CN103420820B - Produce MAL method - Google Patents
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- CN103420820B CN103420820B CN201210150517.XA CN201210150517A CN103420820B CN 103420820 B CN103420820 B CN 103420820B CN 201210150517 A CN201210150517 A CN 201210150517A CN 103420820 B CN103420820 B CN 103420820B
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Abstract
The present invention relates to a kind of method by isobutene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol, mainly solve in prior art the not high and bad problem of reappearance of MAL yield. The present invention is by adopting to be selected from SiO2Or Al2O3In at least one be carrier contain the active component Mo by following general formula12BiaFebCocCedXeYfZgOx, wherein X is at least one being selected from W, V, Ni, Cr, Mn, Nb or Re; Y is at least one being selected from Sn, Sr, Zn, Ti or Zr; Z is that at least one the technical scheme being selected from K, Rb, Na, Li, Tl or Cs has solved this problem preferably, can be used in the industrial production of MAL.
Description
Technical field
The present invention relates to a kind of method of producing MAL.
Background technology
Methyl methacrylate (MMA) is a kind of important Organic Chemicals and chemical products, mainly for the production of poly-Methyl methacrylate (lucite, PMMA), polyvinyl chloride auxiliary agent A CR and the second monomer as acrylic fiber production process, all rightFor the production of coating, adhesive, lubricant, textile dyestuff etc.
MMA conventional production methods is the Acetone cyanohydrin method taking acetone and hydrogen cyanide as raw material, but this technique is used high poison, highCorrosive hydrogen cyanide and sulfuric acid, a large amount of hydrogen sulfate ammonia of by-product, therefore requires harsh and produces larger to environment production equipmentPressure. After last century the eighties, Japanese catalyst, mitsubishi rayon and Asahi Kasei Corporation develop in succession with hybrid C 4 cutMiddle isobutene/tert-butyl alcohol is raw material MMA production technology processed, and because this process environments pollution is little, product cost is low, becomes very soon orderFront world's second largest MMA production technology. In recent years, Britain Lucite company developed the MMA taking ethene, methyl alcohol and CO as raw materialProduction technology, and set up commercial plant in 2007 in Singapore. Claim according to the said firm: adopt this technique significantly to reduceCost of material. But its technology maturation and macroeconomic need further to be checked.
The technique of producing methyl methacrylates as raw material three steps oxidations taking isobutene or the tert-butyl alcohol mainly comprises: one, and differentButylene or tert-butyl alcohol catalytic gas phase oxidation under molecular oxygen exists becomes MAL; Two, MAL exists at molecular oxygenLower catalytic gas phase oxidation becomes methacrylic acid; Three, methacrylic acid and methyl alcohol generation esterification generate methyl methacrylate.At present, about the existing a large amount of reports of patent of isobutene or Oxidation of t-Butanol synthesize methyl acrylic aldehyde, nearly all patent all relates toAnd to Mo, Bi, Fe tri-dvielements, they are the requisite components of catalyst; And the improvement of catalyst is mainly from catalystActivity and stability aspect carry out, as added transition metal to improve activity in active constituent, increase the single of product and receive;Add rare earth element to improve redox ability; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, stabilizing catalyst activityComponent, improves the service life of catalyst etc.
Have a lot of patent reports for isobutene or tert-butyl alcohol Selective Oxidation MAL:
In USPat4250339, day disclosure special permission 57-72937 and CN1131059A, use the unit such as tellurium (Te), thallium (TI)Element is as the key component of catalyst, and to improve the activity and selectivity of catalyst, but these materials are in the long-term fortune of catalystTurn over the loss that is easy to disperse in journey, thereby cause the performance degradation of catalyst.
USPat5250485A proposes by the composition of improvement catalyst and their usage ratio and catalyst preparation sideMethod, improves isobutene or tert-butyl alcohol conversion ratio and target product yield. Isobutene conversion reaches 98.0%, MALSelective 85.3%, methacrylic acid is selective 4.5%, and MAL and methacrylic acid are total recovery 85.0%, still reason notThink.
JPPat57-119837 is by adding macromolecular compound to control catalyst surface structure, for isobutene orThe Selective Oxidation of the tert-butyl alcohol, but still the problem that exists reactivity to reduce with the reaction time requires further improvement.
Summary of the invention
Technical problem to be solved by this invention is to exist in the reaction of isobutene or Preparation of Methacrolein by Oxidation of Tertiary Butyl AlcoholThe problem that MAL yield is lower, provides a kind of new isobutene or Preparation of Methacrolein by Oxidation of Tertiary Butyl Alcohol method. The partyMethod is produced metering system aldehyde reaction for isobutene or tert-butyl alcohol selective oxidation, have isobutene or tert-butyl alcohol conversion ratio high,The advantage that MAL yield is high.
For solving the problems of the technologies described above, in the present invention, adopt technical scheme as follows: a kind of isobutene or the tert-butyl alcohol are selected oxygenBe combined to the method for MAL, taking isobutene or the tert-butyl alcohol and oxygen as raw material, the mol ratio of isobutene or the tert-butyl alcohol and oxygenFor 1:2～10, be 350～400 DEG C in reaction temperature, reaction pressure is 0.1～0.12Mpa, air speed is 800～1200h-1，The mol ratio of isobutene or the tert-butyl alcohol and water is under the condition of 1:1～4, and raw material contacts with catalyst, and reaction generates MAL,Wherein catalyst used is to be selected from SiO2Or Al2O3In at least one be carrier contain the active component by following general formulaMo12BiaFebCocCedXeYfZgOx, in formula, the span of a is 0.05～6.0; The span of b is 0.05～8.5; C'sSpan is 0.05～15.0; The span of d is 0.01～9.0; The span of e is 0～5.0; The span of f is0.05～15.0; The span of g is 0.01～5.0; X is at least one being selected from W, V, Ni, Cr, Mn, Nb or Re; Y isBe selected from least one in Sn, Sr, Zn, Ti or Zr; Z is at least one being selected from K, Rb, Na, Li, Tl or Cs; A, b, c, d,E, f and g be the atom ratio of representative element bismuth, iron, cobalt, cerium, X, Y and Z respectively, and x meets the required oxygen of other element valenceTotal atom number, in catalyst, the consumption of carrier is catalyst weight 5～40%.
The solid content of catalyst after oven dry is 25-75%.
In technique scheme, the mol ratio preferable range of isobutene or the tert-butyl alcohol and oxygen is 1:2～5.
The preparation method of the catalyst adopting in the inventive method is as follows:
A) ammonium molybdate of Kaolinite Preparation of Catalyst aequum is dissolved in water, then by molten carrier silicon required Kaolinite Preparation of CatalystGlue, aluminium oxide or its mixture add formation solution I;
B) metal salt solution of Kaolinite Preparation of Catalyst active component aequum is dissolved in and in water, forms solution II;
C) under agitation, solution II is added in solution I and forms catalyst pulp;
D) catalyst pulp is by dry, and making the solid content of catalyst after oven dry is 25-75%, then is urged through roastingAgent finished product.
In technique scheme, baking temperature is 70-100 DEG C, and be 6-24h drying time.
The present invention finds this multicomponent composite oxide catalytic for isobutene or Preparation of Methacrolein by Oxidation of Tertiary Butyl AlcoholAgent, the adding of Ce component in catalyst, the quantity of the active Lattice Oxygen species can obviously improve catalyst reaction time, and latticeOxygen has important effect to the activity that improves catalyst. The mensurable bonded atom of electronegativity attracts the ability of electronics, Bi3+'sPauling electronegativity value is 2.02, V5+Pauling electronegativity value be 1.6, all than Mo6+Pauling electronegativity value(2.35) little, the mobility of lattice oxygen that they produce in reaction is to Mo6+Surface produce active sites or make its regeneration. And CePauling electronegativity value is 1.12, and electronegativity is less, and the Lattice Oxygen of its generation is also transferred to Mo6+Surface produce activated sites, thereforeCan be by adding Ce effectively to improve the catalytic performance of catalyst. Catalyst of the present invention is selected for isobutene or the tert-butyl alcoholOxidation is prepared in metering system aldehyde reaction, is 1:2～10 in the mol ratio of isobutene or the tert-butyl alcohol and oxygen, in reaction temperature is350～400 DEG C, reaction pressure is 0.1～0.12Mpa, and air speed is 800～1200h-1, the rubbing of isobutene or the tert-butyl alcohol and waterYou are than being that under the condition of 1:1～4, its isobutene or tert-butyl alcohol conversion ratio can reach 98.5%, and MAL and methacrylic acid are selectedProperty can reach 92.5%, and product MAL and methacrylic acid yield can reach 91.1%, have obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[comparative example]
By 100 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 100 grams 70 DEG C, stirs it is all dissolved, and addsThe Ludox that enters 63.2 gram 40% (wt.) is made material A.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams after stirring and dissolving againBi(NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of Mn (NO3)2Solution (50%), 0.3 gram of Zn (NO3)2·6H2O, 0.5 gram of CsNO3After stirring and dissolving, make material B.
Solution B is added in solution A, form catalyst pulp, and at 80 DEG C, stir aging 2 hours, 70 DEG C, slurry is dryDry 6h, slurry solid content is 25%, and then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 DEG C. This catalyst compositionAnd preparation condition lists in table 1, be 1:2 in the mol ratio of isobutene and oxygen; It is 350 DEG C in reaction temperature; Reaction pressure is 0.1Mpa; Air speed is 1000h-1; The mol ratio of isobutene and water is to check and rate under 1:2 condition, and it the results are shown in table 2.
[embodiment 1]
By 100 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 100 grams 70 DEG C, stirs it is all dissolved, and addsEnter the Ludox of 89.4 gram 40% (wt.), 35.8 gram of 20% aluminium colloidal sol and 19.1 grams of (NH4)6H5[H2(WO4)6] make material A.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams after stirring and dissolving againBi(NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 6.1 grams of Ce (NO3)3·6H2O, 0.7 gram of Zn (NO3)2·6H2O、0.3Gram CsNO3After stirring and dissolving, make material B.
Solution B is added in solution A, form catalyst pulp, and at 80 DEG C, stir aging 2 hours, 80 DEG C, slurry is dryDry 12h, slurry solid content is 50%, and then high-temperature roasting obtains catalyst finished product, and sintering temperature is 400 DEG C～550 DEG C. This is urgedAgent composition and preparation condition are listed in table 1, are 1:2 in the mol ratio of isobutene and oxygen; It is 350 DEG C in reaction temperature; Reaction pressurePower is 0.1Mpa; Air speed is 1000h-1; The mol ratio of isobutene and water is to check and rate under 1:2 condition, and it the results are shown in table 2.
[embodiment 2]
By 100 grams of (NH4)6Mo7O24·4H2O joins in the warm water of 100 grams 70 DEG C, stirs it is all dissolved, and addsEnter the Ludox of 78.9 gram 40% (wt.), 47.7 gram of 20% aluminium colloidal sol and 8.24 grams of NH4VO3Make material A.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams after stirring and dissolving againBi(NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 6.1 grams of Ce (NO3)3, 0.7 gram of Zn (NO3)2·6H2O, 0.5 gram of CsNO3After stirring and dissolving, make material B.
Solution B is added in solution A, form catalyst pulp, and at 80 DEG C, stir aging 2 hours, 100 DEG C, slurry is dryDry 24h, slurry solid content 75%, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 400 DEG C～550 DEG C. This catalysisAgent composition and preparation condition are listed in table 1, are 1:2 in the mol ratio of the tert-butyl alcohol and oxygen; It is 350 DEG C in reaction temperature; Reaction pressureFor 0.1Mpa; Air speed is 1000h-1; The mol ratio of the tert-butyl alcohol and water is to check and rate under 1:2 condition, and it the results are shown in table 2.
[embodiment 3～11]
Make catalyst by each step of implementing 2, concrete outcome is listed in table 1. At the appreciation condition identical with embodiment 2Under, reaction result is listed in table 2.
[embodiment 12～21]
Under different reaction conditions, the appraisal result of embodiment 1 catalyst is listed in to table 3.
Table 1 catalyst weight composition and preparation condition
| Catalyst weight composition | Solid content/g | |
| Comparative example | Mo12Bi1.5Fe2.0Co3.0Mn1.5Zn0.02Cs0.05+17%SiO2 | 25 |
| Embodiment 1 | Mo12Bi1.5Fe2.0Co3.0Ce0.3W1.5Zn0.05Gs0.01+15% SiO2+3%Al2O3 | 50 |
| Embodiment 2 | Mo12Bi1.5Fe2.0Co3.0Ce0.3V1.5Zn0.05Cs0.05+19%SiO2+4%Al2O3 | 75 3 --> |
| Embodiment 3 | Mo12Bi1.0Fe3.0Co3.0Ce0.3Cr1.5Sn0.01Rb0.08+19%SiO2 | 50 |
| Embodiment 4 | Mo12Bi1.0Fe2.0Co3.0Ce0.4Re1.5Sn0.08Cs0.05+22%SiO2 | 50 |
| Embodiment 5 | Mo12Bi1.0Fe2.0Co3.0Ce0.4Ni1.5Sn0.05Cs0.12+14%SiO2 | 50 |
| Embodiment 6 | Mo12Bi1.0Fe2.0Co3.0Ce0.4Nb1.5Sn0.03K0.05+16%SiO2+4%Al2O3 | 50 |
| Embodiment 7 | Mo12Bi0.5Fe2.0Co2.0Ce0.5Mn0.5Sr0.05K0.05+18%SiO2+5%Al2O3 | 75 |
| Embodiment 8 | Mo12Bi0.5Fe3.0Co2.0Ce0.5Mn0.5Sr0.60Cs0.05+23%SiO2 | 75 |
| Embodiment 9 | Mo12Bi0.5Fe2.0Co2.0Ce0.5Mn0.5Sr0.03Cs0.05+18%SiO2 | 75 |
| Embodiment 10 | Mo12Bi0.5Fe2.0Co2.0Ce0.5Mn0.5Sr0.10Cs0.05+16%SiO2+8%Al2O3 | 75 |
| Embodiment 11 | Mo12Bi0.5Fe3.0Co2.0Ce0.5Mn0.5Sr0.05Rb0.08+19%SiO2+6%Al2O3 | 75 |
Table 2 evaluating catalyst result 1
Evaluating catalyst result 2 under table 3 differential responses condition
Claims (2)
1. a method for isobutene or tert-butyl alcohol selective oxidation synthesize methyl acrylic aldehyde, taking isobutene or the tert-butyl alcohol and oxygen as formerMaterial, the mol ratio of isobutene or the tert-butyl alcohol and oxygen is 1:2～10, is 350～400 DEG C in reaction temperature, reaction pressure is 0.1～0.12Mpa, air speed is 800～1200h-1, the mol ratio of isobutene or the tert-butyl alcohol and water is under the condition of 1:1～4, raw material and catalysisAgent contact, reaction generates MAL, and wherein catalyst used is to be selected from SiO2Or Al2O3In at least one be carrierAnd contain the active component Mo by following general formula12BiaFebCocCedXeYfZgOx, in formula, the span of a is 0.5～6.0; B'sSpan is 0.05～8.5; The span of c is 0.05～15.0; The span of d is 0.01～5.0; The value model of eEnclose is 0～5.0; The span of f is 0.05～15.0; The span of g is 0.01～5.0; X for be selected from V, Ni, Cr, Mn,At least one in Nb or Re; Y is at least one being selected from Sn, Sr, Zn or Ti; Z is for being selected from K, Rb, Na, Li, Tl or CsAt least one; A, b, c, d, e, f and g be the atom ratio of representative element bismuth, iron, cobalt, cerium, X, Y and Z respectively, and x is for meeting otherThe oxygen atom sum that element valence is required, in catalyst, the consumption of carrier is catalyst weight 5～40%;
The preparation method of described catalyst is as follows:
A) ammonium molybdate of Kaolinite Preparation of Catalyst aequum is dissolved in water, then by carrier Ludox required Kaolinite Preparation of Catalyst,Aluminium oxide or its mixture add formation solution I;
B) metal salt solution of Kaolinite Preparation of Catalyst active component aequum is dissolved in and in water, forms solution II;
C) under agitation, solution II is added in solution I and forms catalyst pulp;
D) catalyst pulp is by dry, and making the solid content of catalyst after oven dry is 25-75%, then obtains catalyst through roastingFinished product.
2. the method for isobutene according to claim 1 or tert-butyl alcohol synthesize methyl acrylic aldehyde, is characterized in that isobuteneOr the mol ratio of the tert-butyl alcohol and oxygen is 1:2～5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105498795A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Methacrylaldehyde catalyst and preparation method thereof |
| CN105503558A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Synthesis method of methacrylaldehyde |
| CN104801312B (en) * | 2015-03-17 | 2017-07-07 | 烟台大学 | A kind of composite oxide catalysts and preparation method |
| CN106807394B (en) * | 2017-01-12 | 2019-07-19 | 南京氧簇科技有限公司 | A kind of catalyst and preparation method thereof of isobutylene oxidation synthesizing methyl methacrylaldehyde |
| JP7209578B2 (en) * | 2019-04-15 | 2023-01-20 | 日本化薬株式会社 | Catalyst and its manufacturing method |
| CN115569650A (en) * | 2021-07-06 | 2023-01-06 | 惠生工程（中国）有限公司 | Catalyst for synthesizing unsaturated aldehyde and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| CN1282630A (en) * | 1999-05-25 | 2001-02-07 | 株式会社日本触媒 | Compound oxide catalyst and method for preparing (methyl) propenal and (methgl) acrylic acid |
| CN102091634A (en) * | 2010-12-13 | 2011-06-15 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst used in reaction of preparing methylacrolein by selective oxidation of isobutene/tertiary butanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7265250B2 (en) * | 2003-12-26 | 2007-09-04 | Lg Chem, Ltd. | Method of producing unsaturated aldehyde and/or unsaturated fatty acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| CN1282630A (en) * | 1999-05-25 | 2001-02-07 | 株式会社日本触媒 | Compound oxide catalyst and method for preparing (methyl) propenal and (methgl) acrylic acid |
| CN102091634A (en) * | 2010-12-13 | 2011-06-15 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst used in reaction of preparing methylacrolein by selective oxidation of isobutene/tertiary butanol |
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