CN104649873B - For the method for selectivity of light olefin oxidation - Google Patents

For the method for selectivity of light olefin oxidation Download PDF

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CN104649873B
CN104649873B CN201310585550.XA CN201310585550A CN104649873B CN 104649873 B CN104649873 B CN 104649873B CN 201310585550 A CN201310585550 A CN 201310585550A CN 104649873 B CN104649873 B CN 104649873B
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catalyzer
catalyst
propylene
oxide catalyst
molybdenum
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CN104649873A (en
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景志刚
刘俊保
翟月勤
魏玉丽
李晓银
张维东
南洋
胡晓丽
李自夏
王书峰
林宏
杨红强
韩燕�
李慧文
吴毅
景丽
田爱珍
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China Petroleum and Natural Gas Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J2523/22—Magnesium
    • 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
    • B01J2523/50—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
    • B01J2523/54—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
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/68—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/842—Iron
    • 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
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/845—Cobalt
    • 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
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/847—Nickel

Abstract

The present invention relates to a kind of method of propylene oxidation acrolein, reaction raw materials propylene, water, air enter fixed bed single tube reactor after preheater more than 120 DEG C preheatings, salt bath heating, fixed-bed reactor contain molybdenum, bismuth, iron, cobalt, nickel and antimony element built with Propylene Selectivity oxide catalyst catalyzer, catalyzer, also containing strontium titanate, obtains finished catalyst by after 90 ~ 98% and 0.3 ~ 9% mass percent mixing containing molybdenum, (I) of bismuth and strontium titanate after kneading, shaping, dry, roasting.Catalyst structure is stablized, and active ingredient molybdenum etc. not easily runs off, and phase in version not easily occurs active phase, improves selectivity and the yield of object product.

Description

For the method for selectivity of light olefin oxidation
Technical field
The present invention relates to a kind of for selectivity of light olefin method for oxidation, be particularly useful for propylene or the corresponding unsaturated aldehyde of selective isobutene oxidation generation, be specially adapted to Propylene Selectivity to be oxidized to propenal.
Background technology
Industrial propylene or isobutylene oxidation prepare the reaction unit mainly many reaction tubess of corresponding unsaturated aldehyde, ensureing that catalyzer is not sintered, under the prerequisite of long service life, improve selectivity and object product yield as far as possible, conservation, even if if feed stock conversion, 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] lY 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.
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 runs off, and actively mutually phase in version not easily occurs, 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 a kind of selectivity of light olefin method for oxidation, mainly the preparation method of corresponding unsaturated aldehyde is produced in propylene or selective isobutene oxidation.Particularly propenal, acrylic acid are prepared in Propylene Selectivity oxidation.
Selectivity of light olefin method for oxidation provided by the invention is as follows: adopt fixed bed single tube reactor; Reaction raw materials propylene or iso-butylene, water, air enter reactor, salt bath heating after preheater more than 120 DEG C preheatings, and reaction process condition is: salt temperature 300 ~ 330 DEG C, preferably 305 ~ 325 DEG C; Air speed 800 ~ 2000h -1, preferably 800 ~ 1600h -1, feed composition: propylene or iso-butylene 8 ~ 15 volume %, air 70 ~ 75 volume %, water vapour 15 ~ 21%; Fixed-bed reactor are built with oxide catalyst, and catalyzer contains molybdenum, bismuth, iron, cobalt, nickel and antimony element, mainly form by formula M o abi bfe cco dni esb fsi ga hb io x(I) represent, catalyzer, also containing strontium titanate, obtains finished catalyst by after 90 ~ 98% and 0.3 ~ 9% mass percent mixing containing molybdenum, (I) of bismuth and strontium titanate after kneading, shaping, dry, roasting.Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Co is cobalt, and Ni is nickel, and Sb is antimony, and Si is silicon, and silicon is the carrier added in catalyzer, and A is at least one element be selected from magnesium, barium, lanthanum, and B is selected from least one element in calcium, boron, zinc; 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 0.5 ~ 6, preferably 1.0 ~ 5; C is a number of 0.5 ~ 5, preferably 1 ~ 4; D is a number of 1 ~ 8, preferably 1 ~ 6; E is a number of 0.5 ~ 6, and f is a number of 0.1 ~ 3, and g is a number of 0.2 ~ 55, preferably 1 ~ 16, h be 0.05 ~ 4 a number, i is a number of 0.05 ~ 1.5, and x is the numerical value determined by the oxygen of each oxide compound.
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 308 ~ 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 carry out spraying dry 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.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 ~ 3 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.
Can add active ingredient lanthanum in the catalyst activity component that the present invention (I) represents, lanthanum and nickel, cobalt, antimony etc. form stable crystal phase structure, as Co 3la 2, LaNi 5, La 2sb, LaSb etc., 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, 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 ~ 2.5, 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 dNi eSb fSi gLa hB iO x（Ⅱ）
Multi-metal-oxide catalyst of the present invention (I) adopts common preparation method, prepares as adopted following step.
By A in the compound containing Mo, Bi, Fe, Co, Ni, Sb and logical formula I hb ithe 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).
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, make catalyst stability better.
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 by after 90 ~ 98% and 0.3 ~ 9% mass percent mixing through mediating, obtain finished catalyst after shaping, dry, roasting.
According to the preparation method of above-mentioned catalyzer, more preferably, can also add the lanthanum CeO2-ZrO2 solid solution that mass percentage is 0.1 ~ 3, such catalyzer thermostability and good hydrothermal stability, wherein strontium titanate and lanthanum CeO2-ZrO2 solid solution mass percentage are 0.3 ~ 9%.
More preferably, containing catalyzer (I) 92 ~ 97% in catalyzer, also has strontium titanate 2 ~ 7%.
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.
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, weisspiessglanz, strontium nitrate, titanium dioxide, borax, boric acid, nitrocalcite, zinc 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.
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 169.5 grams of ammonium molybdates and be dissolved in (water temperature more than 65 DEG C) in 1000ml pure water, obtain slurries (1), then get 76.8 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 40.4 grams of iron nitrates, 58.2 grams of nickelous nitrates, 3.7 grams of magnesium nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Get 77.6 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), then 56 grams of ANTIMONY TRIOXIDE SB 203 99.8 PCT, obtain active ingredient slurries (a).10.1 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 for 2 hours, 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 2Fe 1.25Co 3.3Ni 2.5Sb 1.2Si 3.1Mg 0.25O 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) 94 part, strontium titanate oxide compound 4 parts, lanthanum CeO2-ZrO2 solid solution Ce 0.6zr 0.3la 0.22o 22 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 Ce 0.6zr 0.3la 0.22o 2be not add catalyzer with the form of solid solution, oxide, strontium titanate is not add with the form of Whole Oxygen compound, and lanthanum, cerium, zirconium, titanium and strontium are introduced in co-precipitation mode, and obtained comparative catalyst, reaction conditions is with the appreciation condition of catalyzer 1.Comparative catalyst 1 mainly consists of
Mo 12Bi 2Fe 1.25Co 3.3Ni 2.5Sb 1.2Si 3.1Mg 0.25Ce 0.6Zr 0.3La 0.22Ti 0.2Sr 0.2O x。
Comparative example 2
The preparation of comparative catalyst 2 and composition content copper comparative example 1, but do not add lanthanum CeO2-ZrO2 solid solution Ce 0.6zr 0.3la 0.22o 2, identical with comparative example 1, titanium and strontium neither add with the form of Whole Oxygen compound, but with coprecipitation method Kaolinite Preparation of Catalyst, comparative catalyst 2 mainly consists of
Mo 12Bi 2Fe 1.25Co 3.3Ni 2.5Sb 1.2Si 3.1Mg 0.25Ti 0.2Sr 0.2O x。
Propylene oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer 1 of 45ml or comparative example catalyzer 1 or 2, salt bath heating, salt temperature 312 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 73 volume %, water vapour 17 volume %.React 24 hours, embodiment 1 beds hot localised points temperature 362 DEG C, beds upper temp is higher than beds bottom bed temperature.Propylene conversion 99.2%, acrolein selectivity 88.3%, propenal yield 81.7%, acrolein+acrylic acid yield 92.6%.Temperature distribution is more reasonable, is conducive to the steady running of catalyzer long period.Through the reaction of 2000 hours, bed hot localised points temperature 363 DEG C, beds upper temp was higher than beds bottom bed temperature.Propylene conversion 98.9%, acrolein selectivity 88.4%, propenal yield 81.6%, acrolein+acrylic acid yield 92.5%.Active ingredient molybdenum etc. not easily runs off, and phase in version not easily occurs active phase, and catalyst structure is stablized, and improves selectivity and the yield of object product, meets the steady running of device long period.Sampling analysis in comparative example catalyzer 1 and 2 oxidizing reaction 24 hours, bed hot localised points temperature 363 DEG C and 360 DEG C, propylene conversion 98.8% and 98.3%, acrolein selectivity 83.0% and 82.1%, propenal yield 75.7% and 75.5%, acrolein+acrylic acid yield 87.0% and 86.6%.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 560 DEG C of roastings, mainly consist of: Mo 12bi 5fe 4co 5ni 1.5sb 0.8si 1.2sr 0.1la 0.5b 0.1o x, get catalyzer (I) 92 part, strontium titanate oxide compound 5.5 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 550 DEG C, roasting obtains catalyzer 2 in 4 hours.
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer 2 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 1200h -1import the mixed gas of propylene 8 volume %, air 72 volume %, water vapour 20 volume %, sampling analysis in oxidizing reaction 24 hours, bed hot localised points temperature 352 DEG C, propylene conversion 98.8%, acrolein selectivity 88.5%, propenal yield 81.1%, acrolein+acrylic acid yield 91.1%.
Embodiment 3
With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 10 hours, namely obtain catalyzer (I) through 400 DEG C of roastings.Mainly consist of: Mo 12bi 0.8fe 3co 8ni 4sb 2si 0.8ti 0.5ca 0.2o 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 550 DEG C, roasting obtains catalyzer 3 in 4 hours.
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer 3 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 2000h -1import the mixed gas of propylene 11 volume %, air 72 volume %, water vapour 17 volume %.Oxidizing reaction is after 24 hours, bed hot localised points temperature 371 DEG C, propylene conversion 99.3%, acrolein selectivity 88.7%, propenal yield 81.6%, acrolein+acrylic acid yield 92.4%.Oxidizing reaction is after 2000 hours, bed hot localised points temperature 370 DEG C, propylene conversion 99.4%, acrolein selectivity 88.9%, propenal yield 81.8%, acrolein+acrylic acid yield 92.5%.Active ingredient molybdenum etc. not easily runs off, and phase in version not easily occurs active phase, and catalyst structure is stablized, and is applicable to the steady running of device long period.
Embodiment 4
With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 6 hours, namely obtain catalyzer (I) through 480 DEG C of roastings.Mainly consist of: Mo 12bi 3fe 2.1co 1.3ni 1.1sb 3si 1.6mg 0.1la 1.0o x, get catalyzer (I) 98 part, strontium titanate oxide compound 2 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 500 DEG C, roasting obtains catalyzer 4 in 5 hours.
Propylene oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, loads the above-mentioned catalyzer of 45ml, salt bath heating temperature 313 DEG C along propylene feed orienting response device bed.From above-mentioned reaction tubes ingress with air speed 1700h -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 362 DEG C, propylene conversion 98.9%, acrolein selectivity 88.5%, propenal yield 81.5%, acrolein+acrylic acid yield 92.0%.
Embodiment 5
With the preparation process of embodiment 1 catalyzer 1 and main raw material identical, within 5 hours, namely obtain catalyzer (I) through 550 DEG C of roastings.Mainly consist of: Mo 12bi 1fe 4.8co 5.7ni 5.4sb 1.0si 1sr 0.3o x, get catalyzer (I) 96 part, strontium titanate oxide compound 3.5 parts, lanthanum CeO2-ZrO2 solid solution Ce 0.7zr 0.2la 0.31o 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 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 45ml, salt bath heating temperature 310 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 9 volume %, air 71 volume %, water vapour 20 volume %.Sampling analysis in oxidizing reaction 24 hours, bed hot localised points temperature 359 DEG C, propylene conversion 98.8%, acrolein selectivity 88.3%, propenal yield 81.3%, acrolein+acrylic acid yield 91.9%.
Embodiment 2 catalyzer is at salt bath heating temperature 312 DEG C, air speed 1000h -1, propylene 10 volume %, air 70 volume %, water vapour 20 volume % condition under reaction 24 hours and 500 hours, bed hot localised points temperature is respectively 363 DEG C, 362 DEG C, propylene conversion 98.9%, 98.7%, acrolein selectivity 87.9%, 88.1%, propenal yield 81.2%, 81.0%, acrolein+acrylic acid yield 91.3%, 91.1%.Temperature distribution is more reasonable, and catalyst activity component structure is stablized, and is conducive to the steady running of catalyzer long period.Embodiment 2 and 4 catalyzer is at salt bath heating temperature 312 DEG C, air speed 1000h -1, propylene 10 volume %, air 70 volume %, water vapour 20 volume % condition under stablize 6 hours after adjust salt temperature to 355 DEG C (stopping propylene) again, after 10 hours, be down to 312 DEG C again, embodiment 2 and 4 is (salt bath heating temperature 312 DEG C, air speed 1000h under similarity condition -1, propylene 10 volume %, air 70 volume %, water vapour 20 volume %) react 24 hours, bed hot localised points temperature is respectively 361 DEG C, 355 DEG C, propylene conversion 98.8%, 97.5%, acrolein selectivity 87.8%, 84.5%, propenal yield 81.0%, 75.7%, acrolein+acrylic acid yield 91.0%, 83.8%.Under the condition through water vapour 20 volume %, salt bath heating temperature 355 DEG C of hydrothermal treatment consists, relative to embodiment 4, embodiment 2 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 selectivity of light olefin method for oxidation, it is characterized in that, reaction raw materials propylene or iso-butylene, water, air enter reactor, salt bath heating after preheater more than 120 DEG C preheatings, and reaction process condition is: salt temperature 300 ~ 330 DEG C, air speed 800 ~ 2000h -1, feed composition: propylene or iso-butylene 8 ~ 15 volume %, air 70 ~ 75 volume %, water vapour 15 ~ 21 volume %, fixed-bed reactor are built with oxide catalyst, and described oxide catalyst includes molybdenum, bismuth, iron, cobalt, nickel and antimony element, and it mainly consists of catalyzer (I), and described catalyzer (I) is by formula M o abi bfe cco dni esb fsi ga hb io xrepresent, wherein: silicon is the carrier added in catalyzer, A is at least one element be selected from magnesium, barium, lanthanum, and B is selected from least one element in calcium, boron, zinc, O is oxygen, a, b, c, d, e, f, g, h, i represents each Elements Atom ratio respectively, wherein a is a number of 12, b is a number of 0.5 ~ 6, c is a number of 0.5 ~ 5, d is a number of 1 ~ 8, e is a number of 0.5 ~ 6, f is a number of 0.1 ~ 3, g is a number of 0.2 ~ 55, h is a number of 0.05 ~ 4, i is a number of 0.05 ~ 1.5, x is the numerical value determined by the oxygen of each oxide compound, oxide catalyst is also containing strontium titanate, through mediating after described catalyzer (I) and described strontium titanate mix by the mass percent with 90 ~ 98% and 0.3 ~ 9%, shaping, dry, described oxide catalyst is obtained after roasting.
2. method according to claim 1, is characterized in that in oxide catalyst used also containing the lanthanum CeO2-ZrO2 solid solution that mass percentage is 0.1 ~ 3.
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 ~ 1600h -1.
5. method according to claim 1, is characterized in that beds lower floor temperature is lower than beds upper strata temperature.
6. method according to claim 1, is characterized in that described oxide catalyst comprises catalyzer (I) 92 ~ 97%, also comprises strontium titanate 2 ~ 7%.
7. method according to claim 1, it is characterized in that the preparation method of described oxide catalyst used comprises with coprecipitation method Kaolinite Preparation of Catalyst (I), strontium titanate, by catalyzer (I), strontium titanate by after 90 ~ 98% and 0.3 ~ 9% mass percent mixing through mediating, obtain described oxide catalyst 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 ~ 2.5, and described oxide catalyst mainly forms as shown in logical formula II, Mo abi bfe cco dni esb 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 ~ 5, c is a number of 1 ~ 4, and d is a number of 1 ~ 6, and g is a number of 1 ~ 16.
10. method according to claim 1, is characterized in that the method for preparing catalyst that used catalyst (I) represents comprises the steps: A in the compound containing Mo, Bi, Fe, Co, Ni, Sb and catalyzer (I) hb ithe each elementary composition compound dissolution related to and mix, form slurries after carrying out co-precipitation, in slurry production process, add silicon-dioxide, dry, shaping, roasting, obtained catalyzer (I).
The preparation method of 11. catalyzer according to claim 7, is characterized in that also adding the lanthanum CeO2-ZrO2 solid solution that mass percentage is 0.1 ~ 3 in described oxide catalyst.
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FR2826959A1 (en) * 2001-07-06 2003-01-10 Atofina Preparation of acrolein from propylene by a redox reaction using a redox system comprising a mixed oxide
CN102247862A (en) * 2010-05-18 2011-11-23 中国石油天然气股份有限公司 Multilayer composite metal oxide catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2826959A1 (en) * 2001-07-06 2003-01-10 Atofina Preparation of acrolein from propylene by a redox reaction using a redox system comprising a mixed oxide
CN102247862A (en) * 2010-05-18 2011-11-23 中国石油天然气股份有限公司 Multilayer composite metal oxide catalyst and preparation method thereof

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