CN104649885B - A kind of method being prepared unsaturated acids by unsaturated aldehyde - Google Patents

A kind of method being prepared unsaturated acids by unsaturated aldehyde Download PDF

Info

Publication number
CN104649885B
CN104649885B CN201310585734.6A CN201310585734A CN104649885B CN 104649885 B CN104649885 B CN 104649885B CN 201310585734 A CN201310585734 A CN 201310585734A CN 104649885 B CN104649885 B CN 104649885B
Authority
CN
China
Prior art keywords
catalyst
volume
magnesio
lanthanum
oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310585734.6A
Other languages
Chinese (zh)
Other versions
CN104649885A (en
Inventor
翟月勤
刘俊保
吴毅
范国宁
李晓银
魏玉丽
陈跟平
曹帅英
王春龙
张士玉
王芳
杨芳
耿占杰
高杜娟
高冬梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Natural Gas Co Ltd
Original Assignee
China Petroleum and Natural Gas Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Natural Gas Co Ltd filed Critical China Petroleum and Natural Gas Co Ltd
Priority to CN201310585734.6A priority Critical patent/CN104649885B/en
Publication of CN104649885A publication Critical patent/CN104649885A/en
Application granted granted Critical
Publication of CN104649885B publication Critical patent/CN104649885B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17—Copper
    • 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
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/24—Strontium
    • 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
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/27—Zinc
    • 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
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/37—Lanthanides
    • B01J2523/3706—Lanthanum
    • 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
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/41—Silicon
    • 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
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/47—Titanium
    • 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
    • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
    • B01J2523/48—Zirconium
    • 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
    • B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
    • B01J2523/53—Antimony
    • 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
    • B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
    • B01J2523/55—Vanadium
    • 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
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/64—Tellurium
    • 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
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/68—Molybdenum

Landscapes

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

Abstract

The present invention relates to a kind of method that unsaturated aldehyde prepares unsaturated acids, adopt fixed bed reactors, after the preheated device of reaction raw materials more than 160 DEG C preheating, enter reactor, salt bath heating, salt temperature 240～265 DEG C, air speed 800～2200h-1, feed composition: acrylic aldehyde or methylacrolein 8～12 volume %, steam 11～17%, oxygen 9～17 volume %, nitrogen 60～72 volume %；Fixed bed reactors are built with oxidation catalyst, and catalyst contains molybdenum, vanadium, copper and antimony element, mainly comprises by formula M oaVbCucSbdSreSifMgNhOx(I) represent, catalyst possibly together with magnesio lanthanum hexaaluminate, containing molybdenum, (I) of vanadium and magnesio lanthanum hexaaluminate by after 91～98% and 0.5～10% mass percent mixing through kneading, molding, dry, obtain finished catalyst after roasting.The method can stably produce acrylic acid by long period.

Description

A kind of method being prepared unsaturated acids by unsaturated aldehyde
Technical field
The present invention relates to a kind of method that unsaturated aldehyde prepares unsaturated acids, the method that especially acrylic aldehyde or methylacrolein selective oxidation prepare acrylic or methacrylic acid.
Background technology
Industrial acrylic aldehyde or the oxidation of aldehydes reaction unit preparing corresponding unsaturated acids of metering system are 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, conservation, even if if feed stock conversion, 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.
Aoxidize acrolein acrylic acid catalyst about propylene fraction and be mainly molybdenum system multicomponent catalyst.Key component in catalyst includes Fe2(MoO4)3、α-Bi2(MoO4)3、CoMoO4And NiMoO4, wherein α-Bi2(MoO4)3It is Active sites, plays selective oxidation effect；Fe2(MoO4)3Play redox facilitation；CoMoO4And NiMoO4Play Stability Analysis of Structures effect.But, catalyst prepared by employing coprecipitation method is many due to component, and process is complicated, and catalyst stabilization differs, although initial activity is significantly high, but inactivation is fast.Cause that many components Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalysqt deactivation and stability decline a lot of because have, be reduced (Fe including catalyst activity component3+→Fe2+), the formation of different metal oxides, and because of the sublimation of local abnormal high temperature (focus) caused Mo component and irreversible crystalline phase change etc..These factors all can cause the change of specificity of catalyst, causes the reduction of catalyst activity and shortens the service life of catalyst.By decaying catalyst is carried out phenetic analysis, it has been found that Fe2(MoO4)3It is reduced into FeMoO4, and α-Bi2(MoO4)3It is changed into γ-Bi2MoO6。
Solve the problems referred to above, put forward the patent that high catalytic activity relates to relatively more, for instance, CN1210511 refer to a kind of method preparing composite oxides by co-precipitation, and in it is raw materials used, Co is or/and the ratio shared by Ni is higher, in order to Fe in rugged catalyst3+, it is to avoid its too fast reduction；Composite oxide catalysts additionally exists the MoO of free state3, it is possible to supplement because of the loss of the Mo caused that distils.But each active component is uniformly distributed in the composite oxides prepared by coprecipitation, as active center α-Bi2(MoO4)3Integrated distribution is not in catalyst coating；Which suppress the Activity and stabill of catalyst.
The open a kind of O composite metallic oxide catalyst of CN200410048021.7, catalyst is by 1. molybdenum, vanadium, copper main active component and 2. requisite at least by the stable component of antimony and titanium and composite oxides that 3. nickel, ferrum, silicon, aluminum, alkali metal, alkaline-earth metal form.2. and 3. it is wherein can composite oxides that within the scope of 120 DEG C to 900 DEG C prepared by roasting.This catalyst shows the permanent stability under high activity and good selectivity.The open a kind of acrylic acid catalyst for producing of CN200510059468.9, it is characterized in that, following formula M oaVbWcCudOx (1) metallic element represented composition oxide and/or composite oxides be must catalyst component acrylic acid catalyst for producing in, need to control tungsten and be partially in that the face side of this catalyst, and/or copper is in that the core side of this catalyst partially, to improve catalyst activity.Tungsten is in that the face side of this catalyst partially, and/or copper is in that the core side of this catalyst is difficult to accurately control partially.
CN1121441 disclose a kind of for the gas by acrylic aldehyde or containing acrolein gas Yu a kind of molecule-containing keto carry out in vapour phase oxidation reaction produce acrylic acid catalyst, this catalyst includes (A) a kind of composite oxides, there is molybdenum and vanadium as base stock, and be suitable to by vapor phase catalytic oxidation acrylic aldehyde to produce acrylic acid, (B) a kind of solid peracid, its acid strength (Ho) is not more than-11.93 (Ho≤-11.93).This invention adopts molybdenum vanadium type composite oxides to combine with a kind of acid strength solid acid less than-11.93, improves the low temperature high activity of catalyst.The open a kind of acrylic acid catalyst for producing of CN200510059468.9, it is characterized in that, following formula M oaVbWcCudOx (1) metallic element represented composition oxide and/or composite oxides be must catalyst component acrylic acid catalyst for producing in, need to control tungsten and be partially in that the face side of this catalyst, and/or copper is in that the core side of this catalyst partially, to improve catalyst activity.Tungsten is in that the face side of this catalyst partially, and/or copper is in that the core side of this catalyst is difficult to accurately control partially.The open a kind of methylacrolein acrylic acid catalyst of selective oxidation synthesizing methyl of CN1647854, the composition formula of this catalyst is: x (Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z is carrier dilution thermal conducting agent；Mo, P, K, Sb, Cu and As respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic；A represents at least one element in tungsten W, vanadium V, niobium Nb, ferrum 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 catalyst on the one hand by adding Sb, Cu and As；On the other hand by adding MoO3Improve the heat stability of catalyst, heat conductivility and mechanical strength with carrier heat conduction diluent, effectively the decomposition of inhibitory activity component heteropolyacid salt and reduce beds hot(test)-spot temperature, it is to avoid the loss of Mo and As, extend catalyst service life.Similar also has CN101579631.
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.
The open a kind of polymetal oxide materials of CN1109800: in formula, A is Mo12VaXb 1Xc 2Xd 3Xe 4Xf 5Xg 6Ox(coexisting phase), the crystallite (giving the raw data about X-ray diffraction fingerprint in round parentheses) that its part B comprises the X-ray diffraction pattern with at least one following copper molybdate: Cu3(MoO4)2(OH)2(lindgrenite, the index card 36-405 of JCPDS-ICDD index (1991)), Cu4Mo6O20(A.Moini et al., Inorg.Chem.25(21) (1986), 3782-3785), Cu4Mo5O17(the index card 39-181 of JCPDS-ICDD index (1991)), etc..CN1462211 relates to a kind of method prepared containing Mo, V, Cu and the multiple-phase multi-metal oxide materials of other optional element.According to the present invention, at least one phase is pre-formed independently, and is dispersed in the precursor material of plastically deformable of another phase.Then this mixture is dried and calcines.Polymetal oxide materials is suitable as at catalytic gas phase oxidation organic compound, particularly acrolein oxidation is becoming in acrylic acid the active material of catalyst used.[A] p [B] q [C] r (I), phase A, B and the C in multimetal oxide compositions 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 crystal structure class α-CuMo of oxometallate crystallite copper molybdate of crystal structure types of at least one following copper molybdate4[the registration card 22-242 of JCPDS-ICDD card index, (1991)], Cu6Mo5O18[the registration card 40-865 of JCPCS-ICDD card index, (1991)], Cu4-xMo3O12, wherein x=0-0.25 [registration card 24-56 and the 26-547 of JCPCS-ICDD card index, (1991)], etc..
Polymetal oxide materials [A] p [B] q [C] r (I) of the open a kind of formula (I) of CN1295499, with containing molybdenum, vanadium, copper and antimony and one or more other metals specific and have the polymetal oxide materials of multicomponent structure and prepare acrylic acid catalyst as with the gas phase catalytic oxidation reaction of acrylic aldehyde.In formula, A is Mo12VaX1bX2 cX3 dX4 eX5 fX6 gOx, B is X1 7CuhHiOy, C is X1 8SbjHkOz, X1For W, Nb, Ta, Cr and/or Ce.Promoter phase B is made up of the crystallite of these copper molybdate or containing such copper molybdate crystallite: α-CuMoO4[the reference diffraction pattern in the index card 22-242 of JCPDS-ICDD retrieval 1991], Cu6Mo5O18[the reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrieval 1991], Cu4-xMo3O12Wherein, x is 0-0.25 [the reference diffraction pattern in index card 24-56 and the 26-547 of JCPDS-ICDD retrieval 1991], etc..Region C can have metaantimmonic acid copper Cu9Sb4O19The crystallite of structure or Cu4SbO4.5The crystallite of structure.CN1093950 discloses the compositions of one kind of multiple metal-oxides, Mo, V, W, Cu, Ni including the oxidised form as basis, its premise is to there is following ratio: Mo:V=12:1 to 2:1 between each elemental composition, Mo:W=60:1 to 3:1, Mo:Cu=24:1 to 2:1, Cu:Ni=5:1 to 1:3.X1It is one or more alkali metal；X2It is one or more alkaline-earth metal；X3It is Cr, Mn, Ce and/or Nb；X4It is Sb and/or Bi；X5It is Si, Al, Ti and/or Zr.CN87103192 discloses a kind of method producing composite oxide catalysts, wherein include coherent element source compound to mix Aquo System is formed complex and this complex is carried out heat treatment by the production method of the Mo-Bi composite oxide catalysts of following chemical formulation, adopt a kind of compound of waltherite complex of (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X as Bi source, this complex at least contains 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 catalyst2(MoO4)3、MoO3Fe2(MoO4)3With β-CoMoO4、y-Bi2MoO6And γ-Bi2MoO6.CN101690900A discloses a kind of preparation method preparing acrylic aldehyde and acrylic acid catalyst, and catalyst is supported thing by active component and inert alumina carrier forms；Active component mainly comprises element, selected from Mo, Bi, Co and/or Ni and Fe, also comprises the trace element such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P, W；Wherein active component represents by following statement formula: MoaBibCocNidFeeXfYgZhOiIn formula, X represents at least one of K, Na, Rb and Cs, and Y represents at least one in B, P and W, and Z represents at least one in Mg, Ca, Zn.The ratio that active component is supported on carrier accounts for the 5-70% of overall catalyst weight；Active component is uneven distribution, CoMoO4、NiMoO4The kernel of catalyst activity component it is positioned at Deng the aluminate of divalent metal；Fe2(MoO4)3And the MoO of free state3Invest the outer layer of kernel；And the outermost layer of active component is bismuth molybdate, form the state of core-shell structure copolymer layer distributed.In active component, bivalence molybdate is mainly beta phase structure, and α phase structure content in active component is very low or is absent from.Catalyst has high activity and high stability.CN1280036 mono-kind produces the catalyst of unsaturated aldehyde and unsaturated carboxylic acid, described production is by making at least one compound selected from propylene, isobutene., the tert-butyl alcohol and methyl tertiary butyl ether(MTBE) carry out vapour-phase oxidation with oxygen molecule or the gas containing oxygen molecule and realize, it is characterized in that this catalyst is a kind of combined oxidation compositions, contain: (A) is containing composite oxides as key component of molybdenum, bismuth and ferrum, itself it is the known catalyst reacted for described vapor phase catalytic oxidation, and (B) is containing composite oxides as key component of cerium and zirconium.Catalyst has long catalytic life and makes running steady in a long-term be possibly realized.Wherein component (B), is the composite oxides represented by below general formula (2): CepZrqFrOy.The zirconium oxide of high degree of dispersion inhibits the gathering of cerium oxide, to keep the latter to the promotion functions absorbing and discharging oxygen significantly in course of reaction, thus accelerating the oxidation reaction of isobutene., therefore improves catalysis activity.Additionally, further suppress the irreversible activity of component (A) composite oxides caused because of over reduction in time to reduce (namely the stability of composite oxides improves), so that catalytic life prolongation.This catalysis activity that improve and the catalytic life extended inhibit reaction temperature to raise in time, thus reducing the molybdenum distillation at hot spot.This catalyst is used for isobutylene oxidation.
Accordingly, it is desirable to provide acrylic aldehyde, acrylic acid catalyst are prepared in Propylene Selectivity oxidation, acrolein oxidation reaction can carry out under low temperature, high-load condition.Temperature of reactor distribution is more reasonable, active component molybdenum etc. not easily because of sublimation, and activity to be not susceptible to phase in version, purpose selectivity of product and yield mutually high.
Acrolein 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 acrolein selectivity oxidation technology that a kind of reaction condition relaxes, improving selectivity and the yield of purpose product as far as possible, long period stably operates, to obtain bigger economic benefit.
Summary of the invention
It is an object of the invention to provide a kind of method that unsaturated aldehyde prepares unsaturated acids, the method that especially acrylic aldehyde or methylacrolein selective oxidation produce corresponding unsaturated acids.Acrylic acid is prepared in particularly suitable acrolein selectivity oxidation.Reacting under low temperature, high-load condition, and improve selectivity and the yield of purpose product as far as possible, long period stably operates, to obtain bigger economic benefit.
A kind of method being prepared unsaturated acids by unsaturated aldehyde, the process conditions of oxidation reaction are not limited especially, as following process conditions can be adopted: reaction raw materials acrylic aldehyde or entrance reactor after methylacrolein, water, the preheated device of oxygen more than 160 DEG C preheating, salt bath heating, salt temperature 240～265 DEG C, it is preferable that 245～260 DEG C；Air speed 800～2200h-1, it is preferable that 800～1700h-1, feed composition: acrylic aldehyde or methylacrolein 8～12 volume %, steam 11～17%, oxygen 9～17 volume %, nitrogen 60～72 volume %；Fixed bed reactors are built with oxidation catalyst, and catalyst contains molybdenum, vanadium, copper and antimony element, mainly comprises by formula M oaVbCucSbdSreSifMgNhOx(I) representing, catalyst is possibly together with magnesio lanthanum hexaaluminate LaMgAl11O19, containing molybdenum, (I) of vanadium and magnesio lanthanum hexaaluminate by after 91～98% and 0.5～10% mass percent mixing through kneadings, molding, dry, obtain finished catalyst after roasting.
Wherein: Mo is molybdenum, V is vitriol, and Cu is copper, and Sb is antimony, and Sr is strontium, and Si is silicon, and silicon is the carrier added, and M is chosen from least one element in zinc, calcium, lanthanum, phosphorus, boron；N is chosen from least one element in tellurium, zirconium, titanium；O is oxygen；A, b, c, d, e, f, g, h represent each Elements Atom ratio respectively, and wherein a=12, b are numbers of 2～7, it is preferable that 2～6；C is a number of 0.5～5, it is preferable that 0.5～4；D is a number of 0.5～5, it is preferable that 1.0～4；E is a number of 0.1～2.5, and f is a number of 0.5～40, it is preferable that 0.5～25；G is a number of 0.1～4, and h is a number of 0.05～3, and x is the numerical value determined by the oxygen of each oxide.
The present invention adopts propylene two-step oxidizing process to prepare acrylic aldehyde acrylic acid, and one section of Propylene Selectivity oxidation acrolein, catalyst uses molybdenum-bismuth series catalysts, and acrylic acid is prepared in two-stage nitration acrolein selectivity oxidation, uses catalyst of the present invention.It is designed with thermocouple inside the present invention one, second stage reactor, for each spot temperature of assaying reaction device, in order to prevent propylene deep oxidation in lower catalyst agent from affecting yield, and make catalyst coking, the present invention controls acrolein oxidation (two-stage nitration) catalyst lower floor temperature lower than catalyst upper strata temperature, reaction bed temperature is adjusted by controlling salt temperature, salt temperature is preferably controlled in 245～260 DEG C, the long-life being so conducive to catalyst uses, and acrolein oxidation reaction can long period steady running.
It is highly preferred that containing catalyst (I) 92～97% in catalyst of the present invention, containing magnesio lanthanum hexaaluminate 1～8%.
The preparation method of catalyst of the present invention, prepare catalyst (I), magnesio lanthanum hexaaluminate including by coprecipitation, by catalyst (I), magnesio lanthanum hexaaluminate by after 88～96% and 0.5～10% mass percent mixing through kneadings, molding, dry, obtain finished catalyst after roasting.
The preferred lanthanum of M in the catalyst Formula (I) of the present invention, lanthanum and antimony, copper etc. can form stable crystal phase structure, such as LaSb, La5Sb3、Cu2La、Cu5La etc., thus suppressing part active component molybdenum to lose from catalyst surface because of distillation, active component molybdenum not easily runs off, and delays activity deterioration rate, catalyst activity and good stability.With molybdenum, vanadium ratio suitably, in logical formula I, h is a number of 0.5～3 to lanthanum.The preferred Lanthanum (III) nitrate in lanthanum source of the present invention, the preferred sodium stannate of Xi Yuan, stannous chloride.Catalyst mainly comprises and is represented by logical formula II: MoaVbCucSbdSreSifLagNhOx(II).
The composite multi-metal oxide catalyst (I) of the present invention adopts common preparation method, as following step can be adopted to prepare.
By M in the compound containing Mo, V, Cu, Sb, Sr and logical formula IgNhEach elemental constituent compound that part relates to dissolves and mix homogeneously in proportion, forms serosity after carrying out co-precipitation, adds one or more in silicon dioxide, aluminium oxide or carborundum, dry in slurry production process, and molding, roasting obtains catalyst (I) powder.
Catalyst of the present invention (I) powder and finished catalyst are required at 400～550 DEG C roasting 3～10h, compare the catalyst not distinguishing roasting, and 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.
Under Oxygen Condition, catalyst molybdenum isoreactivity component under the high temperature conditions not only easily distils and runs off, and phase in version easily occurs activity compatible, and activity occurs phase in version to cause that active selectable is decreased obviously mutually.Such as activity phase VMo3O11It is changed into MoO3, CoMoO4It is changed into Co3O4, CuMoO4It is changed into MoO3Deng.
Namely active component molybdenums in catalyst etc. enable maintenance and do not run off, and before and after the reaction of molybdenum equal size, basic change is little, but through long-term operation activity compatible, phase in version easily occurs.Magnesio lanthanum hexaaluminate is added in catalyst by the present invention, making active phase more stable, being not susceptible to phase in version thus improving catalyst activity and selectivity.
The compound of each component of catalyst of the present invention can use the nitrate of each element, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate etc..Such as ammonium molybdate, ammonium metavanadate, copper nitrate, Schweinfurt green, stibium oxide, strontium nitrate, zinc nitrate, calcium nitrate, Lanthanum (III) nitrate, phosphoric acid, boric acid, tellurium oxide, zirconium oxide, titanium oxide etc..
After catalyst slurry 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.
The catalyst of the present invention can directly use, it is possible to is carried on inert carrier and uses.Involved inert carrier can be the mixture of one or more of aluminium oxide, silicon dioxide, carborundum etc..
Acrolein oxidation of the present invention reaction can carry out under low temperature, high-load condition.Catalyst activity component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version, purpose selectivity of product and yield height mutually；Beds upper strata temperature is higher than upper strata temperature, and temperature of reactor distribution is more reasonable, and catalyst life is long, and acrolein oxidation reaction can long period steady running.
Evaluating catalyst performance index definition is as follows:
Detailed description of the invention
Illustrate that acrylic acid is prepared in acrolein selectivity oxidation with specific embodiment below, but the scope of the present invention is not limited to these embodiments.The analysis method of product composition adopts method generally in the art.
Embodiment 1
1. prepare catalyst (I)
Under agitation, take 180.1 grams of ammonium molybdates, ammonium metavanadate 19.9 grams, it is dissolved in 1000ml pure water (water temperature more than 65 DEG C), obtain serosity (1), then take 98.9 grams of copper nitrates, 26.7 grams of strontium nitrates, 2.5 grams of zinc nitrates are dissolved in 1000ml pure water (water temperature more than 65 DEG C), it is sufficiently stirred for mix homogeneously, obtains serosity (2).Then, serosity (1) mixes with serosity (2), obtains serosity (3), adds 1.4 grams of titanium dioxide, 64.4 grams of antimony oxides, obtains active component serosity (a).Active component serosity (a) adds 4.6 grams of silicon dioxide and 3.1 grams of graphite, 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 through the extruded hollow columnar granule for φ 4.5 × 5mm of banded extruder, dry rear 460 DEG C of roastings 5 hours for 110 DEG C, preparing catalyst (I), this catalyst (I) mainly comprises as Mo12V2Cu5Sb1.3Sr1.2Si0.9Zn0.1Ti0.2Ox。
By magnesium nitrate, Lanthanum (III) nitrate and aluminium hydroxide according to LaMgAl11O19Stoichiometric proportion mix homogeneously, add deionized water and also stir, then spray drying, gained powder through 1100 DEG C of roastings 10 hours, obtains particle diameter magnesio lanthanum hexaaluminate LaMgAl below 20 μm again through methods such as ball millings after 160 DEG C dry11O19。
Taking catalyst (I) 92 part, magnesio lanthanum hexaaluminate 8 parts, add deionized water and mediate in kneader, the extruded hollow columnar granule for φ 4.5 × 5mm, dry under 120 DEG C of conditions, at 550 DEG C, roasting obtains catalyst 1 in 3.5 hours.
Comparative example 1
Preparing comparative catalyst 1 according to the proportioning that mainly comprises of embodiment 1, but magnesio lanthanum hexaaluminate is not add catalyst with the form of solid solution, oxide, but prepare catalyst with coprecipitation method, reaction condition is with the appreciation condition of catalyst 1.Comparative catalyst 1 mainly comprise for:
Mo12V2Cu5Sb1.3Sr1.2Si0.9Zn0.1Ti0.2La0.3Mg0.3Al3.3Ox。
Fixing sheet pipe reactor internal diameter 25mm, inside sets thermocouple, loads the above-mentioned catalyst 1 of 50ml or comparative example catalyst 1, salt bath heating, salt temperature 250 DEG C along feedstock direction reactor bed.Tube inlet sentences air speed 1200h from the reactions above-1Enter the mixing gas of acrylic aldehyde 8 volume %, oxygen 12 volume %, steam 15 volume %, nitrogen 65 volume %.Reacting 24 hours Example 1 and comparative example 1 beds hot(test)-spot temperature respectively 275 DEG C and 279 DEG C, acrolein conversion rate is 99.2% and 98.7%, acrylic acid selectivity 90.6% and 89.7%, acrylic acid yield 89.3% and 88.1%.Through the reaction of 2000 hours, bed hot localised points temperature 276 DEG C and 278 DEG C, acrolein conversion rate is 99.1% and 97.9%, acrylic acid selectivity 90.5% and 88.2%, acrylic acid yield 89.2% and 85.7%.Embodiment catalyst activity component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version, active phase Stability Analysis of Structures mutually.Purpose selectivity of product and yield are high, and catalyst performance stabilised meets device long period steady running.Comparative example catalyst selectivity is poor, and acrylic aldehyde, acrylic acid yield are low.
Embodiment 2
The preparation of catalyst 2
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, within 4 hours, namely obtain catalyst (I) through 480 DEG C of roastings.Catalyst (I) mainly comprises as Mo12V6Cu0.6Sb0.5Sr1.9Si2.3La3Zr0.3Ti0.2Ox,
Taking catalyst (I) 97 part, magnesio lanthanum hexaaluminate 3 parts, add deionized water and mediate in kneader, the extruded hollow columnar granule for φ 4.5 × 5mm, dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyst 2 in 3.5 hours.
Fixing sheet pipe reactor internal diameter 25mm, inside sets thermocouple, loads the above-mentioned catalyst of 45ml, salt bath heating, salt temperature 255 DEG C along feedstock direction reactor bed.Tube inlet sentences air speed 1700h from the reactions above-1Enter the mixing gas of acrylic aldehyde 9 volume %, oxygen 13 volume %, steam 16 volume %, nitrogen 62 volume %.Reacting 24 hours beds hot(test)-spot temperatures 281 DEG C, acrolein conversion rate is 99.3%, acrylic acid selectivity 90.4%, acrylic acid yield 89.1%.Through the reaction of 2000 hours, bed hot localised points temperature 280 DEG C, acrolein conversion rate is 99.2%, acrylic acid selectivity 90.5%, acrylic acid yield 89.0%.Catalyst activity component molybdenum etc. are not easily because of sublimation, and it is high that activity is not susceptible to phase in version, purpose selectivity of product and yield mutually, catalyst performance stabilised.
Embodiment 3
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, within 4 hours, namely obtain catalyst (I) through 500 DEG C of roastings.Catalyst (I) mainly comprises as Mo12V4Cu3.5Sb3.5Sr0.1Si1.1La1.0Zr0.2Ox, taking catalyst (I) 94 part, magnesio lanthanum hexaaluminate 6 parts, add deionized water and mediate in kneader, the extruded hollow columnar granule for φ 4.5 × 5mm, dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyst 3 in 4 hours.
Fixing sheet pipe reactor internal diameter 25mm, inside sets thermocouple, loads the above-mentioned catalyst of 50ml, salt bath heating, salt temperature 257 DEG C along feedstock direction reactor bed.Tube inlet sentences air speed 2000h from the reactions above-1Enter the mixing gas of acrylic aldehyde 10 volume %, oxygen 14 volume %, steam 15 volume %, nitrogen 61 volume %.Reacting 24 hours beds hot(test)-spot temperatures 282 DEG C, acrolein conversion rate is 99.5%, acrylic acid selectivity 90.3%, acrylic acid yield 89.2%.Through the reaction of 2000 hours, bed hot localised points temperature 280 DEG C, acrolein conversion rate is 99.3%, acrylic acid selectivity 90.2%, acrylic acid yield 89.1%.Catalyst activity component molybdenum etc. are not easily because of sublimation, and it is high that activity is not susceptible to phase in version, purpose selectivity of product and yield mutually, catalyst performance stabilised.
Embodiment 4
Preparation process and primary raw material with embodiment 2 catalyst 2 are identical, within 7 hours, namely obtain catalyst (I) 370 DEG C of roastings.Catalyst (I) mainly comprises as Mo12V7Cu1.8Sb5Sr2.4Si1.2B0.6La2Te0.1Ox,
Taking catalyst (I) 98 part, magnesio lanthanum hexaaluminate 2 parts, add deionized water and mediate in kneader, the extruded hollow columnar granule for φ 4.5 × 5mm, dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyst 4 in 4 hours.
Fixing sheet pipe reactor internal diameter 25mm, inside sets thermocouple, loads the above-mentioned catalyst of 50ml, salt bath heating, salt temperature 245 DEG C along feedstock direction reactor bed.Tube inlet sentences air speed 1100h from the reactions above-1Enter the mixing gas of acrylic aldehyde 11 volume %, oxygen 14 volume %, steam 15 volume %, nitrogen 60 volume %.Reacting 24 hours beds hot(test)-spot temperatures 270 DEG C, acrolein conversion rate is 99.1%, acrylic acid selectivity 90.0%, acrylic acid yield 89.0%.Through the reaction of 2000 hours, bed hot localised points temperature 271 DEG C, acrolein conversion rate is 99.2%, acrylic acid selectivity 90.1%, acrylic acid yield 89.0%.Catalyst activity component molybdenum etc. not easily runs off, and it is high that activity is not susceptible to phase in version, purpose selectivity of product and yield mutually, catalyst performance stabilised.

Claims (10)

1. the method being prepared unsaturated acids by unsaturated aldehyde, adopt fixed bed reactors, it is characterized in that adopting following process conditions: reaction raw materials acrylic aldehyde or entrance reactor after methylacrolein, water, the preheated device of oxygen more than 160 DEG C preheating, salt bath heating temperature 240～265 DEG C, air speed 800～2200h-1, feed composition: acrylic aldehyde or methylacrolein 8～12 volume %, steam 11～17%, oxygen 9～17 volume %, nitrogen 60～72 volume %；Fixed bed reactors are built with oxidation catalyst, and catalyst contains molybdenum, vanadium, copper and antimony element, mainly comprises by formula M oaVbCucSbdSreSifMgNhOx(I) represent, catalyst possibly together with magnesio lanthanum hexaaluminate, containing molybdenum, (I) of vanadium and magnesio lanthanum hexaaluminate by after 91～98% and 0.5～10% mass percent mixing through kneading, molding, dry, obtain finished catalyst after roasting；Wherein: silicon is the carrier added, and M is chosen from least one element in zinc, calcium, lanthanum, phosphorus, boron；N is chosen from least one element in tellurium, zirconium, titanium；O is oxygen；A, b, c, d, e, f, g, h represent each Elements Atom ratio respectively, wherein a=12, b is a number of 2～7, c is a number of 0.5～5, and d is a number of 0.5～5, and e is a number of 0.1～2.5, f is a number of 0.5～40, g is a number of 0.1～4, and h is a number of 0.05～3, and x is the numerical value determined by the oxygen of each oxide.
2. method according to claim 1, it is characterised in that described method is applied to acrolein selectivity oxidation and prepares acrylic acid.
3. method according to claim 2, it is characterised in that salt temperature 245～260 DEG C, air speed 800～1700h-1.
4. method according to claim 2, it is characterised in that catalyst for oxidation of acrolein bed lower floor temperature is lower than beds upper strata temperature.
5. method according to claim 1, it is characterised in that containing catalyst (I) 92～97% in used catalyst, containing magnesio lanthanum hexaaluminate 1～8%.
6. method according to claim 1, it is characterised in that the preparation method of used catalyst includes preparing catalyst (I), magnesio lanthanum hexaaluminate by coprecipitation.
7. method according to claim 1, it is characterised in that in used catalyst (I), b is a number of 2～6, c is a number of 0.5～4, and d is a number of 1.0～4, and f is a number of 0.5～25.
8. method according to claim 1, it is characterized in that in used catalyst (I), M is lanthanum, h is a number of 0.5～3, and catalyst (I) mainly comprises and represented by logical formula II: MoaVbCucSbdSreSifLagNhOx (II).
9. the method according to any one of claim 5～8, it is characterized in that the preparation of used catalyst (I) comprises the steps: that each elemental constituent compound by MgNh part in the compound containing Mo, V, Cu, Sb, Sr and logical formula I relates to dissolves and mix homogeneously in proportion, serosity is formed after carrying out co-precipitation, slurry production process adds silicon dioxide and/or carborundum, dry, molding, roasting obtains catalyst (I) powder.
10. the preparation method of catalyst according to claim 6, it is characterised in that catalyst (I) and finished catalyst roasting 3～10h at 400～550 DEG C.__
CN201310585734.6A 2013-11-19 2013-11-19 A kind of method being prepared unsaturated acids by unsaturated aldehyde Active CN104649885B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310585734.6A CN104649885B (en) 2013-11-19 2013-11-19 A kind of method being prepared unsaturated acids by unsaturated aldehyde

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310585734.6A CN104649885B (en) 2013-11-19 2013-11-19 A kind of method being prepared unsaturated acids by unsaturated aldehyde

Publications (2)

Publication Number Publication Date
CN104649885A CN104649885A (en) 2015-05-27
CN104649885B true CN104649885B (en) 2016-07-06

Family

ID=53241593

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310585734.6A Active CN104649885B (en) 2013-11-19 2013-11-19 A kind of method being prepared unsaturated acids by unsaturated aldehyde

Country Status (1)

Country Link
CN (1) CN104649885B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109647471B (en) * 2017-10-12 2020-10-16 中国石油化工股份有限公司 Catalyst for increasing yield of partial anhydride
CN109647465B (en) * 2017-10-12 2020-10-16 中国石油化工股份有限公司 Catalyst for synthesizing partial anhydride

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1069948A1 (en) * 1998-04-06 2001-01-24 Basf Aktiengesellschaft Multi-metal oxide materials with a two-phase structure
CN101507927A (en) * 2009-02-10 2009-08-19 上海华谊丙烯酸有限公司 Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process
CN102039141A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Catalyst for preparing unsaturated acid from unsaturated aldehyde by oxidization and preparation method of catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4426069B2 (en) * 2000-06-12 2010-03-03 株式会社日本触媒 Acrylic acid production method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1069948A1 (en) * 1998-04-06 2001-01-24 Basf Aktiengesellschaft Multi-metal oxide materials with a two-phase structure
CN101507927A (en) * 2009-02-10 2009-08-19 上海华谊丙烯酸有限公司 Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process
CN102039141A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Catalyst for preparing unsaturated acid from unsaturated aldehyde by oxidization and preparation method of catalyst

Also Published As

Publication number Publication date
CN104649885A (en) 2015-05-27

Similar Documents

Publication Publication Date Title
US8481790B2 (en) Catalyst for producing unsaturated aldehyde by oxidation of lower olefin at high space velocity
EP1867387B1 (en) Method for manufacturing a catalyst for use in the production of methacrylic acid
CN101495229A (en) Multi-metal oxide catalyst and method for producing (meth)acrylic acid by using the same
CN100490973C (en) Catalyst for selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid and its use
CN104646016B (en) Unsaturated aldehyde oxidation catalyst and preparation method
CN104649885B (en) A kind of method being prepared unsaturated acids by unsaturated aldehyde
CN104649892B (en) A kind of method of unsaturated aldehyde selective oxidation
CN104649876B (en) A kind of preparation method of methacrylaldehyde
CN104646017B (en) Catalyst of selective oxidation of acraldehyde and preparation method thereof
CN104649894B (en) Acrolein selectivity oxidation prepares acrylic acid
CN103769143B (en) A kind of unsaturated aldehyde oxidation catalyst and preparation method
CN104649872B (en) A kind of method of selectivity of light olefin oxidation
CN104646013B (en) Catalyst for unsaturated aldehyde selective oxidation and preparation method thereof
CN104646012B (en) Propylene selectivity oxidation catalyst and preparation method
CN104646018B (en) A kind of unsaturated aldehyde catalyst for selective oxidation and preparation method thereof
CN104841446B (en) Catalyst for selective oxidation of propylene and preparation method of catalyst
CN104649875B (en) A kind of Propylene Selectivity method for oxidation
JP6628386B1 (en) Catalyst for unsaturated carboxylic acid production
CN104649893B (en) A kind of method preparing unsaturated acids
CN104646015B (en) A propylene oxidation catalyst and a preparing method thereof
JP3999972B2 (en) Method for producing acrylic acid or methacrylic acid
CN104649873B (en) For the method for selectivity of light olefin oxidation
CN104646011B (en) A kind of low-carbon alkene oxidation catalyst and preparation method
JP3999965B2 (en) Method for producing acrylic acid or methacrylic acid
JP3999974B2 (en) Method for producing acrylic acid or methacrylic acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant