CN106423188B - Acrylic acid catalyst and preparation method - Google Patents
Acrylic acid catalyst and preparation method Download PDFInfo
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Abstract
The present invention relates to the catalyst synthesized for acrylic acid, the preparation method of catalyst and acrylic acid synthetic method, mainly solve the problems, such as that acrylic acid yield is low in the prior art.The present invention is by using 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；It is loaded in B thereon with it：20 60 parts of active component Mo12VaCubWcSbdYeZfOg；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 acrylic acid yield 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 of existing acrylic acid yield, provides the catalyst synthesized for acrylic acid.The catalyst is closed for acrolein oxidation
It is reacted at acrylic acid, has the characteristics that 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 tungsten
At least one of carbide；The carbide of more preferable tungsten, or more preferably include the carbide of tungsten, further include ammonium tungstate,
At least one of ammonium metatungstate, ammonium paratungstate and tungstic acid.The carbide of tungsten can be tungsten carbide (molecular formula WC) and
Ditungsten carbide (molecular formula W2C at least one), more preferably includes tungsten carbide and ditungsten carbide simultaneously, and the two is improving propylene
There is synergistic effect in terms of sour yield.Such as, but not limited to improve acrylic acid yield synergistic effect in terms of tungsten carbide in
The molar ratio of tungsten carbide and ditungsten carbide is 1:2~3:1, preferably 1:2~2:1, most preferably 1:1~2:1.And when tungsten
The molar ratio of tungsten carbide and ditungsten carbide is 1 in carbide:2~2:1, further 1:1~2:When 1, tungsten carbide and carbonization two
Tungsten has synergistic effect in terms of improving acrylic acid selectivity.
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 active component in the present invention, W and Sb have synergistic effect, when W is with tungsten especially in the preparation of catalyst
When the form of carbide 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 is 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, after 1000 hours, acrolein conversion rate can up to 99.3%, product propylene acid yield
Up to 90.2%, 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：240~350 DEG C
Reaction time：2000 hours
Volume feed：Methacrylaldehyde:Air:Water vapour=1:(2.5~5):(1~3)
Raw material volume air speed：1000~1600 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), 24.8 grams of ditungsten carbide (W2C), 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 5
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of copper oxide
(CuO), 19.2 grams of tungsten carbides (WC), 6.2 grams of ditungsten carbide (W2C), 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 6
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of copper oxide
(CuO), 17.1 grams of tungsten carbides (WC), 8.3 grams of ditungsten carbide (W2C), 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 7
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of copper oxide
(CuO), 12.8 grams of tungsten carbides (WC), 12.4 grams of ditungsten carbide (W2C), 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 8
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of copper oxide
(CuO), 8.5 grams of tungsten carbides (WC), 16.6 grams of ditungsten carbide (W2C), 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 9
By 200 grams of ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 5.9 grams of copper oxide
(CuO), 6.4 grams of tungsten carbides (WC), 18.6 grams of ditungsten carbide (W2C), 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 10
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 11
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 (molar ratio) | 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 | WC | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 4 | W2C | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 5 | WC+W2C(3:1) | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 6 | WC+W2C(2:1) | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 7 | WC+W2C(1:1) | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 8 | WC+W2C(1:2) | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 9 | WC+W2C(1:3) | Mo12V3Cu1.0W1.4Sb0.5Fe0.5K0.1Og |
| Embodiment 10 | WC | Mo12V3Cu1.0W0.1Sb5Fe0.5K0.1Og |
| Embodiment 11 | WC | Mo12V4Cu0.1W5Sb0.1K1Og |
Table 2, comparative example and embodiment investigate result
Claims (17)
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 the carbide of tungsten.
2. catalyst according to claim 1, which is characterized in that the compound of tungsten is the carbide of tungsten.
3. catalyst according to claim 1 or 2, which is characterized in that the carbide of tungsten includes tungsten carbide and ditungsten carbide
At least one.
4. catalyst according to claim 1 or 2, which is characterized in that the carbide of tungsten includes tungsten carbide and ditungsten carbide.
5. catalyst according to claim 4, which is characterized in that the molar ratio of tungsten carbide and ditungsten carbide is 1：2~3：
1。
6. catalyst according to claim 4, which is characterized in that the molar ratio of tungsten carbide and ditungsten carbide is 1：2~2：
1。
7. catalyst according to claim 4, which is characterized in that the molar ratio of tungsten carbide and ditungsten carbide is 1：1~2：
1。
8. 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.
9. the preparation method of any catalyst, includes the following steps in claim 1-8：
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.
10. preparation method according to claim 9, it is characterised in that the molding uses extrusion molding, the preparation
Method specifically includes：By ammonium heptamolybdate, ammonium metavanadate, the compound of tungsten, Sb2O3, the compound of Cu, the compound of Y and Z change
Object, carrier, binder, pore creating material, suitable deionized water and nitric acid are closed, is mediated, extrusion molding.
11. preparation method according to claim 9 or 10, it is characterised in that the compound of Cu is selected from copper oxide, oxidation
At least one of cuprous and copper nitrate.
12. preparation method according to claim 9 or 10, it is characterised in that the compound of Y is its oxide and/or nitric acid
Salt.
13. preparation method according to claim 9 or 10, it is characterised in that wherein the compound of Z is hydroxide.
14. preparation method according to claim 10, it is characterised in that wherein pore creating material is methylcellulose or PEG.
15. preparation method according to claim 14, it is characterised in that the weight average molecular weight of wherein pore creating material be 4000 to
150000。
16. preparation method according to claim 10, it is characterised in that wherein binder is selected from Ludox, Aluminum sol, titanium
At least one of colloidal sol, montmorillonite and kaolin.
17. 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 1-8 and generates acrylic acid.
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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 |
| CN106423186A (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 CN201510493368.0A patent/CN106423188B/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 |
| CN106423186A (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 |
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