CN104649872B - A kind of method of selectivity of light olefin oxidation - Google Patents
A kind of method of selectivity of light olefin oxidation Download PDFInfo
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- CN104649872B CN104649872B CN201310581633.1A CN201310581633A CN104649872B CN 104649872 B CN104649872 B CN 104649872B CN 201310581633 A CN201310581633 A CN 201310581633A CN 104649872 B CN104649872 B CN 104649872B
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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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
- C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
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- 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
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Abstract
The method that the present invention relates to the oxidation of a kind of selectivity of light olefin, fixed bed single tube reactor is entered after more than the 120 DEG C preheatings of the preheated device of reaction raw materials propylene, water, air, salt bath heating, fixed bed reactors are built with Propylene Selectivity oxidation catalyst, catalyst contains molybdenum, bismuth, iron, nickel, cobalt and wolfram element, and catalyst is possibly together with magnesium-based lanthanum hexaaluminate.Catalyst structure is stable, and active component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version mutually, improves selectivity and the yield of purpose product.
Description
Technical field
The present invention relates to a kind of selectivity of light olefin method for oxidation, be particularly suited for propylene or isobutene selects
Property oxidation generate corresponding unsaturated aldehyde, be particularly well-suited to Propylene Selectivity is oxidized to methacrylaldehyde.
Background technology
Industrial propylene or isobutylene oxidation are prepared the reaction unit of corresponding unsaturated aldehyde and are mainly many reaction tubes,
Ensureing that catalyst is not sintered, on the premise of service life length, improves as far as possible selectively and purpose product is received
Rate, conservation, if even if feed stock conversion, methacrylaldehyde, acrylic acid yield improve 0.1～0.5 percentage point,
The amount of the product obtained increases with hundreds of～thousands of tons of level, and its economic benefit is also the most considerable.
It is mainly molybdenum system multicomponent catalyst about propylene fraction oxidation acrolein, acrylic acid catalyst.Due to
It is strong exothermal reaction that the acrylic acid reaction of methacrylaldehyde is prepared in Propylene Selectivity oxidation, so being passed through ratio in course of reaction
The steam that heat is big, effectively to remove reaction heat, but the active component molybdenum in catalyst etc. are at gas such as steam
Easy loss under the washing away of stream.And, under the high temperature conditions, in catalyst, part active component molybdenum is from catalyst
Surface loses because of distillation.The loss of active component molybdenum cause reduce the activity of catalyst, selectivity, intensity and
Service life, and molybdenum is in the deposition in reaction system downstream, and blocking pipeline affects the long-term operation of system.
It addition, the active component molybdenum etc. in catalyst i.e. enables and keeps not running off, basic before and after the reaction of molybdenum equal size
Change is little, but through long-term operation activity compatible, phase in version easily occurs.Key component bag in catalyst
Include Fe2(MoO4)3、α-Bi2(MoO4)3、CoMoO4And NiMoO4, wherein α-Bi2(MoO4)3It is to live in surface
Property center, plays selective oxidation effect；Fe2(MoO4)3Play redox facilitation；CoMoO4With
NiMoO4Play Stability Analysis of Structures effect.But, catalyst prepared by employing coprecipitation method is many due to component, mistake
Journey is complicated, and catalyst stabilization differs, although initial activity is the highest, but inactivation is fast.Cause many components
It is a lot, wherein because have that Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalysqt deactivation and stability decline
Change including sublimation and the irreversible crystalline phase because of local abnormal high temperature (focus) caused Mo component
Deng.These factors all can cause the change of specificity of catalyst, causes the reduction of catalyst activity and shortens catalysis
The service life of agent.By decaying catalyst being carried out phenetic analysis, find Fe2(MoO4)3It is reduced into
FeMoO4, and α-Bi2(MoO4)3It is changed into γ-Bi2MoO6。
Solving the problems referred to above, the patent related to is the most, such as, for suppressing the loss of molybdenum, CN1583261
Disclose a kind of gas for the gas containing unsaturated aldehyde Yu a kind of molecule-containing keto and carry out selective oxygen in the gas phase
Changing the O composite metallic oxide catalyst of reaction, its catalyst consists of: [MoaVbCucXd]Ym[SbeZ1 f
Z2 g]nOxWherein Mo is molybdenum, and V is vanadium, and Cu is copper, and Sb is antimony, and X is at least selected from tungsten and the one of niobium
Element, Y is at least selected from titanium, a kind of element of antimony, Z1It is at least chosen from Fe and a kind of element of nickel, Z2
It is at least selected from silicon, aluminium, a kind of element of alkali and alkaline earth metal ions, a, b, c, d, e, f, g and x
Representing the atomic ratio number of its element, time on the basis of a=12, b is a number of 1 to 6, and c is 0.5 to 4
One number, d is a number of 0.05 to 4, and e is a number of 0.1 to 30, and f is a number of 0 to 25,
G is a number of 0.01 to 20；X is by the number met needed for each metallic element combined oxidation state；Urge
Agent is made up of its each element oxide or composite oxides.
In order to improve the stability of catalyst, the open a kind of acrylic acid catalyst of CN1130172, respectively with partially
Ammonium vanadate and copper nitrate, and with Low Valent Vanadium oxide and/or at a low price Cu oxide part replace ammonium metavanadate and/or
Copper nitrate makees the catalyst obtained by the raw material of vanadium metal and copper or in addition to above-mentioned raw materials, uses antimony oxidation at a low price
Thing and/or the catalyst that tin-oxide obtains at a low price demonstrate there is a strengthened peak (vanadium-molybdenum at d=4.00
Reactive compound is peculiar) and the V of a remitted its fury is had at d=4.382O5Specific peak.So, above-mentioned
The catalyst obtained has the catalysis activity of raising, and long-term performance can go out stability.Similar also has patent
Document 1: Japanese Unexamined Patent Publication 2002-233757 publication, patent document 2: Japanese Unexamined Patent Publication 8-299797 public affairs
Report, patent document 3: Japanese Unexamined Patent Publication 9-194213 publication, patent document 4: Japanese Unexamined Patent Application Publication 2004-504288
Number publication；CN102066000A.
For improving the activity of catalyst, selectivity and catalyst life, CN200980112659.3 discloses one
Kind comprise the coating catalyst of following components: (a) carrier, before (b) comprises molybdenum oxide or form molybdenum oxide
The ground floor of body compound, (c) comprises the second layer containing molybdenum He the poly-metal deoxide of at least one other metal.
The preferably molybdenum oxide of ground floor is MoO3, the poly-metal deoxide of the second layer is many metals that formula II represents
Oxide: Mo12BiaCrbX1 cFedX2 eX3 fOy.This catalyst is the application type catalyst including carrier.Invention
Purpose be suppression heterogeneously catalysed partial gas phase oxidation methacrylaldehyde be acrylic acid coating catalysqt deactivation, have and change
The inactivation performance entered.This invention is not expressly recited catalyst for being catalyzed propylene oxidation acrolein, propylene
The reactivity worth evaluating data of acid, such as conversion ratio, selectivity, yield etc..The open one of CN87103192
The method producing composite oxide catalysts, the Mo-Bi composite oxide catalytic wherein represented with following chemical formula
The production method of agent includes coherent element source compound to mix form compound in Aquo System and be combined this
Thing is heat-treated, and uses the one of the waltherite compound of (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X
Compound, as Bi source, at least contains required Na and/or X of part wherein in this compound: X represent 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=1-10, e=0.05-3, f=0.01-1,
G=0-1, h=0.04-0.4, i=0-3, j=0-48, k is a number meeting other element oxide state.Solve Bi
Can in composite oxide catalysts homodisperse problem.Containing α-Bi in catalyst2(MoO4)3、MoO3Fe2
(MoO4)3With β-CoMoO4、y-Bi2MoO6And γ-Bi2MoO6.The open one of CN101690900A
Preparing the preparation method of methacrylaldehyde and acrylic acid catalyst, catalyst is supported thing and inert alumina by active component
Carrier forms；Active component mainly comprises element, 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；The wherein following table of active component
The formula of stating represents: MoaBibCocNidFeeXfYgZhOiIn formula, X represents at least one of K, Na, Rb and Cs,
Y represents that at least one in B, P and W, Z represent at least one in Mg, Ca, Zn.Live
The ratio that property component is supported on carrier accounts for the 5-70% of overall catalyst weight；Active component is uneven distribution,
CoMoO4、NiMoO4Aluminate Deng divalent metal is positioned at the kernel of catalyst activity component；Fe2(MoO4)3
And the MoO of free state3Invest the outer layer of kernel；And the outermost layer of active component is bismuth molybdate, formation core-
The state of shell layer distributed.In active component, divalence molybdate is mainly beta phase structure, and α phase structure is in active component
Middle content is the lowest or does not exists.Catalyst has high activity and high stability.CN1280036 mono-kind produces not
Saturated aldehyde and the catalyst of unsaturated carboxylic acid, described production be by make at least one be selected from propylene, isobutene,
The compound of the tert-butyl alcohol and methyl tertiary butyl ether(MTBE) and oxygen molecule or the gas containing oxygen molecule carry out vapour-phase oxidation and
Realize, it is characterised in that this catalyst is a kind of combined oxidation compositions, contains: (A) containing molybdenum, bismuth and
Iron, as the composite oxides of key component, itself is known for urging that described vapor phase catalytic oxidation reacts
Agent, and (B) containing cerium and zirconium as the composite oxides of key component.Catalyst has long catalytic life also
Make to operate steadily in the long term to be possibly realized.Wherein component (B), is the composite oxides represented by below general formula (2):
CepZrqFrOy.The zirconium oxide of high degree of dispersion inhibits the gathering of cerium oxide, to keep the latter in course of reaction
To absorbing and discharge the promotion functions of oxygen significantly, thus accelerate the oxidation reaction of isobutene, therefore improve
Catalysis activity.Additionally, further suppress component (A) composite oxides caused because of over reduction in time not
Reversible activity reduces (i.e. the stability of composite oxides improves), so that catalytic life extends.This carry
High catalysis activity and the catalytic life extended inhibit reaction temperature to raise in time, thus reduce molybdenum
Distillation at hot spot.This catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparation for producing methacrylaldehyde and renovation process.Catalyst
For having the composite oxides of following atomic ratio: Mo: Bi: Co: Ni: Fe=
10-14∶1.2-2.0∶4.8-5.6∶2-3∶1-2；This catalyst has the pore size distribution more concentrated, and moderate is total
Pore volume, wherein the mesopore of about 5-10nm accounts for more than the 70% of total pore size distribution, forms short and thick pore passage structure,
This feature gives the anti-carbon deposition ability that catalyst is stronger, catalyst surface not easy-sintering, it is possible to extend catalyst
Service life.And the renovation process provided by the present invention, decaying catalyst carries out 1-3 in an oxidizing atmosphere
It calcination processing, catalyst activity is suitable with fresh catalyst.CN87103192 produces Mo-Bi-Na composite oxygen
The method of compound catalyst product, the method includes that mixing coherent element source compound forms compound, then carries out
Being heat-treated, the basic bismuth carbonate of the required Na of part is as Bi source compound using the most solid solution.Catalyst
Activity by means of Bi and Na import specific water-insoluble compound formed catalyst and changed greatly
Kind.
CN1109803 relates to multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, and one
Individual or multiple element phosphor, arsenic, boron, germanium and silicon；And relate to described composition and prepared by catalytic gas phase oxidation
Purposes in terms of methacrylic acid, improves methacrylic acid activity and selectivity.The open one of CN1109802 is many
Metal oxide composition, they have two phase structure and comprise molybdenum, hydrogen, one or more element phosphors, arsenic,
Boron, germanium and silicon and copper, improve methacrylic acid activity and selectivity.CN1298861A is then to use to add
The composite oxides of magnesium, aluminium and silicon.CN1321110A is combined using antimony oxide and antimony acetate as activity the most respectively
The antimony source of metal oxide.To solve under high-load condition, catalytic mechanical intensity is good, the problem that activity is high.
The open a kind of O composite metallic oxide catalyst of CN200410048021.7, catalyst is by 1. molybdenum, vanadium, copper
Main active component and the most requisite at least by antimony and the stable component of titanium and 3. nickel, iron, silicon, aluminium,
The composite oxides of alkali metal, alkaline-earth metal composition.The most 2. and 3. it is can be in the range of 120 DEG C to 900 DEG C
Composite oxides prepared by roasting.This catalyst shows the permanent stability under high activity and good selectivity.
CN1121441 discloses a kind of for being existed by methacrylaldehyde or the gas containing acrolein gas and a kind of molecule-containing keto
Carrying out oxidation reaction in vapour phase and produce acrylic acid catalyst, this catalyst includes (A) a kind of composite oxides,
There is molybdenum and vanadium as base stock, and be suitable to by vapor phase catalytic oxidation methacrylaldehyde to produce acrylic acid, and (B)
A kind of solid peracid, its acid strength (Ho) is not more than-11.93 (Ho≤-11.93).This invention uses molybdenum vanadium type composite oxygen
Compound combines with a kind of acid strength solid acid less than-11.93, improves the low temperature high activity of catalyst.
The open a kind of acrylic acid catalyst for producing of CN200510059468.9, is characterized in that, at following formula
MoaVbWcCudOx(1) oxide of the metallic element composition represented and/or composite oxides are necessary catalyst
In the acrylic acid catalyst for producing of composition, need to control tungsten and be partially the face side of this catalyst, and/or copper
Partially it is the core side of this catalyst, to improve catalyst activity.Tungsten is the face side of this catalyst partially, and/
Or copper is that the core side of this catalyst is difficult to accurately control partially.The open a kind of acrolein oxidation of CN102039143A
Prepare the preparation method of acrylic acid catalyst, a) preparation method of composite oxide coating: will containing Mo,
The water-soluble metal salt of V, W, Cu, Sb composition is dispersed in water/organic phase mixed system in 30-100 DEG C；
Keeping organic solvent and water weight ratio is 5～50%；Reaction generates composite oxides presoma slurries；Pass through again
Distillation, drying, roasting prepare catalyst activity component；B) above-mentioned active component mainly comprises element, is selected from
Mo, V, Cu, W, Sb one of which or several；Wherein active component following formula represents:
MoaVbCucWdSbeOf, this catalyst uses the mixed system of water and lower alcohol to prepare, and catalyst has higher
Specific surface area and special microstructure, there is relatively high-ratio surface and difficult drop-off, and bearing capacity can reach
To 50% and more than, solve shorter problem in application type catalyst service life.
The open a kind of MAL acrylic acid catalyst of selective oxidation synthesizing methyl of CN1647854, this is urged
The composition formula of agent is: x (Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z are that carrier dilutes heat conduction
Agent；Mo, P, K, Sb, Cu and As are respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic；A represent tungsten W,
At least one element in vanadium V, niobium Nb, iron Fe and lead Pb；D represents boron, gallium Ga, indium In, germanium
At least one element in Ge and silicon Si；Q represents at least one element in rubidium Rb, caesium Cs and thallium Tl, this
Bright one side improves the activity and selectivity of catalyst by adding Sb, Cu and As；On the other hand pass through
Add MoO3 and carrier heat conduction diluent improve the heat endurance of catalyst, heat conductivility and mechanical strength,
Effectively inhibitory activity component heteropolyacid salt decomposition and reduce beds hot(test)-spot temperature, it is to avoid Mo and
The loss of As, extends catalyst service life.
The open a kind of polymetal oxide materials of CN1109800: in formula, A is Mo12VaXb 1Xc 2
Xd 3Xe 4Xf 5Xg 6Ox(coexisting phase), its part B comprises and has the X-ray of at least one following copper molybdate and spread out
Penetrate the crystallite (giving the firsthand information about X-ray diffraction fingerprint in round parentheses) of pattern:
Cu3(MoO4)2(OH)2(lindgrenite, the card index 36-405 of JCPDS-ICDD index (1991)),
Cu4Mo6O20(A.Moini et al., Inorg.Chem.25(21) (1986), 3782-3785), Cu4Mo5O17
(the card index 39-181 of JCPDS-ICDD index (1991)), etc..CN1462211 relates to a kind of system
Standby containing Mo, V, Cu and the method for the multiple-phase multi-metal oxide materials of other optional element.According to this
Invention, at least one phase is pre-formed independently, and in the precursor material of the plastically deformable being dispersed in another phase.
Then this mixture is dried and calcines.Polymetal oxide materials is suitable as at catalytic gas phase oxidation organic
Compound, particularly acrolein oxidation is being become in acrylic acid the active material of catalyst used.
[A] p [B] q [C] r (I), phase A in multimetal oxide compositions, B and C can be unbodied and/or
Crystallization.Phase B is advantageously made up of the crystallite of oxometallate, or comprises there is X-ray diffraction
Pattern and and then the crystalline substance of oxometallate crystallite copper molybdate of crystal structure types of at least one following copper molybdate
Body structure class α-CuMo4[the registration card 22-242 of JCPDS-ICDD card index, (1991)],
Cu6Mo5O18[the registration card 40-865 of JCPCS-ICDD card index, (1991)], Cu4-xMo3O12, its
Middle x=0-0.25 [registration card 24-56 and 26-547 of JCPCS-ICDD card index, (1991)], etc..Should
Catalyst is to improve selectivity.
Polymetal oxide materials [A] p [B] q [C] r (I) of the open a kind of formula of CN1295499 (I), with containing molybdenum,
Vanadium, copper and antimony and one or more other metals specific also have the polymetal oxide materials of multicomponent structure
Acrylic acid catalyst is prepared as with the gas phase catalytic oxidation reaction of methacrylaldehyde.In formula, A is
Mo12VaX1bX2 cX3 dX4 eX5 fX6 gOx, B is X1 7CuhHiOy, C is X1 8SbjHkOz, X1For W, Nb,
Ta, Cr and/or Ce.Co-catalyst phase B is made up of the crystallite of these copper molybdate or micro-containing such copper molybdate
Brilliant: α-CuMoO4[the reference diffraction pattern in the index card 22-242 of JCPDS-ICDD retrieval 1991],
Cu6Mo5O18[the reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrieval 1991], Cu4-x
Mo3O12Wherein, x is the 0-0.25 [reference in index card 24-56 and 26-547 of JCPDS-ICDD retrieval 1991
Diffraction pattern], etc..Region C can have metaantimmonic acid copper Cu9Sb4O19The crystallite of structure or Cu4SbO4.5Structure micro-
Brilliant.CN1093950 discloses the composition of one kind of multiple metal oxides, including the oxidation shape as basis
Mo, V, W, Cu, Ni of formula, its premise is to there is following ratio: Mo:V=12:1 between each elemental composition
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 relate to containing Cu, Mo and at least one selected from element W,
The oxo metal compound of the HT copper molybdate structure type of the element in V, Nb and Ta, its preparation method, and they
In preparation, containing molybdenum, vanadium, copper and to contain having of one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium many
Application in the composite metal oxide material of phase structure.CN1394812 is at the catalysis gas for organic compound
Phase oxidation reaction catalyst in use poly-metal deoxide, described poly-metal deoxide contain Mo, V and
At least one in element W, Nb, Ti, Zr, Hf, Ta, Cr, Si and Ge, and it is former to have special three-dimensional
Son arrangement.CN1500770 contains molybdenum, vanadium, copper and contains in elemental tungsten, niobium, tantalum, chromium and cerium a kind of or many
Planting the composite metal oxide material having heterogeneous structure of element, they are by catalytic gas phase oxidation of acrolein system third
Application in olefin(e) acid, and containing Cu, Mo and at least one element in element W, V, Nb and Ta
The oxo metal compound of HT copper molybdate structure type.
It addition, under the high temperature conditions, in catalyst, part active component molybdenum loses because of distillation from catalyst surface.
The mixed airflows such as methacrylaldehyde, air (oxygen), nitrogen and steam wash away the activity that also can make in catalyst
Component runs off.For suppression molybdenum distillation loss cause activity decay, CN1121504 by mix copper component and
There is specified particle diameter and the zirconium of specific surface area and/or titanium and/or cerium, dissipation effect and the mistake of molybdenum composition can be suppressed
Degree reduction.Catalyst includes by lower formula (I) MOaVbWcCudXeYf(I) oxygen of the metallic element composition represented
Compound or composite oxides.CN1445020 adds a small amount of tellurium and plays stably free molybdenum trioxide and copper molybdate
The effect of crystal structure, sublimation and the over reduction of molybdenum have suppressed；CN1583261 with molybdenum, vanadium,
Copper, tungsten and/or niobium are key component, the composite oxides constituted with other element or its hopcalite
The loss of composition catalyst suppression molybdenum.
Accordingly, it is desirable to provide methacrylaldehyde, acrylic acid catalyst are prepared in Propylene Selectivity oxidation, anti-in propylene oxidation
Should carry out under low temperature, high-load condition.Temperature of reactor distribution is more reasonable, catalyst activity component molybdenum
Etc. not easily runing off, and activity to be not susceptible to phase in version, purpose selectivity of product and yield mutually high.
Propylene Selectivity is aoxidized, first has to select the oxidation catalyst of function admirable, secondly also will be in gentleness
Operating condition under react, to adapt to industrial high-speed, high selective requirement.Accordingly, it would be desirable to open
The Propylene Selectivity oxidation technology sent out reaction condition a kind of and relax.On the premise of suppression focus, improve as far as possible
The selectivity of purpose product and yield, to obtain bigger economic benefit.
Summary of the invention
The present invention provides a kind of selectivity of light olefin method for oxidation, mainly propylene or selective isobutene oxidation
Produce the preparation method of corresponding unsaturated aldehyde.Methacrylaldehyde, acrylic acid is prepared in particularly Propylene Selectivity oxidation
Method.
The selectivity of light olefin method for oxidation that the present invention provides is as follows: use fixed bed single tube reactor；Reaction
Reactor is entered after raw material propylene or isobutene, water, more than the 120 DEG C preheatings of the preheated device of air, salt bath heating,
Reaction process condition is: salt temperature 300～340 DEG C, preferably 305～330 DEG C；Air speed 800～2000h-1, excellent
Select 800～1500h-1, feed composition: propylene or isobutene 8～14 volume %, air 70～74 volume %, water
Steam 15～19%；Fixed bed reactors built with oxidation catalyst, catalyst contain molybdenum, bismuth, iron, nickel,
Cobalt and wolfram element, mainly comprise by formula M oa′Bib′Fec′Nid′Coe′WfAh′BiSijOy(I) represent, wherein:
Mo is molybdenum, and Bi is bismuth, and Fe is iron, and Co is cobalt, and Ni is nickel, and W is tungsten, and Si is silicon, and silicon is catalyst
The carrier of middle addition, A is at least one element in zinc, titanium, potassium；B be selected from tin, chromium, rubidium,
At least one element in lanthanum；O is oxygen；A ', b ', c ', d ', e ', f, h ', i, j represent each element respectively
Atomic ratio, wherein a ' is a number of 12-14, and b ' is a number of 0.5-6, preferably 1.0-5；C ' is 0.2-4
A number, preferably 0.2-3；D ' is a number of 0.2-5, preferably 0.5-4；E ' is a number of 0.2-5,
Preferably 0.5-4, f are numbers of 0.1-3.5, and h ' is a number of 0.1-5, and i is a number of 0.1-3.5, j
Being a number of 0.5-30, y is the numerical value determined by the oxygen of each oxide.Catalyst is possibly together with magnesium-based six aluminic acid
Lanthanum, containing molybdenum, (I) of bismuth and magnesium-based lanthanum hexaaluminate by 90～98% and 1～10% mass percent mixing after warp
Mediate, be molded, be dried, obtain finished catalyst after roasting.
Inside reactor of the present invention is provided with thermocouple, is used for measuring each spot temperature of reactor, in order to prevent propylene
In lower catalyst agent, deep oxidation affects reaction yield, and makes catalyst coking, and the present invention controls under catalyst
Layer temperature, less than catalyst upper strata temperature, adjusts reaction bed temperature, salt bath temperature by controlling salt temperature
Degree is preferably controlled in 305～320 DEG C, is so conducive to the long-life of catalyst to use, and propylene oxidation reaction can
Long period steady running.
It is highly preferred that catalyst of the present invention can contain catalyst (I) 91～96%, containing magnesium-based
Lanthanum hexaaluminate 1.5～6%.
Being preferably added to active component lanthanum in formula of the present invention (I), lanthanum and bismuth, cobalt, tin can form stable crystalline substance
Phase structure, such as BiLa, BiLa2、Co3La2、LaNi5, LaSn etc., the good dispersion of molybdenum, thus suppress
Amount of activated component molybdenum loses because of distillation from catalyst surface, and active component molybdenum not easily runs off, catalyst reaction
Front and back active component molybdenum content is basically unchanged, and delays activity deterioration rate, catalyst activity and good stability.Lanthanum
With molybdenum, cobalt ratio suitably, in formula (I), B is lanthanum, and i is a number of 0.1～3.5.Xi Yuan of the present invention
Preferably sodium stannate, stannous chloride.Mainly comprise and represented by (II):
Moa′Bib′Fec′Nid′Coe′WfAhBiSijOy(II).
The multi-metal-oxide catalyst (I) of the present invention uses common preparation method, as used
Prepared by following step, by A in the compound containing Mo, Bi, Fe, Fe, Co, W and formula (I)hBi
Each elemental constituent compound that part relates to dissolves in proportion and mixes, and forms slurries after being co-precipitated,
Slurry production process adds one or more in silica, aluminum oxide or carborundum, dries, shaping,
Roasting obtains catalyst (I) powder.
Under Oxygen Condition, catalyst molybdenum isoreactivity component under the high temperature conditions is not only easy to run off, and activity phase
Being susceptible to phase in version, activity occurs phase in version to cause active selectable to be decreased obviously mutually.Such as activity phase
CoMoO4It is changed into Co3O4, Fe2(MoO4)3It is transformed into FeMoO4, α-Bi2(MoO4)3It is changed into
γ-Bi2MoO6Deng.
Active component molybdenums in catalyst etc. i.e. enable holding and do not run off, and before and after the reaction of molybdenum equal size, basic change is not
Greatly, but easily there is phase in version through long-term operation activity compatible.Lanthanum-magnesium aluminate oxide is added by the present invention
In catalyst, make active phase more stable, be not susceptible to phase in version thus improve catalyst activity and selection
Property, make catalyst long period steady running.
The preparation method of catalyst of the present invention, prepares catalyst (I), magnesium-based lanthanum hexaaluminate including by coprecipitation,
By catalyst (I), magnesium-based lanthanum hexaaluminate by 90～98% with 1～10% mass percent mixing after through mediate, become
Type, it is dried, obtains finished catalyst after roasting.
Catalyst of the present invention (I) powder and finished catalyst be required at 400～580 DEG C roasting 3～
10h, compares the catalyst not distinguishing roasting, and repeatedly roasting can improve activity and the stability of catalyst.Permissible
Be open roasting can also be enclosed roasting, calcination atmosphere can be the indifferent gas such as helium, nitrogen, argon gas
Body.
The compound of each component in catalyst Formula of the present invention (I) can use each element nitrate,
Ammonium salt, sulfate, oxide, hydroxide, chloride, acetate etc., such as lanthanum nitrate, magnesium nitrate, chromium
Acid ammonium, rubidium nitrate, zinc nitrate, titanium dioxide, sodium stannate etc..
After catalyst slurry of the present invention is dried, it is usually preferred to use extrusion molding, granulating and forming, compression molding etc.
Forming method is processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circle
Post or spherical.
The present invention in order to improve the intensity of catalyst, efflorescence degree, can add in above-mentioned catalyst glass fibre,
In graphite, ceramic or various whisker one or more.
Catalyst activity of the present invention is high, and good stability, active component not easily runs off, and activity is not susceptible to mutually
Phase in version, is suitable for propylene long period selective oxidation acrolein, acrylic acid.
Evaluating catalyst performance index definition is as follows:
Detailed description of the invention
With specific embodiment, the method that Propylene Selectivity aoxidizes is described below, but the scope of the present invention is not limited to
These embodiments.Following example use propylene be propylene content >=99.6%(volume fraction) high concentration
Propylene.The analysis method of product composition uses method generally in the art.
Embodiment 1
The preparation of catalyst 1
Under agitation, take 217.5 grams of ammonium molybdates and be dissolved in 1000ml pure water (water temperature more than 65 DEG C),
Obtain slurries (1), then take 56.3 grams of cobalt nitrates, 43.5 grams of nickel nitrates, 88.9 grams of ferric nitrates, 23 grams secondary
Ammonium tungstate, 42.9 grams of lanthanum nitrates are dissolved in 500ml pure water (water temperature more than 65 DEG C), are thoroughly mixed all
Even, obtain slurries (2).Take 170.8 grams of bismuth nitrates again, be dissolved under agitation in dust technology, starched
Liquid (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then by slurries (3)
Add in slurries (4), obtain active component slurries (a).
Active component slurries (a) and 7.9 grams of silicon dioxide powders are carried out heat drying after coprecipitation reaction, at nitrogen
In be heat-treated 3 hours with 150 DEG C, then 500 DEG C of roastings 4 hours, size-reduced, grind, sieving processes
Catalyst (I) powder, mainly comprises as Mo14Bi4Fe2.5Ni1.7Co2.2W1.0La1.5Si1.5Oy(I).
By magnesium nitrate, lanthanum nitrate and aluminium hydroxide according to LaMgAl11O19Stoichiometric proportion mix, add
Enter deionized water and stir, being then spray-dried, gained powder through 160 DEG C be dried after through 1100 DEG C of roastings
10 hours, then obtain particle diameter magnesium-based lanthanum hexaaluminate LaMgAl below 20 μm by methods such as ball millings11O19。
Take catalyst (I) 95 part, magnesium-based lanthanum hexaaluminate 5 parts, add deionized water and mediate in kneader,
The extruded hollow columnar particle for φ 4.5 × 5mm, is dried under the conditions of 120 DEG C, and at 500 DEG C, roasting 3.5 is little
Time obtain catalyst 1.
Comparative example 1
Prepare comparative catalyst 1 according to the proportioning that mainly comprises of embodiment 1, but magnesium-based lanthanum hexaaluminate be not with
The form of solid solution, oxide adds catalyst, but prepares catalyst with coprecipitation method, and reaction condition is with urging
The appreciation condition of agent 1.Comparative catalyst 1 mainly comprise for:
Mo14Bi4Fe2.5Ni1.7Co2.2W1.0La1.8Si1.5Mg0.3Al3.3Oy
Propylene method for oxidation
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, fills along propylene feed orienting response device bed
Enter the above-mentioned catalyst of 50ml 1 or comparative example catalyst 1, salt bath heating temperature 312 DEG C.Manage from the reactions above
Porch is with air speed 1600h-1Import propylene 11 volume %, air 71 volume %, steam 18 volume %
Mixed gas.Oxidation reaction is sample analysis (following example are identical with comparative example) in 24 hours, and embodiment is urged
Agent bed hot localised points temperature 364 DEG C, beds upper temp is higher than beds bottom bed temperature
Spend 3 DEG C.Propylene conversion 99.1%, acrolein selectivity 88.9%, methacrylaldehyde yield 81.5%, methacrylaldehyde+
Acrylic acid yield 92.1%.Embodiment beds hot(test)-spot temperature is not higher than 364 DEG C than salt temperature, reaction
2000 hours sample analysis, bed hot localised points temperature 362 DEG C, beds upper temp is higher than catalyst
Bed bottom bed temperature 4 DEG C.Propylene conversion 99.0%, acrolein selectivity 88.7%, methacrylaldehyde yield
81.3%, acrolein+acrylic acid yield 92.3%.Temperature Distribution is more reasonable, and beneficially catalyst long period is steady
Fixed operating.Catalyst structure is stable, and active component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version mutually, carries
The selectivity of high purpose product and yield, make catalyst long period steady running.Comparative example catalyst 1 aoxidizes
Sample analysis in reacting 24 hours, bed hot localised points temperature 368 DEG C, propylene conversion 98.4%, methacrylaldehyde
Selective 87.5%, methacrylaldehyde yield 80.1%, acrolein+acrylic acid yield 90.0%.Comparative example catalyst selects
Selecting property is poor, and methacrylaldehyde, acrylic acid yield are low.
Embodiment 2
The preparation of catalyst 2
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, through 550 DEG C of roastings 3 hours and get final product
Catalyst (I).Catalyst (I) mainly comprise into:
Mo14Bi1.2Fe1.2Ni4.5Co3.1W0.3Zn1.1Ti1.2Sn0.3Si3.1Oy(I)
Take catalyst (I) 91 part, magnesium-based lanthanum hexaaluminate 9 parts, add deionized water and mediate in kneader,
The extruded hollow columnar particle for φ 4.5 × 5mm, is dried under the conditions of 120 DEG C, and at 500 DEG C, roasting 3.5 is little
Time obtain catalyst 2.
Propylene method for oxidation
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, fills along propylene feed orienting response device bed
Enter the above-mentioned catalyst of 45ml or comparative example catalyst, salt bath heating temperature 308 DEG C.Tube inlet from the reactions above
Sentence air speed 1600h-1Import propylene 9 volume %, air 70 volume %, the mixing of steam 21 volume %
Gas, oxidation reaction is sample analysis (following example are identical with comparative example), bed hot localised points in 24 hours
Temperature 363 DEG C, propylene conversion 99.0%, acrolein selectivity 88.7%, methacrylaldehyde yield 81.4%, third
Olefine aldehydr+acrylic acid yield 92.0%.
Embodiment 3
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, through 400 DEG C of roastings 8 hours and get final product
Catalyst (I).Mainly comprise as Mo14Bi6Fe3Ni0.6Co1.6W3Zn1.5Cr0.1Rb0.2Si4.1Oy(I).
Take catalyst (I) 97 part, magnesium-based lanthanum hexaaluminate 3 parts, add deionized water and mediate in kneader, extruding
Being shaped to the hollow columnar particle of φ 4.5 × 5mm, be dried under the conditions of 120 DEG C, at 500 DEG C, roasting obtains for 4 hours
Catalyst 3.
Propylene method for oxidation
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, fills along propylene feed orienting response device bed
Enter the above-mentioned catalyst of 50ml or comparative example catalyst, salt bath heating temperature 325 DEG C.Tube inlet from the reactions above
Sentence air speed 1800h-1Import propylene 9 volume %, air 73 volume %, the mixing of steam 18 volume %
Gas.Oxidation reaction is sample analysis (following example are identical with comparative example), bed hot localised points in 24 hours
Temperature 365 DEG C, propylene conversion 99.3%, acrolein selectivity 88.8%, methacrylaldehyde yield 81.5%, third
Olefine aldehydr+acrylic acid yield 92.2%.
Embodiment 4
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, through 550 DEG C of roastings 5 hours and get final product
Catalyst (I).Mainly comprise as Mo13Bi4.6Fe1.7Ni3.3Co5W2La0.8Sn0.5Si2.7Oy(I), take and urge
Agent (I) 93 part, magnesium-based lanthanum hexaaluminate 7 parts, add deionized water and mediate in kneader, extruded
For the hollow columnar particle of φ 4.5 × 5mm, being dried under the conditions of 120 DEG C, at 500 DEG C, roasting is catalyzed for 4 hours
Agent 4.
Propylene method for oxidation
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, fills along propylene feed orienting response device bed
Enter the above-mentioned catalyst of 45ml or comparative example catalyst, salt bath heating temperature 316 DEG C.Tube inlet from the reactions above
Sentence air speed 1600h-1Import propylene 11 volume %, air 74 volume %, the mixing of steam 15 volume %
Gas.Oxidation reaction is sample analysis (following example are identical with comparative example), bed hot localised points in 24 hours
Temperature 365 DEG C, propylene conversion 99.2%, acrolein selectivity 88.7%, methacrylaldehyde yield 81.7%, third
Olefine aldehydr+acrylic acid yield 92.4%.Oxidation reaction is sample analysis after 2000 hours, bed hot localised points temperature
366 DEG C, propylene conversion 99.0%, acrolein selectivity 88.5%, methacrylaldehyde yield 81.8%, methacrylaldehyde+
Acrylic acid yield 92.2%.
Claims (11)
1. a selectivity of light olefin method for oxidation, it is characterised in that；Reaction raw materials propylene or isobutene, water, air are preheated
Enter fixed bed single tube reactor after device more than 120 DEG C preheating, salt bath heating temperature 300～340 DEG C, air speed 800～
2000h-1, feed composition: propylene or isobutene 8～14 volume %, air 70～74 volume %, steam 15～19%；
Fixed bed reactors are built with oxidation catalyst, and catalyst contains molybdenum, bismuth, iron, nickel, cobalt and wolfram element, mainly comprises
By formula M oa′Bib′Fec′Nid′Coe′WfAh′BiSijOy(I) representing, silicon is the carrier added in catalyst, and A is
At least one element in zinc, titanium, potassium；B is at least one element in tin, chromium, rubidium, lanthanum；O is oxygen；
A ', b ', c ', d ', e ', f, h ', i, j represent each Elements Atom ratio respectively, and wherein a ' is the one of 12-14
Number, b ' is a number of 0.5-6, and c ' is a number of 0.2-4, and d ' is a number of 0.2-5, and e ' is 0.2-5
A number, f is a number of 0.1-3.5, and h ' is a number of 0.1-5, and i is a number of 0.1-3.5, and j is 0.5-30
A number, y be by each oxide oxygen determine numerical value；Catalyst is possibly together with magnesium-based lanthanum hexaaluminate, containing molybdenum, (I) of bismuth
With magnesium-based lanthanum hexaaluminate by 90～98% and 1～10% after mass percent mixing through mediating, be molded, being dried, after roasting
Obtain finished catalyst.
Method the most according to claim 1, it is characterised in that containing catalyst (I) 91～96% in used catalyst, contain
There is magnesium-based lanthanum hexaaluminate 1.5～6%.
Method the most according to claim 1, it is characterised in that salt temperature 305～330 DEG C.
Method the most according to claim 1, it is characterised in that air speed 800～1500h-1。
Method the most according to claim 1, it is characterised in that beds lower floor temperature is less than beds upper strata temperature.
Method the most according to claim 1, it is characterised in that salt temperature 305～320 DEG C.
Method the most according to claim 1, it is characterised in that in used catalyst (I), in catalyst (I), b ' is 1-5
A number, c ' is a number of 0.2-3, and d ' is a number of 0.5-4, and e ' is a number of 0.5-4.
Method the most according to claim 1, it is characterised in that in used catalyst (I), B is lanthanum, i is the one of 0.1～3.5
Number.
9. according to the method described in any one of claim 1～8, it is characterised in that the preparation of used catalyst (I) includes walking as follows
Rapid: 1) will be containing Mo, A in Bi, Fe, the compound of Co, W and formula (I)h′BiThe each elemental constituent related to
Compound dissolves and mixes, and forms slurries after being co-precipitated, and adds silica or carbonization in slurry production process
One or more in silicon, dry, and shaping, roasting obtains catalyst (I) powder.
The preparation method of catalyst the most according to claim 1, it is characterised in that include preparing catalyst (I), magnesium by coprecipitation
Base lanthanum hexaaluminate, by catalyst (I), magnesium-based lanthanum hexaaluminate by 90～98% and 1～10% mass percent mixing after through pinching
Close, be molded, be dried, obtain finished catalyst after roasting.
11. catalyst according to claim 10, it is characterised in that after catalyst (I) shaping and finished catalyst is at 400～580 DEG C
Lower roasting 3～10h.
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| US5144091A (en) * | 1990-07-21 | 1992-09-01 | Basf Aktiengesellschaft | Preparation of acrolein or methacrolein by actalytic gas-phase oxidation of propene or isobutene |
| CN101012066A (en) * | 2007-01-26 | 2007-08-08 | 北京化工大学 | Method of preparing hexaaluminate inorganic material by burning urea |
| CN102627537A (en) * | 2011-02-02 | 2012-08-08 | 日本化药株式会社 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN102874860A (en) * | 2012-09-08 | 2013-01-16 | 辽宁石油化工大学 | Method for preparing magnesium aluminate lanthanum powder through combustion method |
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|---|---|---|---|---|
| EP0456837A1 (en) * | 1989-12-06 | 1991-11-21 | Nippon Shokubai Co., Ltd. | Process for producing methacrolein and methacrylic acid |
| US5144091A (en) * | 1990-07-21 | 1992-09-01 | Basf Aktiengesellschaft | Preparation of acrolein or methacrolein by actalytic gas-phase oxidation of propene or isobutene |
| CN101012066A (en) * | 2007-01-26 | 2007-08-08 | 北京化工大学 | Method of preparing hexaaluminate inorganic material by burning urea |
| CN102627537A (en) * | 2011-02-02 | 2012-08-08 | 日本化药株式会社 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
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