CN104437533B - Catalyst of methylacrolein and methacrylic acid and preparation method thereof - Google Patents
Catalyst of methylacrolein and methacrylic acid and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to for the catalyst and preparation method thereof of synthesizing methyl acrylic aldehyde and methacrylic acid and methylacrolein and the synthetic method of methacrylic acid, mainly solve the problem of poor catalyst stability of Selective Oxidation for isobutene. present in prior art.The present invention is by using methylacrolein and the catalyst of methacrylic acid, and the active component of described catalyst has below general formula: Mo12BiaFebCocXdYeZfOx；In formula, X is at least one in W, V, Ni, Cr, Mn, Nb, Re, La；Y is at least one in Sn, Sr, Zn, Ti or Zr；Z is the scheme of at least one in Na, Li, Tl, K, Cs, Mg or Ca, preferably resolves problem above, can be used in the commercial production of methylacrolein and methacrylic acid.
Description
Technical field
The present invention relates to methylacrolein and the catalyst of methacrylic acid, preparation method and methylacrolein and methacrylic acid synthetic method.
Background technology
Methyl methacrylate (MMA) is a kind of organic chemical industry's intermediate mainly for the production of lucite, the most also includes the production of the products such as coating, binding agent, lubricant, penetrating agent and PVC modifier.The main technique used that produces of MMA is Acetone cyanohydrin method in early days, and due to this mature technology, product yield is high and is widely used.But this art production process uses hydrocyanic acid and sulphuric acid, by-product a large amount of sulphuric acid cyanogen ammonium, environment is caused bigger pressure, therefore promotes the developmental research of MMA new technology.After last century the eighties, the companies such as Japan's catalyst, mitsubishi rayon and Asahi Chemical Industry is developed to mix C4In fraction, isobutene ./tert-butyl alcohol is raw material MMA production technology, and this technique produces methylacrolein (MAL) initially with isobutene. or the tert-butyl alcohol, and then MAL further aoxidizes and be esterified generation methyl methacrylate (MMA).Avoid in process of production using due to this technique and there is hypertoxic hydrocyanic acid, therefore, compared with sending out with .alpha.-hydroxyisobutyronitrile., it is to avoid the generation of spent acid and equipment corrosion problem, ambient pressure is reduced, product cost is low, is quickly become current world's second largest MMA production technology.
It is the emphasis that isobutylene oxidation method prepares MMA research that selective isobutene aoxidizes the catalyst research of methylacrolein processed.It is currently used for the catalyst of this section of reaction mainly based on molybdenum bismuth metal composite oxide system, and adds the auxiliary agents such as ferrum, cobalt, alkali metal and improve selectivity and the stability of reaction.Preparing methylacrolein due to isobutene. or Oxidation of t-Butanol is a strong exothermal reaction, easily produces hot-spot at beds, causes oxidation activity component Mo played a major role to run off in course of reaction, and then shortening catalyst service life.Japanese Laid-Open Patent 59-193136 prepares the material with molybdenum trioxide by being loaded in by molybdenum trioxide on inertia heat resistant inorganic material, but selectivity of catalyst is not high enough for commercial Application.US
Pat5250485A proposes the composition by improving catalyst and their usage ratio and method for preparing catalyst, improves isobutene. or tert-butyl alcohol conversion ratio and target product yield.Patent CN1099024A is come by the method adding molybdenum trioxide in the catalyst but is still suffered from the problem that catalyst activity is low.Japanese Laid-Open Patent 57-56044 proposes to add in catalyst by molybdenum compound, and by the roasting in 550～700 DEG C of oxygen containing atmosphere after heat treatment in 200～700 DEG C of reducing atmospheres of this mixture, the stability of catalyst does not still reach meeting of commercial Application.
Summary of the invention
One of the technical problem to be solved is problem low for the catalyst activity and selectivity of the Selective Oxidation of isobutene. in prior art, there is provided a kind of for synthesizing methyl acrylic aldehyde with the catalyst of methacrylic acid, the feature that this catalyst is active and selectivity is good.
The two of the technical problem to be solved are to provide the preparation method of one of a kind of above-mentioned technical problem described catalyst.
The three of the technical problem to be solved are methylacrolein and the methacrylic acid synthetic methods using one of above-mentioned technical problem described catalyst.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: methylacrolein and the catalyst of methacrylic acid, and the active component of described catalyst has below general formula: Mo12BiaFebCocXdYeZfOx
In formula, X is at least one in W, V, Ni, Cr, Mn, Nb, Re, La；Y is at least one in Sn, Sr, Zn, Ti or Zr；Z is at least one in Na, Li, Tl, K, Cs, Mg or Ca；The atom ratio of a, b, c, d, e, f representative element Bi, Fe, Co, X, Y and Z respectively, 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 0.01～3.0；The span of f is 0～15.0；X is to meet the oxygen atom sum needed for other element valence.
Can individually use described active component as catalyst in technique scheme, but preferably described active component be carried on the common vector of this area and make loaded catalyst, described carrier preferably is selected from SiO2Or Al2O3In at least one；In loaded catalyst, vector contg is preferably 5～40wt%.
At least one in X is preferably Mn or Cr, Y is preferably Zr, the span of a is preferably 1～2, the span of b is preferably 1 ~ 3, the span of c is preferably 2～4, the span of d is preferably 0.05～0.2, and the span of e is preferably 0.1～0.3, has best technique effect during the span of f preferably 0.05～0.2.
For solving the two of above-mentioned technical problem, 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, and step includes:
(1) ammonium molybdate aqueous solution is mixed to get mixture I with at least one in Ludox or Alumina gel；
(2) oxide or the nitrate of metal following in above-mentioned formula are dissolved in water and obtain mixtures II: Bi, Fe, Co, X、Y and Z；
(3) under stirring, mixtures II is added mixture I and obtain mixtures III；
(4) mixtures III and additive are mixed to get mixture IV；
(5) regulate pH=4 ~ 9 with ammonia, stir ripening, evaporation, molding, finally calcination activation 1 ~ 10 hour at 400 ~ 700 DEG C at 50 ~ 90 DEG C；
At least one in iron molybdate, molybdenum trioxide, iron sesquioxide, ferroso-ferric oxide, bismuth oxide and nickel oxide of described additive.Described additive is preferably made up of iron molybdate and at least one metal-oxide in molybdenum trioxide, iron sesquioxide, ferroso-ferric oxide, bismuth oxide and nickel oxide.As most preferred technical scheme, described additive is made up of iron molybdate and molybdenum trioxide, and the weight ratio of iron molybdate and molybdenum trioxide is preferably 2:1～1:2.
In technique scheme, described additive preferably comprises 0.1～5 wt% of catalyst weight.The time of ripening is preferably 1 ~ 10 hour；The temperature of evaporation is preferably 80 ~ 100 DEG C.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows: methylacrolein and the synthetic method of methacrylic acid, and with isobutene. and oxygen as raw material, water is diluent, and isobutene. is 1:2 ~ 1:10 with the mol ratio of oxygen；It it is 350 ~ 400 DEG C in reaction temperature；Reaction pressure is 0.1 ~ 0.12 MPa;Raw material volume air speed is 800 ~ 1200 h-1；Under the conditions of the mol ratio of isobutene. and water is 1:1 ~ 1:4, contacting at catalyst described in any one of one of above-mentioned technical problem, reaction generates methylacrolein and methacrylic acid.
In technique scheme, isobutene. is preferably 1:2 ~ 1:4 with the mol ratio of oxygen.
The key problem in technology of the present invention is to add described additive in preparation process in the catalyst to realize isobutylene oxidation synthesis methylacrolein processed and the high activity of metering system acid reaction and high selectivity.The catalyst of the present invention is prepared in methylacrolein reaction for isobutene. selective oxidation, reaction temperature be 350 DEG C, raw material volume air speed be 1000 hours-1Under conditions of run after 1000h, its isobutene conversion is up to 99.9%, and methylacrolein and methacrylic acid overall selectivity are up to 92.5%, and product methylacrolein and methacrylic acid total recovery are up to 92.4%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
Comparative example
1
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes 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 of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.32 gram of KNO3With 0.46 gram of CsNO3, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2Material B is made after O stirring and dissolving.
Material B is under agitation added in material A, form catalyst pulp, adding ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, extrusion molding, obtains the cylinder of φ 3.5x3.5mm, and then high-temperature roasting obtains finished catalyst, sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
1
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2In the water of O join 20 grams 70 DEG C, after stirring and dissolving, add 34.3 grams of Bi (NO3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.32 gram of KNO3With 0.46 gram of CsNO3, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2Mixtures II is made after O stirring and dissolving.
Add in mixture I by lower for mixtures II stirring, after mix and blend, add 18.6 grams of Fe2Mo3O12, adding ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
2
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3 、0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Under agitation being added by mixtures II in mixture I, mixing adds 18.6 grams of MoO after stirring evenly3, adding ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
3
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, is stirring evenly and then adding into 18.6 grams of Fe2O3, adding ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
4
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, is stirring evenly and then adding into 18.6 grams of Fe3O4, adding ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
5
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, is stirring evenly and then adding into 18.6 grams of Bi2O3, adding ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
6
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, is stirring evenly and then adding into 9.3 grams of Fe2Mo3O12With 9.3 grams of Fe2O3Forming catalyst pulp, add ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Present inventor finds, when additive includes Fe simultaneously2Mo3O12And Fe2O3Time in terms of improving isobutene conversion and selectivity of product, there is synergism.The data of embodiment 1, embodiment 3 and embodiment 6 that this is given from table 1 and table can intuitively be found out.
Embodiment
7
By 100 grams of (NH4)6Mo7O24·4H2O joins in the water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 20 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, is stirring evenly and then adding into 9.3 grams of Fe2Mo3O12With 9.3 grams of Bi2O3Forming catalyst pulp, add ammonia, regulation pH is 7, and stirs ripening 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Present inventor finds, when additive includes Fe simultaneously2Mo3O12And Bi2O3Time in terms of improving isobutene conversion and selectivity of product, there is synergism.The data of embodiment 1, embodiment 5 and embodiment 7 that this is given from table 1 and table can intuitively be found out.
Embodiment
8
By 100 grams of (NH4)6Mo7O24·4H2O joins in the hot water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 63.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mix homogeneously, add 9.3 grams of Fe2Mo3O12With 9.3 grams of MoO3, adding ammonia regulation pH is 7, and stirs aging 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Present inventor finds, when additive includes Fe simultaneously2Mo3O12And MoO3Time in terms of improving isobutene conversion and selectivity of product, there is synergism.The data of embodiment 1, embodiment 2 and embodiment 8 that this is given from table 1 and table can intuitively be found out.And, from the isobutene conversion of embodiment 6～8 and the comparison of selectivity of product it can be seen that Fe2Mo3O12And MoO3Between synergism higher.
Embodiment
9
By 100 grams of (NH4)6Mo7O24·4H2O joins in the hot water of 100 grams 70 DEG C, and stirring makes it all dissolve, add 78.9 grams of concentration be the Ludox of 40wt%, 47.7 grams of concentration be the Alumina gel of 20wt% and 8.24 grams of NH4VO3Make mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mix homogeneously, add 18.6 grams of Fe2Mo3O12With 9.3 grams of MoO3, adding ammonia regulation pH value is 7, and stirs aging 2 hours at 50 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 6 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
10
By 100 grams of (NH4)6Mo7O24·4H2O joins in the hot water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 77.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mix homogeneously, add 9.3 grams of Fe2Mo3O12With 18.6 grams of MoO3, adding ammonia regulation pH value is 7, and stirs aging 2 hours at 60 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 8 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
11
By 100 grams of (NH4)6Mo7O24·4H2O joins in the hot water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 101.8 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 25.1 grams of concentration are the Mn (NO of 50wt%3)2Aqueous solution, 0.47 gram of Cr2O3, 6.1 grams of Zr (NO3)4·5H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mix homogeneously, add 4.7 grams of Fe2Mo3O12With 4.7 grams of MoO3, adding ammonia regulation pH value is 7, and stirs aging 2 hours at 70 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 10 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 1000 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
12
By 100 grams of (NH4)6Mo7O24·4H2O joins in the hot water of 100 grams 70 DEG C, and stirring makes it all dissolve, and adds the Ludox that 56.2 grams of concentration is 40wt% and makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 20.8 grams of Ni (NO3)2, 0.32 gram of KNO3, 0.46 gram of CsNO3, 8.85 grams of Yb (NO3)3·5H2O and 1.02 grams of Ce (NO3)3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mix homogeneously, add 9.3 grams of Fe2Mo3O12With 9.3 grams of MoO3, adding ammonia regulation pH value is 7, and stirs aging 2 hours at 80 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
13
By 100 grams of (NH4)6Mo7O24·4H2O joins in the hot water of 100 grams 70 DEG C, and stirring makes it all dissolve, add 70.2 grams of concentration be the Ludox of 40wt%, 35.1 grams of concentration be that the Alumina gel of 20wt% makes mixture I.
By 38.5 grams of Fe (NO3)3·9H2O joins in 70 DEG C of hot water of 150 grams, adds 34.3 grams of Bi (NO after stirring and dissolving3)3·5H2O, 41.2 grams of Co (NO3)2·6H2O, 0.32 gram of KNO3, 0.46 gram of CsNO3, 5.90 grams of Yb (NO3)3·5H2O and 2.04 grams of Ce (NO3)3Mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mix homogeneously, add 9.3 grams of Fe2Mo3O12With 9.3 grams of MoO3, adding ammonia regulation pH value is 7, and stirs aging 2 hours at 90 DEG C, it is 80wt% that 100 DEG C of slurry is evaporated to solid content, and extrusion molding obtains the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains finished catalyst, and sintering temperature is 490 DEG C, roasting time 4 hours.This catalyst composition and preparation condition are listed in table 1, and the mol ratio at isobutene. Yu oxygen is 1:2；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 2.
Embodiment
14
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene. Yu oxygen；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 800 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:1, and its result is listed in table 3.
Embodiment
15
Catalyst embodiment 8 prepared is 1:3 in the mol ratio of isobutene. Yu oxygen；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 800 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:3, and its result is listed in table 3.
Embodiment
16
Catalyst embodiment 8 prepared is 1:4 in the mol ratio of isobutene. Yu oxygen；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 800 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:4, and its result is listed in table 3.
Embodiment
17
Catalyst embodiment 8 prepared is 1:5 in the mol ratio of isobutene. Yu oxygen；It it is 350 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 800 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:4, and its result is listed in table 3.
Embodiment
18
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene. Yu oxygen；It it is 360 DEG C in reaction temperature；Reaction pressure is 0.11 MPa;Raw material volume air speed is 800 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 3.
Embodiment
19
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene. Yu oxygen；It it is 370 DEG C in reaction temperature；Reaction pressure is 0.12 MPa;Raw material volume air speed is 800 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 3.
Embodiment
20
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene. Yu oxygen；It it is 380 DEG C in reaction temperature；Reaction pressure is 0.1 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 3.
Embodiment
21
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene. Yu oxygen；It it is 390 DEG C in reaction temperature；Reaction pressure is 0.12 MPa;Raw material volume air speed is 1000 h-1；The mol ratio of isobutene. and water is to check and rate 100 h under the conditions of 1:2, and its result is listed in table 3.
Table 1 catalyst forms
Table 2 different catalysts evaluation result
Evaluating catalyst result under the conditions of table 3 differential responses
Claims (9)
1. methylacrolein and the catalyst of methacrylic acid, the active component of described catalyst has a below general formula:
Mo12BiaFebCocXdYeZfOx
In formula, X is at least one in W, V, Ni, Cr, Mn, Nb, Re, La；Y be selected from Sn, Sr, Zn,
At least one in Ti or Zr；Z is at least one in Na, Li, Tl, K, Cs, Mg or Ca；a、b、c、d、
The atom ratio of e, f representative element Bi, Fe, Co, X, Y and Z respectively, the span of a is 0.05～6.0；B takes
Value scope 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
It is 0.01～3.0；The span of f is 0～15.0；X is to meet the oxygen atom sum needed for other element valence；
Described catalyst uses the method comprised the steps to prepare:
(1) ammonium molybdate aqueous solution is mixed to get mixture I with at least one in Ludox or Alumina gel；
(2) oxide or the nitrate of metal following in above-mentioned formula are dissolved in water and obtain mixtures II: Bi, Fe,
Co, X, Y and Z；
(3) under stirring, mixtures II is added mixture I and obtain mixtures III；
(4) mixtures III and additive are mixed to get mixture IV；
(5) regulate pH=4～9 with ammonia, stir ripening, evaporation, molding at 50～90 DEG C, finally roast at 400～700 DEG C
Burn activation 1～10 hour；
Described additive is by iron molybdate with selected from molybdenum trioxide, iron sesquioxide, ferroso-ferric oxide, bismuth oxide and nickel oxide
In at least one metal-oxide composition.
Catalyst the most according to claim 1, it is characterised in that described catalyst is loaded catalyst, the load of catalyst
Body is selected from SiO2Or Al2O3In at least one.
Catalyst the most according to claim 2, it is characterised in that in described catalyst, vector contg is 5～40wt%.
4. the preparation method of the catalyst described in claim 1, step includes:
(1) ammonium molybdate aqueous solution is mixed to get mixture I with at least one in Ludox or Alumina gel；
(2) oxide or the nitrate of metal following in above-mentioned formula are dissolved in water and obtain mixtures II: Bi, Fe,
Co, X, Y and Z；
(3) under stirring, mixtures II is added mixture I and obtain mixtures III；
(4) mixtures III and additive are mixed to get mixture IV；
(5) regulate pH=4～9 with ammonia, stir ripening, evaporation, molding at 50～90 DEG C, finally roast at 400～700 DEG C
Burn activation 1～10 hour；
Described additive is by iron molybdate with selected from molybdenum trioxide, iron sesquioxide, ferroso-ferric oxide, bismuth oxide and nickel oxide
In at least one metal-oxide composition.
5. according to the preparation method of the catalyst described in claim 4, it is characterised in that described additive accounts for catalyst weight
0.1～5wt%.
The preparation method of catalyst the most according to claim 4, it is characterised in that the time of ripening is 1～10 hour.
The preparation method of catalyst the most according to claim 4, it is characterised in that the temperature of evaporation is 80～100 DEG C.
8. methylacrolein and the synthetic method of methacrylic acid, with isobutene. and oxygen as raw material, water is diluent, isobutene. with
The mol ratio of oxygen is 1:2～1:10；It it is 350～400 DEG C in reaction temperature；Reaction pressure is 0.1～0.12MPa；Raw material volume air speed
It is 800～1200h-1；Under the conditions of the mol ratio of isobutene. and water is 1:1～1:4, urging according to any one of claims 1 to 3
Agent contacts, and reaction generates methylacrolein and methacrylic acid.
Synthetic method the most according to claim 8, it is characterised in that isobutene. is 1:2～1:4 with the mol ratio of oxygen.
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| CN108355721B (en) * | 2018-02-02 | 2020-11-13 | 上海东化环境工程有限公司 | Modified carrier, supported catalyst and application thereof |
| CN111389410A (en) * | 2020-04-17 | 2020-07-10 | 中国科学院过程工程研究所 | Composite metal oxide catalyst and preparation method thereof |
| 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 |
| CN113908876A (en) * | 2021-10-28 | 2022-01-11 | 惠生工程（中国）有限公司 | Carbon quantum dot induction-based multi-metal composite oxide catalyst and preparation method and application thereof |
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