CN104649875A - Propylene selective oxidation method - Google Patents

Abstract

The invention relates to a method for preparing acrolein by propylene oxidation, wherein reaction raw materials of propylene, water and air enter a fixed bed single-tube reactor after being preheated by a preheater at a temperature of more than 120 ℃, and are heated by a salt bath, wherein the volume percent of the propylene is 8-14%, the volume percent of the air is 70-74%, and the water vapor is 15-20%; an oxidation catalyst is filled in the fixed bed reactor, the catalyst contains molybdenum, bismuth, iron, cobalt, tungsten and potassium elements, the catalyst also contains strontium titanate, and the finished catalyst is obtained after the molybdenum and bismuth-containing and the strontium titanate are mixed according to the mass percent of 90-98% and 0.4-10%, kneaded, formed, dried and roasted. The catalyst has stable structure, active components such as molybdenum and the like are not easy to lose, the active phase is not easy to generate phase transformation, and the selectivity and the yield of target products are improved. Acrolein and acrylic acid can be stably produced for a long period.

Description

A kind of Propylene Selectivity method for oxidation

Technical field

The present invention relates to a kind of Propylene Selectivity method for oxidation, be particularly useful for Propylene Selectivity oxidation and prepare propenal.

Background technology

Industrial propylene oxidation prepares the reaction unit mainly many reaction tubess of propenal, 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, propenal 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.

About propylene fraction oxidation acrolein, acrylic acid catalyst mainly molybdenum system multicomponent catalyst.Preparing the acrylic acid reaction of propenal due to Propylene Selectivity oxidation is strong exothermal reaction, so pass into the large water vapour of specific heat in reaction process, effectively to remove reaction heat, but the easy losses under the washing away of the air-flows such as water vapour such as the active ingredient molybdenum in catalyzer.And under the high temperature conditions, in catalyzer, part active ingredient molybdenum loses from catalyst surface because of distillation.The loss of active ingredient molybdenum causes reducing the activity of catalyzer, selectivity, intensity and work-ing life, and molybdenum is in the deposition in reactive system downstream, blocks the long-term operation of pipeline influential system.

In addition, the active ingredient molybdenum in catalyzer etc. i.e. enable maintenance is not run off, and before and after the reaction of molybdenum equal size, basic change is little, but is through long-term operation activity compatible and easily phase in version occurs.Main ingredient in catalyzer comprises Fe ₂(MoO ₄) ₃, α-Bi ₂(MoO ₄) ₃, CoMoO ₄and NiMoO ₄, wherein α-Bi ₂(MoO ₄) ₃be Active sites, play selective oxidation effect; Fe ₂(MoO ₄) ₃play redox promoter action; CoMoO ₄and NiMoO ₄play Stability Analysis of Structures effect.But, adopt the catalyzer prepared of coprecipitation method due to component many, process is complicated, and catalyst stabilization differs, although initial activity is very high, inactivation is fast.What cause many components Mo-Bi-Co-Fe-O catalyzer and Mo-V-O catalyst deactivation and stability to decline is a lot of because have, comprising because of locally abnormal high temperature (focus) cause the sublimation of Mo component and irreversible crystalline phase change etc.These factors all can cause the change of specificity of catalyst, cause the reduction of catalyst activity and shorten work-ing life of catalyzer.By carrying out phenetic analysis to decaying catalyst, find Fe ₂(MoO ₄) ₃be reduced into FeMoO ₄, and α-Bi ₂(MoO ₄) ₃change γ-Bi into ₂moO ₆.

Solve the problem, the patent related to is many, such as, for suppressing the loss of molybdenum, CN1583261 discloses a kind of O composite metallic oxide catalyst for carrying out selective oxidation reaction in the gas phase containing the gas of unsaturated aldehyde and a kind of gas of molecule-containing keto, and its catalyzer consists of: [Mo _av _bcu _cx _d] 1Y _m[Sb _ez ¹ _fz ² _g] _no _xwherein Mo is molybdenum, and V is vanadium, and Cu is copper, and Sb is antimony, and X is a kind of element being at least selected from tungsten and niobium, and Y is a kind of element being at least selected from titanium, antimony, Z ₁a kind of element of at least chosen from Fe and nickel, Z ₂it is a kind of element being at least selected from silicon, aluminium, alkali and alkaline earth metal ions, a, b, c, d, e, f, g and x represent the atomic ratio number of its element, when a=12 is benchmark, b is a number of 1 to 6, c is a number of 0.5 to 4, and d is a number of 0.05 to 4, and e is a number of 0.1 to 30, f is a number of 0 to 25, and g is a number of 0.01 to 20; X is by the number met needed for each metallic element combined oxidation state; Catalyzer is made up of its each element oxide or composite oxides.

In order to improve the stability of catalyzer, CN1130172 discloses a kind of acrylic acid catalyst, use ammonium meta-vanadate and cupric nitrate respectively, and with Low Valent Vanadium oxide compound and/or at a low price copper oxide part replace catalyzer that raw material that ammonium meta-vanadate and/or cupric nitrate make vanadium metal and copper obtains or except above-mentioned raw materials except, using sb oxide and/or low price tin-oxide obtain at a low price catalyzer to demonstrate has a strengthened peak (vanadium-molybdenum active compound is peculiar) at d=4.00 and has the V of a strength reduction at d=4.38_ ₂o ₅specific peak.Like this, catalyzer obtained above has the catalytic activity of raising, and long-term performance can go out stability.Similar also has patent documentation 1: Japanese Unexamined Patent Publication 2002-233757 publication, patent documentation 2: Japanese Unexamined Patent Publication 8-299797 publication, patent documentation 3: Japanese Unexamined Patent Publication 9-194213 publication, patent documentation 4: Japanese Unexamined Patent Application Publication 2004-504288 publication; CN102066000A.

For improving the activity of catalyzer, selectivity and catalyst life, 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.CN87103192 discloses a kind of method of producing composite oxide catalysts, wherein comprise coherent element source compound to mix in Aquo System by the production method of the Mo-Bi composite oxide catalysts of following chemical formulation and form mixture and this mixture is heat-treated, adopt a kind of compound of the Bismuth carbonate mixture of (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X as Bi source, in this mixture at least containing required Na and/or X of part wherein: X represents Mg, Ca, Zn, Ce and/or Sm; Y represents K, Rb, Cs and/or Tl; Z represents B, P, As and/or W; A-K represents respective atomic ratio, and as a=12, b=0.5-7, c=0-10, d=0-10, c+d=1-10, e=0.05-3, f=0.01-1, g=0-1, h=0.04-0.4, i=0-3, j=0-48, k is a number meeting other element oxide state.Solve Bi can in composite oxide catalysts homodisperse problem.Containing α-Bi in catalyzer ₂(MoO ₄) ₃, MoO ₃fe ₂(MoO ₄) ₃with β-CoMoO ₄, y-Bi ₂moO ₆and γ-Bi ₂moO ₆.CN101690900A discloses a kind of preparation method preparing propenal and acrylic acid catalyst, and catalyzer supports thing by active ingredient and inert alumina carrier forms; The main component of active ingredient, is selected from Mo, Bi, Co and/or Ni and Fe, also comprises the trace elements such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P, W; Wherein the following statement formula of active ingredient represents: Mo _abi _bco _cni _dfe _ex _fy _gz _ho _iin formula, X represents at least one of K, Na, Rb and Cs, and Y represents at least one be selected from B, P and W, and Z represents at least one be selected from Mg, Ca, Zn.The active ingredient ratio be supported on carrier accounts for the 5-70% of overall catalyst weight; Active ingredient is uneven distribution, CoMoO ₄, NiMoO ₄aluminate Deng divalent metal is positioned at the kernel of catalyst activity component; Fe ₂(MoO ₄) ₃and the MoO of free state ₃invest the skin of kernel; And the outermost layer of active ingredient is bismuth molybdate, form the state of core-shell structure copolymer layer distributed.In active ingredient, divalence molybdate is mainly beta phase structure, and α phase structure content in active ingredient is very low or do not exist.Catalyzer has high reactivity and high stability.CN1280036 mono-kind produces the catalyzer of unsaturated aldehyde and unsaturated carboxylic acid, described production is by making at least one be selected from propylene, iso-butylene, the compound of the trimethyl carbinol and methyl tertiary butyl ether and oxygen molecule or the gas containing oxygen molecule carry out vapor phase oxidation and realize, it is characterized in that this catalyzer is a kind of combined oxidation compositions, contain: (A) is containing molybdenum, bismuth and iron are as the composite oxides of main ingredient, it itself is the known catalyzer reacted for described vapor phase catalytic oxidation, (B) containing cerium and the zirconium composite oxides as main ingredient.Catalyzer has long catalytic life and makes running steady in a long-term become possibility.Wherein component (B) is the composite oxides represented with following general formula (2): Ce _pzr _qf _ro _y.The zirconium white of high dispersing inhibits the gathering of cerium oxide, to keep the latter to the promotion functions absorbing and discharge oxygen significantly in reaction process, thus accelerates the oxidizing reaction of iso-butylene, therefore improves catalytic activity.In addition, the irreversible activity that further suppress component (A) composite oxides caused because of over reduction in time reduces (i.e. the stability raising of composite oxides), thus catalytic life is extended.This catalytic activity that improve and the catalytic life extended inhibit temperature of reaction to raise in time, thus reduce the distillation of molybdenum at hot spot.This catalyzer is used for isobutylene oxidation.

CN102489309A discloses a kind of catalyst preparing for the production of propenal and renovation process.Catalyzer is the composite oxides with following atomic ratio: Mo: Bi: Co: Ni: Fe=10-14: 1.2-2.0: 4.8-5.6: 2-3: 1-2; This catalyzer has the pore distribution of comparatively concentrating, moderate total pore volume, wherein the mesopore of about 5-10nm accounts for more than 70% of total pore distribution, form short and thick pore passage structure, this feature gives catalyzer stronger anti-carbon deposition ability, catalyst surface is easy-sintering not, can work-ing life of extending catalyst.And by renovation process provided by the invention, decaying catalyst carries out 1-3 days calcination processing in an oxidizing atmosphere, and catalyst activity is suitable with live catalyst.CN87103192 produces the method for Mo-Bi-Na composite oxide catalysts product, the method comprises mixes coherent element source compound and form mixture, then heat-treats, and using at least solid solution, the Bismuth Subcarbonate of the required Na of part is as Bi source compound.The activity of catalyzer is able to great improvement by means of Bi and Na imports the catalyzer of specific water-insoluble compound formation.CN101850259A discloses the preparation method that propylene oxidation under a kind of high-speed prepares the catalyzer of propenal, and this catalyzer is based on Mo-Bi-Fe-Co complex metal oxides, and general formula is; MoaBibFecCodXeYfZgOh, wherein Mo represents molybdenum, Bi represents bismuth, Fe represents iron, Co represents cobalt, X be selected from W, Sb, As, P, Ni, Sn and Pb at least one element, Y is at least one element be selected from Zn, Cr, Mn, Ru, Ag, Pd and Ru, and Z is at least one element be selected from Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba; A, b, c, d, e, f and g represent the atomic ratio of each element, and namely as a=12, b is 0.1 ~ 7, c be 0.5 ~ 8, d+e be 0.5 ~ 20, f be 0 ~ 1, g is the numeral of 0 ~ 2, h for being determined by the oxidation state of above-mentioned each element; This catalyzer is obtained by coprecipitation method, and the precursor compound by component used obtains the pulpous state liquid that pH is 1.5 ~ 3.0 under co-precipitation, after the rapid drying of this pulpous state liquid, adds shaping, the roasting of dilution thermal conducting agent and obtains catalyzer; Or in above-mentioned gained pulpous state liquid, add dilution thermal conducting agent, after rapid drying, shaping, roasting and obtain catalyzer.This catalyzer has selected the dilution thermal conducting agent with excellent heat conductivity performance to be incorporated in catalyzer, and dilution thermal conducting agent is silica flour, solves the rendezvous problem of focus under high-speed, makes catalyzer have selectivity excellent.This invention mainly improves selectivity of catalyst by adding dilution thermal conducting agent silica flour in catalyst preparation process.Silica flour is more common in the preparation of propenal acrylic acid catalyst.

CN1109803 relates to multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, one or more element phosphor, arsenic, boron, germanium and silicon; And relate to described composition and prepared the purposes in methacrylic acid by catalytic gas phase oxidation, improve activity and selectivity.CN1109802 discloses a kind of multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, one or more element phosphor, arsenic, boron, germanium and silicon and copper, improves base vinylformic acid activity and selectivity.CN1298861A adopts the composite oxides adding magnesium, aluminium and silicon.CN1321110A is then respectively using weisspiessglanz and antimony acetate as the antimony source of active complex metal oxides.Under solving high-load condition, catalytic mechanical intensity is good, active high problem.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.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.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.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 _fthis catalyzer adopts the mixed system preparation of water and lower alcohol, and catalyzer has higher specific surface area and special microtexture, has 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.

CN1109800 discloses a kind of polymetal oxide materials: in formula, A is Mo ₁₂v _ax _b ¹x _c ²x _d ³x _e ⁴x _f ⁵x _g ⁶o _x(coexisting phase), its part B comprises the crystallite (giving the starting material about X-ray diffraction fingerprint in parenthesis) of the X-ray diffraction pattern with the following copper molybdate of at least one: Cu ₃(MoO ₄) ₂(OH) ₂(lindgrenite, the index card 36-405 of JCPDS-ICDD index (1991)), Cu ₄mo ₆o ₂₀(people such as A.Moini, Inorg.Chem.25(21) (1986), 3782-3785), Cu ₄mo ₅o ₁₇(the index card 39-181 of JCPDS-ICDD index (1991)), etc.CN1462211 relates to a kind of method preparing multiple-phase multi-metal oxide materials containing Mo, V, Cu and other optional element.According to this invention, at least one phase is pre-formed independently, and is dispersed in the precursor material of the plastically deformable of another phase.Then this mixture carries out drying and calcining.Polymetal oxide materials is suitable as at catalytic gas phase oxidation organic compound, particularly acrolein oxidation is being become the active material of catalyzer used in vinylformic acid.[A] p [B] q [C] r (I), the phase A in multimetal oxide compositions, B and C can be unbodied and/or crystallizations.Phase B is advantageously made up of the crystallite of oxometallate, or comprises there is X-ray diffraction pattern and and then the crystalline structure class α-CuMo of oxometallate crystallite copper molybdate of crystal structure types of the following copper molybdate of at least one ₄[the registration card 22-242 of JCPDS-ICDD card index, (1991)], Cu ₆mo ₅o ₁₈[the registration card 40-865 of JCPCS-ICDD card index, (1991)], Cu _4-xmo ₃o ₁₂, wherein x=0-0.25 [registration card 24-56 and 26-547 of JCPCS-ICDD card index, (1991)], etc.This catalyzer is to improve selectivity.

CN1295499 discloses polymetal oxide materials [A] p [B] q [C] r (I) of a kind of formula (I), with containing molybdenum, vanadium, copper and antimony and one or more other metals specific and the polymetal oxide materials with multicomponent structure prepares acrylic acid catalyzer as with the gas phase catalytic oxidation reaction of propenal.In formula, A is Mo ₁₂v _ax ¹bX ² _cx ³ _dx ⁴ _ex ⁵ _fx ⁶ _go _x, B is X ¹ ₇cu _hh _io _y, C is X ₁ ⁸sb _jh _ko _z, X ₁for W, Nb, Ta, Cr and/or Ce.Promotor phase B is made up of the crystallite of these copper molybdate or contains such copper molybdate crystallite: α-CuMoO ₄[the reference diffractogram in the index card 22-242 of JCPDS-ICDD retrieval 1991], Cu ₆mo ₅o ₁₈[the reference diffractogram in the index card 40-865 of JCPDS-ICDD retrieval 1991], Cu _4-xmo ₃o ₁₂wherein, x is 0-0.25 [the reference diffractogram in index card 24-56 and 26-547 of JCPDS-ICDD retrieval 1991], etc.Region C can have metaantimmonic acid copper Cu ₉sb ₄o ₁₉the crystallite of structure or Cu ₄sbO _4.5the crystallite of structure.CN1093950 discloses the composition of one kind of multiple metal oxides, comprise Mo, V, W, Cu, the Ni of the oxidised form as basal component, its prerequisite there is following ratio between each elemental composition: Mo:V=12:1 to 2:1, Mo:W=60:1 to 3:1, Mo:Cu=24:1 to 2:1, Cu:Ni=5:1 to 1:3.X ₁one or more basic metal; X ₂one or more alkaline-earth metal; X ₃cr, Mn, Ce and/or Nb; X ₄sb and/or Bi; X ₅si, Al, Ti and/or Zr.CN1387945 relates to the oxo metallide of the HT copper molybdate structure type being selected from the element in element W, V, Nb and Ta containing Cu, Mo and at least one, its preparation method, and they also contain the application had in the composite metal oxide material of heterogeneous structure of one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium in preparation containing molybdenum, vanadium, copper.The poly-metal deoxide that CN1394812 uses in the catalyzer of the catalytic vapor phase oxidation reaction for organic compound, said poly-metal deoxide contains at least one in Mo, V and element W, Nb, Ti, Zr, Hf, Ta, Cr, Si and Ge, and has special Three-dimensional atom arrangement.CN1500770 contains molybdenum, vanadium, the composite metal oxide material that have heterogeneous structure of copper also containing one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium, they are by the application in catalytic gas phase oxidation of acrolein vinylformic acid, and are selected from the oxo metallide of the HT copper molybdate structure type of the element in element W, V, Nb and Ta containing Cu, Mo and at least one.

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.Catalyzer comprises by following formula (I) MO _av _bw _ccu _dx _ey _f(I) oxide compound of the metallic element composition represented or composite oxides.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.

Therefore, need to provide Propylene Selectivity to be oxidized and prepare propenal, acrylic acid catalyst, can carry out under low temperature, high-load condition in propylene oxidation reaction.Temperature of reactor distribution is more reasonable, and active ingredient molybdenum etc. not easily because of sublimation, and actively mutually phase in version not easily occur, object selectivity of product and yield high.

For Propylene Selectivity oxidation, first want the oxide catalyst that selectivity is excellent, secondly also will react under the operational condition of gentleness, to adapt to the requirement of industrial high-speed, highly selective.Therefore, the Propylene Selectivity oxidizing process developing the mitigation of a kind of reaction conditions is needed.Under the prerequisite suppressing focus, improve selectivity and the yield of object product as far as possible, to obtain larger economic benefit.

Summary of the invention

The invention provides the method for a kind of Propylene Selectivity oxidation, mainly propenal, acrylic acid are prepared in Propylene Selectivity oxidation.

The method that propenal is prepared in Propylene Selectivity oxidation provided by the invention is as follows: adopt fixed bed single tube reactor; Reaction raw materials propylene, water, air enter reactor, salt bath heating after preheater more than 120 DEG C preheatings, and reaction process condition is: salt temperature 300 ~ 335 DEG C, preferably 305 ~ 325 DEG C; Air speed 800 ~ 1800h ^-1, preferably 800 ~ 1400h ^-1, feed composition: propylene 8 ~ 14 volume %, air 70 ~ 74 volume %, water vapour 15 ~ 20%; Fixed-bed reactor are built with oxide catalyst, and catalyzer contains molybdenum, bismuth, iron, cobalt, tungsten and potassium element, mainly form by formula M o _abi _bfe _cco _dw _ek _fsi _ga _hb _io _x(I) represent: wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Co is cobalt, and W is tungsten, and K is potassium, and Si is silicon, and silicon is the carrier added in catalyzer, and A is at least one element be selected from manganese, boron, lanthanum; B is at least one element be selected from magnesium, calcium or barium; O is oxygen; A, b, c, d, e, f, g, h, i represent each Elements Atom ratio respectively, and wherein a is a number of 12, and b is a number of 1.0 ~ 7, preferably 1.0 ~ 6; C is a number of 1 ~ 6, preferably 1 ~ 5; D is a number of 1 ~ 8, preferably 1 ~ 5; E is a number of 0.2 ~ 5, and f is a number of 0.1 ~ 3.2, and g is a number of 0.2 ~ 55, preferably 1 ~ 20, h be 0.01 ~ 2 a number, i is a number of 0 ~ 2, and x is the numerical value determined by the oxygen of each oxide compound.Catalyzer, also containing strontium titanate, obtains finished catalyst by after 90 ~ 98% and 0.4 ~ 10% mass percent mixing containing molybdenum, (I) of bismuth and strontium titanate after kneading, shaping, dry, roasting.

Inside reactor of the present invention is provided with thermopair, for each spot temperature of assaying reaction device, reaction yield is affected in order to prevent propylene deep oxidation in lower catalyst agent, and make catalyzer coking, the present invention controls catalyzer lower floor temperature lower than catalyzer upper strata temperature, and adjust reaction bed temperature by controlling salt temperature, salt temperature preferably controls at 305 ~ 325 DEG C, the long lifetime being conducive to catalyzer like this uses, and propylene oxidation reaction can long period steady running.

The preparation method of strontium titanate is not limited, as adopted with the following method: by SrCl ₂and TiCl ₄the ratio of 1.0 ~ 1.1 mixes in molar ratio, then adds (NH ₄) ₂cO ₃solution and ammoniacal liquor stir, the pH value of ammoniacal liquor regulator solution is 9.5 ~ 10.5, then spraying dry, gained powder is dried and to be placed in air atmosphere 1000 ~ 1200 DEG C of roastings 4 ~ 10 hours at 120 ~ 150 DEG C of temperature, obtains SrTiO finally by the method such as comminution by gas stream, ball milling ₃.Also can prepare like this: by Strontium carbonate powder, titanium dioxide according to SrTiO ₃stoichiometric ratio mix, add in deionized water the suspension forming high dispersive, then spraying dry is carried out to it, gained powder is dried and to be placed in air atmosphere 1000 ~ 1200 DEG C of roastings 4 ~ 10 hours at 120 ~ 150 DEG C of temperature, obtains SrTiO finally by the method such as comminution by gas stream, ball milling ₃.

More preferably, the lanthanum CeO2-ZrO2 solid solution that mass percentage is 0.1 ~ 4 can also be added in catalyzer, catalyzer thermostability and good hydrothermal stability, lanthanum CeO2-ZrO2 solid solution (La of the present invention _xce _yzr _1-0.8x-yo ₂(0<x<1,0<y<1,0<x+y<1) coprecipitation method preparation conveniently.

More preferably, containing catalyzer (I) 92 ~ 97% in catalyzer, also has strontium titanate 1.5 ~ 8%.

Can add active ingredient lanthanum in the catalyst activity component that the present invention (I) represents, lanthanum and bismuth, cobalt can form stable crystal phase structure, as BiLa, BiLa ₂, Co ₃la ₂deng, the good dispersity of molybdenum, thus suppress part active ingredient molybdenum to lose from catalyst surface because of distillation, active ingredient molybdenum not easily runs off, and before and after catalyst reaction, active ingredient molybdenum content is substantially constant, delays active deterioration rate, catalyst activity and good stability.Lanthanum and molybdenum, cobalt ratio are suitable, and in logical formula I, A is lanthanum, and h is a number of 0.05 ~ 1.5, and i is a number of 0.01 ~ 1.2, and molybdenum is competed in the add membership and bismuth and cobalt of too much lanthanum, affects catalyst activity.Catalyzer mainly forms as shown in logical formula II.

Mo _aBi _bFe _cCo _dW _eK _fSi _gLa _hB _iO _x（Ⅱ）

Multi-metal-oxide catalyst of the present invention (I) adopts common preparation method, prepares as adopted following step.

Will containing Mo, Bi, in the compound of Fe, Co, W, K and logical formula I AhBi each elementary composition compound dissolution related to and mix, slurries are formed after carrying out co-precipitation, add in silicon-dioxide, aluminum oxide or silicon carbide in slurry production process one or more, dry, shaping, roasting obtains catalyzer (I).

The preparation method of catalyzer of the present invention, comprise with coprecipitation method Kaolinite Preparation of Catalyst (I), strontium titanate, by catalyzer (I), strontium titanate and/or lanthanum CeO2-ZrO2 solid solution by after 90 ~ 98% and 0.4 ~ 10% mass percent mixing through mediating, obtain finished catalyst after shaping, dry, roasting.

Catalyzer of the present invention (I) and finished catalyst all need roasting 3 ~ 10h at 400 ~ 580 DEG C, and compare the catalyzer of not roasting respectively, repeatedly roasting can improve activity and the stability of catalyzer.Can be open roasting also can be enclosed roasting, calcination atmosphere can be the rare gas elementes such as helium, nitrogen, argon gas.

Under Oxygen Condition, catalyzer under the high temperature conditions molybdenum isoreactivity component not only easily runs off, and activity compatible easily phase in version occurs, and activity phase in version occurs mutually and causes active selectable obviously to decline.As active phase CoMoO ₄be converted into Co ₃o ₄, Fe ₂(MoO ₄) ₃be transformed into FeMoO ₄, α-Bi ₂(MoO ₄) ₃change γ-Bi into ₂moO ₆deng.

Active ingredient molybdenum in catalyzer etc. i.e. enable maintenance is not run off, and before and after the reaction of molybdenum equal size, basic change is little, but is through long-term operation activity compatible and easily phase in version occurs.Strontium titanate and/or lanthanum CeO2-ZrO2 solid solution add in catalyzer by the present invention, make active phase more stable, not easily phase in version occur thus improve catalyst activity and selectivity, making the steady running of catalyzer long period.

The compound of each component of catalyzer of the present invention can use the nitrate, ammonium salt, vitriol, oxide compound, oxyhydroxide, muriate, acetate etc. of each element, as lanthanum nitrate, magnesium nitrate, potassium manganate, Manganse Dioxide, ammonium borate, boric acid, titanium dioxide, nitrate of baryta etc., nitrocalcite, strontium nitrate etc.

After catalyst slurry of the present invention is 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.

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 the above-mentioned catalyzer (I).

Evaluating catalyst performance index definition is as follows:

Embodiment

With specific embodiment, the method that Propylene Selectivity is oxidized is described below, but scope of the present invention is not limited to these embodiments.Following examples adopt propylene be propylene content >=99.6%(volume fraction) high density propylene.The analytical procedure of product composition adopts this area universal method.

Embodiment 1

The preparation of catalyzer 1

Under agitation, get 197 grams of ammonium molybdates and be dissolved in (water temperature more than 65 DEG C) in 1000ml pure water, obtain slurries (1), then get 73 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 1.88 grams of saltpetre, 6.86 grams of magnesium nitrates, 112.7 grams of iron nitrates, 15.1 grams of lanthanum nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Get 45.1 grams of Bismuth trinitrates again, be dissolved under agitation in dust technology, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), are then added in slurries (4) by slurries (3), obtain active ingredient slurries (a).11.7 grams of silicon dioxide powders and 4 grams of graphite 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, dry rear 550 DEG C of roastings 4 hours for 105 DEG C, and then grind to form the fine powder of less than 40 μm, obtained catalyzer (I), mainly consists of: Mo ₁₂bi ₁fe ₃co _2.7w ₂k _0.2si _2.1mg _0.4la _0.5o _x.

A certain amount of cerous nitrate, lanthanum nitrate, zirconium nitrate is taken according to stoichiometric ratio, be mixed with mixing solutions, when constantly stirring, to mixed solution and dripping ammonia soln, it is made to carry out coprecipitation reaction, then through suction filtration, 120 DEG C of oven dry, 950 DEG C of roastings 10 hours, and then grind to form the fine powder of less than 40 μm, obtained Ce _0.6zr _0.3la _0.22o ₂, Ce _0.5zr _0.4la _0.2o ₂, Ce _0.7zr _0.2la _0.31o ₂.

By Strontium carbonate powder, titanium dioxide according to SrTiO ₃stoichiometric ratio mix, add in deionized water the suspension forming high dispersive, then carry out spraying dry to it, gained powder is dried and to be placed in air atmosphere 1100 DEG C of roastings 10 hours at 120 ~ 150 DEG C of temperature, obtains SrTiO finally by ball milling ₃.

Get catalyzer (I) 93 part, strontium titanate oxide compound 4.5 parts, lanthanum CeO2-ZrO2 solid solution Ce _0.5zr _0.4la _0.2o ₂2.5 parts, add deionized water and mediate in kneader, extrusion molding is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 450 DEG C, roasting obtains catalyzer 1 in 6.5 hours.

Comparative example 1

Main composition and ratio according to embodiment 1 prepares comparative catalyst 1, but lanthanum cerium zirconium is not add catalyzer with the form of solid solution, oxide, strontium titanate is not add with the form of Whole Oxygen compound, but with coprecipitation method Kaolinite Preparation of Catalyst, reaction conditions is with the appreciation condition of catalyzer 1.Comparative catalyst 1 mainly consists of: Mo ₁₂bi ₁fe ₃co _2.7w ₂k _0.2si _2.1mg _0.4ce _0.5zr _0.4la _0.2ti _0.2sr _0.2la _0.5o _x.

Comparative example 2

Main composition and ratio according to comparative example 1 prepares comparative catalyst 2, but strontium titanate is not add catalyzer with the form of solid solution, oxide, titanium and strontium add in co-precipitation mode, not containing lanthanum CeO2-ZrO2 solid solution in catalyzer, but with coprecipitation method Kaolinite Preparation of Catalyst, reaction conditions is with the appreciation condition of catalyzer 1.Comparative catalyst 2 mainly consists of:

Mo ₁₂Bi ₁Fe ₃Co _2.7W ₂K _0.2Si _2.1Mg _0.4Ce _0.5Zr _0.4La _0.2La _0.5O _x。

Propylene oxidation method

Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer of 40ml or comparative example catalyzer, salt bath heating temperature 312 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 1100h ^-1import the mixed gas of propylene 11 volume %, air 75 volume %, water vapour 14 volume %.Bed hot localised points temperature 364 DEG C, beds upper temp is higher than beds bottom bed temperature 4 DEG C.Propylene conversion 99.2%, acrolein selectivity 88.4%, propenal yield 82.1%, acrolein+acrylic acid yield 92.5%.Temperature distribution is more reasonable, is conducive to the steady running of catalyzer long period.Through the reaction of 2000 hours, embodiment 1 bed hot localised points temperature 363 DEG C, beds upper temp was higher than beds bottom bed temperature.Propylene conversion 99.1%, acrolein selectivity 88.3%, propenal yield 82.1%, acrolein+acrylic acid yield 92.4%.Comparative example catalyzer 1 is after reaction in 2000 hours, and propylene conversion is respectively 98.1%, and acrolein selectivity is respectively 84.3, and propenal yield is respectively 75.5%, and acrolein+acrylic acid yield is respectively 87.4%.Embodiment catalyst activity component molybdenum etc. not easily runs off, and phase in version not easily occurs active phase, and catalyst activity component structure is stablized, and improves selectivity and the yield of object product, and catalyst structure is stablized, can long period steady running.Sampling analysis in comparative example catalyzer 1 and 2 oxidizing reaction 24 hours, bed hot localised points temperature is respectively 365 DEG C and 363 DEG C, propylene conversion is respectively 98.8%, 98.3%, acrolein selectivity is respectively 85.3%, 85.4%, propenal yield is respectively 78.1%, 77.8%, and acrolein+acrylic acid yield is respectively 88.1%, 87.7%.Comparative example catalyst selectivity is poor, and propenal, vinylformic acid yield are low.

Embodiment 2

The preparation of catalyzer 2

With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 3 hours, namely obtain catalyzer (I) through 550 DEG C of roastings, mainly consist of: Mo ₁₂bi ₅fe ₅co ₆w ₃k ₂ba _0.3si _1.2b _0.5o _x.Get catalyzer (I) 98 part, strontium titanate oxide compound 1.5 parts, lanthanum CeO2-ZrO2 solid solution Ce _0.5zr _0.4la _0.2o ₂0.5 part, add deionized water and mediate in kneader, extrusion molding is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyzer 2 in 4.5 hours.

Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer of 45ml, salt bath heating temperature 316 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 1600h ^-1import the mixed gas of propylene 10 volume %, air 73 volume %, water vapour 17 volume %.Sampling analysis in oxidizing reaction 24 hours, bed hot localised points temperature 366 DEG C, propylene conversion 99.3%, acrolein selectivity 88.6%, propenal yield 81.7%, acrolein+acrylic acid yield 92.2%.

Embodiment 3

With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 6 hours, namely obtain catalyzer (I) through 400 DEG C of roastings.Mainly consist of: Mo ₁₂bi ₇fe ₁co ₈w _0.3k _3.2si _5.1ca _0.3mn _1.8o _x, get catalyzer (I) 95 part, strontium titanate oxide compound 4 parts, lanthanum CeO2-ZrO2 solid solution Ce _0.6zr _0.3la _0.22o ₂1 part, add deionized water and mediate in kneader, extrusion molding is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 530 DEG C, roasting obtains catalyzer 3 in 5 hours.

Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer of 50ml, salt bath heating temperature 308 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 1000h ^-1import the mixed gas of propylene 9 volume %, air 71 volume %, water vapour 20 volume %.Sampling analysis in oxidizing reaction 24 hours, bed hot localised points temperature 358 DEG C, propylene conversion 98.7%, acrolein selectivity 88.1%, propenal yield 81.2%, acrolein+acrylic acid yield 91.5%.

Embodiment 4

With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, through 480 DEG C of roastings, 5 hours catalyzer (I).Mainly consist of: Mo ₁₂bi _3.5fe ₄co _4.5w ₁k _0.5si _2.4mn _0.1mg _0.2o _x.Get catalyzer (I) 91 part, strontium titanate oxide compound 5.5 parts, lanthanum CeO2-ZrO2 solid solution Ce _0.7zr _0.2la _0.31o ₂3.5 parts, add deionized water and mediate in kneader, extrusion molding is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyzer 4 in 5 hours.

Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer 4 of 45ml, salt bath heating temperature 305 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 900h ^-1import the mixed gas of propylene 9 volume %, air 72 volume %, water vapour 19 volume %, sampling analysis in oxidizing reaction 24 hours, bed hot localised points temperature 351 DEG C, propylene conversion 98.6%, acrolein selectivity 88.4%, propenal yield 81.0%, acrolein+acrylic acid yield 91.0%.

Embodiment 5

With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 3 hours, namely obtain catalyzer (I) through 560 DEG C of roastings.Mainly consist of: Mo ₁₂bi _2.2fe _2.3co _1.2w ₅k _1.4si _1.6la _1.2ba _0.3o _x.Get catalyzer (I) 97 part, strontium titanate oxide compound 3 parts, adds deionized water and mediates in kneader, and extrusion molding is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 480 DEG C, roasting obtains catalyzer 5 in 6 hours.

Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer of 50ml, salt bath heating temperature 310 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 1000h ^-1import the mixed gas of propylene 10 volume %, air 71 volume %, water vapour 19 volume %.Oxidizing reaction is sampling analysis after 24 hours, bed hot localised points temperature 361 DEG C, propylene conversion 99.2%, acrolein selectivity 88.3%, propenal yield 81.3%, acrolein+acrylic acid yield 91.7%.Oxidizing reaction is sampling analysis after 2000 hours, bed hot localised points temperature 360 DEG C, propylene conversion 99.1%, acrolein selectivity 88.4%, propenal yield 81.2%, acrolein+acrylic acid yield 91.8%.Catalyst activity component molybdenum etc. not easily runs off, and phase in version not easily occurs active phase, and catalyst activity component structure is stablized.

Embodiment 6

With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 4 hours, namely obtain catalyzer (I) through 500 DEG C of roastings.Mainly consist of Mo ₁₂bi ₃fe ₂co _1.7w ₄k _1.0si _1.0la _2.1ba _0.3o _x.Get catalyzer (I) 95 part, strontium titanate oxide compound 5 parts, adds deionized water and mediates in kneader, and extrusion molding is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 520 DEG C, roasting obtains catalyzer 6 in 5 hours.

Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer of 50ml, salt bath heating temperature 320 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 1900h ^-1import the mixed gas of propylene 11 volume %, air 71 volume %, water vapour 18 volume %.Oxidizing reaction is sampling analysis after 24 hours, bed hot localised points temperature 370 DEG C, propylene conversion 99.1%, acrolein selectivity 88.4%, propenal yield 81.6%, acrolein+acrylic acid yield 92.3%.Oxidizing reaction is sampling analysis after 2000 hours, bed hot localised points temperature 368 DEG C, propylene conversion 99.2%, acrolein selectivity 88.5%, propenal yield 81.5%, acrolein+acrylic acid yield 92.2%.

Embodiment 4 catalyzer is at salt bath heating temperature 312 DEG C, air speed 1100h ^-1, propylene 11 volume %, air 69 volume %, water vapour 20 volume % condition under reaction 24 hours and 500 hours, bed hot localised points temperature is respectively 363 DEG C, 361 DEG C, propylene conversion 99.0%, 98.8%, acrolein selectivity 88.0%, 88.2%, propenal yield 81.4%, 81.6%, acrolein+acrylic acid yield 91.5%, 92.4%.Temperature distribution is more reasonable, and catalyst activity component structure is stablized, and is conducive to the steady running of catalyzer long period.Embodiment 4 and 6 catalyzer is at salt bath heating temperature 312 DEG C, air speed 1100h ^-1, propylene 11 volume %, air 69 volume %, water vapour 20 volume % condition under stablize 6 hours after adjust salt temperature to 350 DEG C (stopping propylene) again, after 10 hours, be down to 312 DEG C again, embodiment 4 and 6 is (salt bath heating temperature 312 DEG C, air speed 1100h under similarity condition ^-1, propylene 11 volume %, air 69 volume %, water vapour 20 volume %) react 24 hours, bed hot localised points temperature is respectively 360 DEG C, 354 DEG C, propylene conversion 99.1%, 98.0%, acrolein selectivity 88.0%, 85.1%, propenal yield 81.3%, 76.5%, acrolein+acrylic acid yield 91.4%, 87.5%.Under the condition through water vapour 20 volume %, salt bath heating temperature 350 DEG C of hydrothermal treatment consists, relative to embodiment 6, embodiment 4 catalyzer thermostability and good hydrothermal stability, catalyst activity component structure is stablized, and meets the steady running of catalyzer long period.

Claims (11)

1., for a Propylene Selectivity method for oxidation, it is characterized in that; Reaction raw materials propylene, water, air enter reactor after preheater more than 120 DEG C preheatings, and reaction process condition is: salt temperature 300 ~ 335 DEG C, air speed 800 ~ 1800h ^-1, feed composition: propylene 8 ~ 14 volume %, air 70 ~ 74 volume %, water vapour 15 ~ 20%; Fixed-bed reactor are built with oxide catalyst, and catalyzer contains molybdenum, bismuth, iron, cobalt, tungsten and potassium element, mainly form by formula M o _abi _bfe _cco _dw _ek _fsi _ga _hb _io _x(I) represent: silicon is the carrier added in catalyzer, and A is at least one element be selected from manganese, boron, lanthanum; B is at least one element be selected from magnesium, calcium or barium; O is oxygen; A, b, c, d, e, f, g, h, i represent each Elements Atom ratio respectively, wherein a is a number of 12, b is a number of 1.0 ~ 7, and c is a number of 1 ~ 6, and d is a number of 1 ~ 8, e is a number of 0.2 ~ 5, f is a number of 0.1 ~ 3.2, and g is a number of 0.2 ~ 55, and h is a number of 0.01 ~ 2, i is a number of 0 ~ 2, and x is the numerical value determined by the oxygen of each oxide compound; Catalyzer, also containing strontium titanate, obtains finished catalyst by after 90 ~ 98% and 0.4 ~ 10% mass percent mixing containing molybdenum, (I) of bismuth and strontium titanate after kneading, shaping, dry, roasting.

2. method according to claim 1, is characterized in that in used catalyst also containing the lanthanum CeO2-ZrO2 solid solution that mass percentage is 0.1 ~ 4.

3. method according to claim 1, is characterized in that salt temperature 305 ~ 325 DEG C.

4. method according to claim 1, is characterized in that air speed 800 ~ 1400h ^-1.

5. method according to claim 1, is characterized in that beds lower floor temperature is lower than catalysis

Agent bed upper strata temperature.

6. method according to claim 1, is characterized in that catalyzer contains catalyzer (I) 92 ~ 97%, also has strontium titanate 1.5 ~ 8%.

7. method according to claim 1, it is characterized in that the preparation method of used catalyst comprises with coprecipitation method Kaolinite Preparation of Catalyst (I), strontium titanate oxide compound, catalyzer (I), strontium titanate oxide compound, by 90 ~ 98% and 0.4 ~ 10% mass percent mixing, obtain finished catalyst through mediating, after shaping, dry, roasting.

8. method according to claim 1, it is characterized in that in used catalyst (I), A is lanthanum, h is a number of 0.05 ~ 1.5, and i is a number of 0.01 ~ 1.2, and catalyzer mainly forms as shown in logical formula II: Mo _abi _bfe _cco _dw _ek _fsi _gla _hb _io _x(II).

9. method according to claim 1, it is characterized in that in used catalyst (I), b is a number of 1.0 ~ 6, c is a number of 1 ~ 5, and d is a number of 1 ~ 5, and g is a number of 1 ~ 20.

10. method according to claim 1, it is characterized in that method for preparing catalyst that used catalyst (I) represents comprises the steps: containing Mo, Bi, in the compound of Fe, Co, W, K and logical formula I AhBi each elementary composition compound dissolution related to and mix, form slurries after carrying out co-precipitation, in slurry production process, add one or more in silicon-dioxide, aluminum oxide or silicon carbide, dry, shaping, roasting obtains catalyzer (I).

The preparation method of 11. catalyzer according to claim 7, it is characterized in that catalyzer (I) and finished catalyst all roasting 3 ~ 10h at 400 ~ 580 DEG C, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.