CN104549349A - Catalyst for synthesizing methylacrolein and methacrylic acid - Google Patents
Catalyst for synthesizing methylacrolein and methacrylic acid Download PDFInfo
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- CN104549349A CN104549349A CN201310512195.3A CN201310512195A CN104549349A CN 104549349 A CN104549349 A CN 104549349A CN 201310512195 A CN201310512195 A CN 201310512195A CN 104549349 A CN104549349 A CN 104549349A
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Abstract
The invention relates to a catalyst for synthesizing methylacrolein and methacrylic acid, a preparation method of the catalyst and a method for synthesizing methylacrolein and methacrylic acid in order to mainly solve the problem of poor stability of a catalyst for selective oxidation reaction of isobutene in the prior art. The problem is better solved through the scheme that the catalyst for synthesizing methylacrolein and methacrylic acid has an active component with the following general formula: Mo12BiaFebCocXdYeZfOx, wherein X is at least one selected from W, V, Ni, Cr, Mn, Nb, Re and La, Y is at least one selected from Sn, Sr, Zn, Ti or Zr, and Z is at least one selected from Na, Li, Tl, K, Cs, Mg or Ca. The catalyst can be used for industrial production of methylacrolein and methacrylic acid.
Description
Technical field
The present invention relates to the catalyst of MAL and methacrylic acid, preparation method and MAL 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, also comprises the production of the products such as coating, adhesive, lubricant, bleeding agent and PVC modifier in addition.The technique that the production of early stage MMA mainly adopts is Acetone cyanohydrin method, and due to this mature technology, product yield is high and be widely used.But use hydrogen cyanide and sulfuric acid in this art production process, by-product a large amount of sulfuric acid cyanogen ammonium, causes larger pressure to environment, therefore facilitates the developmental research of MMA new technology.After last century the eighties, the companies such as Japanese catalyst, mitsubishi rayon and Asahi Chemical Industry are developed with mixed C
4in cut, isobutene/tert-butyl alcohol is raw material MMA production technology, and first this technique adopt isobutene or the tert-butyl alcohol to produce MAL (MAL), and then oxidation and esterification generate methyl methacrylate (MMA) to MAL further again.Because this technique avoids using the hydrogen cyanide with severe toxicity in process of production, therefore, compared with sending out with acetone cyanohydrin, avoid generation and the equipment corrosion problem of spent acid, environmental pressure is reduced, product cost is low, becomes current world's second largest MMA production technology very soon.
The catalyst research of selective isobutene oxidation MAL processed is the emphasis that isobutylene oxidation legal system is studied for MMA.The current catalyst for this section of reaction mainly based on molybdenum bismuth composite metal oxide system, and adds the selective and stability that the auxiliary agents such as iron, cobalt, alkali metal improve reaction.Preparing MAL due to isobutene or Oxidation of t-Butanol is a strong exothermal reaction, easily produces hot-spot at beds, causes the oxidation activity component Mo played a major role to run off in course of reaction, and then shortens catalyst service life.Japanese Laid-Open Patent 59-193136 is by being loaded on inertia heat resistant inorganic material the obtained material with molybdenum trioxide by molybdenum trioxide, but catalyst is selective for not high enough commercial Application.US Pat5250485A proposes by improving the composition of 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 still be there is the low problem of catalyst activity.Japanese Laid-Open Patent 57-56044 proposes molybdenum compound to add in catalyst, and by the roasting in 550 ~ 700 DEG C of oxygen containing atmosphere again 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 technical problem to be solved by this invention is problem low for the catalyst activity and selectivity of the Selective Oxidation of isobutene in prior art, there is provided a kind of catalyst for the synthesis of MAL and methacrylic acid, this catalyst has the good feature of activity and selectivity.
Two of technical problem to be solved by this invention is to provide the preparation method of one of a kind of above-mentioned technical problem described catalyst.
Three of technical problem to be solved by this invention is the MAL and the methacrylic acid synthetic method that adopt 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: the catalyst of MAL and methacrylic acid, and the active component of described catalyst has following general formula: Mo
12bi
afe
bco
cx
dy
ez
fo
x
In formula, X is at least one be selected from W, V, Ni, Cr, Mn, Nb, Re, La; Y is at least one be selected from Sn, Sr, Zn, Ti or Zr; Z is at least one be selected from Na, Li, Tl, K, Cs, Mg or Ca; The atom ratio of a, b, c, d, e, f difference representative element Bi, Fe, Co, X, Y and Z, 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 for meeting the oxygen atom sum needed for other element valence.
Described active component can be adopted separately in technique scheme as catalyst, but preferably described active constituent loading is made loaded catalyst on the common vector of this area, described carrier is preferably from SiO
2or Al
2o
3in at least one; In loaded catalyst, vector contg is preferably 5 ~ 40wt%.
At least one in Mn or Cr is preferably as X, 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 that the span that the span of d is preferably 0.05 ~ 0.2, e is preferably 0.1 ~ 0.3, f has best technique effect when being preferably 0.05 ~ 0.2.
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, and step comprises:
(1) at least one in ammonium molybdate aqueous solution and Ludox or Alumina gel is mixed to get mixture I;
(2) oxide of metal following in above-mentioned general formula or nitrate are dissolved in water 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 ammoniacal liquor, stir slakings at 50 ~ 90 DEG C, evaporation, shaping, finally calcination activation 1 ~ 10 hour at 400 ~ 700 DEG C;
Described additive is selected from least one in bismuth molybdate, molybdenum trioxide, di-iron trioxide, tri-iron tetroxide, bismuth oxide and nickel oxide.Described additive is preferably made up of bismuth molybdate and at least one metal oxide be selected from molybdenum trioxide, di-iron trioxide, tri-iron tetroxide, bismuth oxide and nickel oxide.As most preferred technical scheme, described additive is made up of bismuth molybdate and molybdenum trioxide, and the weight ratio of bismuth molybdate and molybdenum trioxide is preferably 2:1 ~ 1:2.
In technique scheme, described additive preferably accounts for 0.1 ~ 5 wt% of catalyst weight.The time of slaking is preferably 1 ~ 10 hour; The temperature of evaporation is preferably 80 ~ 100 DEG C.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the synthetic method of MAL and methacrylic acid, and with isobutene and oxygen for raw material, water is diluent, and the mol ratio of isobutene and oxygen is 1:2 ~ 1:10; 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; The mol ratio of isobutene and water is under 1:1 ~ 1:4 condition, catalyst exposure described in any one of one of above-mentioned technical problem, and reaction generates MAL and methacrylic acid.
In technique scheme, the mol ratio of isobutene and oxygen is preferably 1:2 ~ 1:4.
Key problem in technology of the present invention adds high activity and the high selectivity that described additive realizes isobutylene oxidation synthesis MAL processed and metering system acid reaction in preparation process in the catalyst.Catalyst of the present invention is used for isobutene selective oxidation and prepares in MAL reaction, reaction temperature be 350 DEG C, raw material volume air speed is 1000 hours
-1condition under run 1000h after, its isobutene conversion is up to 99.9%, and MAL and methacrylic acid overall selectivity are up to 92.5%, and product MAL and methacrylic acid total recovery are up to 92.4%, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
comparative example 1
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO of 50wt%
3)
2the aqueous solution, 0.32 gram of KNO
3with 0.46 gram of CsNO
3, 0.47 gram of Cr
2o
3, 6.1 grams of Zr (NO
3)
45H
2mixtures II is made after O stirring and dissolving.
Mixtures II is under agitation added in mixture I, form catalyst pulp, add ammoniacal liquor, regulate pH to be 7, and at 80 DEG C, stir slaking 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 1
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in the water of 20 grams 70 DEG C, adds 34.3 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 41.2 grams of Co (NO
3)
26H
2o, 25.1 grams of concentration are the Mn (NO of 50wt%
3)
2the aqueous solution, 0.32 gram of KNO
3with 0.46 gram of CsNO
3, 0.47 gram of Cr
2o
3, 6.1 grams of Zr (NO
3)
45H
2mixtures II is made after O stirring and dissolving.
Add in mixture I under mixtures II is stirred, after mix and blend, add 18.6 grams of Bi
2mo
3o
12, add ammoniacal liquor, regulate pH to be 7, and at 80 DEG C, stir slaking 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 2
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO 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
3,0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing stirs evenly, add 18.6 grams of MoO
3, add ammoniacal liquor, regulate pH to be 7, and at 80 DEG C, stir slaking 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 3
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after stirring, add 18.6 grams of Fe
2o
3, add ammoniacal liquor, regulate pH to be 7, and at 80 DEG C, stir slaking 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 4
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after stirring, add 18.6 grams of Fe
3o
4, add ammoniacal liquor, regulate pH to be 7, and at 80 DEG C, stir slaking 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 5
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after stirring, add 18.6 grams of Bi
2o
3, add ammoniacal liquor, regulate pH to be 7, and at 80 DEG C, stir slaking 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 6
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after stirring, add 9.3 grams of Bi
2mo
3o
12with 9.3 grams of Fe
2o
3form catalyst pulp, add ammoniacal liquor, pH is regulated to be 7, and at 80 DEG C, stirring slaking 2 hours, it is 80wt% that 100 DEG C, slurry is evaporated to solid content, extrusion molding, obtain 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
Present inventor finds, when additive comprises Bi simultaneously
2mo
3o
12and Fe
2o
3time raising isobutene conversion and selectivity of product in there is synergy.Can intuitively find out in the data of this embodiment 1, embodiment 3 and embodiment 6 of providing from table 1 and table.
embodiment 7
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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
2o, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after stirring, add 9.3 grams of Bi
2mo
3o
12with 9.3 grams of Bi
2o
3form catalyst pulp, add ammoniacal liquor, pH is regulated to be 7, and at 80 DEG C, stirring slaking 2 hours, it is 80wt% that 100 DEG C, slurry is evaporated to solid content, extrusion molding, obtain 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
Present inventor finds, when additive comprises Bi simultaneously
2mo
3o
12and Bi
2o
3time raising isobutene conversion and selectivity of product in there is synergy.Can intuitively find out in the data of this embodiment 1, embodiment 5 and embodiment 7 of providing from table 1 and table.
embodiment 8
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the hot water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 63.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing, add 9.3 grams of Bi
2mo
3o
12with 9.3 grams of MoO
3, add ammoniacal liquor and regulate pH to be 7, and at 80 DEG C, stir aging 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
Present inventor finds, when additive comprises Bi simultaneously
2mo
3o
12and MoO
3time raising isobutene conversion and selectivity of product in there is synergy.Can intuitively find out in the data of this embodiment 1, embodiment 2 and embodiment 8 of providing from table 1 and table.And, as can be seen from the isobutene conversion of embodiment 6 ~ 8 and selectivity of product relatively, Bi
2mo
3o
12and MoO
3between synergy stronger.
embodiment 9
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the hot water of 100 grams 70 DEG C, stirs and makes it all dissolve, add the Ludox that 78.9 grams of concentration are 40wt%, Alumina gel and 8.24 grams of NH that 47.7 grams of concentration are 20wt%
4vO
3make mixture I.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing, add 18.6 grams of Bi
2mo
3o
12with 9.3 grams of MoO
3, adding ammoniacal liquor adjust ph is 7, and at 50 DEG C, stir aging 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 2.
embodiment 10
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the hot water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 77.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing, add 9.3 grams of Bi
2mo
3o
12with 18.6 grams of MoO
3, adding ammoniacal liquor adjust ph is 7, and at 60 DEG C, stir aging 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 2.
embodiment 11
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the hot water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 101.8 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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, 25.1 grams of concentration are the Mn (NO 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, 0.46 gram of CsNO
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing, add 4.7 grams of Bi
2mo
3o
12with 4.7 grams of MoO
3, adding ammoniacal liquor adjust ph is 7, and at 70 DEG C, stir aging 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 1000 h under 1:2 condition, and it the results are shown in table 2.
embodiment 12
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the hot water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adding 56.2 grams of concentration is that mixture I made by the Ludox of 40wt%.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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, 20.8 grams of Ni (NO
3)
2, 0.32 gram of KNO
3, 0.46 gram of CsNO
3, 8.85 grams of Yb (NO
3)
35H
2o and 1.02 gram of Ce (NO
3)
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing, add 9.3 grams of Bi
2mo
3o
12with 9.3 grams of MoO
3, adding ammoniacal liquor adjust ph is 7, and at 80 DEG C, stir aging 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 2.
embodiment 13
By 100 grams of (NH
4)
6mo
7o
244H
2o joins in the hot water of 100 grams 70 DEG C, stirs and makes it all dissolve, and adds Ludox that 70.2 grams of concentration are 40wt%, Alumina gel that 35.1 grams of concentration is 20wt% makes mixture I.
By 38.5 grams of Fe (NO
3)
39H
2o joins in 70 DEG C 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, 0.32 gram of KNO
3, 0.46 gram of CsNO
3, 5.90 grams of Yb (NO
3)
35H
2o and 2.04 gram of Ce (NO
3)
3mixtures II is made after stirring and dissolving.
Mixtures II is under agitation added in mixture I, after mixing, add 9.3 grams of Bi
2mo
3o
12with 9.3 grams of MoO
3, adding ammoniacal liquor adjust ph is 7, and at 90 DEG C, stir aging 2 hours, it is 80wt% that 100 DEG C, 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 list in table 1, are 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 2.
embodiment 14
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:1 condition, and it the results are shown in table 3.
embodiment 15
Catalyst embodiment 8 prepared is 1:3 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:3 condition, and it the results are shown in table 3.
embodiment 16
Catalyst embodiment 8 prepared is 1:4 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:4 condition, and it the results are shown in table 3.
embodiment 17
Catalyst embodiment 8 prepared is 1:5 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:4 condition, and it the results are shown in table 3.
embodiment 18
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 3.
embodiment 19
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 3.
embodiment 20
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 3.
embodiment 21
Catalyst embodiment 8 prepared is 1:2 in the mol ratio of isobutene and oxygen; 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 check and rate 100 h under 1:2 condition, and it the results are shown in table 3.
Table 1 catalyst forms
Table 2 different catalysts evaluation result
Evaluating catalyst result under table 3 differential responses condition
Claims (9)
1. the catalyst of MAL and methacrylic acid, the active component of described catalyst has following general formula: Mo
12bi
afe
bco
cx
dy
ez
fo
x
In formula, X is at least one be selected from W, V, Ni, Cr, Mn, Nb, Re, La; Y is at least one be selected from Sn, Sr, Zn, Ti or Zr; Z is at least one be selected from Na, Li, Tl, K, Cs, Mg or Ca; The atom ratio of a, b, c, d, e, f difference representative element Bi, Fe, Co, X, Y and Z, 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 for meeting the oxygen atom sum needed for other element valence.
2. catalyst according to claim 1, it is characterized in that described catalyst is loaded catalyst, the carrier of catalyst is selected from SiO
2or Al
2o
3in at least one.
3. catalyst according to claim 2, is characterized in that in described catalyst, vector contg is 5 ~ 40wt%.
4. the preparation method of catalyst according to claim 1, step comprises:
(1) at least one in ammonium molybdate aqueous solution and Ludox or Alumina gel is mixed to get mixture I;
(2) oxide of metal following in above-mentioned general formula or nitrate are dissolved in water 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 ammoniacal liquor, stir slakings at 50 ~ 90 DEG C, evaporation, shaping, finally calcination activation 1 ~ 10 hour at 400 ~ 700 DEG C;
Described additive is selected from least one in bismuth molybdate, molybdenum trioxide, di-iron trioxide, tri-iron tetroxide, bismuth oxide and nickel oxide.
5. the preparation method of the catalyst according to claim 4, is characterized in that described additive accounts for 0.1 ~ 5 wt% of catalyst weight.
6. the preparation method of catalyst according to claim 4, is characterized in that the time of slaking is 1 ~ 10 hour.
7. the preparation method of catalyst according to claim 4, is characterized in that the temperature of evaporating is 80 ~ 100 DEG C.
8. the synthetic method of MAL and methacrylic acid, with isobutene and oxygen for raw material, water is diluent, and the mol ratio of isobutene and oxygen is 1:2 ~ 1:10; 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; The mol ratio of isobutene and water is under 1:1 ~ 1:4 condition, catalyst exposure according to any one of claims 1 to 3, and reaction generates MAL and methacrylic acid.
9. synthetic method according to claim 8, is characterized in that the mol ratio of isobutene and oxygen is 1:2 ~ 1:4.
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| CN111068700A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Supported catalyst for synthesizing acrylic acid by acrolein oxidation and application thereof |
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| WO2021018095A1 (en) * | 2019-07-31 | 2021-02-04 | 浙江大学 | Catalyst for preparing acrylic acid or acrolein and preparation method therefor |
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