CN107282059B - Catalyst for producing acrylic acid - Google Patents
Catalyst for producing acrylic acid Download PDFInfo
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- CN107282059B CN107282059B CN201610225971.5A CN201610225971A CN107282059B CN 107282059 B CN107282059 B CN 107282059B CN 201610225971 A CN201610225971 A CN 201610225971A CN 107282059 B CN107282059 B CN 107282059B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to a catalyst for producing acrylic acid, which mainly solves the problem of low activity of the catalyst in the prior art. The invention comprises the following components in parts by weight: a: 40-80 parts of SiO2、Al2O3、ZrO2Or TiO2At least one carrier; and B supported thereon: 20-60 parts of active component Mo12VaCubQnYfOg(ii) a Wherein Q represents at least one element selected from Cr, Mn, Sb, W and B; y is at least one element selected from alkali metals or alkaline earth metals, so that the technical scheme can better solve the problem and can be used for the industrial production of acrylic acid.
Description
Technical Field
The invention relates to a catalyst for synthesizing acrylic acid from acrolein, a preparation method and an acrylic acid synthesis method.
Background
Currently, the industrial production of acrylic acid by propylene oxidation employs a two-step process, the first step is to oxidize propylene to acrolein under the action of a Mo-Bi composite oxide catalyst, and the second step is to oxidize acrolein to acrylic acid under the action of a Mo-V composite oxide catalyst. The acrylic acid and the acrylic ester have wide application, the crude acid is mainly used for producing water-soluble paint and adhesive, and the refined acid is mainly used for producing super absorbent polymer SAP. With the development of the building, electronics, and automotive industries, the demand and capacity for acrylic acid are increasing worldwide.
To date, many patents have granted inventions related to catalysts for the process of producing acrylic acid from acrolein, most of which are catalysts containing molybdenum-vanadium (Mo-V), such as Chinese patent CN 1070468C, CN 1031488A, CN1146438A, CN 100378058C, CN 1031050C, CN 1169619C, CN 1583261A and CN 1146439A, etc., the catalysts described in these patents are prepared by making a solution of a multi-metal compound in the presence of a solvent or water, adding an insoluble oxide to the solution, evaporating the insoluble oxide under heating and stirring, and then calcining, pulverizing and molding, while the catalysts disclosed in the presently-disclosed patents have large differences in the elemental composition, such as the catalyst disclosed in Chinese patent CN 1169619C having molybdenum, vanadium and copper as the main active components, and adding tellurium as necessary, tellurium is thought to make the active phase molybdenum oxide and copper molybdate of this catalyst more stable and to retard the deactivation of the catalyst due to Mo loss, the catalysts disclosed in Chinese patent CN 1583261A are catalysts composed of ① molybdenum, vanadium, copper as the main active components, vanadium, copper, and the essential stable components of titanium and antimony, and at least one of alkali metals selected from the group consisting of tungsten oxides of tungsten, molybdenum, tungsten, molybdenum.
However, the catalyst of the prior art has low activity and low yield of acrylic acid.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low acrolein conversion rate and low acrylic acid yield in the reaction for producing acrylic acid by oxidizing acrolein in the prior art, and provides a catalyst for producing acrylic acid. The catalyst is used for the reaction of synthesizing acrylic acid by acrolein oxidation, and has the characteristics of high acrolein conversion rate and high acrylic acid yield.
The second technical problem to be solved by the present invention is a process for producing acrylic acid using the catalyst of one of the above technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the catalyst for generating acrylic acid comprises the following components in parts by weight:
a: 40-80 parts of SiO2、Al2O3、ZrO2Or TiO2At least one carrier; and B' supported thereon: 20-60 parts of active component Mo12VaCubQnYfOg；
Wherein Mo, V, Cu and O represent the elements molybdenum, vanadium, copper and oxygen; q represents at least one element selected from Cr, Mn, Sb, W and B; y is at least one element selected from alkali metals or alkaline earth metals; a. b, f and g represent the atomic ratio of the respective elements, based on the atomic ratio of Mo element as 12, a is 0.5-4.0, b is 0.1-5.0, n is 0-13.0, f is 0-1.0, and g is the number of oxygen atoms required to satisfy the total valence of other elements.
In the above technical solution, the active ingredient preferably has the following composition: mo12VaCubWcBdXeYfOg(ii) a Wherein W and B are tungsten and boron respectively, and X represents at least one element of Cr, Mn and Sb; c. d and e represent the atomic ratio of W, B to X; the value range of c is more than 0 and less than 5.0, the value range of d is more than 0 and less than 3.0, and the value range of e is 0-5.0. The inventors of the present application have surprisingly found that when both W and B are contained in the active component, both elements have a synergistic effect in increasing the selectivity of acrylic acid and the conversion of acrolein.
The key point of the catalyst of the present invention is not in the geometry and size of the catalyst, so there is no particular limitation on the shape and size of the catalyst, and various shapes and sizes of existing supports can be used in the present invention and comparable results are obtained. For example, the carrier of the present invention may take the form of a sphere, raschig ring, or cylinder, etc. The spherical diameter can be preferably 3-5 mm; the outer diameter of the raschig ring can be preferably 4-7 mm, the inner diameter is preferably 1.5-3 mm, and the length is preferably 3-5 mm; the cylindrical outer diameter can be preferably 4-7 mm, and the length is preferably 3-5 mm.
In the above technical scheme, the catalyst can be prepared by a method comprising the following steps:
mixing ammonium heptamolybdate, ammonium metavanadate, compounds of Cu, Q and Y, a carrier, a binder and water, kneading into a mass, extruding and molding, drying and roasting to obtain the catalyst.
In the above technical solution, the compound of Cu is preferably at least one selected from the group consisting of copper oxide, cuprous oxide, and copper nitrate; more preferably copper nitrate.
In the above embodiment, the compound of Q (except W and B) is preferably an oxide or nitrate thereof, and more preferably tungsten oxide.
In the above embodiment, when Q is W, the compound of W is preferably at least one selected from tungsten trioxide and ammonium tungstate.
In the above embodiment, when Q is B, the compound of B is preferably at least one selected from boric acid, boron oxide, and alkali metal borate, and boric acid is more preferably used.
In the above-mentioned embodiment, the compound of Y is preferably an oxide or hydroxide thereof, and more preferably a hydroxide.
In the above technical scheme, the binder is preferably one selected from silica sol, aluminum sol, titanium sol, montmorillonite and kaolin; silica sol and kaolin are more preferred.
In the above technical solution, the kneaded mass for extrusion molding may further include a pore-forming agent. For example, but not limited to, the pore former is crystalline cellulose or PEG, the weight average molecular weight is preferably 4000 to 15 ten thousand, and the addition amount is preferably 0 to 10% of the weight of the catalyst.
In the technical scheme, the amount of water is not required, the standard of facilitating agglomeration is adopted, 15-25% of the total powder mass is preferred, and the adding amount of nitric acid is 2-10% of the total powder mass.
To solve the second technical problem, the technical solution of the present invention is as follows:
a process for producing acrylic acid, which comprises oxidizing acrolein with an oxidizing agent containing elemental oxygen in the presence of the catalyst as set forth in any one of the above-mentioned technical problems to obtain acrylic acid.
In the technical scheme, the reaction temperature is preferably 240-350 ℃.
In the above technical scheme, the oxidant may be air.
In the above technical scheme, the reaction raw materials, in addition to acrolein and air as an oxidant, may further include water vapor to increase the service life of the catalyst, and the ratio of acrolein, air and water vapor in the reaction raw materials is preferably 1 (2.5-8) to (1-3) in terms of volume ratio.
In the technical scheme, the volume airspeed of the reaction raw materials is 800-1600 hours-1。
Use the bookThe catalyst of the invention is used for preparing acrylic acid by selective oxidation of acrolein, and the reaction temperature is 260 ℃ and the reaction space velocity is 1400 hours-1Under the condition, after 1000 hours, the conversion rate of acrolein can reach 99.2%, the yield of the product acrylic acid can reach 88.7%, and a better technical effect is obtained.
In the examples given below, the evaluation conditions for the investigation of the catalyst were:
a reactor: a fixed bed reactor with an inner diameter of 25.4 mm and a reactor length of 750 mm;
catalyst loading: 150 g;
reaction temperature: 260 ℃;
reaction time: 2000 hours;
the volume ratio of raw materials is as follows: acrolein, air, water vapor 1:3.2: 2.1;
volume space velocity of raw materials: 1400 hours-1；
The reaction product was absorbed with dilute acid at 0 ℃ and the product was analyzed by gas chromatography. And calculating the carbon balance, wherein the carbon balance is effective data when the carbon balance is 95-105%.
Acrolein conversion, product yield and selectivity are defined as:
the invention is further illustrated by the following examples:
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
To a compounding tank A equipped with a stirring motor, 1000ml of deionized water at 100 ℃ was added, and 180 g of ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O), 20.5 g of copper nitrate(Cu(NO3)2·3H2O), 39.6 g of ammonium metavanadate (NH)4VO3) 34.4 g of tungsten trioxide (WO)3) 6.3 g of antimony tartrate and 0.34 g of potassium hydroxide (KOH) were stirred at 80 ℃ for 2 hours to form a catalyst slurry, which was rotary evaporated to obtain a powder.
Then pre-roasting the obtained powder for 1 hour at 250 ℃ to obtain an active component, taking 280 g of the active component for molding, wherein 10 g of methylcellulose (weight average molecular weight 20000), 25 g of kaolin and 7076 g of carrier SiO are used260 g of deionized water, kneading for 2 hours to prepare stripes, forming to obtain Raschig rings with the outer diameter of 5mm, the inner diameter of 1.5mm and the length of 5mm, and then roasting for 2 hours to obtain a finished catalyst, wherein the roasting temperature is 400 ℃, and the reaction evaluation results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
To a compounding tank A equipped with a stirring motor, 1000ml of deionized water at 100 ℃ was added, and 180 g of ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O), 20.5 g of copper nitrate (Cu (NO)3)2·3H2O), 39.6 g of ammonium metavanadate (NH)4VO3) 10.3 g of boron oxide (B)2O3) 6.3 g of antimony tartrate and 0.34 g of potassium hydroxide (KOH) were stirred at 80 ℃ for 2 hours to form a catalyst slurry, which was rotary evaporated to obtain a powder.
Then pre-roasting the obtained powder for 1 hour at 250 ℃ to obtain an active component, taking 280 g of the active component for molding, wherein 10 g of methylcellulose (weight average molecular weight 20000), 25 g of kaolin and 7076 g of carrier SiO are used260 g of deionized water, kneading for 2 hours to prepare stripes, forming to obtain Raschig rings with the outer diameter of 5mm, the inner diameter of 1.5mm and the length of 5mm, and then roasting for 2 hours to obtain a finished catalyst, wherein the roasting temperature is 400 ℃, and the reaction evaluation results are shown in Table 1.
[ example 1 ]
To a compounding tank A equipped with a stirring motor, 1000ml of deionized water at 100 ℃ was added, and 180 g of ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O), 20.5 g nitreAcid copper (Cu (NO)3)2·3H2O), 39.6 g of ammonium metavanadate (NH)4VO3) 17.2 g of tungsten trioxide (WO)3) 5.2 g of boron oxide (B)2O3) 6.3 g of antimony tartrate and 0.34 g of potassium hydroxide (KOH) were stirred at 80 ℃ for 2 hours to form a catalyst slurry, which was rotary evaporated to obtain a powder.
Then pre-roasting the obtained powder for 1 hour at 250 ℃ to obtain an active component, taking 280 g of the active component for molding, wherein 10 g of methylcellulose (weight average molecular weight 20000), 25 g of kaolin and 7076 g of carrier SiO are used260 g of deionized water, kneading for 2 hours to prepare stripes, forming to obtain Raschig rings with the outer diameter of 5mm, the inner diameter of 1.5mm and the length of 5mm, and then roasting for 2 hours to obtain a finished catalyst, wherein the roasting temperature is 400 ℃, and the reaction evaluation results are shown in Table 1.
[ examples 2 to 8 ]
Catalysts having different compositions in the following table were prepared in substantially the same manner as in example 1, and the results of reaction evaluation are shown in table 1.
TABLE 1 catalyst composition and evaluation results
Claims (8)
1. The catalyst for generating acrylic acid comprises the following components in parts by weight:
a: 40-80 parts of SiO2、Al2O3、ZrO2Or TiO2At least one carrier; and B' supported thereon: 20-60 parts of active component Mo12VaCubWcBdXeYfOg；
Wherein Mo, V, Cu and O represent the elements molybdenum, vanadium, copper and oxygen; w and B are tungsten element and boron element respectively, and X represents at least one element of Cr, Mn and Sb; y is at least one element selected from alkali metals or alkaline earth metals; a. b, c, d, e, f and g represent the atomic ratio of the respective elements, based on the atomic ratio of Mo element is 12, a is 0.5-4.0, b is 0.1-5.0, c is more than 0 and less than 5.0, d is more than 0 and less than 3.0, e is 0-5.0, f is 0-1.0, and g is the number of oxygen atoms needed to satisfy the total valence of other elements.
2. The catalyst of claim 1, prepared by a process comprising the steps of:
mixing ammonium heptamolybdate, ammonium metavanadate, compounds of Cu, W, B, X and Y, a carrier, a binder and water, kneading into a mass, extruding and molding, drying and roasting to obtain the catalyst.
3. The catalyst according to claim 2, wherein the compound of Cu is at least one selected from the group consisting of cupric oxide, cuprous oxide and cupric nitrate.
4. The catalyst of claim 2 wherein the compound of W, B, X is an oxide or nitrate thereof.
5. The catalyst of claim 2, wherein the compound of Y is an oxide or hydroxide thereof.
6. The catalyst according to claim 2, wherein the binder is selected from the group consisting of silica sol, alumina sol, titanium sol, montmorillonite and kaolin.
7. A process for producing acrylic acid, comprising oxidizing acrolein in the presence of the catalyst according to any one of claims 1 to 6 with an oxidant containing elemental oxygen to obtain acrylic acid.
8. The process according to claim 7, wherein the reaction temperature is 240 to 350 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610225971.5A CN107282059B (en) | 2016-04-13 | 2016-04-13 | Catalyst for producing acrylic acid |
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| CN201610225971.5A CN107282059B (en) | 2016-04-13 | 2016-04-13 | Catalyst for producing acrylic acid |
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| CN107282059B true CN107282059B (en) | 2020-08-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110639495B (en) * | 2018-06-27 | 2022-09-06 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin by synthesis gas and application of catalyst in synthesizing low-carbon olefin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1764631A (en) * | 2003-03-25 | 2006-04-26 | 巴斯福股份公司 | Heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid |
| CN103521234A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof |
| CN103769149A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing propenoic acid through oxidation of propenal, as well as preparation and application of catalyst |
| CN103769148A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769145B (en) * | 2012-10-23 | 2015-10-28 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation of acrolein and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1764631A (en) * | 2003-03-25 | 2006-04-26 | 巴斯福股份公司 | Heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid |
| CN103521234A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof |
| CN103769149A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing propenoic acid through oxidation of propenal, as well as preparation and application of catalyst |
| CN103769148A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst |
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