CN102040505B - Method for preparing unsaturated acid by oxidation of unsaturated aldehyde - Google Patents
Method for preparing unsaturated acid by oxidation of unsaturated aldehyde Download PDFInfo
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- CN102040505B CN102040505B CN200910201623.4A CN200910201623A CN102040505B CN 102040505 B CN102040505 B CN 102040505B CN 200910201623 A CN200910201623 A CN 200910201623A CN 102040505 B CN102040505 B CN 102040505B
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Abstract
The invention relates to a method for preparing unsaturated acid by oxidation of unsaturated aldehyde, and solves the problems of low yield and selectivity of unsaturated acid in the prior art. According to the invention, unsaturated aldehyde selected from acrolein or methacrolein, and oxygen-containing gas selected from air or oxygen are adopted as raw materials, and the raw materials are allowed to contact a catalyst to prepare acrylic acid or methacrylic acid at a temperature of 220-340 DEG C and an air speed of 800-1800 h<-1>, wherein the molar ratio of oxygen in oxygen-containing gas to unsaturated aldehyde is 0.4-0.9, at least one of SiO2, Al2O3, or TiO2 is adopted as the catalyst carrier, and the catalyst contains an active ingredient represented by the following general formula: Mo12VaCubXcYdZeOx, in which X is selected from at least one of W, Cr, and Nb; Y is selected from at least one of Fe, Bi, Sb, Ce, La, Zr, and Th; and Z is selected from at least one of alkali metals or alkaline earth metals. The invention provides a solution, which is useful in the industrial production of preparing unsaturated acid from alpha-beta unsaturated aldehyde.
Description
Technical field
The present invention relates to a kind of method of being produced unsaturated acid by unsaturated aldehyde oxidation, particularly about the method for propenal or Methylacrylaldehyde oxidation preparing propone acid or methacrylic acid.
Background technology
It is important chemical process that α, β unsaturated aldehyde and unsaturated acid are prepared in the selective oxidation of alkene, the catalyzer that wherein contains Mo, V by a kind of active ingredient of production and application of unsaturated aldehyde unsaturated carboxylic acid processed.The improvement of catalyzer is mainly to carry out from the activity of catalyzer, selectivity and stability aspect, as added transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element to improve redox ability, improve catalyst stability; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, stabilizing catalyst activity component, improves the work-ing life of catalyzer etc.
For propenal selective oxidation, have a lot of patent reports:
US7220698B2 proposes a kind of method for production of acrylic acid, use catalyzer take Mo-V as essential component, in preparation process, add a kind of catalyzer poison of trace, control catalyst reaction bed focus, suppress the thermal destruction of catalyzer, acrolein conversion rate large 98.8%.US7456129B2 improves catalyst performance production vinylformic acid, acrolein conversion rate 98.9%, vinylformic acid selectivity 95.1% by controlling carrier strength of acid.CN1089081 avoids reacting the generation of focus by changing the arrangement mode of catalyzer, improve reaction achievement, and propenal and acrylic acid total recovery reach 90.4%.CN1183088C introduces a kind of method for production of acrylic acid, and wherein specified raw material is used in catalyzer preparation, and acrolein conversion rate is the highest by 99.6%, and vinylformic acid selectivity is up to 96.0%, and vinylformic acid yield is up to 95.2%.By unsaturated aldehyde, be oxidized and produce the method for unsaturated acid and have the not high enough problem of yield above.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to have the not high problem of object product unsaturated acid reaction yield, and a kind of new method by unsaturated aldehyde oxidation unsaturated acid processed is provided.It is high that the method has unsaturated aldehyde transformation efficiency, the advantage that object product unsaturated acid selectivity is good, yield is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method by unsaturated aldehyde oxidation unsaturated acid processed, to be selected from the unsaturated aldehyde of propenal or Methylacrylaldehyde and the oxygen-containing gas that is selected from air or oxygen as raw material, in temperature, be that 220～340 ℃, air speed are 800～1800h
-1, in oxygen-containing gas, oxygen and unsaturated aldehyde mol ratio are under 0.4～0.9: 1 condition, and raw material and catalyzer contact reacts generate acrylic or methacrylic acid, and wherein catalyzer used is with SiO
2, Al
2o
3or TiO
2in at least one be carrier, the active ingredient that contains following general formula:
Mo
12V
aCu
bX
cY
dZ
eO
x
In formula, X is selected from least one in W, Cr or Nb;
Y is selected from least one in Fe, Bi, Sb, Ce, La, Zr or Th;
Z is selected from least one in basic metal or alkaline-earth metal;
The span of a is 1.0～10.0;
The span of b is 0.5～8.0;
The span of c is 0.8～11.0;
The span of d is 0.5～6.0;
The span of e is 0.5～5.0;
X meets the required Sauerstoffatom sum of other element valence;
In catalyzer, the consumption of carrier is catalyst weight 5～40%;
Wherein in catalyst preparation process, add at least one reductive agent being selected from oxalic acid, formic acid, acetic acid, formaldehyde or acetaldehyde.
In technique scheme, temperature of reaction preferable range is 240～320 ℃; Air speed preferable range is 1000～1500h
-1; In oxygen-containing gas, the mol ratio preferable range of oxygen and unsaturated aldehyde is 0.5～0.8; Reductive agent preferred version is oxalic acid; The consumption preferable range of reductive agent is catalyst weight 2～10%, and more preferably scope is 3～7%.
The present invention is owing to having added a kind of organic reducing agent in catalyst preparation process, this compound can regulating catalyst component in the redox state of vanadium, promote its dissolving, make catalyzer evenly and be easy to preparation, thereby decompose at roasting process the reactivity worth that affects catalyst metal redox condition and catalyzer finished product physical and chemical performance and improved catalyzer.Catalyzer in the inventive method is prepared vinylformic acid for propenal selective oxidation, in temperature of reaction, is that 220～340 ℃, reaction velocity are 800～1800 hours
-1condition under, its acrolein conversion rate is up to 99.2%, vinylformic acid selectivity is up to 98.5%, product vinylformic acid yield is up to 97.7%, has obtained good technique effect.
In the embodiment providing below, to the investigation appreciation condition of catalyzer, be:
Reactor: fixed-bed reactor, 25.4 millimeters of internal diameters, 750 millimeters of reactor length
Catalyst filling amount: 150 grams
Raw material: water vapor 33.3%
Reaction product absorbs with 0 ℃ of diluted acid, uses gas chromatographic analysis product.And calculate carbon balance, when carbon balance is valid data during at (95～105) %.
Reaction conversion ratio, product yield and optionally definition:
Below by embodiment, the present invention is further elaborated.
Embodiment
[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 aluminium colloidal sol and the 16.6 grams of (NH of the silicon sol of 68.6 gram 40% (wt.), 63.3 gram 20% (wt.)
4)
6h
5[H
2(WO
4)
6] make material A.
By 32.8 grams of Ce (NO
3)
36H
2o adds in 70 ℃ of hot water of 20 grams, adds 26.3 grams of Zr (NO after stirring and dissolving again
3)
46H
2o, 31.9 grams of Cu (NO
3)
23H
2o, 64.1 grams of Bi (NO
3)
35H
2o, 9.2 grams of CsNO
3, 3.3 grams of KOH make material B after dissolving.
In 50 grams of water, add 18.7 grams of NH
4vO
3and 20.5 grams of oxalic acid form material C.
Material B and C are dripped in material A, form catalyst pulp, and at 80 ℃, stir aging 2 hours, extrusion moulding after 120 ℃ of oven dry removal most of moisture of slurry, obtains
cylinder, then high-temperature roasting obtains catalyzer finished product, maturing temperature is 480 ℃, roasting time 2 hours.Gained catalyzer composition is listed in table 1.This catalyzer is used for propenal Selective Oxidation vinylformic acid at 280 ℃ of temperature of reaction, reaction velocity 1400 hours
-1, check and rate under the condition of oxygen/aldehyde mol ratio=0.68, it the results are shown in table 2.
[embodiment 2～11]
According to the process identical with embodiment 1, just change catalyzer composition and institute and add reductive agent consumption and kind, its catalyzer forms and lists in respectively table 1 and table 2 for propenal Selective Oxidation evaluation result.
[embodiment 12]
Embodiment 3 catalyzer are listed in to table 3 for propenal Selective Oxidation reaction result under different evaluation condition.
Embodiment 3 catalyzer are listed in to table 4 for Methylacrylaldehyde Selective Oxidation methacrylic acid reaction result
Table 2 catalyzer is for acrolein oxidation reaction result
| Catalyzer numbering | Vinylformic acid yield (%) | Vinylformic acid selectivity (%) | Acrolein conversion rate (%) |
| Embodiment 1 | 96.4 | 98.9 | 97.5 |
| Embodiment 2 | 97.3 | 98.7 | 98.6 |
| Embodiment 3 | 97.7 | 98.5 | 99.2 |
| Embodiment 4 | 94.7 | 96.1 | 98.5 |
| Embodiment 5 | 93.9 | 97.0 | 96.8 |
| Embodiment 6 | 96.4 | 96.8 | 99.6 |
| Embodiment 7 | 96.6 | 98.2 | 98.4 |
| Embodiment 8 | 96.7 | 97.7 | 99.0 |
| Embodiment 9 | 96.9 | 98.4 | 98.5 |
| Embodiment 10 | 96.5 | 99.1 | 97.4 |
| Embodiment 11 | 97.2 | 98.9 | 98.3 |
Table 3 embodiment 3 catalyzer are for acrolein oxidation reaction result
Table 4 embodiment 3 catalyzer are for Methylacrylaldehyde oxidizing reaction result
Claims (1)
1. by the method for unsaturated aldehyde oxidation unsaturated acid processed, take propenal and oxygen as raw material, in temperature, be that 280 ℃, air speed are 1400h
-1, under the condition of oxygen/aldehyde mol ratio=0.68, raw material and catalyzer contact reacts generate vinylformic acid, and wherein catalyzer used is expressed as:
Mo
12V
2.2Cu
2.3Fe
2.5Cr
1.6Ce
1.2Zr
1.5Ba
0.4Rb
0.8K
0.7Sr
0.8+13％SiO
2+6％Al
2O
3+4％TiO
2
Wherein in catalyst preparation process, add formic acid as reductive agent;
Evaluation result demonstration, its vinylformic acid yield is 97.3%, and vinylformic acid selectivity is 98.7%, and acrolein conversion rate is 98.6%.
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|---|---|---|---|
| CN200910201623.4A CN102040505B (en) | 2009-10-13 | 2009-10-13 | Method for preparing unsaturated acid by oxidation of unsaturated aldehyde |
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| CN102040505A CN102040505A (en) | 2011-05-04 |
| CN102040505B true CN102040505B (en) | 2014-04-23 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2012253913B2 (en) * | 2011-05-11 | 2017-03-02 | Archer Daniels Midland Company | Processes for making acrylic-type monomers and products made therefrom |
| CN103894205B (en) * | 2012-12-27 | 2016-02-10 | 中国石油化工股份有限公司 | Acrylic acid catalyst and preparation method thereof |
| CN104437533B (en) * | 2013-09-24 | 2017-01-04 | 中国石油化工股份有限公司 | Catalyst of methylacrolein and methacrylic acid and preparation method thereof |
| CN104549353B (en) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | MAL and the catalyst of methacrylic acid and its preparation method |
| CN104549349B (en) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | MAL and the catalyst of methacrylic acid |
| CN104923246B (en) * | 2014-03-17 | 2017-09-15 | 中国石油化工股份有限公司 | Aoxidize the catalyst of legal system unsaturated aldehyde and unsaturated acids |
| CN107282069B (en) * | 2016-04-13 | 2019-12-10 | 中国石油化工股份有限公司 | catalyst for oxidation of acrolein to acrylic acid |
| CN110479299B (en) * | 2019-09-06 | 2021-09-28 | 山东科技大学 | Low-temperature flue gas denitration catalyst and preparation method thereof |
| CN112547082B (en) * | 2019-09-25 | 2023-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE830297A (en) * | 1974-06-17 | 1975-10-16 | PROCESS FOR THE PRODUCTION OF UNSATURATED ACIDS FROM THE CORRESPONDING ALDEHYDES | |
| US4250054A (en) * | 1976-06-01 | 1981-02-10 | The Standard Oil Company (Ohio) | Catalysts for producing unsaturated aliphatic acids |
| CN1054972A (en) * | 1989-11-06 | 1991-10-02 | 日本触媒化学工业株式会社 | Method for producing propenoic acid |
| CN1394812A (en) * | 1995-11-16 | 2003-02-05 | 巴斯福股份公司 | Multi-metal oxide |
| CN101507927A (en) * | 2009-02-10 | 2009-08-19 | 上海华谊丙烯酸有限公司 | Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2028180T3 (en) * | 1987-06-05 | 1992-07-01 | Nippon Shokubai Kagaku Kogyo Kabushiki Kaisha | CATALYST FOR OXIDATION OF ACROLEIN AND PROCEDURE FOR ITS PREPARATION. |
| US7115776B2 (en) * | 2002-07-18 | 2006-10-03 | Basf Aktiengesellschaft | Heterogeneously catalyzed gas-phase partial oxidation of at least one organic compound |
| US7524792B2 (en) * | 2003-06-04 | 2009-04-28 | Basf Aktiengesellschaft | Preparation of catalytically active multielement oxide materials which contain at least one of the elements Nb and W and the elements Mo, V and Cu |
| WO2005047226A1 (en) * | 2003-10-29 | 2005-05-26 | Basf Aktiengesellschaft | Method for long term operation of a heterogeneously catalysed gas phase partial oxidation of acrolein in order to form acrylic acid |
-
2009
- 2009-10-13 CN CN200910201623.4A patent/CN102040505B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE830297A (en) * | 1974-06-17 | 1975-10-16 | PROCESS FOR THE PRODUCTION OF UNSATURATED ACIDS FROM THE CORRESPONDING ALDEHYDES | |
| US4250054A (en) * | 1976-06-01 | 1981-02-10 | The Standard Oil Company (Ohio) | Catalysts for producing unsaturated aliphatic acids |
| CN1054972A (en) * | 1989-11-06 | 1991-10-02 | 日本触媒化学工业株式会社 | Method for producing propenoic acid |
| CN1394812A (en) * | 1995-11-16 | 2003-02-05 | 巴斯福股份公司 | Multi-metal oxide |
| CN101507927A (en) * | 2009-02-10 | 2009-08-19 | 上海华谊丙烯酸有限公司 | Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process |
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