CN106423186B - Acrylic acid catalyst and preparation method thereof - Google Patents
Acrylic acid catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106423186B CN106423186B CN201510493137.XA CN201510493137A CN106423186B CN 106423186 B CN106423186 B CN 106423186B CN 201510493137 A CN201510493137 A CN 201510493137A CN 106423186 B CN106423186 B CN 106423186B
- Authority
- CN
- China
- Prior art keywords
- compound
- grams
- catalyst
- preparation
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the preparation method and acrylic acid synthetic method for acrylic acid catalyst, catalyst, mainly solve the problems, such as that acrylic acid yield is low in the prior art.The present invention by terms of parts by weight including 40 80 parts be selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier；Be loaded in 20 60 parts of active component Mo thereon12VaCubWcSbdYeZfOg；Wherein Y is selected from least one of Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr element；Z is the technical solution selected from least one of alkali or alkaline earth metal element, preferably solves the problems, such as this, can be used in the industrial production of 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, it by acrolein oxidation is third that second step, which is under the effect of Mo-V composite oxide catalysts,
Olefin(e) acid.Acrylic acid and its fat purposes are very extensive, and crude acid is mainly used for mainly for the production of water soluble paint and adhesive, smart acid
Produce super absorbent resin SAP.With building, the development of electronics, auto industry, world wide inner acrylic demand and production capacity are not
Disconnected to increase, especially state's inner acrylic production capacity increases severely in recent years, by December, 2013 domestic production capacity from 140,000 in 2000
Ton rises to 189.2 ten thousand tons.
Up to now, catalyst related invention of many patent authorizings for producing acrylic acid method from methacrylaldehyde,
Wherein most of is 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., this
Catalyst described in a little patents, preparation method are mostly that solution is made in more metallic compounds in the presence of solvent or water, then
Insoluble oxide is added and evaporates under heating and stirring dry, then calcines, crush and molding preparation method.And it discloses at present
Patent described in element composition differ greatly, the catalyst principal component as disclosed in Chinese patent CN 1169619C be molybdenum, vanadium and
Copper adds necessary tellurium, it is believed that tellurium can be such that the active phase oxidation molybdenum of this catalyst and copper molybdate more stablizes, Ke Yiyan
Slow catalyst causes to inactivate because of Mo losses；It is main that catalyst, which is by 1. molybdenum, vanadium, copper, disclosed in Chinese patent CN 1583261A
Active component, 2. it is essential at least by titanium and antimony stabilization component and 3. nickel, iron, silicon, aluminium, alkali metal alkaline earth metal group
At complex chemical compound；Catalyst disclosed in Chinese patent CN 1050779C its form substantially molybdenum including oxide form,
Vanadium, tungsten, copper and mickel element；Catalyst disclosed in Chinese patent CN 1146439A contain molybdenum, vanadium, copper and containing elemental tungsten, niobium,
One or more of tantalum, chromium and cerium element, and it is first in elemental tungsten, vanadium, niobium and tantalum containing copper, molybdenum and at least one
The oxo metal oxide of the HT copper molybdate structure types of element.
But the yield of the acrylic acid of the prior art is low.
Invention content
The first technical problem to be solved by the present invention is showed in the art in acrolein oxidation production acrylic acid reaction
The low problem low with acrylic acid yield of existing acrolein conversion rate, provides the catalyst synthesized for acrylic acid.The catalyst
It is reacted for acrolein oxidation acrylic acid synthesizing, has the characteristics that acrolein conversion rate height and acrylic acid high income.
The second technical problem to be solved by the present invention is to provide the preparation side of one of above-mentioned technical problem catalyst
Method.
The third technical problem to be solved by the present invention is to provide third using one of above-mentioned technical problem catalyst
The synthetic method of olefin(e) acid.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
Acrylic acid catalyst, including following components in terms of parts by weight：
A：40-80 parts be selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier；Be loaded in thereon
B：20-60 parts of active component Mo12VaCubWcSbdYeZfOg；
Wherein Mo, V, Cu, W, Sb and O indicate molybdenum, vanadium, copper, tungsten, antimony and oxygen；Y be selected from Fe, Bi, Co, Ni, Ge,
At least one of Ga, Nb, Ce, La, Zr, Sr element；Z is selected from least one of alkali or alkaline earth metal element；a、
B, c, d, e, f and g indicate the atomic ratio of each element, and the value range that the atomic ratio based on Mo elements is 12, a is 0.5
The value range that the value range that the value range of~4.0, b are 0.1~5.0, c is 0.01~5.0, d is 0.01~5.0, e's
The value range that value range is 0~5.0, f is that 0~1.0, g is the required oxygen atom for meeting the total chemical valence of other elements
Number.
The key point of catalyst of the present invention does not lie in the geometry and size of catalyst, thus to the shape of catalyst and
Size is not particularly limited, and the variously-shaped and size of existing carrier is used equally for the present invention and obtains year-on-year result.Such as
The carrier of the present invention can take spherical, Raschig ring or cylinder etc..Preferable 3~the 5mm of spherical diameter；Raschig ring outer diameter can be excellent
Select 4~7mm, internal diameter preferably 1.5~3mm, length preferably 3~5mm；Preferable 4~the 7mm of cylindrical outer diameter, length preferably 3~
5mm。
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：Described in one of above-mentioned technical problem
The preparation method of catalyst described in technical solution, includes the following steps：
By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of Cu, the compound of the compound of Y and Z and
Carrier mixing, molding, dry, roasting obtain the catalyst.
In above-mentioned technical proposal, extrusion molding can be used in the molding, and the preparation method specifically includes at this time：By seven
Ammonium molybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of Cu, the compound of the compound of Y and Z, carrier, binder,
Pore creating material, suitable deionized water and nitric acid are mediated, extrusion molding.
In above-mentioned technical proposal, the compound of Cu preferably is selected from least one of copper oxide, cuprous oxide and copper nitrate.
In above-mentioned technical proposal, the compound of Y is preferably its oxide and/or nitrate.
In above-mentioned technical proposal, the compound of Z is preferably hydroxide.
In above-mentioned technical proposal, the compound of tungsten preferably is selected from ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstic acid and carbon
Change at least one of tungsten；More preferable tungsten carbide, or include more preferably tungsten carbide, further include ammonium tungstate, ammonium metatungstate, secondary tungsten
At least one of sour ammonium and tungstic acid.
In above-mentioned technical proposal, pore creating material can be methylcellulose or PEG.
In above-mentioned technical proposal, the weight average molecular weight of pore creating material is preferably 4000 to 150000.
In above-mentioned technical proposal, the addition of pore creating material preferably accounts for the 0-10% of catalyst weight.
In above-mentioned technical proposal, binder can be selected from Ludox, Aluminum sol, titanium colloidal sol, montmorillonite and kaolin extremely
Few one kind.
In above-mentioned technical proposal, the amount of water does not require, and is advisable suitable for extrusion molding in favor of agglomerating, preferably total powder matter
The 15-25% of amount, for nitric acid addition by taking the nitric acid of a concentration of 50~90wt% as an example, addition is preferably the 2- of total powder quality
10%.In the specific embodiment of the invention, a concentration of 65wt% of nitric acid.
In the present invention, tungsten carbide refers both to WC.
In active component in the present invention, W and Sb have synergistic effect, when W is with WC's especially in the preparation of catalyst
When form introduces, the synergistic effect between W and Sb is especially strong.
To solve above-mentioned technical problem three, 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, the catalyst described in one of above-mentioned technical problem technical solution
In the presence of reaction generate contain acrylic acid.
In above-mentioned technical proposal, the temperature of reaction is preferably 240~350 DEG C, in reaction raw materials described in volume basis third
Olefine aldehydr:Air:Water vapour is preferably 1:(2.5~8):(1~3), reaction raw materials volume space velocity are preferably 800~1600 hours-1。
Acrylic acid is prepared for methacrylaldehyde selective oxidation using the catalyst of the present invention, is 260 DEG C, reacts in reaction temperature
Air speed is 1400 hours-1Under conditions of, it reacts 1000 hours, acrolein conversion rate is up to 99.1%, product propylene acid yield
Up to 89.2%, preferable technique effect is achieved.
In embodiments given below, the investigation evaluation condition to catalyst is：
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：1000 hours
Volume feed：Methacrylaldehyde:Air:Water vapour=1:3:2
Raw material volume air speed：1400 hours-1
Reaction product is absorbed with 0 DEG C of diluted acid, with gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance 95~
It is valid data when 105%.
The definition of acrolein conversion rate, product yield and selectivity is：
Below by embodiment, the present invention is further elaborated：
Specific implementation mode
Comparative example 1
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of copper oxide
(CuO), 48.4 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 3.7 grams of iron 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 it is dry-mixed in kneader
1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to mediate 1h, after material is agglomerating, is put into twin-screw and squeezes
Extruded moulding in machine, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasts 2 hours and is urged
Agent finished product, calcination temperature are 500 DEG C, and catalyst composition is listed in table 1, and 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 copper oxide
(CuO), 26.4 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 0.64 gram of potassium hydroxide (KOH), 10 grams of methyl
Cellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin dry-mixed 1h in kneader, then by 15 grams of nitric acid
It is added in powder with 100 grams of deionized waters, continues kneading 1h and be put into extruded moulding in double screw banded extruder after material is agglomerating,
It is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasts and obtains within 2 hours finished catalyst, roasting temperature
Degree is 500 DEG C, and catalyst composition is listed in table 1, and 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 copper oxide
(CuO), 48.4 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 6.9 grams of antimony oxide (Sb2O3), 3.7 grams of iron 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
Gram kaolin dry-mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powders, continue to mediate 1h, wait for
After material is agglomerating, it is put into extruded moulding in double screw banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the drawing that 1.5mm length is 5mm
Then western ring roasts and obtains within 2 hours finished catalyst, calcination temperature is 500 DEG C, and catalyst composition is listed in table 1, reaction examination knot
Fruit 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 copper oxide
(CuO), 30.3 grams of tungstic acid (WO3), 6.9 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 0.64 gram of hydrogen-oxygen
Change potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin are in kneader
Dry-mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to mediate 1h, after material is agglomerating, is put into double spiral shells
Extruded moulding in bar banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, is then roasted 2 hours
To finished catalyst, calcination temperature is 500 DEG C, and 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 copper oxide
(CuO), 25.6 grams of tungsten carbides (WC), 6.9 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 0.64 gram of hydroxide
Potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin do in kneader
Mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue kneading 1h and is put into twin-screw after material is agglomerating
Extruded moulding in banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasts 2 hours and obtains
Finished catalyst, calcination temperature are 500 DEG C, and 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 copper oxide
(CuO), 2.5 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 69.5 grams of antimony oxide (Sb2O3), 3.7 grams of iron 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
Gram kaolin dry-mixed 1h in kneader, then 15 grams of nitric acid and 100 grams of deionized waters are added in powders, continue to mediate 1h, wait for
After material is agglomerating, it is put into extruded moulding in double screw banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the drawing that 1.5mm length is 5mm
Then western ring roasts and obtains within 2 hours finished catalyst, calcination temperature is 500 DEG C, and catalyst composition is listed in table 1, reaction examination knot
Fruit 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 copper oxide
(CuO), 2.2 grams of tungstic acid (WO3), 69.5 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 0.64 gram of hydrogen-oxygen
Change potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin are in kneader
Dry-mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to mediate 1h, after material is agglomerating, is put into double spiral shells
Extruded moulding in bar banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, is then roasted 2 hours
To finished catalyst, calcination temperature is 500 DEG C, and 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 copper oxide
(CuO), 1.9 grams of tungsten carbides (WC), 69.5 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 0.64 gram of hydroxide
Potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin do in kneader
Mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue kneading 1h and is put into twin-screw after material is agglomerating
Extruded moulding in banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasts 2 hours and obtains
Finished catalyst, calcination temperature are 500 DEG C, and 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 copper oxide
(CuO), 127.3 grams of ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O), 1.4 grams of antimony oxide (Sb2O3) and 6.4 grams of hydroxides
Potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin do in kneader
Mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue kneading 1h and is put into twin-screw after material is agglomerating
Extruded moulding in banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasts 2 hours and obtains
Finished catalyst, calcination temperature are 500 DEG C, and 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 copper oxide
(CuO), 108.3 grams of tungstic acid (WO3), 1.4 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 6.4 grams of hydrogen-oxygens
Change potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin are in kneader
Dry-mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue to mediate 1h, after material is agglomerating, is put into double spiral shells
Extruded moulding in bar banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, is then roasted 2 hours
To finished catalyst, calcination temperature is 500 DEG C, and 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 copper oxide
(CuO), 91.5 grams of tungsten carbides (WC), 1.4 grams of antimony oxide (Sb2O3), 3.7 grams of iron oxide (Fe2O3) and 6.4 grams of hydroxides
Potassium (KOH), 10 grams of methylcellulose (weight average molecular weight 20000), 230 grams of carrier S iO2, 25 grams of kaolin do in kneader
Mixed 1h, then 15 grams of nitric acid and 100 grams of deionized waters are added in powder, continue kneading 1h and is put into twin-screw after material is agglomerating
Extruded moulding in banded extruder, it is 5mm to obtain outer diameter, and internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasts 2 hours and obtains
Finished catalyst, calcination temperature are 500 DEG C, and 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 acid | 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 acid | Mo12V3Cu1.0W0.1Sb5Fe0.5K0.1Og |
| Embodiment 6 | Tungsten carbide | Mo12V3Cu1.0W0.1Sb5Fe0.5K0.1Og |
| Embodiment 7 | Ammonium tungstate | Mo12V4Cu0.1W5Sb0.1K1Og |
| Embodiment 8 | Tungstic acid | Mo12V4Cu0.1W5Sb0.1K1Og |
| Embodiment 9 | Tungsten carbide | Mo12V4Cu0.1W5Sb0.1K1Og |
Table 2, comparative example and embodiment investigate result
Claims (12)
1. acrylic acid catalyst, including following components in terms of parts by weight：
A：40-80 parts be selected from SiO2、Al2O3、ZrO2Or TiO2At least one of carrier；Be loaded in thereon
B：20-60 parts of active component Mo12VaCubWcSbdYeZfOg；
Wherein Mo, V, Cu, W, Sb and O indicate molybdenum, vanadium, copper, tungsten, antimony and oxygen；Y be selected from Fe, Bi, Co, Ni, Ge, Ga,
At least one of Nb, Ce, La, Zr, Sr element；Z is selected from least one of alkali or alkaline earth metal element；a、b、c、
D, e, f and g indicate the atomic ratio of each element, the value range that the atomic ratio based on Mo elements is 12, a is 0.5~
The value range that the value range that 4.0, b value range is 0.1~5.0, c is 0.01~5.0, d is taking for 0.01~5.0, e
The value ranging from value range of 0~5.0, f is the number that 0~1.0, g is the required oxygen atom for meeting the total chemical valence of other elements
Mesh；
The preparation method of the catalyst, includes the following steps：By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3、Cu
Compound, the compound of the compound of Y and Z and carrier mixing, molding, dry, roasting obtain the catalyst；Wherein,
The compound of tungsten includes tungsten carbide.
2. catalyst according to claim 1, which is characterized in that the compound of tungsten is tungsten carbide.
3. catalyst according to claim 1, which is characterized in that the compound of tungsten further includes ammonium tungstate, ammonium metatungstate, secondary
At least one of ammonium tungstate and tungstic acid.
4. the preparation method of any catalyst, includes the following steps in claim 1-3：
By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of Cu, the compound of Y and Z compound and carrier
Mixing, molding, dry, roasting obtain the catalyst.
5. preparation method according to claim 4, it is characterised in that the molding uses extrusion molding, the preparation side
Method specifically includes：By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of Cu, the compound of Y and Z chemical combination
Object, carrier, binder, pore creating material, suitable deionized water and nitric acid are mediated, extrusion molding.
6. preparation method according to claim 4 or 5, it is characterised in that the compound of Cu is sub- selected from copper oxide, oxidation
At least one of copper and copper nitrate.
7. preparation method according to claim 4 or 5, it is characterised in that the compound of Y is its oxide and/or nitric acid
Salt.
8. preparation method according to claim 4 or 5, it is characterised in that wherein the compound of Z is hydroxide.
9. preparation method according to claim 5, it is characterised in that wherein pore creating material is methylcellulose or PEG.
10. preparation method according to claim 9, it is characterised in that the weight average molecular weight of wherein pore creating material be 4000 to
150000。
11. preparation method according to claim 5, it is characterised in that wherein it is molten to be selected from Ludox, Aluminum sol, titanium for binder
At least one of glue, montmorillonite and kaolin.
12. synthesis of conjugated carboxylic alkeneacid is wanted using the material including methacrylaldehyde, air and water vapour as reaction raw materials in such as right
It asks to react in the presence of any catalyst in 1-3 and generates acrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493137.XA CN106423186B (en) | 2015-08-12 | 2015-08-12 | Acrylic acid catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493137.XA CN106423186B (en) | 2015-08-12 | 2015-08-12 | Acrylic acid catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423186A CN106423186A (en) | 2017-02-22 |
| CN106423186B true CN106423186B (en) | 2018-07-17 |
Family
ID=58093473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510493137.XA Active CN106423186B (en) | 2015-08-12 | 2015-08-12 | Acrylic acid catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423186B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013167405A1 (en) * | 2012-05-10 | 2013-11-14 | Basf Se | Process for the heterogeneously catalysed gas-phase partial oxidation of (meth)acrolein to (meth)acrylic acid |
| CN103521235A (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 |
| CN103877987A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid and preparation method thereof |
| CN104226328A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrylic acid, preparation method thereof and synthetic method of acrylic acid |
| CN104437581A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method of catalyst |
| 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 |
-
2015
- 2015-08-12 CN CN201510493137.XA patent/CN106423186B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013167405A1 (en) * | 2012-05-10 | 2013-11-14 | Basf Se | Process for the heterogeneously catalysed gas-phase partial oxidation of (meth)acrolein to (meth)acrylic acid |
| CN103521235A (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 |
| CN103877987A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid and preparation method thereof |
| CN104226328A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrylic acid, preparation method thereof and synthetic method of acrylic acid |
| CN104437581A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and preparation method of catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423186A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106423186B (en) | Acrylic acid catalyst and preparation method thereof | |
| US8481790B2 (en) | Catalyst for producing unsaturated aldehyde by oxidation of lower olefin at high space velocity | |
| EP2832718B1 (en) | Process for producing acrylic acid using fixed-bed multitubular reactor | |
| US7638458B2 (en) | Complex metal oxide catalyst with high (meth) acrylic acid selectivity | |
| CN104437581B (en) | Catalyst for acrylic acid synthesis and preparation method of catalyst | |
| WO2008013376A1 (en) | Multi-metal oxide catalyst and method for producing (meth)acrylic acid by using the same | |
| CN105664961B (en) | Acrylic acid catalyst | |
| EP1350566B1 (en) | Process for the preparation of unsaturated aldehydes and/or carboxylic acids by gas phase oxidation using a Mo-Bi-Fe based catalyst | |
| EP1503856B1 (en) | Method for preparing a catalyst for partial oxidation of propylene | |
| CN106423188B (en) | Acrylic acid catalyst and preparation method | |
| CN114669306B (en) | Catalyst for preparing (methyl) acrylonitrile by (methyl) acrolein ammoxidation, and preparation method and application thereof | |
| CN105080558B (en) | Acrylic acid catalyst and preparation method thereof | |
| CN107282059B (en) | Catalyst for producing acrylic acid | |
| CN107282069B (en) | catalyst for oxidation of acrolein to acrylic acid | |
| CN104923245B (en) | Acrylic acid catalyst and acrylic acid synthetic method | |
| CN103157484B (en) | Catalysts and its preparation method | |
| CN111068649A (en) | Catalyst for preparing acrylic acid and method for synthesizing acrylic acid from acrolein | |
| CN101462062B (en) | Catalyst and method for producing methylacrolein by fractional catalytic oxidation | |
| JP5451271B2 (en) | Method for producing unsaturated aldehyde or unsaturated carboxylic acid | |
| CN106881128B (en) | Heteropolyacid salt catalyst, preparation method and application thereof | |
| CN105664959B (en) | Unsaturated acids catalyst and preparation method thereof | |
| CN104923247B (en) | By the catalyst of methacrylaldehyde acrylic acid synthesizing | |
| CN110280256A (en) | A kind of catalyst and preparation method thereof being used to prepare methacrylaldehyde | |
| CN111068653A (en) | Catalyst for synthesizing acrylic acid from acrolein and application thereof | |
| CN104649893B (en) | A kind of method preparing unsaturated acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |