��356 DEG C, bed F3Section hot localised points temperature is 357 DEG C��360 DEG C, and propylene conversion is 99.1%, acrolein selectivity 88.3%, acrylic aldehyde yield 80.6%, acrolein+acrylic acid yield 91.4%. Catalyst activity component molybdenum etc. not easily runs off, and stable performance has good water repelling property, and Propylene Selectivity oxidation reaction long period stably carries out.
Embodiment 4:
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, and internal layer adds 147.1 grams of silicon dioxide, are then a granulated into, through banded extruder extruding, rolling, the ball shape that diameter is 2mm, and outer layer adds 11.1 grams of silicon dioxide. Coating layer thickness, at 0.5��2.0mm, namely obtains catalyst 4 in 5 hours through 550 DEG C of roastings. Catalyst 4 internal layer parent mainly comprises as Mo12Bi1.5Fe0.5Co2.4Si20.4Mg0.2Ox(i), outer layer mainly comprise into:
Mo13Bi4.6Fe1.7Ni3.3Co5W2Mg0.4La0.8Sn0.5Si2.7Oy()
The individual constituent content of outer layer is higher by 0.7%��9.4% than this constituent content of internal layer.
Along reactor feedstocks gas Way in load 14mlCN201010180103.2 embodiment 3 catalyst (F1Section), the above-mentioned catalyst of 26ml or comparative example catalyst (F2Section), enter reactor after the preheated device of reaction raw materials propylene, water, air 160 DEG C preheating, salt bath heating, oxidation reaction process conditions are: salt bath heating temperature 308 DEG C. Tube inlet sentences air speed 1350h from the reactions above-1Import the mixing gas of propylene 11 volume %, air 73 volume %, steam 15 volume %. Oxidation reaction 24 hours, F2Section hot localised points temperature 360 DEG C, propylene conversion 98.8%, acrolein selectivity 88.8%, acrylic aldehyde yield 81.2%, acrolein+acrylic acid yield 91.7%.
Embodiment 5:
Independent loading catalyst 4, oxidation reaction condition is with embodiment 4. F2Section hot localised points temperature 367 DEG C, propylene conversion 98.6%, acrolein selectivity 86.0%, acrylic aldehyde yield 77.2%, acrolein+acrylic acid yield 89.0%.
Comparative example 3:
Individually filling CN201010180103.2 embodiment 3 catalyst, oxidation reaction condition is with embodiment 4. F2Section hot localised points temperature 3559 DEG C, propylene conversion 98.5%, acrolein selectivity 86.0%, acrylic aldehyde yield 75.8%, acrolein+acrylic acid yield 87.0%.

Claims (13)

1. the preparation method of an acrylic aldehyde, adopt fixed bed reactors, it is characterized in that reactor at least divides two conversion zones along reaction raw materials entrance to outlet, close to first section of conversion zone of reactor feedstocks entrance equipped with internal layer concentration higher than Mo-Bi system double-layer catalyst (II) of outer layer concentration, mainly comprising of catalyst (II) is represented by formula M oaBibNicCsdCueTifAgBhCiOj, wherein: Mo is molybdenum, Bi is bismuth, Ni is nickel, Cs is caesium, Cu is copper, Ti is titanium, A is chosen from arsenic, tellurium, manganese, cerium, niobium, zirconium, rubidium, at least one element in cadmium and germanium,The B at least one element in cobalt, boron, strontium, tantalum, alkali and alkaline earth metal ions; The C at least one element in vanadium, stannum, gallium, zinc, ferrum, tungsten and antimony; O is oxygen; Wherein, a, b, c, d, e, f, g, h, i, j represent each Elements Atom ratio respectively; Described catalyst (II) has double-decker, and from internal layer parent to outer layer, each reactive element concentration reduces successively; Latter end conversion zone close to reactor outlet is built-in has double-decker catalyst (I), mainly comprises and is represented by formula (i) and () respectively: Mo from catalyst inner layer to outer layeraBibFecCoeSigAhOx(i), Moa��Bib��Fec��Nid��Coe��WfAh��BiSijOy(), silicon is carrier, and A is chosen from least one element in zinc, titanium, magnesium, B is chosen from least one element in stannum, chromium, rubidium, lanthanum, O is oxygen, a, b, c, e, a ', b ', c ', d ', e ', f, g, h, h ', i, j represents each Elements Atom ratio respectively, wherein a, a ' is a number of 12-14, b, b ' is a number of 0.5-6, c, c ' is a number of 0.2-4, d ' is a number of 0.2-5, e, e ' is a number of 0.2-5, f is a number of 0.1-3.5, g is a number of 0.1-40, h, h ' is a number of 0.1-5, i is a number of 0.1-3.5, j is a number of 0.5-30, x, y is the numerical value determined by the oxygen of each oxide, one or more addition at ectonexine in not commensurability silicon dioxide or carborundum make catalyst there is gradient difference from inside to exterior active combination of components substrate concentration, in molar content, the each constituent content of outer layer is higher by 0.1��25% than this constituent content of internal layer parent, the process conditions of oxidation reaction are: enter reactor, salt bath heating, salt temperature 300��340 DEG C, air speed 800��2100h after the preheated device of reaction raw materials propylene, water, oxygen more than 160 DEG C preheating-1, feed composition: propylene 8��14 volume %, air 70��73 volume %, steam 15��18% volume.
2. method according to claim 1, it is characterised in that reactor divides F along reaction raw materials entrance to outlet1Conversion zone, F2Conversion zone and F3Conversion zone, F1Conversion zone is higher than Mo-Bi system double-layer catalyst (II) of outer layer concentration, F equipped with internal layer concentration3Conversion zone reactor is built-in to be had and mainly comprises the double-decker catalyst (I) represented by formula (i) and (), F2Conversion zone is equipped with F1Section and F3The mixed catalyst of section two-stage catalytic agent.
3. method according to claim 2, it is characterised in that F1Conversion zone length is less than the 1/3, F of total reactor length2Conversion zone length is less than the 1/3, F of total reactor length3Conversion zone length is less than the 1/2 of total reactor length.
4. method according to claim 2, it is characterised in that F2The ratio of conversion zone mixed catalyst meets following condition:Wherein, internal layer concentration is V lower than the Mo-Bi system double-layer catalyst volume of outer layer concentration2, internal layer concentration is V higher than the Mo-Bi system double-layer catalyst volume of outer layer concentration1��
5. method according to claim 1, it is characterised in that reactor divides F along reaction raw materials entrance to outlet1Conversion zone and F2Conversion zone.
6. method according to claim 1, it is characterised in that salt temperature 305��330 DEG C, air speed 800��1800h-1��
7. method according to claim 1, it is characterised in that each constituent content of used catalyst (I) ectomesoderm is higher by 0.1��15% than this constituent content of internal layer parent.
8. method according to claim 1, it is characterised in that each constituent content of used catalyst (I) ectomesoderm is higher by 0.5��12% than this constituent content of internal layer parent.
9. method according to claim 1, it is characterised in that in used catalyst (I), b, b ' are numbers of 1-5, c, c ' are numbers of 0.2-3, and d ' is a number of 0.5-4, and e, e ' are numbers of 0.5-4.
10. method according to claim 1, it is characterised in that in used catalyst (I), B is lanthanum.
11. according to the method described in any one of claim 1,7,8,9, it is characterised in that the preparation method of used catalyst (I) comprises the steps: 1) will containing A in Mo, Bi, Fe, the compound of Co and logical formula IhThe each elemental constituent compound dissolution related to and mix homogeneously, carry out being formed after co-precipitation internal layer parent serosity, slurry production process add one or more in silicon dioxide, aluminium oxide or carborundum, dries, molding, roasting obtains catalyst inner layer parent; 2) outer layer catalyst is prepared according to the method for preparation catalyst inner layer parent, outer layer preparation process controls one or more the addition in silicon dioxide, aluminium oxide or carborundum so that in outer layer catalyst, each concentration of element is higher than the concentration of this element of adjacent inner layer; 3) outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after fired, obtains finished catalyst.
12. method according to claim 11, it is characterised in that after the parent molding of used catalyst (I) internal layer and outer layer roasting 3��10h at 400��580 DEG C after application.
13. method according to claim 11, it is characterised in that used catalyst (I) outer layer thickness is 0.1��2.0mm.
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