CN103769159A - Catalyst used for synthesizing methacrolein and preparation method thereof - Google Patents

Catalyst used for synthesizing methacrolein and preparation method thereof Download PDF

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CN103769159A
CN103769159A CN201210412581.0A CN201210412581A CN103769159A CN 103769159 A CN103769159 A CN 103769159A CN 201210412581 A CN201210412581 A CN 201210412581A CN 103769159 A CN103769159 A CN 103769159A
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catalyst
grams
span
reaction
isobutene
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李静霞
张顺海
姜家乐
吴粮华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst used for synthesizing methacrolein and a preparation method thereof, as well as a synthesis method of methacrolein, and mainly solves the problem in the prior art that the activity and the selectivity of the catalyst, which is used in a selective oxidation reaction of isobutene, are low. According to the technical scheme, Cs and K are both included in the active components of the catalyst to excellently solve the problem in the prior art, and the catalyst can be applied to the industrial production of methacrolein.

Description

For the synthesis of the Catalysts and its preparation method of MAL
Technical field
The present invention relates to the synthetic method for the synthesis of Catalysts and its preparation method and the MAL of MAL.
Background technology
Methyl methacrylate (MMA) is a kind of important Organic Chemicals and chemical products, mainly for the production of polymethyl methacrylate (lucite, PMMA), polyvinyl chloride auxiliary agent A CR and as the second monomer of acrylic fiber production process, can also be for the production of coating, adhesive, lubricant, textile dyestuff etc.
MMA conventional production methods is the Acetone cyanohydrin method take acetone and hydrogen cyanide as raw material, but this technique is used hydrogen cyanide and the sulfuric acid of high poison, highly corrosive, and therefore a large amount of hydrogen sulfate ammonia of by-product require harsh and environment is produced to larger pressure production equipment.After last century the eighties, Japan's catalyst, mitsubishi rayon and Asahi Kasei Corporation develop in succession take isobutene/tert-butyl alcohol in hybrid C 4 cut as raw material MMA production technology processed, because this process environments pollution is little, product cost is low, becomes very soon current world's second largest MMA production technology.In recent years, Lucite company of Britain developed the MMA production technology take ethene, methyl alcohol and CO as raw material, and had set up commercial plant in 2007 in Singapore.Claim according to the said firm: adopt this technique can significantly reduce cost 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 take isobutene or the tert-butyl alcohol mainly comprises: one, and isobutene or tert-butyl alcohol catalytic gas phase oxidation under molecular oxygen exists becomes MAL; Two, MAL catalytic gas phase oxidation under molecular oxygen exists 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 to Mo, Bi, Fe tri-dvielements, and they are the requisite components of catalyst; And the improvement of catalyst is mainly to carry out from activity and the stability aspect of catalyst, as added transition metal to improve activity in active constituent, increases 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 activity component, the service life of improving catalyst; Add alkali metal Cs mainly to regulate the Acidity of Aikalinity of catalyst, improve the selective etc. of reaction.
Preparing MAL due to isobutene or Oxidation of t-Butanol is a strong exothermal reaction, easily produce hot-spot at beds, cause the oxidation activity component Mo playing a major role to run off in course of reaction, and then shorten catalyst service life, in patent CN1145946A and CN1467032A, adopt the loss that adds the component Ce with heat resistance and resistance to reduction to suppress Mo, reach the object in extending catalyst life-span.In US Pat4250339, day disclosure special permission 57-72937 and CN1131059A, use the key component of the element such as tellurium (Te), thallium (TI) as catalyst, to improve the activity and selectivity of catalyst, the loss but these materials are easy to disperse in the long-term operation process of catalyst, thus the performance degradation of catalyst caused.US Pat5250485A proposes, by the composition of improvement catalyst and their usage ratio and method for preparing catalyst, to improve isobutene or tert-butyl alcohol conversion ratio and target product yield.By adding macromolecular compound to control catalyst surface structure, for the Selective Oxidation of isobutene or the tert-butyl alcohol, but still there is the problem that catalyst activity is low in JP Pat57-119837, requires further improvement.Isobutene conversion reaches 98.0%, and MAL is selective 85.3%, and methacrylic acid is selective 4.5%, and MAL and methacrylic acid are total recovery 85.0%, still not ideal enough.In the catalyst that patent JP Pat51-101 911 proposes, add alkaline components Cs, but catalyst reaction activity is lower.
Summary of the invention
One of technical problem to be solved by this invention is the low problem of catalyst activity and selectivity for the Selective Oxidation of isobutene or the tert-butyl alcohol in prior art, a kind of catalyst for the synthesis of MAL is provided, and this catalyst has advantages of that activity and selectivity is high.
Two of technical problem to be solved by this invention is to provide the preparation method of the described catalyst of one of a kind of above-mentioned technical problem.
Three of technical problem to be solved by this invention is the synthetic methods that adopt the MAL of one of above-mentioned technical problem described catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for the synthesis of MAL, the active component of described catalyst has following general formula: Mo 12bi afe bco ccs dk ex fy gz ho x, in formula, X is at least one being selected from W, V, Ni, Cr, Mn, Nb, Re, La or Ce; Y is at least one being selected from Sn, Sr, Zn, Ti or Zr; Z is catalyst a, b, c, d, e, f, g and the h atom ratio of representative element Bi, Fe, Co, Sc, Rb, X, Y and Z respectively that is selected from least one composition in Na, Li, Tl, Mg or Ca, and the span of a is 0.05～6.0; The span of b is 0.05～10.0; The span of c is 0.05～15.0; The span of d is 0.01～3.0; The span of e is 0.05～3.0; The span of f is 0～15.0; The span of g is 0～5.0; The span of h is 0.01～3.0; X meets the required oxygen atom sum of other element valence.
In technique scheme, d is preferably 1:1.5 ~ 2.5 with the ratio of e; Described catalyst can adopt separately described active component as catalyst, but preferably described activity is carried on the common vector of this area and makes loaded catalyst, and described carrier is preferably from SiO 2or Al 2o 3in at least one; In described loaded catalyst, vector contg is preferably 5～40% by weight percentage.
In technique scheme, when X is preferably at least one in Mn or Cr, Y is preferably Zr, and the span of a is preferably 1～2, the span of b is preferably 1 ~ 3, the span that the span that the span of c is preferably 2～4, d is preferably 0.05～0.2, e is preferably 0.1～0.5, the span of f is preferably 1～2, the span of g is preferably 0～0.5, h value and is preferably 0, and d has best technique effect while being 1:2 with the ratio of e.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of the described catalyst of one of above-mentioned technical problem, the compound of respective components element is dissolved in the water respectively, mix to stir evenly and regulate pH=4 ~ 9 with ammoniacal liquor afterwards, stir slaking at 50 ~ 90 ℃, evaporation, then at 150 ~ 250 ℃ of preroast aftershapings, finally calcination activation 1 ~ 10 hour in air stream at 400 ~ 700 ℃.
In technique scheme, the time of slaking is preferably 1 ~ 10 hour; The temperature of evaporation is preferably 80 ~ 100 ℃.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of synthetic method of MAL, consist of isobutene with molar ratio computing reaction raw materials: oxygen: water=1:2 ~ 10:1 ~ 4, it is 350 ~ 400 ℃ in reaction temperature, reaction pressure is 0.1 ~ 0.12 MPa, and raw material volume space velocity is 1600 ~ 3000 h -1condition under, raw material contacts with catalyst described in one of above-mentioned technical problem any one, reaction generate MAL.
In technique scheme, the mol ratio of isobutene and oxygen is preferably 1:2 ~ 4.
Key problem in technology of the present invention be in the preparation process in catalyst except Mo, Bi, Fe, Co, by add two components of Cs and K to realize high activity and the high selectivity of the synthetic metering system aldehyde reaction processed of isobutylene oxidation simultaneously.Because pib molecule has two methyl that are equal to, make pib molecule there is alkalescence, acidic site in Selective Oxidation on catalyst surface easily makes it that deep oxidation reaction occurs, when adding in catalyst after the alkali metal K and Cs with different ions radius, can reach catalyst surface and inside configuration Acidity of Aikalinity are regulated simultaneously.Catalyst of the present invention is prepared MAL reaction for isobutene selective oxidation, is that 350 ℃, raw material volume space velocity are 1800 hours in reaction temperature -1condition under, its isobutene conversion is up to 98.5%, MAL is selectively up to 90.5%, product MAL yield is up to 89.1%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated:
The specific embodiment
comparative example 1
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 63.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2mn (the NO of O, 25.1 grams of 50wt% 3) 2the aqueous solution, 0.47 gram of Cr 2o 3, 6.1 grams of Zr (NO 3) 45H 2after O stirring and dissolving, make material B.
Material B is under agitation added in material A, form catalyst pulp, add ammoniacal liquor, regulating pH is 7, and at 80 ℃, stirs slaking 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains catalyst finished product, sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, consist of isobutene: oxygen: water is 1:2:2 take molar ratio computing reaction raw materials; Be 350 ℃ in reaction temperature, reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
comparative example 2
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds 63.2 grams of 40%(wt.) Ludox make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2mn (the NO of O, 25.1 grams of 50wt% 3) 2the aqueous solution, 0.47 gram of Cr 2o 3, 6.1 grams of Zr (NO 3) 45H 2o, 0.32 gram of KNO 3after stirring and dissolving, make material B.
Material B is under agitation added in material A, form catalyst pulp, add ammoniacal liquor, regulating pH is 7, and at 80 ℃, stirs slaking 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains catalyst finished product, sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
comparative example 3
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 63.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2mn (the NO of O, 25.1 grams of 50wt% 3) 2the aqueous solution, 0.47 gram of Cr 2o 3, 6.1 grams of Zr (NO 3) 45H 2o, 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Material B is under agitation added in material A, form catalyst pulp, add ammoniacal liquor, regulating pH is 7, and at 80 ℃, stirs slaking 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains catalyst finished product, sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consist of at isobutene take molar ratio computing reaction raw materials: oxygen: water, as 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
comparative example 4
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 63.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2mn (the NO of O, 25.1 grams of 50wt% 3) 2the aqueous solution, 0.47 gram of Cr 2o 3, 6.1 grams of Zr (NO 3) 45H 2o, 0.69 gram of RbNO 3, 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Material B is under agitation added in material A, form catalyst pulp, add ammoniacal liquor, regulating pH is 7, and at 80 ℃, stirs slaking 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains catalyst finished product, sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa; Raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
comparative example 5
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 63.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2mn (the NO of O, 25.1 grams of 50wt% 3) 2the aqueous solution, 0.47 gram of Cr 2o 3, 6.1 grams of Zr (NO 3) 45H 2o, 0.32 gram of KNO 3, 0.69 gram of RbNO 3after stirring and dissolving, make material B.
Material B is under agitation added in material A, form catalyst pulp, add ammoniacal liquor, regulating pH is 7, and at 80 ℃, stirs slaking 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains catalyst finished product, sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 1
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 63.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 0.47 gram of Cr 2o 3, 6.1 grams of Zr (NO 3) 45H 2o, 0.32 gram of KNO 3with 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH is 7, and at 80 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 2
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 78.9 gram of 40 wt%, 47.7 grams of 20wt% aluminium colloidal sols and 8.24 grams of NH 4vO 3make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 0.7 gram of Zn (NO 3) 26H 2o, 10.25 grams of Ce (NO 3) 3, 1.8 grams of Yb (NO 3) 3, 0.32 gram of KNO 3with 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 9, and at 50 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 6 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1600 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 3
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 77.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 6.15 grams of Ce (NO 3) 3, 1.3 grams of Yb (NO 3) 3, 0.32 gram of KNO 3with 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 9, and at 60 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 8 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 2000 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 4
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 101.8 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 2.05 grams of Ce (NO 3) 3, 0.6 gram of Yb (NO 3) 3, 27.7 grams of Ni (NO 3) 2, 1.6 grams of KNO 3with 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 4, and at 70 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 10 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 3000 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 5
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 56.2 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 2.05 grams of Ce (NO 3) 3, 3.0 grams of Yb (NO 3) 3, 20.8 grams of Ni (NO 3) 2, 1.0 grams of KNO 3with 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 9, and at 80 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 6
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 70.2 gram of 40 wt%, 35.1 grams of 20wt% aluminium colloidal sols to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 6.15 grams of Ce (NO 3) 3, 0.64 gram of KNO 3with 0.46 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, add 9.3 grams of Nb 2o 5, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 9, and at 90 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains catalyst finished product, sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 7
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 77.2 gram of 40 wt%, 37.1 grams of 20wt% aluminium colloidal sols to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 6.15 grams of Ce (NO 3) 3, 1.67 grams of Mn (NO 3) 2, 0.5 gram of Sr (NO 3) 2, 0.16 gram of KNO 3, 0.92 gram of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 9, and at 80 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 8
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds the Ludox of 112.3 gram of 40 wt% to make material A.
By 38.5 grams of Fe (NO 3) 39H 2o joins in 70 ℃ of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving again 3) 35H 2o, 41.2 grams of Co (NO 3) 26H 2o, 6.15 grams of Ce (NO 3) 3, 1.67 grams of Mn (NO 3) 2, 3.0 grams of Sr (NO 3) 2, 0.32 gram of KNO 3, 1.83 grams of CsNO 3after stirring and dissolving, make material B.
Solution B is under agitation added in solution A, form catalyst pulp, adding ammoniacal liquor to regulate pH value is 9, and at 80 ℃, stir aging 2 hours, it is 70wt% that 100 ℃, slurry is evaporated to solid content, extrusion molding, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 490 ℃, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1.Consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 2.
embodiment 9
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:1, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 10
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:3:3, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 11
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:4:4, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 12
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:5:4, is 350 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 13
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 360 ℃ in reaction temperature, and reaction pressure is 0.11 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 14
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 370 ℃ in reaction temperature, and reaction pressure is 0.12 MPa, and raw material volume space velocity is 1800 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 15
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:2, is 380 ℃ in reaction temperature, and reaction pressure is 0.1 MPa, and raw material volume space velocity is 2000 h -1condition under check and rate 100 h, it the results are shown in table 3.
embodiment 16
Catalyst prepared by embodiment 1 is consisting of isobutene take molar ratio computing reaction raw materials: oxygen: water is 1:2:1, is 390 ℃ in reaction temperature, and reaction pressure is 0.12 MPa, and raw material volume space velocity is 3000 h -1condition under check and rate 100 h, it the results are shown in table 3.
Table 1 catalyst composition
Figure 847215DEST_PATH_IMAGE001
Table 2 different catalysts evaluation result
Figure 222833DEST_PATH_IMAGE002
Evaluating catalyst result under table 3 differential responses condition
Figure 909029DEST_PATH_IMAGE003

Claims (9)

1. for the synthesis of a catalyst for MAL, the active component of described catalyst has following general formula: Mo 12bi afe bco ccs dk ex fy gz ho x
In formula, X is at least one being selected from W, V, Ni, Cr, Mn, Nb, Re, La or Ce; Y is at least one being selected from Sn, Sr, Zn, Ti or Zr; Z is catalyst a, b, c, d, e, f, g and the h atom ratio of representative element Bi, Fe, Co, Cs, K, X, Y and Z respectively that is selected from least one composition in Na, Li, Tl, Mg or Ca, and the span of a is 0.05～6.0; The span of b is 0.05～10.0; The span of c is 0.05～15.0; The span of d is 0.01～3.0; The span of e is 0.05～3.0; The span of f is 0～15.0; The span of g is 0～5.0; The span of h is 0～3.0; X meets the required oxygen atom sum of other element valence.
2. catalyst according to claim 1, is characterized in that d and the ratio of e are 1:1.5 ~ 2.5.
3. catalyst according to claim 1, is characterized in that described catalyst is loaded catalyst, and the carrier of catalyst is selected from SiO 2or Al 2o 3in at least one.
4. catalyst according to claim 3, is characterized in that by weight percentage in described catalyst, vector contg is 5～40%.
5. the preparation method of catalyst claimed in claim 3, is characterized in that the compound of respective components element to dissolve respectively, mixes to stir evenly to regulate pH=4 ~ 9 with ammoniacal liquor afterwards, stir slaking at 50 ~ 90 ℃, evaporation, moulding, finally 400 ~ 700 ℃ of calcination activations 1 ~ 10 hour.
6. the preparation method of catalyst according to claim 5, the time that it is characterized in that slaking is 1 ~ 10 hour.
7. the preparation method of catalyst according to claim 5, is characterized in that the temperature of evaporation is 80 ~ 100 ℃.
8. a synthetic method for MAL, consists of isobutene with molar ratio computing reaction raw materials: oxygen: water=1:2 ~ 10:1 ~ 4; Be 350 ~ 400 ℃ in reaction temperature, reaction pressure is 0.1 ~ 0.12 MPa, and raw material volume space velocity is 1600 ~ 3000 h -1condition under, raw material contacts with catalyst described in any one in claim 1 to 4, reaction generate MAL.
9. synthetic method according to claim 8, the mol ratio that it is characterized in that isobutene and oxygen is 1:2 ~ 4.
CN201210412581.0A 2012-10-25 2012-10-25 Catalyst used for synthesizing methacrolein and preparation method thereof Pending CN103769159A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462062A (en) * 2009-01-07 2009-06-24 合肥海力科技开发有限公司 Catalyst and method for producing methylacrolein by fractional catalytic oxidation
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
CN102247862A (en) * 2010-05-18 2011-11-23 中国石油天然气股份有限公司 Multilayer composite metal oxide catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462062A (en) * 2009-01-07 2009-06-24 合肥海力科技开发有限公司 Catalyst and method for producing methylacrolein by fractional catalytic oxidation
CN102247862A (en) * 2010-05-18 2011-11-23 中国石油天然气股份有限公司 Multilayer composite metal oxide catalyst and preparation method thereof
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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