CN107282069A - Acrolein oxidation generates the catalyst of acrylic acid - Google Patents
Acrolein oxidation generates the catalyst of acrylic acid Download PDFInfo
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- CN107282069A CN107282069A CN201610225886.9A CN201610225886A CN107282069A CN 107282069 A CN107282069 A CN 107282069A CN 201610225886 A CN201610225886 A CN 201610225886A CN 107282069 A CN107282069 A CN 107282069A
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the catalyst that acrolein oxidation generates 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 Mo12VaQnYfOg；Wherein Q represents at least one of Cr, Cu, Mn, W, Sb, Ag 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 synthesized for acrylic acid the problem of acrolein conversion rate is low and acrylic acid yield is low.The catalyst
For the reaction of acrolein oxidation acrylic acid synthesizing, with acrolein conversion rate is high and the characteristics of acrylic acid high income.
The second technical problem to be solved by the present invention is the production acrylic acid using one of the above-mentioned technical problem catalyst
Method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
Acrolein oxidation generates the catalyst of acrylic acid, 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 Mo12VaQnYfOg；
Wherein Mo, V and O represent molybdenum, vanadium and oxygen；Q is represented in Cr, Cu, Mn, W, Sb, Ag extremely
A kind of few element；Y is selected from least one of alkali metal or alkaline-earth metal element；A, n, f and g represent that they are each
From the atomic ratio of element, the atomic ratio based on Mo elements is that 12, a span is 0.5~4.0, n value model
The span enclosed for 0.1~16.0, f is that 0~1.0, g is the required oxygen atom for meeting the total chemical valence of other elements
Number.
In above-mentioned technical proposal, the preferred Mo of active constituent12VaCubWcAgdXeYfOg；Cu, W and Ag are represented
Elemental copper, tungsten and silver, X represent at least one of Cr, Mn, Sb element；B span is 0.1~5.0, c
Span be 0~5.0, d span for more than 0 and less than 1.0, e span is 0~5.0.
Present inventor find, in the presence of W, two elements of Cu and Ag in active constituent simultaneously in the presence of,
This two elements have synergy in terms of improving acrylic acid selectivity and improving acrolein conversion rate.
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, Q and Y compound, carrier, binding agent and water are mixed, continues kneading and treats
Material is agglomerating, extruded moulding, and dry and roasting obtains the catalyst.
In above-mentioned technical proposal, in addition to W compound, Q compound is preferably its oxide or nitrate.
In above-mentioned technical proposal, W compound is preferably at least one of tungstic acid and ammonium tungstate, more preferably three oxygen
Change tungsten.
In above-mentioned technical proposal, Cu compound is preferably at least one of cupric oxide, cuprous oxide and copper nitrate,
More preferably copper nitrate.
In above-mentioned technical proposal, Y compound is preferably its oxide or hydroxide, more preferably hydroxide.
In above-mentioned technical proposal, carrier is selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier, preferably
SiO2And TiO2。
In above-mentioned technical proposal, the one kind of binding agent in Ludox, Alumina gel, titanium colloidal sol, montmorillonite and kaolin,
It is preferred that Ludox and kaolin.
In above-mentioned technical proposal, pore creating material can also be included in material to be extruded group.Such as, but not limited to described pore creating material
For avicel cellulose or PEG, weight average molecular weight can be 4000 to 150,000, and addition can account 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：
Acrolein oxidation produces acrylic acid, is included in any one of the technical scheme of one of above-mentioned technical problem
In the presence of catalyst, 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 99.5%, product propylene acid
Yield achieves preferable technique effect up to 89%.
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), 14.4 grams of silver nitrate (AgNO3), 39.6 grams of ammonium metavanadate (NH4VO3)、34.4
Gram 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.
【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), 10.3 grams of copper nitrate (Cu (NO3)2·3H2O), 7.2 grams of silver nitrate (AgNO3)、
39.6 grams of ammonium metavanadate (NH4VO3), 34.4 grams of tungstic acid (WO3), 6.3 grams of antimony tartrates and 0.34 gram of hydrogen-oxygen
Change potassium (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.
Embodiment 1 and comparative example 1 and comparative example 2 find out that copper and silver are improving acrylic acid selectivity and methacrylaldehyde turn on year-on-year basis
There is synergy in terms of rate.
【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. acrolein oxidation generates the catalyst of acrylic acid, 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 Mo12VaQnYfOg；
Wherein Mo, V and O represent molybdenum, vanadium and oxygen；Q is represented in Cr, Cu, Mn, W, Sb, Ag
At least one element；Y is selected from least one of alkali metal or alkaline-earth metal element；A, n, f and g represent them
The atomic ratio of respective element, the atomic ratio based on Mo elements is that 12, a span is 0.5~4.0, n value
The span that scope is 0.1~16.0, f is that 0~1.0, g is the required oxygen atom for meeting the total chemical valence of other elements
Number.
2. the catalyst described in claim 1, is prepared using the method comprised the following steps：
Ammonium heptamolybdate, ammonium metavanadate, Q and Y compound, carrier, binding agent and water are mixed, continues kneading and treats
Material is agglomerating, extruded moulding, dries and roasting obtains the catalyst.
3. catalyst according to claim 2, it is characterised in that wherein Q compound is its oxide or nitrate.
4. catalyst according to claim 2, it is characterised in that wherein Y compound is its oxide or hydroxide
Thing.
5. catalyst according to claim 2, it is characterised in that wherein carrier is selected from SiO2、Al2O3、ZrO2
Or TiO2At least one of carrier.
6. catalyst according to claim 2, it is characterised in that wherein binding agent is selected from Ludox, Alumina gel, titanium
One kind in colloidal sol, montmorillonite and kaolin.
7. acrolein oxidation produces acrylic acid, it is included in catalyst any one of claim 1~6 and deposits
Under, acrylic acid is obtained with the oxidizing methacrylaldehyde of the oxygen containing simple substance.
8. method according to claim 7, it is characterized in that the temperature of reaction is 240~350 DEG C.
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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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610225886.9A CN107282069B (en) | 2016-04-13 | 2016-04-13 | catalyst for oxidation of acrolein to acrylic acid |
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| CN107282069A true CN107282069A (en) | 2017-10-24 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121441A (en) * | 1994-05-31 | 1996-05-01 | 株式会社日本触媒 | Catalyst for production of acrylic acid and method for production of acrylic acid by the use of the catalyst |
| WO2000053558A1 (en) * | 1999-03-10 | 2000-09-14 | Basf Aktiengesellschaft | Method for the catalytic gas phase oxidation of propene into acrylic acid |
| CN1321110A (en) * | 1999-09-17 | 2001-11-07 | 日本化药株式会社 | Catalyst |
| CN102040505A (en) * | 2009-10-13 | 2011-05-04 | 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 |
-
2016
- 2016-04-13 CN CN201610225886.9A patent/CN107282069B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121441A (en) * | 1994-05-31 | 1996-05-01 | 株式会社日本触媒 | Catalyst for production of acrylic acid and method for production of acrylic acid by the use of the catalyst |
| WO2000053558A1 (en) * | 1999-03-10 | 2000-09-14 | Basf Aktiengesellschaft | Method for the catalytic gas phase oxidation of propene into acrylic acid |
| CN1321110A (en) * | 1999-09-17 | 2001-11-07 | 日本化药株式会社 | Catalyst |
| CN102040505A (en) * | 2009-10-13 | 2011-05-04 | 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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