CN107282059A - Produce the catalyst of acrylic acid - Google Patents
Produce the catalyst of acrylic acid Download PDFInfo
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- CN107282059A CN107282059A CN201610225971.5A CN201610225971A CN107282059A CN 107282059 A CN107282059 A CN 107282059A CN 201610225971 A CN201610225971 A CN 201610225971A CN 107282059 A CN107282059 A CN 107282059A
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- catalyst
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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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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the catalyst of production acrylic acid, the problem of catalyst activity is relatively low in the prior art is mainly solved.The present invention by terms of parts by weight including following components：A：40 80 parts be selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier；B thereon is loaded in it：20 60 parts of active component Mo12VaCubQnYfOg；Wherein Q represents at least one of Cr, Mn, Sb, W and B element；Y is the technical scheme selected from least one of alkali metal or alkaline-earth metal element, preferably solves the problem, the industrial production available for acrylic acid.
Description
Technical field
The present invention relates to by the catalyst of methacrylaldehyde acrylic acid synthesizing, preparation method and acrylic acid synthetic method.
Background technology
Industrial propylene aoxidizes acrylic acid processed and uses two-step method at present, and the first step is in Mo-Bi composite oxide catalysts
Propylene is oxidized to methacrylaldehyde under effect, second step is by acrolein oxidation under the effect of Mo-V composite oxide catalysts
For acrylic acid.Acrylic acid and its fat purposes are quite varied, and thick acid is mainly for the production of water soluble paint and adhesive, essence acid
Mainly for the production of super absorbent resin SAP.With building, electronics, auto industry development, world wide inner propene
Sour demand and production capacity are continuously increased.
Up to now, the relevant invention of many patent authorizings are used to producing acrylic acid method from methacrylaldehyde catalyst, its
In it is most of be the catalyst containing molybdenum-vanadium (Mo-V), such as Chinese patent CN 1070468C, CN 1031488A,
CN 1146438A, CN 100378058C, CN 1031050C, CN 1169619C, CN 1583261A and CN
1146439A etc., the catalyst described by these patents, its preparation method is generally many metallic compounds in solvent or water
In the presence of solution is made, add insoluble oxide and evaporate dry under heating and stirring, then calcine, crush and be molded
Preparation method.And the element composition described in presently disclosed patent differs greatly, such as Chinese patent CN 1169619C
Disclosed catalyst principal component is molybdenum, vanadium and copper, adds necessary tellurium, it is believed that tellurium can make the activity of this catalyst
Phase oxidation molybdenum and copper molybdate are more stablized, and catalyst can be delayed to cause inactivation because Mo is lost in；Chinese patent CN
It by 1. molybdenum, vanadium, copper is main active component that catalyst disclosed in 1583261A, which is, 2. it is essential at least by titanium and
The stable component of antimony and 3. nickel, iron, silicon, aluminium, the complex chemical compound of alkali metal alkaline earth metal composition；Chinese patent
Catalyst disclosed in CN 1050779C its constitute the molybdenum including oxide form, vanadium, tungsten, copper and mickel element substantially；In
Catalyst disclosed in state patent CN 1146439A contains molybdenum, vanadium, copper and contained in elemental tungsten, niobium, tantalum, chromium and cerium
One or more kinds of elements, and contain copper, molybdenum and at least one element in elemental tungsten, vanadium, niobium and tantalum
The oxo metal oxide of HT copper molybdate structure types.
But the catalyst activity of prior art is relatively low, acrylic acid yield is low.
The content of the invention
One of technical problems to be solved by the invention are now to be deposited in the art in acrolein oxidation production propylene acid reaction
There is provided the catalyst of production acrylic acid the problem of acrolein conversion rate is low and acrylic acid yield is low.The catalyst is used for
Acrolein oxidation acrylic acid synthesizing reacts, with acrolein conversion rate is high and the characteristics of acrylic acid high income.
The two of the technical problems to be solved by the invention are the acrylic acid of the catalyst using one of above-mentioned technical problem
Production method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
The catalyst of acrylic acid is generated, including following components in terms of parts by weight：
A：40-80 parts be selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier；It is loaded in thereon with it
B '：20-60 parts of active component Mo12VaCubQnYfOg；
Wherein Mo, V, Cu and O represent molybdenum, vanadium, copper and oxygen；Q is represented in Cr, Mn, Sb, W and B
At least one element；Y is selected from least one of alkali metal or alkaline-earth metal element；A, b, f and g represent it
Each element atomic ratio, the span that the atomic ratio based on Mo elements is 12, a is taking for 0.5~4.0, b
The span that the span that value scope is 0.1~5.0, n is 0~13.0, f is that 0~1.0, g is to meet other elements
The number of the required oxygen atom of total chemical valence.
In above-mentioned technical proposal, the active component preferably has following composition：Mo12VaCubWcBdXeYfOg；Wherein
W and B are respectively wolfram element and boron element, and X represents at least one of Cr, Mn, Sb element；C, d, e table
Show W, B and X atomic ratio；C span for more than 0 and less than 5.0, d span be more than 0 and
Less than 3.0, e span are 0~5.0.Present inventor is unusual to be found, when containing W in active component simultaneously
During with B, two kinds of elements have synergy in terms of acrylic acid selectivity and acrolein conversion rate is improved.
The key point of catalyst of the present invention does not lie in the geometry and size of catalyst, therefore to the shape and chi of catalyst
Very little to be not particularly limited, the variously-shaped and size of existing carrier is used equally for the present invention and obtains year-on-year result.For example
The carrier of the present invention can take spherical, Raschig ring or cylinder etc..Preferable 3~the 5mm of spherical diameter；Outside Raschig ring
Preferable 4~the 7mm in footpath, internal diameter preferably 1.5~3mm, length preferably 3~5mm；Preferable 4~the 7mm of cylindrical outer diameter,
Length preferably 3~5mm.
In above-mentioned technical proposal, the catalyst can be prepared using the method comprised the following steps：
Ammonium heptamolybdate, ammonium metavanadate, Cu, Q and Y compound, carrier, binding agent and water are mixed, are kneaded into
Group, extrusion molding, is dried and roasting obtains the catalyst.
In above-mentioned technical proposal, Cu compound is preferably selected from least one in cupric oxide, cuprous oxide and copper nitrate
Kind；More preferably copper nitrate.
In above-mentioned technical proposal, Q compound (except W and B) is preferably its oxide or nitrate, more preferably
Tungsten oxide.
In above-mentioned technical proposal, when Q is W, W compound preferably is selected from least one of tungstic acid and ammonium tungstate.
In above-mentioned technical proposal, when Q is B, B compound preferably is selected from boric acid, boron oxide, alkali borate
At least one, more preferably boric acid.
In above-mentioned technical proposal, Y compound is preferably its oxide or hydroxide, more preferably hydroxide.
In above-mentioned technical proposal, binding agent preferably is selected from one in Ludox, Alumina gel, titanium colloidal sol, montmorillonite and kaolin
Kind；More preferably Ludox and kaolin.
In above-mentioned technical proposal, the group being kneaded into for extrusion molding can also include pore creating material.Such as, but not limited to make
Hole agent is avicel cellulose or PEG, and weight average molecular weight is preferably 4000 to 150,000, and addition preferably accounts for catalyst weight
0-10%.
In above-mentioned technical proposal, the amount of water is not required, in favor of it is agglomerating be standard, the 15-25% of preferably total powder quality,
Nitric acid addition is the 2-10% of total powder quality.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
Acrylic acid is produced, is included in catalyst any one of the technical scheme of one of above-mentioned technical problem and exists
Under, acrylic acid is obtained with the oxidizing methacrylaldehyde of the oxygen containing simple substance.
In above-mentioned technical proposal, the temperature of reaction is preferably 240~350 DEG C.
In above-mentioned technical proposal, the optional air of oxidant.
In above-mentioned technical proposal, reaction raw materials are in addition to methacrylaldehyde and air as oxidant, to increase the longevity of catalyst
Life, can also include vapor, now with methacrylaldehyde in volume basis reaction raw materials:Air:Water vapour is preferably 1:(2.5~
8):(1~3).
In above-mentioned technical proposal, reaction raw materials volume space velocity is 800~1600 hours-1。
Acrylic acid is prepared for methacrylaldehyde selective oxidation using the catalyst of the present invention, is 260 DEG C, reaction in reaction temperature
Air speed is 1400 hours-1Under conditions of, after 1000 hours, its acrolein conversion rate is up to 99.2%, product propylene acid
Yield achieves preferable technique effect up to 88.7%.
In embodiments given below, it is to the investigation appreciation condition of catalyst：
Reactor：Fixed bed reactors, 25.4 millimeters of internal diameter, 750 millimeters of reactor length；
Catalyst filling amount：150 grams；
Reaction temperature：260℃；
Reaction time：2000 hours；
Volume feed：Methacrylaldehyde:Air:Water vapour=1:3.2:2.1；
Raw material volume air speed：1400 hours-1；
Reaction product is absorbed with 0 DEG C of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance 95~
It is valid data when 105%.
Acrolein conversion rate, the definition of product yield and selectivity are：
Below by embodiment, the present invention is further elaborated：
Embodiment
【Comparative example 1】
In the dispensing equipped with stirring motor fills A, 1000ml 100 DEG C of deionized waters are added, by 180 gram of seven molybdic acid
Ammonium ((NH4)6Mo7O24·4H2O), 20.5 grams of copper nitrate (Cu (NO3)2·3H2O), 39.6 grams of ammonium metavanadates
(NH4VO3), 34.4 grams of tungstic acid (WO3), 6.3 grams of antimony tartrates and 0.34 gram of potassium hydroxide (KOH),
Stirred 2 hours at 80 DEG C, powder is obtained after forming catalyst pulp, rotary evaporation.
The powder of acquisition is obtained into active component after 1 hour by 250 DEG C of preroast again, taken from obtained active component
Going out 280 grams is used to be molded, wherein 10 grams of methylcellulose (weight average molecular weight 20000), 25 grams of kaolin, 7076
Gram carrier S iO2, 60 grams of deionized waters, kneading agent bar, shaping in 2 hours obtain external diameter for 5mm, internal diameter is 1.5mm
Length is 5mm Raschig ring, and then roasting obtains finished catalyst for 2 hours, and sintering temperature is 400 DEG C, and reaction is examined
Result is commented to be listed in table 1.
【Comparative example 2】
In the dispensing equipped with stirring motor fills A, 1000ml 100 DEG C of deionized waters are added, by 180 gram of seven molybdic acid
Ammonium ((NH4)6Mo7O24·4H2O), 20.5 grams of copper nitrate (Cu (NO3)2·3H2O), 39.6 grams of ammonium metavanadates
(NH4VO3), 10.3 grams of boron oxide (B2O3), 6.3 grams of antimony tartrates and 0.34 gram of potassium hydroxide (KOH), at 80 DEG C
Lower stirring 2 hours, powder is obtained after forming catalyst pulp, rotary evaporation.
The powder of acquisition is obtained into active component after 1 hour by 250 DEG C of preroast again, taken from obtained active component
Going out 280 grams is used to be molded, wherein 10 grams of methylcellulose (weight average molecular weight 20000), 25 grams of kaolin, 7076
Gram carrier S iO2, 60 grams of deionized waters, kneading agent bar, shaping in 2 hours obtain external diameter for 5mm, internal diameter is 1.5mm
Length is 5mm Raschig ring, and then roasting obtains finished catalyst for 2 hours, and sintering temperature is 400 DEG C, and reaction is examined
Result is commented to be listed in table 1.
【Embodiment 1】
In the dispensing equipped with stirring motor fills A, 1000ml 100 DEG C of deionized waters are added, by 180 gram of seven molybdic acid
Ammonium ((NH4)6Mo7O24·4H2O), 20.5 grams of copper nitrate (Cu (NO3)2·3H2O), 39.6 grams of ammonium metavanadates
(NH4VO3), 17.2 grams of tungstic acid (WO3), 5.2 grams of boron oxide (B2O3), 6.3 grams of antimony tartrates and 0.34
Gram potassium hydroxide (KOH), is stirred 2 hours at 80 DEG C, and powder is obtained after forming catalyst pulp, rotary evaporation.
The powder of acquisition is obtained into active component after 1 hour by 250 DEG C of preroast again, taken from obtained active component
Going out 280 grams is used to be molded, wherein 10 grams of methylcellulose (weight average molecular weight 20000), 25 grams of kaolin, 7076
Gram carrier S iO2, 60 grams of deionized waters, kneading agent bar, shaping in 2 hours obtain external diameter for 5mm, internal diameter is 1.5mm
Length is 5mm Raschig ring, and then roasting obtains finished catalyst for 2 hours, and sintering temperature is 400 DEG C, and reaction is examined
Result is commented to be listed in table 1.
【Embodiment 2~8】
Catalyst with different compositions in following table is prepared using method substantially the same manner as Example 1, appraisal result is reacted
It is shown in Table 1.
Table 1, catalyst composition and evaluation result
Claims (8)
1. the catalyst of acrylic acid is generated, including following components in terms of parts by weight：
A：40-80 parts be selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier；It is loaded in thereon with it
B '：20-60 parts of active component Mo12VaCubQnYfOg；
Wherein Mo, V, Cu and O represent molybdenum, vanadium, copper and oxygen；Q is represented in Cr, Mn, Sb, W and B
At least one element；Y is selected from least one of alkali metal or alkaline-earth metal element；A, b, n, f and g are represented
The atomic ratio of each of which element, the span that the atomic ratio based on Mo elements is 12, a is 0.5~4.0, b's
The span that the span that span is 0.1~5.0, n is 0~13.0, f is that 0~1.0, g is to meet other members
The number of the required oxygen atom of plain total chemical valence.
2. the catalyst described in claim 1, is prepared using the method comprised the following steps：
Ammonium heptamolybdate, ammonium metavanadate, Cu, Q and Y compound, carrier, binding agent and water are mixed, are kneaded into
Group, extrusion molding, is dried and roasting obtains the catalyst.
3. catalyst according to claim 2, it is characterised in that Cu compound is selected from cupric oxide, cuprous oxide
At least one of with copper nitrate.
4. catalyst according to claim 2, it is characterized in that Q compound is its oxide or nitrate.
5. catalyst according to claim 2, it is characterised in that Y compound is its oxide or hydroxide.
6. catalyst according to claim 2, it is characterised in that binding agent be selected from Ludox, Alumina gel, titanium colloidal sol,
One kind in montmorillonite and kaolin.
7. produce acrylic acid, be included in the presence of catalyst any one of claim 1~6, with containing
The oxidizing methacrylaldehyde of simple substance oxygen obtains acrylic acid.
8. method according to claim 7, it is characterized in that the temperature of reaction is 240~350 DEG C.
Priority Applications (1)
| 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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| 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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| CN107282059A true CN107282059A (en) | 2017-10-24 |
| CN107282059B CN107282059B (en) | 2020-08-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639495A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin from synthesis gas and application of catalyst in synthesizing low-carbon olefin |
Citations (5)
| 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 |
| 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 |
| CN103769145A (en) * | 2012-10-23 | 2014-05-07 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation of acrolein 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 |
-
2016
- 2016-04-13 CN CN201610225971.5A patent/CN107282059B/en active Active
Patent Citations (5)
| 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 |
| CN103769145A (en) * | 2012-10-23 | 2014-05-07 | 中国石油天然气股份有限公司 | Catalyst for selective oxidation of acrolein and preparation method thereof |
| 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 |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639495A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin from synthesis gas and application of catalyst in synthesizing low-carbon olefin |
| 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 |
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| CN107282059B (en) | 2020-08-07 |
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