CN107282069B - catalyst for oxidation of acrolein to acrylic acid - Google Patents
catalyst for oxidation of acrolein to acrylic acid Download PDFInfo
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- CN107282069B CN107282069B CN201610225886.9A CN201610225886A CN107282069B CN 107282069 B CN107282069 B CN 107282069B CN 201610225886 A CN201610225886 A CN 201610225886A CN 107282069 B CN107282069 B CN 107282069B
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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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 generating acrylic acid by oxidizing acrolein, which mainly solves the problem of low catalyst activity in the prior art and comprises the following components in parts by weight, 40-80 parts of at least one carrier selected from SiO 2, Al 2 O 3, ZrO 2 or TiO 2, and 20-60 parts of an active component Mo 12 V a Q n Y f O g loaded on the carrier, wherein Q represents at least one element selected from Cr, Cu, Mn, W, Sb and Ag, and Y is at least one element selected from alkali metals or alkaline earth metals.
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 concerning catalysts for a process for producing acrylic acid from acrolein, most of which are catalysts containing molybdenum-vanadium (Mo-V), such as chinese patents CN 1070468C, CN 1031488a, CN1146438A, CN 100378058C, CN 1031050C, CN 1169619C, CN1583261a and CN1146439A, etc., and the catalysts described in these patents are mostly prepared by a process in which a multimetal compound is prepared into a solution in the presence of a solvent or water, an insoluble oxide is added thereto and evaporated to dryness under heating and stirring, followed by calcination, pulverization and molding. However, the element composition described in the currently published patents has a large difference, for example, the main components of the catalyst disclosed in chinese patent CN 1169619C are molybdenum, vanadium and copper, and necessary tellurium is added, so that tellurium is considered to make the active phase molybdenum oxide and copper molybdate of the catalyst more stable, and can delay the deactivation of the catalyst due to Mo loss; the catalyst disclosed in chinese patent CN1583261A is a composite compound composed of (i) molybdenum, vanadium, and copper as main active components, (ii) a stabilizing component at least composed of titanium and antimony, and (iii) nickel, iron, silicon, aluminum, and alkali metal alkaline earth metal; the catalyst disclosed in chinese patent CN 1050779C comprises the elements molybdenum, vanadium, tungsten, copper and nickel in the form of oxides; chinese patent CN1146439a discloses a catalyst containing molybdenum, vanadium, copper and one or more of the elements tungsten, niobium, tantalum, chromium and cerium, and an oxo metal oxide of HT copper molybdate structure type containing copper, molybdenum and at least one element selected from the elements tungsten, vanadium, niobium and tantalum.
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 existing in the reaction for producing acrylic acid by oxidizing acrolein in the prior art, and provides a catalyst for acrylic acid synthesis. 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 method for producing acrylic acid using the catalyst described in the first technical problem.
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 by oxidizing acrolein comprises the following components in parts by weight:
40-80 parts of at least one carrier selected from SiO 2, Al 2 O 3, ZrO 2 or TiO 2, and 20-60 parts of an active component Mo 12 V a Q n Y f O g;
Wherein Mo, V and O represent the elements molybdenum, vanadium and oxygen; q represents at least one element selected from Cr, Cu, Mn, W, Sb and Ag; y is at least one element selected from alkali metals or alkaline earth metals; a. n, f and g represent the atomic ratio of their respective elements, the atomic ratio based on Mo element is 12, a is in the range of 0.5-4.0, n is in the range of 0.1-16.0, f is in the range of 0-1.0, and g is the number of oxygen atoms required to satisfy the total valence of other elements.
In the technical scheme, the active component is preferably Mo 12 V a Cu b W c Ag d X e Y f O g, Cu, W and Ag represent elements such as copper, tungsten and silver, X represents at least one element selected from Cr, Mn and Sb, the value range of b is 0.1-5.0, the value range of c is 0-5.0, the value range of d is more than 0 and less than 1.0, and the value range of e is 0-5.0.
The inventors of the present application have found that when both elements Cu and Ag are present in the active component in the presence of W, the two 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 Q and Y, a carrier, a binder and water, continuously kneading the materials to form a mass, extruding the mass into strips, drying and roasting to obtain the catalyst.
In the above embodiment, the compound of Q is preferably an oxide or a nitrate thereof in addition to the compound of W.
in the above technical means, the compound of W is preferably at least one of tungsten trioxide and ammonium tungstate, and more preferably tungsten trioxide.
In the above embodiment, the Cu compound is preferably at least one of copper oxide, cuprous oxide, and copper nitrate, and more preferably copper nitrate.
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 solution, the carrier is at least one carrier selected from SiO 2, Al 2 O 3, ZrO 2 or TiO 2, preferably SiO 2 and TiO 2.
In the above technical solution, the binder is selected from one of silica sol, alumina sol, titanium sol, montmorillonite and kaolin, and preferably silica sol and kaolin.
In the above technical solution, the briquette to be extruded 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 may be 4000 to 15 ten thousand, and the amount added may be 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 method for producing acrylic acid by oxidizing acrolein, which comprises oxidizing acrolein with an oxidizing agent containing elemental oxygen in the presence of the catalyst according to any one of the above 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 space velocity of the reaction raw materials is 800-1600 hours -1.
The catalyst of the invention is used for preparing acrylic acid by selective oxidation of acrolein, and under the conditions that the reaction temperature is 260 ℃ and the reaction space velocity is 1400 hours -1, the acrolein conversion rate can reach 99.5 percent and the yield of the product acrylic acid can reach 89 percent after 1000 hours, thereby obtaining better technical effect.
In the examples given below, the evaluation conditions for the investigation of the catalyst were:
A reactor: fixed bed reactor, internal diameter 25.4 mm, reactor length 750 mm
Catalyst loading: 150 g
Reaction temperature: 260 deg.C
Reaction time: 2000 hours
the volume ratio of raw materials is as follows: acrolein, air, steam 1:3.2:2.1
Volume space velocity of raw material 1400 h -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 batch tank A equipped with a stirring motor, 1000ml of deionized water at 100 ℃ was added, and 180 g of ammonium heptamolybdate ((NH 4) 6 Mo 7 O 24.4H 2 O), 20.5 g of copper nitrate (Cu (NO 3) 2.3H 2 O), 39.6 g of ammonium metavanadate (NH 4 VO 3), 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.
And then pre-roasting the obtained powder for 1 hour at 250 ℃ to obtain an active component, taking 280 g of the obtained active component out for forming, wherein 10 g of methylcellulose (weight average molecular weight 20000), 25 g of kaolin, 7076 g of carrier SiO 2 and 60 g of deionized water are kneaded for 2 hours to obtain a bar, forming to obtain a Raschig ring with the outer diameter of 5mm and the inner diameter of 1.5mm and the length of 5mm, and then roasting for 2 hours to obtain a finished catalyst product, wherein the roasting temperature is 400 ℃, and the reaction evaluation results are listed in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
To a batch tank A equipped with a stirring motor, 1000ml of deionized water at 100 ℃ was added, and 180 g of ammonium heptamolybdate ((NH 4) 6 Mo 7 O 24.4H 2 O), 14.4 g of silver nitrate (AgNO 3), 39.6 g of ammonium metavanadate (NH 4 VO 3), 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 then rotary evaporated to obtain a powder.
And then pre-roasting the obtained powder for 1 hour at 250 ℃ to obtain an active component, taking 280 g of the obtained active component out for forming, wherein 10 g of methylcellulose (weight average molecular weight 20000), 25 g of kaolin, 7076 g of carrier SiO 2 and 60 g of deionized water are kneaded for 2 hours to obtain a bar, forming to obtain a Raschig ring with the outer diameter of 5mm and the inner diameter of 1.5mm and the length of 5mm, and then roasting for 2 hours to obtain a finished catalyst product, wherein the roasting temperature is 400 ℃, and the reaction evaluation results are listed in Table 1.
[ example 1 ]
To a batch tank A equipped with a stirring motor, 1000ml of deionized water at 100 ℃ was added, and 180 g of ammonium heptamolybdate ((NH 4) 6 Mo 7 O 24.4H 2 O), 10.3 g of copper nitrate (Cu (NO 3) 2.3H 2 O), 7.2 g of silver nitrate (AgNO 3), 39.6 g of ammonium metavanadate (NH 4 VO 3), 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.
And then pre-roasting the obtained powder for 1 hour at 250 ℃ to obtain an active component, taking 280 g of the obtained active component out for forming, wherein 10 g of methylcellulose (weight average molecular weight 20000), 25 g of kaolin, 7076 g of carrier SiO 2 and 60 g of deionized water are kneaded for 2 hours to obtain a bar, forming to obtain a Raschig ring with the outer diameter of 5mm and the inner diameter of 1.5mm and the length of 5mm, and then roasting for 2 hours to obtain a finished catalyst product, wherein the roasting temperature is 400 ℃, and the reaction evaluation results are listed in Table 1.
As seen from the same ratio of example 1 to comparative examples 1 and 2, copper and silver have a synergistic effect in increasing the selectivity of acrylic acid and the conversion of acrolein.
[ 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 by oxidizing acrolein comprises the following components in parts by weight:
40-80 parts of at least one carrier selected from SiO 2, Al 2 O 3, ZrO 2 or TiO 2, and 20-60 parts of an active component Mo 12 V a Q n Y f O g;
Wherein Mo, V and O represent the elements molybdenum, vanadium and oxygen; q represents Cu and Ag; y is at least one element selected from alkali metals or alkaline earth metals; a. n, f and g represent the atomic ratio of their respective elements, the atomic ratio based on Mo element is 12, a is in the range of 0.5-4.0, n is in the range of 0.1-16.0, f is in the range of 0-1.0, and g is the number of oxygen atoms required to satisfy the total valence of other elements.
2. The catalyst of claim 1, prepared by a process comprising the steps of:
And mixing ammonium heptamolybdate, ammonium metavanadate, compounds of Q and Y, a carrier, a binder and water, continuously kneading the materials to form a mass, extruding the mass into strips, and drying and roasting the strips to obtain the catalyst.
3. the catalyst of claim 2 wherein the compound of Q is an oxide or nitrate thereof.
4. the catalyst of claim 2, wherein the compound of Y is an oxide or hydroxide thereof.
5. The catalyst according to claim 2, wherein the carrier is at least one carrier selected from the group consisting of SiO 2, Al 2 O 3, ZrO 2 and TiO 2.
6. the catalyst of claim 2, wherein the binder is selected from the group consisting of silica sol, alumina sol, titanium sol, montmorillonite and kaolin.
7. A method for producing acrylic acid by oxidizing acrolein, which comprises oxidizing acrolein with an oxidizing agent containing elemental oxygen in the presence of the catalyst according to any one of claims 1 to 6 to obtain acrylic acid.
8. The method according to claim 7, wherein the reaction temperature is 240 to 350 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610225886.9A CN107282069B (en) | 2016-04-13 | 2016-04-13 | catalyst for oxidation of acrolein to acrylic acid |
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| CN201610225886.9A CN107282069B (en) | 2016-04-13 | 2016-04-13 | catalyst for oxidation of acrolein to acrylic acid |
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| CN107282069A CN107282069A (en) | 2017-10-24 |
| CN107282069B true CN107282069B (en) | 2019-12-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100247524B1 (en) * | 1994-05-31 | 2000-03-15 | 겐지 아이다 | Catalyst for producing acrylic acid and method for production of acrylic acid by the use of the catalyst |
| MY119958A (en) * | 1999-03-10 | 2005-08-30 | Basf Ag | Catalytic gas-phase oxidation of propene to acrylic acid |
| JP3883755B2 (en) * | 1999-09-17 | 2007-02-21 | 日本化薬株式会社 | Catalyst production method |
| CN102040505B (en) * | 2009-10-13 | 2014-04-23 | 中国石油化工股份有限公司 | Method for preparing unsaturated acid by oxidation of unsaturated aldehyde |
| 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 |
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