CN104646012B - Propylene selectivity oxidation catalyst and preparation method - Google Patents
Propylene selectivity oxidation catalyst and preparation method Download PDFInfo
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- CN104646012B CN104646012B CN201310585731.2A CN201310585731A CN104646012B CN 104646012 B CN104646012 B CN 104646012B CN 201310585731 A CN201310585731 A CN 201310585731A CN 104646012 B CN104646012 B CN 104646012B
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Abstract
The present invention relates to a kind of multi-metal-oxide catalyst, catalyst contains molybdenum, bismuth, iron, nickel, cobalt and copper, mainly constitutes by formula M oa′Bib′Fec′Nid′Coe′CufSihAiBjOy（Ⅰ）Represent, catalyst also contains lanthanum-magnesium aluminate oxide.Catalyst of the present invention is reacted for selective oxidation of olefins, and active component molybdenum etc. is difficult because of sublimation, and activity is the characteristics of be mutually not susceptible to phase in version, reactivity and selectivity height, long service life.
Description
Technical field
The present invention relates to a kind of catalyst of poly-metal deoxide, for being catalyzed Propylene Selectivity oxidation acrolein.
Background technology
It is industrial at present that acrylic acid, first propylene catalytic gas phase oxidation generation third are mainly prepared using propylene two-step oxidizing process
Olefine aldehydr, methacrylaldehyde is reoxidised into acrylic acid.
The reaction unit that industrial propylene oxidation prepares methacrylaldehyde is mainly many reaction tubes, is ensureing that catalyst is not burnt
On the premise of knot, long service life, selectivity and purpose product yield are improved as far as possible, raw material is saved, if feed stock conversion, third
Even if olefine aldehydr acrylic acid yield improves 0.1~0.5 percentage point, the amount of the product for obtaining is increased with the level of hundreds of~thousands of tons of
Plus, its economic benefit is also very considerable.
It is mainly molybdenum system multicomponent catalyst on propylene fraction oxidation acrolein, acrylic acid catalyst.Due to propylene
It is strong exothermal reaction that selective oxidation prepares the acrylic acid reaction of methacrylaldehyde, so the big water of specific heat is passed through in course of reaction steaming
Gas, effectively to remove reaction heat, but the easy loss under the washing away of the air-flows such as vapor such as active component molybdenum in catalyst.
And, under the high temperature conditions, part active component molybdenum loses from catalyst surface because of distillation in catalyst.Active component molybdenum
Loss causes to reduce the active of catalyst, selectivity, intensity and service life, and molybdenum in the deposition in reaction system downstream, resistance
Plug pipeline influences the long-term operation of system.
In addition, active component molybdenum in catalyst etc. is enabled to keep not being lost in, basic change before and after the reaction of molybdenum equal size
Less, but easily there is phase in version by long-term operation activity compatible.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；Fe2
(MoO4)3Play redox facilitation；CoMoO4And NiMoO4Play Stability Analysis of Structures.However, using coprecipitation method system
Standby catalyst is more due to component, and process is complicated, catalyst stabilization difference, although initial activity is very high, inactivation is fast.Cause many
Component Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalyst inactivation and stability decline factor have a lot, including because
The sublimation of Mo components and the change of irreversible crystalline phase etc. caused by local abnormal high temperature (focus).These factors can all draw
The change of specificity of catalyst is played, is caused the reduction of catalyst activity and is shortened the service life of catalyst.Urged by inactivation
Agent carries out phenetic analysis, finds Fe2(MoO4)3It is reduced into FeMoO4, and α-Bi2(MoO4)3It is changed into γ-Bi2MoO6。
Solve the above problems, the patent being related to is relatively more, for example, being the loss of suppression molybdenum, CN1583261 discloses one kind
It is selectively oxidized the composition metal of reaction in the gas phase with a kind of gas of molecule-containing keto for the gas containing unsaturated aldehyde
Oxide catalyst, its catalyst constitutes and is：[MoaVbCucXd]lYm[SbeZ1 fZ2 g]nOxWherein Mo is molybdenum, and V is vanadium, and Cu is copper,
Sb is antimony, and X is a kind of element at least selected from tungsten and niobium, and Y is at least to be selected from titanium, a kind of element of antimony, Z1It is at least to be selected from iron
With a kind of element of nickel, Z2It is at least to be selected from silicon, aluminium, a kind of element of alkali and alkaline earth metal ions, a, b, c, d, e, f, g and x
The atomic ratio number of its element is represented, when on the basis of a=12, b is 1 to 6 number, and c is 0.5 to 4 number, and d is 0.05
To 4 number, e is 0.1 to 30 number, and f is 0 to 25 number, and g is 0.01 to 20 number；X is by meeting
A number needed for each metallic element combined oxidation state；Catalyst is made up of its each element oxide or composite oxides.
In order to improve the stability of catalyst, CN1130172 discloses a kind of acrylic acid catalyst, respectively with ammonium metavanadate and
Copper nitrate, and with low price barium oxide and/or low price Cu oxide part replace ammonium metavanadate and/or copper nitrate make vanadium metal and
Catalyst obtained by the raw material of copper or in addition to above-mentioned raw materials, is obtained using low price sb oxide and/or low price tin-oxide
Catalyst show in d=4.00 have a strengthened peak (vanadium-molybdenum reactive compound is peculiar) and have in d=4.38_
One V of remitted its fury2O5Specific peak.So, catalyst obtained above has the catalysis activity for improving, and can be long-term
Show stability.Similar also has patent document 1：Japanese Unexamined Patent Publication 2002-233757 publications, patent document 2：It is Japanese special
Open flat 8-299797 publications, patent document 3：Japanese Unexamined Patent Publication 9-194213 publications, patent document 4：Japanese Unexamined Patent Application Publication 2004-
No. 504288 publications；CN102066000A.
To improve the active of catalyst, selectivity and catalyst life, CN200980112659.3 discloses one kind and includes
The coating catalyst of following components：(a) carrier, (b) comprising molybdenum oxide or the precursor compound for forming molybdenum oxide first
Layer, (c) includes the second layer containing molybdenum and the poly-metal deoxide of at least one other metals.It is preferred that the molybdenum oxide of ground floor is
MoO3, the poly-metal deoxide of the second layer is the poly-metal deoxide that formula II is represented：Mo12BiaCrbX1 cFedX2 eX3 fOy.This is urged
Agent is to include the application type catalyst of carrier.Goal of the invention is to suppress heterogeneously catalysed partial gas phase oxidation methacrylaldehyde for propylene
The coating catalyst inactivation of acid, with improved inactivation performance.The invention does not have catalyst is expressly recited for being catalyzed propylene
Oxidation acrolein, such as acrylic acid reactivity worth evaluating data, conversion ratio, selectivity, yield etc..CN87103192 is disclosed
A kind of method for producing composite oxide catalysts, wherein the Mo-Bi composite oxide catalysts represented with following chemical formula
Production method includes being heat-treated formation compound in coherent element source compound incorporation Aquo System and to the compound,
Using (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X waltherite compound a kind of compound as Bi sources, this be combined
In thing at least containing Na and/or X needed for 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, as a=12, b=0.5-7, c=0-10, d=0-10, c+d=1-
10th, e=0.05-3, f=0.01-1, g=0-1, h=0.04-0.4, i=0-3, j=0-48, k are one and meet other element oxide states
Number.Solve the problems, such as that Bi can be dispersed in composite oxide catalysts.Contain α-Bi in catalyst2(MoO4)3、
MoO3Fe2（MoO4）3With β-CoMoO4、y-Bi2MoO6Andγ-Bi2MoO6.CN101690900A discloses one kind and prepares methacrylaldehyde and third
The preparation method of olefin(e) acid catalyst, catalyst supports thing by active component and inert alumina carrier is constituted；Active component is main
Component, selected from Mo, Bi, Co and/or Ni and Fe, also comprising the micro unit such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P, W
Element；Wherein active component is represented with following statement formulas：MoaBibCocNidFeeXfYgZhOiIn formula, X represents K, Na, Rb and Cs extremely
Few one kind, Y represents that, selected from least one in B, P and W, Z is represented selected from least one in Mg, Ca, Zn.Active component is supported
Ratio on carrier accounts for the 5-70% of overall catalyst weight；Active component is in uneven distribution, CoMoO4、NiMoO4Etc. divalence gold
The aluminate of category is located at the kernel of catalyst activity component；Fe2(MoO4)3And the MoO of free state3Invest the outer layer of kernel；And
The outermost layer of active component is bismuth molybdate, forms the state of core-shell structure copolymer layer distributed.Divalence molybdate is mainly β in active component
Phase structure, content is very low in active component or does not exist for α phase structures.Catalyst has high activity and high stability.
A kind of catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid of CN1280036, described production is selected from by making at least one
The compound and oxygen molecule of propylene, isobutene, the tert-butyl alcohol and methyl tertiary butyl ether(MTBE) or the gas containing oxygen molecule carry out vapour phase oxygen
Change and realize, it is characterised in that the catalyst is a kind of combined oxidation compositions, is contained：(A) containing molybdenum, bismuth and iron as master
Want the composite oxides of component, itself be the known catalyst for vapor phase catalytic oxidation reaction, and (B) containing cerium and
Zirconium as key component composite oxides.Catalyst has catalytic life long and makes it possible to operate steadily in the long term.Its
Middle component (B), is the composite oxides represented with below general formula (2)：CepZrqFrOy.The zirconium oxide of high degree of dispersion inhibits oxygen
Change the aggregation of cerium, it is different so as to accelerate to keep the latter during the course of the reaction to significantly absorbing and discharging the promotion functions of oxygen
The oxidation reaction of butylene, therefore improve catalysis activity.Additionally, further suppress the component because causing with time over reduction
(A) the irreversible activity of composite oxides reduces (i.e. the stability of composite oxides is improved), so that catalytic life is prolonged
It is long.This catalysis activity that improve and the catalytic life for extending inhibit reaction temperature to be raised with the time, so as to reduce
Distillation of the molybdenum in hot spot.The catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparation and renovation process for producing methacrylaldehyde.Catalyst be with
The composite oxides of following atomic ratios：Mo: Bi: Co: Ni: Fe=10-14: 1.2-2.0: 4.8-5.6: 2-3: 1-2；The catalyst
With the pore size distribution more concentrated, the mesopore of moderate total pore volume, wherein 5-10nm or so accounts for more than the 70% of total pore size distribution, shape
Into short and thick pore passage structure, this feature assigns catalyst stronger anti-carbon deposition ability, catalyst surface not easy-sintering, can
Extend the service life of catalyst.And passing through the renovation process that the present invention is provided, decaying catalyst is carried out in an oxidizing atmosphere
1-3 days calcination processings, catalyst activity is suitable with fresh catalyst.CN87103192 produces Mo-Bi-Na composite oxide catalytics
The method of agent product, the method includes that mixing coherent element source compound forms compound, then is heat-treated, will at least
The basic bismuth carbonate of Na is used as Bi source compounds needed for solid solution part.The activity of catalyst imports specific water by means of Bi and Na
Insoluble compound formed catalyst and be able to greatly improve.
CN1109803 is related to multimetal oxide compositions, and they have two phase structure and comprising molybdenum, hydrogen, one or many
Individual element phosphor, arsenic, boron, germanium and silicon；And it is related to the composition in terms of methacrylic acid is prepared by catalytic gas phase oxidation
Purposes, improves activity and selectivity.CN1109802 discloses a kind of multimetal oxide compositions, and they have two phase structure simultaneously
Comprising molybdenum, hydrogen, one or more element phosphors, arsenic, boron, germanium and silicon and copper, base acrylic acid activity and selectivity is improved.
CN1298861A is then the composite oxides using addition magnesium, aluminium and silicon.CN1321110A is then respectively with antimony oxide and antimony acetate
As the antimony source of active metal composite oxide.To solve under high-load condition, catalytic mechanical intensity is good, and activity is high to ask
Topic.CN200410048021.7 discloses a kind of O composite metallic oxide catalyst, and catalyst is by 1. molybdenum, vanadium, copper chief active
Component and 2. it is essential at least by antimony and titanium stable component and 3. nickel, iron, silicon, aluminium, alkali metal, alkaline-earth metal are constituted
Composite oxides.Wherein 2. and 3. it is the composite oxides that preparation can be calcined in the range of 120 DEG C to 900 DEG C.The catalyst
Show the permanent stability under high activity and good selectivity.CN1121441 discloses a kind of for by methacrylaldehyde or containing third
Olefine aldehydr gas carries out oxidation reaction in vapour phase and produces acrylic acid catalyst, the catalyst bag with a kind of gas of molecule-containing keto
A kind of (A) composite oxides are included, with molybdenum and vanadium as base stock, and is suitable to by vapor phase catalytic oxidation methacrylaldehyde to produce
Acrylic acid, and a kind of (B) solid peracid, its acid strength (Ho) are not more than -11.93 (Ho≤- 11.93).The invention uses molybdenum vanadium type
Composite oxides are combined with a kind of solid acid of acid strength no more than -11.93, improve the low temperature high activity of catalyst.
CN200510059468.9 discloses a kind of acrylic acid catalyst for producing, it is characterized in that, in following formula M oaVbWcCudOx (1)
The oxide of the metallic element composition of expression and/or the acrylic acid catalyst for producing that composite oxides are necessary catalyst component
In, it is necessary to control the face side that tungsten is the catalyst partially, and/or copper is the core side of the catalyst partially, to improve catalyst
Activity.Tungsten is the face side of the catalyst partially, and/or copper is that the core side of the catalyst is difficult accurate control partially.
CN102039143A discloses the preparation method that a kind of acrolein oxidation prepares acrylic acid catalyst, a) composite oxide coating
Preparation method：Water-soluble metal salt containing Mo, V, W, Cu, Sb composition is dispersed in into water/organic in 30-100 DEG C to mix
In system；It is 5~50% to keep organic solvent and water weight ratio；Reaction generation composite oxides presoma slurries；Again by steaming
Evaporate, dry, being calcined prepared catalyst activity component；B) the main component of above-mentioned active component, selected from Mo, V, Cu, W, Sb its
In one or more；Wherein active component is represented with following formula：MoaVbCucWdSbeOf, the catalyst is using water and lower alcohol
Prepared by mixed system, catalyst has specific surface area and special microstructure higher, with compared with high-ratio surface and being difficult
Come off, and bearing capacity can reach 50% and more than, solve the problems, such as that application type catalyst service life is shorter.
CN1647854 discloses a kind of acrylic acid catalyst of MAL selective oxidation synthesizing methyl, the catalyst
Constituting formula is：x(Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z are that carrier dilutes thermal conducting agent；Mo, P, K, Sb, Cu and As
Respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic；A represents at least one of tungsten W, vanadium V, niobium Nb, iron Fe and lead Pb element；D represent boron,
At least one of gallium Ga, indium In, germanium Ge and silicon Si element；Q represents at least one of rubidium Rb, caesium Cs and thallium Tl element, the invention
On the one hand the activity and selectivity of catalyst is improved by adding Sb, Cu and As；On the other hand by adding MoO3And carrier
Heat conduction diluent improves heat endurance, heat conductivility and the mechanical strength of catalyst, effectively inhibitory activity component heteropoly acid
The decomposition of salt and reduction beds hot(test)-spot temperature, it is to avoid the loss of Mo and As, extend catalyst service life.
CN1109800 discloses a kind of polymetal oxide materials：A is Mo in formula12VaXb 1Xc 2Xd 3Xe 4Xf 5Xg 6Ox(coexist
Phase), crystallites of its part B comprising the X-ray diffraction pattern with least one following copper molybdate（Given in round parentheses
Close the firsthand information of X-ray diffraction fingerprint）：Cu3(MoO4)2(OH)2（Lindgrenite, JCPDS-ICDD indexes（1991）Index card
Piece 36-405）, Cu4Mo6O20（A.Moini et al., Inorg.Chem.25（21）（1986）, 3782-3785）, Cu4Mo5O17
（JCPDS-ICDD indexes（1991）Card index 39-181）, etc..CN1462211 be related to one kind prepare containing Mo, V, Cu and
The method of the multiple-phase multi-metal oxide materials of other optional elements.According to the invention, at least one mutually independently advance shape
Into, and be dispersed in the precursor material of the plastically deformable of another phase.Then the mixture is dried and calcines.Multi-metal oxygen
Compound material is suitable as in catalytic gas phase oxidation organic compound, particularly by acrolein oxidation into used in acrylic acid
The active material of catalyst.[A] p [B] q [C] r (I), phase A, B and C in multimetal oxide compositions can be unbodied
And/or crystallization.Advantageously it is made up of the crystallite of oxometallate for phase B, or comprising with X-ray diffraction pattern and entering
And the crystal structure class α-CuMo of the oxometallate crystallite copper molybdate of the crystal structure types of at least one following copper molybdate4
[the registration card 22-242 of JCPDS-ICDD card indexs, (1991)], Cu6Mo5O18[the registration card of JCPCS-ICDD card indexs
40-865, (1991)], Cu4-x Mo3O12, wherein x=0-0.25 [the registration card 24-56 and 26- of JCPCS-ICDD card indexs
547, (1991)], etc..The catalyst is to improve selectivity.
CN1295499 discloses polymetal oxide materials [A] p [B] q [C] r (I) of formula (I) a kind of, with containing molybdenum, vanadium,
Copper and antimony and one or more specific other metal simultaneously have the polymetal oxide materials of multicomponent structure as with propylene
The gas phase catalytic oxidation reaction of aldehyde prepares acrylic acid catalyst.In formula, A is Mo12VaX1bX2 cX3 dX4 eX5 fX6 gOx, B is
X1 7CuhHiOy, C is X1 8SbjHkOz, X1It is W, Nb, Ta, Cr and/or Ce.Co-catalyst phase B is made up of the crystallite of these copper molybdates
Or contain such copper molybdate crystallite：α-CuMoO4[the reference diffraction in the index card 22-242 of JCPDS-ICDD retrievals 1991
Figure], Cu6Mo5O18[reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrievals 1991], Cu4-xMo3O12Wherein, x
It is 0-0.25 [reference diffraction pattern in the index card 24-56 and 26-547 of JCPDS-ICDD retrievals 1991], etc..Region C can be with
With metaantimmonic acid copper Cu9Sb4O19The crystallite or Cu of structure4SbO4.5The crystallite of structure.CN1093950 discloses the oxidation of one kind of multiple metals
The composition of thing, including the oxidised form as basis Mo, V, W, Cu, Ni, with the proviso that between each element composition
There is following ratio：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.
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.CN1387945 is related to contain the unit in Cu, Mo and at least one W, V, Nb and Ta selected from element
The oxo metal compound of the HT copper molybdate structure types of element, its preparation method, and they are preparing containing molybdenum, vanadium, copper and are containing
Have in elemental tungsten, niobium, tantalum, chromium and cerium one or more element have in the composite metal oxide material of heterogeneous structure should
With.The poly-metal deoxide that CN1394812 is used in for the catalyst of the catalytic vapor phase oxidation reaction of organic compound, institute
The poly-metal deoxide said contains at least one in Mo, V and element W, Nb, Ti, Zr, Hf, Ta, Cr, Si and Ge, and with spy
Different Three-dimensional atom arrangement.CN1500770 contains molybdenum, vanadium, copper and contains one or more yuan in elemental tungsten, niobium, tantalum, chromium and cerium
The composite metal oxide material for having heterogeneous structure of element, their answering in by catalytic gas phase oxidation of acrolein acrylic acid
With, and the HT copper molybdate structure types containing the element in Cu, Mo and at least one W, V, Nb and Ta selected from element oxo
Metal compound.
In addition, under the high temperature conditions, part active component molybdenum loses from catalyst surface because of distillation in catalyst.Propylene
Aldehyde, air（Oxygen）, the mixed airflow such as nitrogen and vapor wash away the loss of active component that can also make in catalyst.To suppress
Losss of molybdenum distillation causes active decay, and CN1121504 is by mixing copper component and with specified particle diameter and specific surface area
Zirconium and/or titanium and/or cerium, can suppress the dissipation effect and over reduction of molybdenum composition.Catalyst is included by lower formula (I)
MOaVbWcCudXeYf(I) oxide or composite oxides of the metallic element composition for representing.CN1445020 adds a small amount of tellurium to rise
To the effect of the free molybdenum trioxide of stabilization and copper molybdate crystal structure, the sublimation and over reduction of molybdenum have suppressed；
CN1583261 with molybdenum, vanadium, copper, tungsten and/or niobium as key component, with other elements constitute composite oxides or its oxide
Mixture composition catalyst suppress molybdenum loss.
Accordingly, it is desirable to provide Propylene Selectivity oxidation prepares methacrylaldehyde, acrylic acid catalyst, catalyst activity component molybdenum etc.
Not easily run off, and activity is mutually not susceptible to phase in version, and during acrolein oxidation, temperature of reactor distribution is more reasonable,
And the selectivity and yield of purpose product are improved as far as possible, to obtain bigger economic benefit., can be in low temperature, high-load condition
Under reacted.
The content of the invention
Urged it is an object of the invention to provide a kind of Propylene Selectivity oxidation production methacrylaldehyde, acrylic acid poly-metal deoxide
Agent and preparation method thereof.
The present invention relates to a kind of propylene oxidation catalyst, catalyst contains molybdenum, bismuth, iron, nickel, cobalt and copper, main group
Into by formula M oa′Bib′Fec′Nid′Coe′CufSihAiBjOy（Ⅰ）Represent, wherein：Mo is molybdenum, and Bi is bismuth, and Fe is iron, and Ni is nickel,
Co is cobalt, and Cu is copper, and Si is silicon, and silicon is the carrier of addition in catalyst, and A is selected from least one element in caesium, calcium or barium；
B is selected from least one element in titanium, zinc, potassium, lanthanum；O is oxygen；A ', b ', c ', d ', e ', f, h, i, j represent each element respectively
Atomic ratio, wherein a ' are a numbers of 12-14, and b ' is a number of 1-6, preferably 1.2-5；C ' is a number of 0.2-5, preferably
0.5-3.5；D ' is a number of 1-6, preferably 1.5-4；E ' is a number of 0.5-6, and preferably 1.5-4.5, f are the one of 0.2-4
Number, h is a number of 0.1-30, and i, j are a numbers of 0.05-2.5, and y is the numerical value determined by the oxygen of each oxide.Catalysis
Agent also contains lanthanum-magnesium aluminate oxide（LaMgAl11O19）, containing molybdenum, bismuth（Ⅰ）90~98% Hes are pressed with lanthanum-magnesium aluminate oxide
After the mixing of 0.5~10% mass percent finished catalyst is obtained after mediating, being molded, dry, be calcined.
Lanthanum-magnesium aluminate oxide of the present invention is prepared according to conventional coprecipitation.Such as prepared using following methods：By nitric acid
Magnesium, lanthanum nitrate and aluminium hydroxide are according to LaMgAl11O19Stoichiometric proportion be well mixed, add deionized water simultaneously stir,
Then it is spray-dried, gained powder is calcined 3~12 hours after 160 DEG C of dryings through 1000~1500 DEG C, then by crushing or ball
The methods such as mill obtain lanthanum-magnesium aluminate LaMgAl of the particle diameter below 20 μm11O19。
It is highly preferred that containing in catalyst（Ⅰ）92~97%, also lanthanum-magnesium aluminate oxide 2~8%.
The present invention（Ⅰ）Active component lanthanum is preferably added in the catalyst activity component of expression, lanthanum can be formed with bismuth, cobalt, copper
The crystal phase structure of stabilization, such as BiLa, BiLa2、Co3La2、Cu2La etc., the good dispersion of molybdenum, so as to suppress part active component molybdenum
Lost because of distillation from catalyst surface, active component molybdenum etc. is not easily runed off, active component molybdenum content base before and after catalyst reaction
This is constant, delays active deterioration rate, catalyst activity and good stability.Lanthanum and molybdenum, cobalt ratio are appropriate, formula（Ⅰ）Middle B is
Lanthanum, i is 0.1~1.5 number, and j is 0.1~3 number, and the addition of excessive lanthanum can compete molybdenum, influence with bismuth, cobalt and iron
Catalyst activity.Catalyst is mainly constituted by formula（Ⅱ）Represent：Moa′Bib′Fec′Nid′Coe′CufSihAiLajOy（Ⅱ）.
Multi-metal-oxide catalyst of the invention（Ⅰ）Using common preparation method, following steps can be such as used
It is rapid to prepare, Mo, Bi, the compound and formula of Fe, Co, Ni, Cu will be contained（Ⅰ）Middle AiBjThe each element component composition being related to
Dissolve and be well mixed, slurries are formed after being co-precipitated, silica, aluminum oxide or carborundum are added in slurry production process
In one or more, drying, shaping, be calcined to obtain catalyst (I).
The preparation method of catalyst of the present invention, including catalyst (I), lanthanum-magnesium aluminate oxide are prepared with coprecipitation, will
Catalyst (I), lanthanum-magnesium aluminate oxide are pressed after 90~98% and 0.5~10% mass percent mixes through mediating, being molded, do
Finished catalyst is obtained after dry, roasting.
Under Oxygen Condition, molybdenum isoreactivity component is not only easy to run off catalyst under the high temperature conditions, and activity compatible is easy
Generation phase in version, activity mutually occurs phase in version causes active selectable to be decreased obviously.Such as active phase CuMoO4It is changed into MoO3,
CoMoO4It is converted into Co3O4, Fe2(MoO4)3It is transformed into FeMoO4, α-Bi2(MoO4)3It is changed into γ-Bi2MoO6Deng.
Active component molybdenum in catalyst etc. enables and keeps not being lost in, and basic change is little before and after the reaction of molybdenum equal size,
But easily there is phase in version by long-term operation activity compatible.The present invention adds lanthanum-magnesium aluminate oxide in catalyst, makes
Catalyst activity is mutually more stable, is not susceptible to phase in version so as to improve catalyst activity and selectivity, catalyst is grown week
Phase operates.
Catalyst (I) of the present invention and finished catalyst are required for being calcined 3~10h at 400~580 DEG C, compared to not distinguishing
The catalyst of roasting, repeatedly roasting can improve the activity and stability of catalyst.Can be that open roasting can also be closing
Formula is calcined, and calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.
The compound of each component of catalyst of the present invention can use nitrate, ammonium salt, sulfate, the oxygen of each element
Compound, hydroxide, chloride, acetate etc., such as lanthanum nitrate, magnesium nitrate, calcium chloride, calcium chloride, barium carbonate, barium nitrate, nitre
Sour potassium, zinc nitrate, titanium dioxide, calcium hydroxide, strontium nitrate, ferric nitrate, iron oxide, cobalt nitrate, cobalt oxide, bismuth nitrate, molybdic acid
Ammonium etc..
After catalyst slurry drying of the present invention, it is usually preferred to using shaping sides such as extrusion molding, granulating and forming, compression moldings
Method processing glomeration, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Intensity, efflorescence degree in order to improve catalyst of the invention, can be in above-mentioned catalyst（Ⅰ）Middle addition glass fibre,
One or more in graphite, ceramic or various whiskers.
Evaluating catalyst performance index definition is as follows：
Specific embodiment
Illustrate multi-metal-oxide catalyst and preparation method thereof, and the catalyst in propylene with specific embodiment below
Selective oxidation prepares methacrylaldehyde（ACR）, acrylic acid（AA）Catalytic performance, but the scope of the present invention be not limited to these implementation
Example.The propylene that following examples are used is propylene content >=99.6%（Volume fraction）High concentration propylene.The analysis of product form
Method uses method generally in the art.
Embodiment 1
Under agitation, 236.5 grams of ammonium molybdates are taken to be dissolved in 1000ml pure water（More than 65 DEG C of water temperature）, starched
Liquid（1）, then take 89.1 grams of cobalt nitrates, 64 grams of nickel nitrates, 115.9 grams of ferric nitrates, 22.3 grams of copper nitrates, 34.2 grams of lanthanum nitrates molten
In 500ml pure water（More than 65 DEG C of water temperature）, it is thoroughly mixed uniformly, obtain slurries（2）.162.5 grams of bismuth nitrates are taken again,
It is dissolved in dust technology under agitation, obtains slurries（3）.Then, slurries（1）With slurries（2）Mixing, obtains slurries（4）, so
Afterwards by slurries（3）Add slurries（4）In, 3.8 grams of titanium dioxide and 4 grams of graphite are added, obtain active component slurries（a）.Will
Active component slurries (a) and 7.4 grams of silicon dioxide powders carry out coprecipitation reaction, heated drying, in nitrogen with 150 DEG C of heat at
Reason 3 hours, then 500 DEG C are calcined 4 hours, and size-reduced, grinding, sieving treatment obtain less than 40 μm of fine powder, are catalyst
（Ⅰ）Powder, main composition is：
Mo13Bi3.3Fe2.8Ni2.1Co3.0Cu0.93Si1.2La1.0Ti0.46Oy（Ⅰ）
By magnesium nitrate, lanthanum nitrate and aluminium hydroxide according to LaMgAl11O19Stoichiometric proportion be well mixed, add depart from
Sub- water simultaneously stirs, and is then spray-dried, and gained powder is calcined 10 hours after 160 DEG C of dryings through 1100 DEG C, then by ball
The methods such as mill obtain lanthanum-magnesium aluminate LaMgAl of the particle diameter below 20 μm11O19。
Take catalyst（Ⅰ）93 parts, 7 parts of lanthanum-magnesium aluminate oxide, plus deionized water, in being mediated in kneader, extrusion forming is
The hollow columnar particle of 4.5 × 5mm of φ, dries under the conditions of 120 DEG C, and roasting obtains catalyst 1 in 6.5 hours at 450 DEG C.
Embodiment 2
Preparation process and most of raw material with the catalyst 1 of embodiment 1 is identical, and catalyst is obtained final product within 4 hours through 500 DEG C of roastings
（Ⅰ）, main composition is：Mo13Bi4.2Fe4Ni3Co3.6Cu0.3Si2.2Ba0.3K0.4Oy（Ⅰ）.Take catalyst（Ⅰ）90 parts, lanthanum-magnesium aluminate
10 parts of oxide, plus deionized water, in being mediated in kneader, extrusion forming is the hollow columnar particle of 4.5 × 5mm of φ, 120 DEG C
Under the conditions of dry, at 550 DEG C roasting obtain catalyst 2 within 4 hours.
Embodiment 3
Preparation process and primary raw material with the catalyst 1 of embodiment 1 is identical, and catalyst is obtained final product within 5 hours through 450 DEG C of roastings
（Ⅰ）.Mainly composition is：Mo14Bi5Fe2.5Ni4Co4Cu2Si3.5K0.2La1.8Oy（Ⅰ）.Take catalyst（Ⅰ）95 parts, lanthanum-magnesium aluminate oxygen
5 parts of compound, plus deionized water, in being mediated in kneader, extrusion forming is the hollow columnar particle of 4.5 × 5mm of φ, 120 DEG C of conditions
Lower drying, roasting obtains catalyst 3 in 4 hours at 550 DEG C.
Embodiment 4
Preparation process and primary raw material with the catalyst 1 of embodiment 1 is identical, and catalyst is obtained final product within 7 hours through 400 DEG C of roastings
（Ⅰ）.Mainly composition is：Mo14Bi6Fe5Ni6Co5.8Cu3.8Si1.8Cs0.2La3.3Oy（Ⅰ）.Take catalyst（Ⅰ）97 parts, lanthanum-magnesium aluminate
3 parts of oxide, plus deionized water, in being mediated in kneader, extrusion forming is the hollow columnar particle of 4.5 × 5mm of φ, 120 DEG C of bars
Dried under part, roasting obtains catalyst 4 in 5 hours at 500 DEG C.
Comparative example 1
Comparative catalyst 1 is prepared according to the main composition and ratio of embodiment 1, but lanthanum-magnesium aluminate is aoxidized with solid solution
The form of thing adds catalyst, but prepares catalyst with coprecipitation method, reaction condition with catalyst 1 appreciation condition.It is right
Main composition than catalyst 1 is：
Mo13Bi3.3Fe2.8Ni2.1Co3.0Cu0.93Si1.2La1.3Ti0.46Mg0.3Al3.3Oy
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, and 50ml is loaded along propylene feed orienting response device bed
Above-mentioned catalyst or comparative example catalyst, salt bath heating, 310 DEG C of salt temperature.Tube inlet sentences air speed from the reactions above
1200h-1Import the volume % of propylene 9, the volume % of air 72, the mixed gas of the volume % of vapor 19.Reaction result such as table 1 and table
Shown in 2.Reaction 24 hours and 2000 hours, loads beds hot localised points temperature of the present invention and is not higher than 361 DEG C, catalyst
Active component molybdenum etc. is not easily runed off, and activity is mutually not susceptible to phase in version, catalyst activity component Stability Analysis of Structures.In methacrylaldehyde
In oxidizing process, reaction bed temperature distribution is more reasonable, methacrylaldehyde（ACR）And acrylic acid（AA）Total recovery more than 91.0%,
Catalyst has good water repelling property, and catalyst performance stabilised meets device long period steady running.Comparative example catalyst is selected
Selecting property is poor, and methacrylaldehyde, acrylic acid yield are low.
Table 1 reacts 24 hours post-evaluation results
Table 2 reacts 2000 hours post-evaluation results
Claims (10)
1. the catalyst that a kind of Propylene Selectivity is aoxidized, it is characterised in that catalyst contains molybdenum, bismuth, iron, nickel, cobalt and copper,
Main composition is catalyst (I), and catalyst (I) is by formula M oa′Bib′Fec′Nid′Coe′CufSihAiBjOy(I) represent, its
Middle silicon is carrier, and A is selected from least one element in caesium, calcium or barium；B is selected from least one element in titanium, zinc, potassium, lanthanum；
O is oxygen；A ', b ', c ', d ', e ', f, h, i, j, y represent each element atomic ratio respectively, and wherein a ' is a number of 12-14, and b ' is
One number of 1-6, c ' is a number of 0.2-5, and d ' is a number of 1-6, and e ' is a number of 0.5-6, and f is the one of 0.2-4
Number, h is a number of 0.1-30, and i, j are a numbers of 0.05-2.5, and y is the numerical value determined by the oxygen of each oxide；Catalysis
Agent also contain lanthanum-magnesium aluminate oxide, containing molybdenum, the catalyst (I) of bismuth and lanthanum-magnesium aluminate oxide press 90~98% and 0.5~
After the mixing of 10% mass percent finished catalyst, and catalyst (I) and magnesium aluminate are obtained after mediating, being molded, dry, be calcined
The mass percent sum of lanthanum-oxides is 100%.
2. catalyst according to claim 1, catalyst contains catalyst (I) 92~97%, also lanthanum-magnesium aluminate oxidation
Thing 2~8%, and the mass percent sum of catalyst (I) and lanthanum-magnesium aluminate oxide is 100%.
3. catalyst according to claim 1, it is characterised in that b ' is a number of 1.2-5 in formula (I).
4. catalyst according to claim 1, it is characterised in that c ' is a number of 0.5-3.5 in formula (I).
5. catalyst according to claim 1, it is characterised in that d ' is a number of 1.5-4 in formula (I).
6. catalyst according to claim 1, it is characterised in that e ' is a number of 1.5-4.5 in formula (I).
7. catalyst according to claim 1, it is characterised in that B is lanthanum in formula (I), and i is 0.1~1.5 number,
J is 0.1~2.5 number, and main composition is represented by formula (II)：
Moa′Bib′Fec′Nid′Coe′CufSihAiLajOy (Ⅱ)。
8. the catalyst according to any one of claim 1~7, it is characterised in that the preparation of catalyst (I) comprises the following steps：
Mo, Bi, A in the compound and formula (I) of Fe, Co, Ni, Cu will be containediBjThe each element component composition being related to dissolve and mix
Close uniform, slurries formed after being co-precipitated, silica and/or carborundum are added in slurry production process, drying is molded,
It is calcined to obtain catalyst (I).
9. the preparation method of catalyst according to claim 1, it is characterised in that including preparing catalyst with coprecipitation
(I), lanthanum-magnesium aluminate oxide, catalyst (I), lanthanum-magnesium aluminate oxide is mixed by 86~96% and 0.1~5% mass percent
After conjunction finished catalyst, the wherein quality of catalyst (I) and lanthanum-magnesium aluminate oxide are obtained after mediating, being molded, dry, be calcined
Percentage sum is 100%.
10. method according to claim 9, it is characterised in that catalyst (I) and finished catalyst be required for 400~
3~10h is calcined at 580 DEG C.
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