CN106423186A - Acrylic acid catalyst and preparation method thereof - Google Patents
Acrylic acid catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an acrylic acid catalyst, a preparation method thereof and a synthetic method of acrylic acid, and mainly solves the technical problem in the prior art that acrylic acid is low in yield. According to the technical scheme of the invention, the acrylic acid catalyst comprises 40-80 parts by weight of at least one carrier selected from SiO2, Al2O3, ZrO2 and TiO2; and 20-60 parts by weight of an active component Mo12VaCubWcXdYeZfOg loaded on the carrier. Y is at least one element selected from Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr and Sr, and Z is at least one element selected from alkali metal and alkaline earth metal. In this way, the above technical problem in the prior art is well solved. The acrylic acid catalyst can be used for the industrial production of acrylic acid.
Description
Technical field
The present invention relates to by the catalyst of acrylic aldehyde acrylic acid synthesizing, preparation method and acrylic acid synthetic method.
Background technology
Industrial propylene aoxidizes acrylic acid processed and adopts two-step method at present, and the first step is in Mo-Bi composite oxide catalysts
Under effect, propylene is oxidized to acrylic aldehyde, 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 slightly 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, and particularly state's inner acrylic production capacity increases severely in recent years, by December, 2013 domestic production capacity
140,000 tons from 2000 rise to 189.2 ten thousand tons.
Up to now, many patent authorizings are for the relevant invention of the catalyst that produces acrylic acid method from acrylic aldehyde, its
Middle great majority are 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 mostly is many metallic compounds in solvent or water
In the presence of make solution, add insoluble oxide evaporate under heating and stirring dry, then calcining, pulverize and molding
Preparation method.And elementary composition described in presently disclosed patent differs greatly, such as Chinese patent CN 1169619C
Disclosed catalyst main constituent 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 stable, and catalyst can be delayed to lead to inactivate because Mo runs off；Chinese patent CN
Catalyst disclosed in 1583261A is to be main active component by 1. molybdenum, vanadium, copper, 2. requisite at least by titanium and
The stable component of antimony and 3. nickel, ferrum, silicon, aluminum, the complex chemical compound of alkali metal alkaline earth metal composition；Chinese patent
Catalyst disclosed in CN 1050779C its substantially form molybdenum including oxide form, vanadium, tungsten, copper and mickel element；In
Catalyst disclosed in state patent CN 1146439A contains molybdenum, vanadium, copper and contains in elemental tungsten, niobium, tantalum, chromium and cerium
One or more elements, and containing copper, molybdenum and at least one element in elemental tungsten, vanadium, niobium and the tantalum
The oxo metal-oxide of HT copper molybdate structure type.
But acrylic acid yield of prior art is low.
Content of the invention
One of the technical problem to be solved is that existing production in propylene acid reaction in acrolein oxidation in the art is deposited
Catalyst acrolein conversion rate being low and the low problem of acrylic acid yield, providing for acrylic acid synthesis.This catalyst
For the reaction of acrolein oxidation acrylic acid synthesizing, there is acrolein conversion rate height and acrylic acid high income.
The two of the technical problem to be solved are the preparation methoies providing one of above-mentioned technical problem described catalyst.
The three of the technical problem to be solved are the propylene providing using one of above-mentioned technical problem described catalyst
The synthetic method of acid.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows：
Acrylic acid catalyst, inclusion following components in terms of parts by weight：
A：40-80 part selected from SiO2、Al2O3、ZrO2Or TiO2In at least one carrier；Be loaded in thereon
B：Active component Mo of 20-60 part12VaCubWcSbdYeZfOg；
Wherein Mo, V, Cu, W, Sb and O represent molybdenum, vanadium, copper, tungsten, antimony and oxygen；Y be selected from Fe,
At least one element in Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr；Z is selected from alkali metal or alkali
At least one element in earth metal；A, b, c, d, e, f and g represent the atomic ratio of each of which element, are based on
The span for 12, a for the atomic ratio of Mo element is the value for 0.1～5.0, c for the span of 0.5～4.0, b
Scope be 0.01～5.0, d span be 0.01～5.0, e span be 0～5.0, f span be 0～
1.0, g is the number of the required oxygen atom meeting other total quantivalences of element.
The key point of catalyst of the present invention does not lie in geometry and the size of catalyst, the therefore shape to catalyst and chi
Very little be not particularly limited, the variously-shaped and size of existing carrier is used equally to the present invention the result obtaining on year-on-year basis.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.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：The described skill of one of above-mentioned technical problem
Described in art scheme, the preparation method of catalyst, comprises the following steps：
By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the change of the compound of Cu, the compound of Y and Z
Compound and carrier mixing, molding, drying, roasting obtain described catalyst.
In technique scheme, described molding can adopt extrusion molding, and described preparation method now specifically includes：By seven
Ammonium molybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of the compound of Cu, the compound of Y and Z, load
Body, binding agent, pore creating material, appropriate deionized water and nitric acid, mediate, extrusion molding.
In technique scheme, the compound of Cu preferably is selected from least one in copper oxide, Red copper oxide and copper nitrate.
In technique scheme, the compound of Y is preferably its oxide and/or nitrate.
In technique scheme, the compound of Z is preferably hydroxide.
In technique scheme, the compound of tungsten preferably is selected from ammonium tungstate, ammonium metatungstate, ammonium paratungstate, Tungstic anhydride. and carbon
Change at least one in tungsten；More preferably tungsten carbide, or more preferably include tungsten carbide, also include ammonium tungstate, ammonium metatungstate,
At least one in ammonium paratungstate and Tungstic anhydride..
In technique scheme, pore creating material can be methylcellulose or PEG.
In technique scheme, the weight average molecular weight preferably 4000 to 150000 of pore creating material.
In technique scheme, the addition of pore creating material preferably accounts for the 0-10% of catalyst weight.
In technique scheme, binding agent is selected from Ludox, Alumina gel, titanium colloidal sol, montmorillonite and Kaolin extremely
Few one kind.
In technique scheme, the amount of water does not require, be beneficial to agglomerating be suitable to extrusion molding and be advisable, preferably total powder body matter
The 15-25% of amount, addition is preferably total powder quality to nitric acid addition taking the nitric acid that concentration is 50～90wt% as a example
2-10%.In the specific embodiment of the invention, the concentration of nitric acid is 65wt%.
In the present invention, tungsten carbide refers both to WC.
In active component in the present invention, W and Sb has synergism, especially in the preparation of catalyst when W with
When the form of WC introduces, the synergism between W and Sb is especially strong.
For solving the three of above-mentioned technical problem, technical scheme is as follows：Synthesis of conjugated carboxylic alkeneacid, to include third
The material of olefine aldehydr, air and water vapour is reaction raw materials, is catalyzed described in the described technical scheme of one of above-mentioned technical problem
In the presence of agent, reaction generates and contains acrylic acid.
In technique scheme, the temperature of reaction is preferably 240～350 DEG C, with propylene in reaction raw materials described in volume basis
Aldehyde:Air:Water vapour is preferably 1:(2.5～8):(1～3), reaction raw materials volume space velocity is preferably 800～1600 hours-1.
Catalyst using the present invention prepares acrylic acid for acrylic aldehyde selective oxidation, is 260 DEG C, reacts in reaction temperature
Air speed is 1400 hours-1Under conditions of, react 1000 hours, its acrolein conversion rate is up to 99.1%, product propylene
Sour yield, up to 89.2%, achieves preferable technique effect.
In embodiments given below, to the investigation appreciation condition of catalyst it is：
Reactor：Fixed bed reactors, 25.4 millimeters of internal diameter, 750 millimeters of reactor length
Catalyst filling amount：150 grams
Reaction temperature：260℃
Response time：1000 hours
Volume feed：Acrylic aldehyde:Air:Water vapour=1:3:2
Raw material volume air speed：1400 hours-1
Product is absorbed with 0 DEG C of diluted acid, uses gas chromatographic analysiss product.And calculate Carbon balance, when Carbon balance 95～
It is valid data when 105%.
Acrolein conversion rate, product yield and be optionally defined as：
Below by embodiment, the present invention is further elaborated：
Specific embodiment
Comparative example 1
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 48.4 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 3.7 grams of ferrum oxide (Fe2O3) and 0.64
Gram potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams
Kaolin is dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continues to mediate 1h,
After material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm length
Raschig ring for 5mm, then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, and catalyst forms
It is listed in table 1, reaction appraisal result is listed in table 2.
Comparative example 2
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 26.4 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3) and 0.64 gram of potassium hydroxide
(KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of Kaolin are pinching
1h is dry mixed in conjunction machine, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to mediate 1h, treat that material becomes
After group, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 5mm's for 1.5mm length
Raschig ring, then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, and catalyst composition is listed in table 1,
Reaction appraisal result is listed in table 2.
Embodiment 1
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 48.4 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 6.9 grams of antimony oxide (Sb2O3)、
3.7 grams of ferrum oxide (Fe2O3) and 0.64 gram of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000),
230 grams of carrier S iO2, 25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added
Enter in powder, continue to mediate 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is
5mm, internal diameter is the Raschig ring of 5mm for 1.5mm length, and then roasting obtains finished catalyst, roasting temperature for 2 hours
Spend for 500 DEG C, catalyst composition is listed in table 1, reaction appraisal result is listed in table 2.
Embodiment 2
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 30.3 grams of Tungstic anhydride. (WO3), 6.9 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3)
With 0.64 gram of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Embodiment 3
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 25.6 grams of tungsten carbides (WC), 6.9 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3)
With 0.64 gram of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Embodiment 4
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 2.5 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 69.5 grams of antimony oxide (Sb2O3)、
3.7 grams of ferrum oxide (Fe2O3) and 0.64 gram of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000),
230 grams of carrier S iO2, 25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added
Enter in powder, continue to mediate 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is
5mm, internal diameter is the Raschig ring of 5mm for 1.5mm length, and then roasting obtains finished catalyst, roasting temperature for 2 hours
Spend for 500 DEG C, catalyst composition is listed in table 1, reaction appraisal result is listed in table 2.
Embodiment 5
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 2.2 grams of Tungstic anhydride. (WO3), 69.5 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3)
With 0.64 gram of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Embodiment 6
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of oxygen
Change copper (CuO), 1.9 grams of tungsten carbides (WC), 69.5 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3)
With 0.64 gram of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Embodiment 7
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 44.0 grams of ammonium metavanadate (NH4VO3), 0.7 gram of oxygen
Change copper (CuO), 127.3 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 1.4 grams of antimony oxide (Sb2O3)
With 6.4 grams of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Embodiment 8
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 44.0 grams of ammonium metavanadate (NH4VO3), 0.7 gram of oxygen
Change copper (CuO), 108.3 grams of Tungstic anhydride. (WO3), 1.4 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3)
With 6.4 grams of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Embodiment 9
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 44.0 grams of ammonium metavanadate (NH4VO3), 0.7 gram of oxygen
Change copper (CuO), 91.5 grams of tungsten carbides (WC), 1.4 grams of antimony oxide (Sb2O3), 3.7 grams of ferrum oxide (Fe2O3)
With 6.4 grams of potassium hydroxide (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2、
25 grams of Kaolin are dry mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to pinch
Close 1h, after material is agglomerating, put into extruded moulding in double screw banded extruder, obtaining external diameter is 5mm, and internal diameter is 1.5mm
Length is the Raschig ring of 5mm, and then roasting obtains finished catalyst in 2 hours, and sintering temperature is 500 DEG C, catalyst
Composition is listed in table 1, and reaction appraisal result is listed in table 2.
Table 1, catalyst composition and its tungsten raw material
| Tungsten raw material | Catalyst activity component | |
| Comparative example 1 | Ammonium tungstate | Mo12V3Cu1.0W1.9Fe0.5K0.1Og |
| Comparative example 2 | - | Mo12V3Cu1.0Sb1.9Fe0.5K0.1Og |
| Embodiment 1 | Ammonium tungstate | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 2 | Tungstic anhydride. | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 3 | Tungsten carbide | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 4 | Ammonium tungstate | Mo12V3Cu1.0W0.1Sb5Fe0.5K0.1Og |
| Embodiment 5 | Tungstic anhydride. | Mo12V3Cu1.0W0.1Sb5Fe0.5K0.1Og |
| Embodiment 6 | Tungsten carbide | Mo12V3Cu1.0W0.1Sb5Fe0.5K0.1Og |
| Embodiment 7 | Ammonium tungstate | Mo12V4Cu0.1W5Sb0.1K1Og |
| Embodiment 8 | Tungstic anhydride. | Mo12V4Cu0.1W5Sb0.1K1Og |
| Embodiment 9 | Tungsten carbide | Mo12V4Cu0.1W5Sb0.1K1Og |
Table 2, comparative example and embodiment investigate result
Claims (10)
1. acrylic acid catalyst, inclusion following components in terms of parts by weight：
A：40-80 part selected from SiO2、Al2O3、ZrO2Or TiO2In at least one carrier；Be loaded in thereon
B：Active component Mo of 20-60 part12VaCubWcSbdYeZfOg；
Wherein Mo, V, Cu, W, Sb and O represent molybdenum, vanadium, copper, tungsten, antimony and oxygen；Y be selected from Fe,
At least one element in Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr；Z is selected from alkali metal or alkali
At least one element in earth metal；A, b, c, d, e, f and g represent the atomic ratio of each of which element, are based on
The span for 12, a for the atomic ratio of Mo element is the value for 0.1～5.0, c for the span of 0.5～4.0, b
Scope be 0.01～5.0, d span be 0.01～5.0, e span be 0～5.0, f span be 0～
1.0, g is the number of the required oxygen atom meeting other total quantivalences of element.
2. the preparation method of catalyst described in claim 1, comprises the following steps：
By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the change of the compound of Cu, the compound of Y and Z
Compound and carrier mixing, molding, drying, roasting obtain described catalyst.
3. preparation method according to claim 2 is it is characterised in that described molding adopts extrusion molding, described
Preparation method specifically includes：By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of Cu, Y
The compound of compound and Z, carrier, binding agent, pore creating material, appropriate deionized water and nitric acid, mediate, are extruded into
Type.
4. the preparation method according to Claims 2 or 3 it is characterised in that the compound of Cu be selected from copper oxide,
At least one in Red copper oxide and copper nitrate.
5. the preparation method according to Claims 2 or 3 it is characterised in that Y compound be its oxide and/
Or nitrate.
6. the preparation method according to Claims 2 or 3 is it is characterised in that the wherein compound of Z is hydroxide.
7. preparation method according to claim 3 is it is characterised in that wherein pore creating material is methylcellulose or PEG.
8. preparation method according to claim 7 is it is characterised in that the weight average molecular weight of wherein pore creating material is 4000
To 150000.
9. preparation method according to claim 3 it is characterised in that wherein binding agent be selected from Ludox, Alumina gel,
At least one in titanium colloidal sol, montmorillonite and Kaolin.
10. synthesis of conjugated carboxylic alkeneacid, with include acrylic aldehyde, air and water vapour material as reaction raw materials, such as weigh
Reaction in the presence of profit requires catalyst described in 1 generates acrylic acid.
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Cited By (5)
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| CN106423188A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Acrylic acid catalyst and preparation method thereof |
| CN111068649A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for synthesizing acrylic acid from acrolein |
| CN111068653A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrylic acid from acrolein and application thereof |
| CN111068651A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for acrylic acid production and method for synthesizing acrylic acid from acrolein |
| CN115475623A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by selective oxidation of propylene and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106423188A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Acrylic acid catalyst and preparation method thereof |
| CN106423188B (en) * | 2015-08-12 | 2018-07-13 | 中国石油化工股份有限公司 | Acrylic acid catalyst and preparation method |
| CN111068649A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for synthesizing acrylic acid from acrolein |
| CN111068653A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrylic acid from acrolein and application thereof |
| CN111068651A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for acrylic acid production and method for synthesizing acrylic acid from acrolein |
| CN115475623A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by selective oxidation of propylene and preparation method and application thereof |
| CN115475623B (en) * | 2021-06-16 | 2024-06-28 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein by propylene selective oxidation, preparation method and application thereof |
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