CN104801351B - A kind of preparation method of coated catalysts and the coated catalysts prepared using this method - Google Patents
A kind of preparation method of coated catalysts and the coated catalysts prepared using this method Download PDFInfo
- Publication number
- CN104801351B CN104801351B CN201510149553.8A CN201510149553A CN104801351B CN 104801351 B CN104801351 B CN 104801351B CN 201510149553 A CN201510149553 A CN 201510149553A CN 104801351 B CN104801351 B CN 104801351B
- Authority
- CN
- China
- Prior art keywords
- coated catalysts
- outer layer
- pore volume
- active component
- polyvinylpyrrolidone
- 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
Abstract
The coated catalysts prepared the present invention relates to a kind of preparation method of coated catalysts and using this method.The coated catalysts contain the outer layer active component using phosphorus, molybdenum, vanadium, copper and arsenic as the heteropoly acid of indispensable element of sphere inert carrier and polyvinylpyrrolidone load.The ethanol solution of the scattered slurry and polyvinylpyrrolidone in ethanol of heteropolyacid catalyst powder is sprayed on sphere inert carrier simultaneously during catalyst preparation, coated catalysts are obtained.The hole of specific distribution is formd after the coated catalysts are fired, and with very high intensity, for being catalyzed during (methyl) methacrylaldehyde gaseous oxidation system (methyl) acrylic acid with very high conversion ratio and selectivity.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of coated catalysts and preparation method thereof.
Background technology
MAL gaseous oxidation methacrylic acid is production methyl-prop by source three-step approach of the tert-butyl alcohol/isobutene
One of committed step of e pioic acid methyl ester (MMA), its core is a kind of heteropoly acid structure catalyst using phosphomolybdic acid as representative.It is miscellaneous many
Acid catalyst makes its industry amplification turn into a very big challenge because of its relatively low specific surface area and its characteristics of be difficult to shaping.
Patent document JP11-226411 is proposed to add purified starch in shaping of catalyst and these shallow lakes is removed in roasting
Powder improves the pore volume of catalyst；Patent document CN101980781B proposes to add two kinds of different organic polymers afterwards before the forming
Binding agent improves the methacrylic acid yield of catalyst；Patent document JP08-010621 is mentioned containing catalyst component
The particle diameter of the dried object of mixed solution or slurry is adjusted to the particle in the range of 1~250 μm and then the method being molded to improve
The conversion ratio of catalyst.The above patented method can improve catalyst exposure in gas phase catalytic reaction to a certain extent
Active sites, but still cause substantial amounts of heteropoly acid to fail to be effectively utilized by extrusion or the method for compression molding.
Patent document CN01815995.8 mentions production coated catalysts to improve the effective rate of utilization of catalytic component, but
The catalyst for hardly resulting in high mechanical strength is mentioned simultaneously, because coating is easily peeled off, and the body construction of active catalytic species useful
Directly determine the activity of coated catalysts.
Therefore, it should consider when preparing heteropoly acid preformed catalyst, both improve the body activity of heteropoly acid, and protect
The active sites of heteropoly acid is largely exposed while card catalyst strength, improve the utilization rate of heteropoly acid, this is huge challenge.
The content of the invention
An object of the present invention is：The preparation method of above-mentioned coated catalysts is provided, the preparation method has technique
Simply, the characteristics of catalyst preparation favorable reproducibility.
Another object of the present invention is to：A kind of coated catalysts are provided, this catalyst is miscellaneous more with what is significantly improved
Acid-utilising rate, catalyst strength and catalyst activity.
It is yet a further object of the present invention to provide the purposes of above-mentioned coated catalysts, the catalyst is used for (methyl) propylene
Aldehyde catalytic gas phase oxidation has excellent conversion ratio and selectivity when preparing (methyl) acrylic acid.
To achieve the above objectives, the present invention is adopted the following technical scheme that：
A kind of preparation method of coated catalysts, comprises the following steps：
(1) by containing molybdenum, phosphorus, vanadium, copper, arsenic element compound, and selected from containing tellurium, boron, antimony, germanium, tungsten, uranium, bismuth, iron,
The compound of one or both of cobalt, ruthenium and nickel or multiple element is placed in water, and dissolving obtains solution；
(2) solution in drying steps (1), obtains heteropolyacid catalyst powder；
(3) the heteropolyacid catalyst powder for obtaining step (2) is scattered in ethanol, obtains heteropolyacid catalyst slurry；
(4) heteropolyacid catalyst slurry, the ethanol solution of polyvinylpyrrolidone obtained step (3) is sprayed to parallel
On sphere inert carrier, coated catalysts are obtained；
(5) coated catalysts obtained in calcination stepses (4).
Each element compound can use its oxide, nitre without specifically limited used in step (1) of the present invention
Hydrochlorate, acetate, phosphate, chloride and oxyacid etc., preferably molybdenum trioxide, vanadic anhydride, uranium dioxide, titanium dioxide
The oxides such as tellurium, antimony oxide, iron oxide, the salt, phosphoric acid, arsenic acid, boron such as ferric nitrate, copper nitrate, copper acetate, cupric phosphate
The acids such as acid, telluric acid, phosphotungstic acid.The compound of respective element can be used alone, can also two or more mixing make
With as long as ensuring that step (1) can form transparent settled solution when using.
The temperature of operation is dissolved in step (1) of the present invention for 80~100 DEG C, preferably 90~100 DEG C, because higher
Temperature can accelerate the rate of dissolution of added compound, in the temperature range, using atmospheric pressure reflux or hydro-thermal method,
It is not particularly limited.
The consumption of water in step (1) of the present invention is without particular limitation, as long as can reach the compound of addition
The degree of fully dissolved, can be selected according to the need for follow-up drying means.Preferably, water and institute in molybdate compound
The mol ratio of the molybdenum element contained is 20~100：1.
The particle size range of heteropolyacid catalyst powder is controlled at 0.2~10 μm in step (2) of the present invention, is preferably existed
0.5~6 μm.As the drying means of step (2), pneumatic spray drying, centrifugal spray drying, evaporation drying can be used,
Preferably pneumatic spray drying method of the invention, inlet temperature is 100~250 DEG C, preferably 120~200 DEG C during spray drying；Outlet
Temperature is 60~150 DEG C, preferably 70~110 DEG C；The speed that compressed air sprays from nozzle is 300~3000m/s, preferably 500
~2000m/s.
In step (3) of the present invention, to make scattered its graininess rear in ethanol of heteropolyacid catalyst powder still obtain
Retain, water content≤10wt% in feed ethanol, preferably water content≤5wt% should be controlled, because if the water content in ethanol
It is too high, then be easily caused heteropolyacid catalyst powder occur reunite, particle size growth and occur activity reduction phenomenon.
The consumption of ethanol is without particular limitation in step (3) of the present invention, as long as can make heteropolyacid catalyst powder point
Dissipate uniform and good fluidity.The consumption of ethanol determines the viscosity of heteropolyacid catalyst slurry, in the present invention, heteropoly acid
The viscosity of catalyst pulp is controlled in 5~500mPas, preferably 50~300mPas.When viscosity is less than 5mPas, rear
The good coated catalysts of intensity are difficult to obtain in continuous spraying operation, and too low viscosity can make the ethanol in coating operation environment
Excessive concentration and explosion danger may be triggered；And viscosity be higher than 500mPas when, heteropolyacid catalyst powder disperses bad, and
Shower nozzle is easily blocked in follow-up spraying operation.
In step (4) of the present invention, spray coating operations are performed, by heteropolyacid catalyst slurry, polyvinylpyrrolidone
Ethanol solution simultaneously spray on sphere inert carrier.Spraying operation can use two-fluid or single fluid spray pattern, preferably
Two-fluid spray mode, because its spraying granule is thinner, be evenly more beneficial for heteropolyacid catalyst and polyvinylpyrrolidine
Ketone it is well mixed.
The preferred coating pan of spraying equipment of step (4) of the present invention.
The inventors discovered that heteropolyacid catalyst slurry can solidify when running into the ethanol solution of polyvinylpyrrolidone
Phenomenon, and the speed solidified is related to both proportioning, viscosity and temperature.In spraying operation, both solidification rates are not
Preferably cross slow, otherwise heteropolyacid catalyst and polyvinylpyrrolidone are easily attached on the wall of spraying equipment and make coated catalysts
Load capacity reduction；Solidification rate is also unsuitable too fast, otherwise can make heteropolyacid catalyst and polyvinylpyrrolidone and porcelain ball
Interaction weakens, and the phenomenon that surface active composition comes off easily occurs after roasting.
The viscosity of the ethanol solution of polyvinylpyrrolidone is controlled in 5~500mPas, preferably 50~300mPas；
Simultaneously in view of the dissolubility and follow-up baking operation of polyvinylpyrrolidone, the molecular weight of polyvinylpyrrolidone is 4
Ten thousand~1,300,000, preferably 100,000~1,000,000.The mass ratio of heteropoly acid and polyvinylpyrrolidone is 2~10：1, preferably 4~8:1,
Too high or too low polyvinyl pyrrolidone content is harmful to the structure and intensity of coated catalysts.
Spraying temperature is 40~80 DEG C in step (4) of the present invention, and preferably 50~70 DEG C, too high or too low temperature is equal
Solidification to heteropolyacid catalyst and polyvinylpyrrolidone is unfavorable.
Sphere inert carrier of the present invention, its composition is mainly the elements such as Al, Si, K, Na, Ca, Mg, Ti and Fe
Oxide, such as natural pelelith and artificial Ceramic Balls, a diameter of 3~5mm of carrier, preferably 3.5~4.5mm；Inhale
Water rate is 5~50wt%, preferably 10~20wt%.In the present invention, the mass ratio of sphere inert carrier and outer layer active component is
0.5~2.0：1, preferably 0.6~1.5：1.
In the step (4) of the present invention, in order to improve the solidification effect of heteropolyacid catalyst and polyvinylpyrrolidone, also
Can use shaping assistant, such as ceramic fibre, carbon fiber, glass fibre simultaneously, the consumptions of these shaping assistants for 5~
20wt%, preferably 8~16wt%, in terms of the quality of heteropolyacid catalyst powder.For ceramic fibre, its diameter can be 1~50 μ
M, preferably 2~20 μm, draw ratio is 10~50, preferably 20~50.To make shaping assistant and heteropolyacid catalyst and polyethylene pyrrole
Pyrrolidone is uniformly dispersed, preferably when the ethanol solution of heteropolyacid catalyst slurry, polyvinylpyrrolidone is sprayed parallel, simultaneously
It is added in spraying equipment such as coating pan.
The method of roasting of step (5) floating coat catalyst of the present invention is not particularly limited, and can be used in the art
Any conventional method of roasting known, it is preferred to use the baking inphases method comprised the following steps is calcined：The coated catalysts
2~10h (first paragraph) is stopped under 50~90 DEG C of air atmospheres, 0.5~3h is stopped under 330~400 DEG C of non-oxidizing atmospheres
(second segment), stops 1~10h (the 3rd section) under 250~330 DEG C of oxidizing atmospheres；It is preferred that the coated catalysts 55~
5~10h is stopped under 80 DEG C of air atmospheres, 1~2h is stopped under 350~380 DEG C of non-oxidizing atmospheres, in 280~320 DEG C of oxidations
Property atmosphere under stop 2~5h.Roasting device used has no particular limits, and can use rotary kiln, car-bottom kiln and mesh-belt kiln
Deng, but for the abrasions of coated catalysts and roasting uniformity, preferred mesh-belt kiln.
First paragraph is mainly used in removing ethanol in roasting process of the present invention；Second segment is mainly used in strengthening polyethylene pyrrole
The interaction of pyrrolidone and heteropoly acid, the polyvinylpyrrolidone for the part that makes to be in contact with heteropoly acid is decomposed, but is not destroyed
The body construction of heteropoly acid；3rd section is mainly used in oxidation Decomposition of the decomposition temperature compared with lower part in polyvinylpyrrolidone.
Non-oxidizing atmosphere of the present invention refers to the gas substantially free of oxidizing substance (such as oxygen), such as nitrogen
Gas, helium, argon gas, carbon dioxide etc., but optional can contain water, the particularly preferred nitrogen of non-oxidizing atmosphere.Institute of the present invention
State oxidizing atmosphere and refer to gas or pure oxygen containing oxidizing substance such as oxygen, the preferably volumetric concentration of oxygen is 10~30%
Gas, particularly preferred air, optional can contain water.
Wherein polyvinylpyrrolidone mass loss about 5~20wt% before and after roasting, loss amount depends on polyethylene pyrrole
The molecular weight and sintering temperature of pyrrolidone, molecular weight is lower or sintering temperature is too high, and its mass loss amount is bigger.
By the second segment in method of roasting of the present invention and the 3rd section of program, decomposition temperature is relatively low in polyvinylpyrrolidone
Decomposed pore-creating, the polyvinylpyrrolidone of the part that is in contact with heteropoly acid decomposes pore-creating, and these different ducts are communicated
It is connected so that the heteropoly acid particle in outer layer active component largely exposes, and not only improves the contact with reactant, is conducive to again anti-
The diffusion of product is answered, the general structure of coated catalysts is maintained.To the outer layer active component of the coated catalysts of the present invention
Mercury injection is carried out, aperture is that pore volume contained by 100~2000nm holes accounts for the 60~90% of the outer layer active component total pore volume, excellent
70~85% are selected, wherein aperture is that pore volume contained by 100~500nm holes accounts for the 20~50% of the outer layer active component total pore volume,
It is preferred that 30~45%, aperture is mainly derived from the polyvinylpyrrolidone for the part that is in contact with heteropoly acid for 100~500nm hole
Decompose made hole.
Coated catalysts of the present invention include the outer of sphere inert carrier and polyvinylpyrrolidone carried heteropoly acid
Layer active component, the formula of heteropoly acid is：Mo12PaVbCucAsdXeOf·nH2O, wherein, Mo is molybdenum, and P is phosphorus, and V is vanadium, and Cu is
Copper, As is arsenic, and O is oxygen；X be selected from Te (tellurium), B (boron), Sb (antimony), Ge (germanium), W (tungsten), U (uranium), Bi (bismuth), Fe (iron),
One or two or more kinds of elements in Co (cobalt), Ru (ruthenium) and Ni (nickel), one kind or two preferably in Te, B, Sb, W, U, Bi and Fe
Plant or multiple element；The atomic ratio of various elements is：A=0.5~3, preferably a=1~2；B=0.1~2, preferably b=0.2
~1；C=0.01~1, preferably c=0.05~0.5；D=0.01~2, preferably d=0.05~1；E=0~1, preferably e=0.01
~0.5；F is the atom ratio of oxygen required for meeting each element chemical valence.
According to coated catalysts preparation method provided by the present invention, heteropolyacid catalyst powder is equal by polyvinylpyrrolidone
Solidifying, by controlling calcination procedure, the thin layer polyvinylpyrrolidone contacted with heteropoly acid is selectively removed in roasting, outside
Layer active component forms a large amount of pore structures and heteropoly acid active sites is largely exposed, therefore improves the utilization rate of heteropoly acid；
Remained in additionally, due to most of polyvinylpyrrolidone in catalyst structure, and spraying operation causes outer layer active component knot
Structure is fine and close, therefore coated catalysts have very high intensity.
Coated catalysts of the present invention can be applied to (methyl) methacrylaldehyde gaseous oxidation synthesis (methyl) acrylic acid.It is former
After expecting that the dilute gas mixture and vapor of (methyl) methacrylaldehyde, air or molecule-containing keto are preheated, it is passed through equipped with catalyst
Fixed-bed tube reactor in carry out reaction synthesis (methyl) acrylic acid.In the dilute gas mixture of molecule-containing keto used,
Molecular oxygen may come from pure oxygen, oxygen-enriched or air, and diluent gas can be N2, CO2With two kinds or many of one kind in vapor
Kind.
Raw material, can be with addition to dilute gas mixture and vapor containing (methyl) methacrylaldehyde, air or molecule-containing keto
Containing a small amount of acetaldehyde, methacrylaldehyde, acetone, acrylic acid and acetic acid etc., but preferably its content is as few as possible.It is excellent for raw material sources
The gas that choosing is obtained from isobutene or the tert-butyl alcohol after the oxidation of molybdenum bismuth metal composite oxide, wherein isobutene or the tert-butyl alcohol
Conversion ratio have to be larger than 99%, and otherwise therefore coated catalysts rapid deactivation phenomenon can occur.
Coated catalysts of the present invention are used for the reaction condition that (methyl) acrolein oxidation prepares (methyl) acrylic acid
For：250~360 DEG C of reaction temperature, preferably 280~340 DEG C；Reaction pressure is 0.01~0.15MPa of absolute pressure, preferably often
Pressure；The air speed of reaction raw materials gaseous mixture is 400~4000L/Lcat/h, preferably 800~2000L/Lcat/h；(first in gaseous mixture
Base) methacrylaldehyde molar concentration be 1~15%, preferably 3~8%；O2Mol ratio with (methyl) methacrylaldehyde is 0.5~6：1, it is excellent
Select 1~4：1；The mol ratio 1~15 of vapor and (methyl) methacrylaldehyde：1, preferably 2~10：1.
There is very high anti-wear performance, its abrasion index≤2% using coated catalysts obtained by the present invention；For (first
Base) methacrylaldehyde is when preparing (methyl) propylene acid reaction, and (methyl) acrolein conversion rate and (methyl) acrylic acid selectivity can be with
Stabilization is more than 80%, the high value in existing patent level.After catalyst stabilization operation 2000h, (methyl) methacrylaldehyde
Conversion ratio and (methyl) acrylic acid selectivity kept stable.
Brief description of the drawings
Fig. 1 is the pore size distribution curve of outer layer active component in embodiment 1, and wherein abscissa represents aperture, and unit is micro-
Rice (μm), ordinate represents the pore volume (pore volume) under unit mass catalyst contained by the aperture, and unit is mL/g.
Embodiment
Catalyst provided by the present invention and preparation method thereof, but the present invention are further described by the following examples
Therefore it is not any way limited.
The rate of wear test reference standard of catalyst：HG/T 2976-1999 (chemical fertilizer catalyst rate of wear measure), test
Instrument is KM-5A particle abrasion tests instrument (production of Dalian Peng Hui Science and Technology Development Co., Ltd.s)；The particle size of catalyst powder
Observation calculating is carried out by SEM (Hitachi, model S-4800)；The Estimation of Pore Size of catalyst is using pressure mercury
Instrument is tested (U.S. health tower PoreMaster), and the heteropoly acid outer layer active component of coated catalysts is peeled off into laggard during measure
Row test.
The oxidation of aldehydes conversion ratio for preparing methacrylic acid of metering system and selectivity are defined as follows：
MAL conversion ratio=(MAL of the amount of the material of the MAL of consumption/raw material supply
The amount of material) × 100%
Methacrylic acid selectivity=(the material of the MAL of amount/consumption of the material of the methacrylic acid of generation
Amount) × 100%
Embodiment 1
(1) preparation of catalyst
490.50g molybdenum trioxides (MoO is added into 4000g deionized waters3), 23.44g vanadic anhydrides (V2O5),
Phosphoric acid (the H of 41.08g 85wt% mass concentrations3PO4), 24.71g 80wt% arsenic acid (H3AsO4), 0.88g boric acid
(H3BO3), it is stirred at reflux at 98 DEG C after 1h and adds 2.40g cupric phosphates (Cu3(PO4)2·3H2O), 0.69g cuprous oxide
(Cu2O), glaucous settled solution is obtained after continuing return stirring 10h, the solution is carried out on air flow type spray drying machine
Spray drying, increasing atomizing gas pressure (absolute pressure) is 0.35MPa, and the speed that compressed air sprays from nozzle is 1500m/s, spray
The inlet temperature of mist drying machine is 140~150 DEG C, and outlet temperature is 70~80 DEG C, and the average grain diameter for obtaining catalyst powder is
2.5μm。
Take 200g catalyst powders to be dispersed in the ethanol that 100g water contents are 5wt% and obtain slurry A (viscosity 100mPa
S), take 40g polyvinylpyrrolidones (mean molecule quantity about 100,000) to be dissolved in the ethanol that 40g water contents are 95wt% and obtain molten
Liquid B (viscosity 200mPas), by the slurry A 200g pelelith (diameters for being sprayed to progressive rolling movement in coating pan parallel with solution B
3.5mm, water absorption rate 20wt%) on, the parallel addition 30g ceramic fibres during roller coating, it is 50 DEG C, spin to be coated pot temperature
Process takes 20min altogether, obtains coated catalysts.
Gained coated catalysts are calcined, stops under 5h, 360 DEG C of nitrogen atmospheres and stops under 75 DEG C of air atmospheres
3h is stopped under 1h, 320 DEG C of air atmospheres.The composition for finally giving heteropoly acid is：Mo12P1.3V0.9Cu0.1As0.5B0.05Ox.Coating
The abrasion index test result of catalyst is 1.2%；Aperture pore volume contained by 100~2000nm hole is accounted in outer layer active component
The 85% of outer layer active component total pore volume, aperture pore volume contained by 100~500nm hole accounts for outer layer active component total pore volume
35%, as shown in Figure 1.
(2) oxidation reaction of MAL
The 160mL coated catalysts therefore obtained are loaded in the fixed bed reactors that internal diameter is 2.5mm, with mol ratio
It is raw material for MAL/oxygen/water/nitrogen=1/1.8/4/18.0, air speed is 1100h-1, salt temperature is 300 DEG C, pressure
First is obtained after the oxidation reaction of MAL, successive reaction 50h are carried out under the reaction condition that power (absolute pressure) is 0.13MPa
Base acrolein conversion rate is 84.4%, and Methacrylic acid selectivity is 85.2%.Under this condition after successive reaction 2000h, obtain
It is 84.2% to MAL conversion ratio, Methacrylic acid selectivity is 85.6%.
Embodiment 2
The addition 490.50g molybdenum trioxides into 4000g deionized waters, 20.84g vanadic anhydrides, 0.66g tungstic acids,
The phosphoric acid of the mass concentrations of 43.57g 85%, 29.65g 80wt% arsenic acid is stirred at reflux addition 3.60g phosphorus after 1h at 98 DEG C
Sour copper, 1.04g cuprous oxide and 3.35g cupric oxide, obtain glaucous solution after continuing return stirring 10h, the solution are existed
It is spray-dried on air flow type spray drying machine, increasing atomizing gas pressure is 0.25MPa, the speed that compressed air sprays from nozzle
For 1000m/s, the inlet temperature of spray dryer is 140~150 DEG C, and outlet temperature is 70~80 DEG C, obtains catalyst powder
Average grain diameter be 3.2 μm.
Take 200g catalyst powders to be dispersed in 120g absolute ethyl alcohols and obtain slurry A (viscosity 90mPas), take the poly- second of 35g
Alkene pyrrolidone (mean molecule quantity about 100,000), which is dissolved in 40g absolute ethyl alcohols, obtains solution B (viscosity 150mPas), will starch
Expect that A is parallel with solution B to be sprayed on the 250g peleliths of progressive rolling movement in coating pan (diameter 3.8mm, water absorption rate 15wt%),
Parallel addition 30g ceramic fibres during roller coating, it is 55 DEG C to be coated pot temperature, and spin process takes 25min altogether, obtains coating
Catalyst.
Gained coated catalysts are calcined, specifically stopped under stop 5h, 380 DEG C of nitrogen atmospheres under 75 DEG C of air atmospheres
Stay and stop 3h under 1h, 315 DEG C of air atmospheres.The composition for finally giving heteropoly acid is：Mo12P1.4V0.8Cu0.3As0.6W0.01Ox.Apply
The abrasion index test result of layer catalyst is 0.9%；In heteropoly acid outer layer active component aperture for 100~2000nm hole institute
The 80% of outer layer active component total pore volume is accounted for containing pore volume, it is total that aperture pore volume contained by 100~500nm hole accounts for outer layer active component
The 45% of pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 85.7%, and Methacrylic acid selectivity is 84.5%.Under this condition after successive reaction 2000h, first is obtained
Base acrolein conversion rate is 84.6%, and Methacrylic acid selectivity is 84.9%.
Comparative example 1
It is other to be prepared as described in Example 1 in addition to without using polyvinylpyrrolidone, obtain coating catalysis
Agent, through analysis, the composition of heteropoly acid is：Mo12P1.3V0.9Cu0.1As0.50B0.05Ox.The abrasion index test result of coated catalysts
For 5.9%；Aperture accounts for the 10% of total pore volume for the pore volume contained by 100~2000nm hole in outer layer active component, and aperture is 100
Pore volume contained by~500nm hole accounts for the 3.2% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 50.4%, and Methacrylic acid selectivity is 64.2%.
Comparative example 2
In addition to the ethanol in embodiment 1 to be changed to the ethanol that water content is 20wt%, other sides for pressing embodiment 1
Prepared by method, obtain coated catalysts, and through analysis, the composition of heteropoly acid is：Mo12P1.3V0.9Cu0.1As0.50B0.05Ox.Coating
The abrasion index test result of catalyst is 1.0%；Aperture is contained by 100~2000nm hole in heteropoly acid outer layer active component
Pore volume account for the 80% of total pore volume, aperture accounts for outer layer active component total pore volume for the pore volume contained by 100~500nm hole
41%.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 40.2%, and Methacrylic acid selectivity is 84.5%.
Comparative example 3
Catalyst is prepared according to embodiment 2, difference is that the quality of polyvinylpyrrolidone is changed to 18 grams (accordingly
Obtained solution B viscosity is reduced to 50mPas), it is other to be prepared as described in Example 2, coated catalysts are obtained, are passed through
Analysis, the composition of heteropoly acid is described as：Mo12P1.4V0.8Cu0.3As0.60W0.01Ox.The abrasion index test result of coated catalysts
For 6.9%；Aperture accounts for the 63.5% of total pore volume for the pore volume contained by 100~2000nm hole in heteropoly acid outer layer active component,
Aperture accounts for the 45% of outer layer active component total pore volume for the pore volume contained by 100~500nm hole.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 2
Olefine aldehydr conversion ratio is 70.7%, and Methacrylic acid selectivity is 74.1%.
Comparative example 4
Catalyst is prepared according to embodiment 2, difference is to change pneumatic spray drying into centrifugal spray drying, sprayed
The atomizer rotating speed of mist drying machine is 10600 revs/min, and inlet temperature is 140~150 DEG C, and outlet temperature is 70~80 DEG C, is obtained
Average grain diameter to catalyst powder is 50.1 μm, and the composition of fired rear gained coated catalysts is：
Mo12P1.4V0.8Cu0.3As0.60W0.01Ox.The abrasion index test result of coated catalysts is 5.1%；Heteropoly acid outer layer activearm
Particle diameter accounts for the 75.5% of total pore volume for the pore volume contained by 100~2000nm hole in point, and particle diameter is contained by 100~500nm hole
Pore volume account for the 35% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 30.6%, and Methacrylic acid selectivity is 83.1%.
Embodiment 3
Catalyst is prepared with reference to embodiment 2, difference part is that calcination procedure is：8h, 350 are stopped under 50 DEG C of air atmospheres
Stopped under DEG C nitrogen atmosphere under 1h, 300 DEG C of air atmospheres and stop 3h.The composition for finally giving heteropoly acid is：
Mo12P1.4V0.8Cu0.3As0.6W0.01Ox.The abrasion index test result of coated catalysts is 0.6%；Heteropoly acid outer layer activearm
Aperture accounts for the 75% of total pore volume for the pore volume contained by 100~2000nm hole in point, and aperture is contained by 100~500nm hole
Pore volume accounts for the 35% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 80.1%, and Methacrylic acid selectivity is 80.5%.Under this condition after successive reaction 2000h, first is obtained
Base acrolein conversion rate is 81.0%, and Methacrylic acid selectivity is 80.2%.
Embodiment 4
Catalyst is prepared with reference to embodiment 2, difference part is polyvinylpyrrolidone mean molecule quantity being changed to about 40
Ten thousand.The composition for finally giving heteropoly acid is：Mo12P1.4V0.8Cu0.3As0.6W0.01Ox.The abrasion index test knot of coated catalysts
Fruit is 0.5%；Aperture accounts for the 70% of total pore volume for the pore volume contained by 100~2000nm hole in heteropoly acid outer layer active component,
Aperture accounts for the 33% of outer layer active component total pore volume for the pore volume contained by 100~500nm hole.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 80.3%, and Methacrylic acid selectivity is 80.5%.Under this condition after successive reaction 2000h, first is obtained
Base acrolein conversion rate is 80.7%, and Methacrylic acid selectivity is 80.2%.
Comparative example 5
Catalyst is prepared with reference to embodiment 2, difference part is coating pan temperature control at 20 DEG C, is wrapped during spin
Clothing pot fused glass inside is serious, and the composition for obtaining heteropoly acid is described as：Mo12P1.4V0.8Cu0.3As0.60W0.01Ox.Coated catalysts
Abrasion index test result is 3.9%；Aperture accounts for total pore volume for the pore volume contained by 100~2000nm hole in outer layer active component
85%, aperture for 100~500nm hole contained by pore volume account for the 30% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 57.6%, and Methacrylic acid selectivity is 85.4%.
Comparative example 6
Heteropolyacid catalyst powder is prepared with reference to embodiment 2, then using following steps prepares coating catalyst：Take 200g
Catalyst powder, 35g polyvinylpyrrolidones (mean molecule quantity about 100,000) and 30g ceramic fibres are well mixed, are spraying into
In the case that 95% hydrous ethanol is as binding agent, by said mixture be added to 250g porous inert porcelain ball (diameter 3.6mm,
Water absorption rate 12wt%) on be coated, spin process altogether take 35min, obtain coated catalysts.
Gained coated catalysts are calcined, specifically stopped under stop 5h, 380 DEG C of nitrogen atmospheres under 75 DEG C of air atmospheres
Stay and stop 3h under 1h, 320 DEG C of air atmospheres.The composition for finally giving heteropoly acid is described as：
Mo12P1.4V0.8Cu0.3As0.60W0.01Ox.The abrasion index test result of coated catalysts is 8.5%；Heteropoly acid outer layer activearm
Aperture accounts for the 50% of total pore volume for the pore volume contained by 100~2000nm hole in point, and aperture is contained by 100~500nm hole
Pore volume accounts for the 10.5% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 68.7%, and Methacrylic acid selectivity is 78.2%.
Embodiment 5
490.50g molybdenum trioxides, 18.24g vanadic anhydrides, 9.05g tellurium dioxide are added into 4000g deionized waters
(TeO2), 5.36g uranium dioxide (UO2), the phosphoric acid of the mass concentrations of 43.57g 85%, 24.71g 80wt% arsenic acid
(H3AsO4), addition 3.60g cupric phosphates, 2.03g cuprous oxide and 13.57g copper nitrates (Cu after 1h are stirred at reflux at 98 DEG C
(NO3)2·3H2O), dark blue solution is obtained after continuing return stirring 10h, resulting solution is enterprising in air flow type spray drying machine
Row spray drying, increasing atomizing gas pressure is 0.25MPa, and the speed that compressed air sprays from nozzle is 1600m/s, spray dryer
Inlet temperature be 140~150 DEG C, outlet temperature be 70~80 DEG C, obtain powder average grain diameter be 2.9 μm.
Take 300g catalyst powders to be dispersed in 130g absolute ethyl alcohols and obtain slurry A (viscosity 200mPas), take 50g to gather
Vinylpyrrolidone (mean molecule quantity about 1,000,000), which is dissolved in 80g absolute ethyl alcohols, obtains solution B (viscosity 200mPas), will
The slurry A 400g porous inert porcelain ball (the diameter 3.6mms, water absorption rate that are sprayed in coating pan progressive rolling movement parallel with solution B
On 12wt%), the parallel addition 36g ceramic fibres during roller coating, coating pan controls temperature to be 60 DEG C, and spin process consumes altogether
When 20min, obtain coated catalysts.
Gained coated catalysts are calcined, specifically stopped under stop 5h, 370 DEG C of nitrogen atmospheres under 75 DEG C of air atmospheres
Stay and stop 3h under 1h, 330 DEG C of air atmospheres.The composition for finally giving heteropoly acid outer layer active component is described as：
Mo12P1.4V0.7Cu0.44As0.5U0.07Te0.2Ox.The abrasion index test result of coated catalysts is 1.5%；Heteropoly acid outer layer is lived
Property component in aperture account for the 80% of total pore volume for the pore volume contained by 100~2000nm hole, aperture for 100~500nm hole institute
The pore volume contained accounts for the 40% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 83.4%, and Methacrylic acid selectivity is 86.2%.Under this condition after successive reaction 2000h, first is obtained
Base acrolein conversion rate is 83.6%, and Methacrylic acid selectivity is 85.9%.
Comparative example 7
Except roasting part in embodiment 5 is " other to press embodiment 5 in addition to 1h " cancellations are stopped under 370 DEG C of nitrogen atmospheres
Method prepared, obtain coated catalysts, through analysis, the composition of catalyst is：
Mo12P1.4V0.7Cu0.4As0.50U0.07Te0.2Ox.The abrasion index test result of coated catalysts is 1.1%；Heteropoly acid outer layer is lived
Property component in aperture account for the 45% of total pore volume for the pore volume contained by 100~2000nm hole, aperture for 100~500nm hole institute
The pore volume contained accounts for the 5.8% of outer layer active component total pore volume.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 51.3%, and Methacrylic acid selectivity is 75.6%.
Comparative example 8
Catalyst is prepared with reference to embodiment 5, difference part is coating pan temperature control at 95 DEG C, porcelain during spin
Ball rapid draing, obtains coated catalysts, and through analysis, the composition of catalyst is：Mo12P1.4V0.7Cu0.4As0.50U0.07Te0.2Ox。
The abrasion index test result of coated catalysts is 20.6%；Aperture is 100~2000nm's in heteropoly acid outer layer active component
Pore volume contained by hole accounts for the 75% of total pore volume, and aperture accounts for outer layer active component total pore volume for the pore volume contained by 100~500nm hole
20%.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 77.3%, and Methacrylic acid selectivity is 72.6%.
Comparative example 9
Catalyst is prepared with reference to embodiment 5, difference part is the absolute ethyl alcohol consumption of polyethylene dissolving pyrrolidones
Heteropoly acid rapid curing during 40g (polyvinylpyrrolidonesolution solution viscosity is upgraded to 600mPas), spin is changed to, is applied
Layer catalyst, through analysis, the composition of catalyst is described as：Mo12P1.4V0.7Cu0.4As0.50U0.07Te0.2Ox.The mill of coated catalysts
It is 8.9% to damage index test result；Aperture is accounted for always for the pore volume contained by 100~2000nm hole in heteropoly acid outer layer active component
The 65% of pore volume, aperture accounts for the 15% of outer layer active component total pore volume for the pore volume contained by 100~500nm hole.
Methyl-prop is obtained after carrying out MAL oxidation reaction, successive reaction 50h according to method same as Example 1
Olefine aldehydr conversion ratio is 71.3%, and Methacrylic acid selectivity is 65.4%.
Pass through above-described embodiment and the explanation of comparative example, it can be seen that using coating catalysis obtained by this method for preparing catalyst
Agent has low abrasion index, relatively low loaded by heteropoly acid amount.Under suitable preparation condition, catalyst has high first
Base acrolein conversion rate/Methacrylic acid selectivity and good life-span.
Claims (17)
1. a kind of preparation method of coated catalysts, comprises the following steps：
(1) by containing molybdenum, phosphorus, vanadium, copper, arsenic element compound, and selected from containing tellurium, boron, antimony, germanium, tungsten, uranium, bismuth, iron, cobalt, ruthenium
It is placed in water with the compound of one or more elements in nickel, dissolving obtains solution；
(2) solution in drying steps (1), obtains heteropolyacid catalyst powder；
(3) the heteropolyacid catalyst powder for obtaining step (2) is scattered in ethanol, obtains heteropolyacid catalyst slurry；
(4) heteropolyacid catalyst slurry, the ethanol solution of polyvinylpyrrolidone obtained step (3) sprays to spherical parallel
On inert carrier, coated catalysts are obtained；
(5) coated catalysts that calcination stepses (4) are obtained；The roasting comprises the following steps：The coated catalysts 50~
2~10h is stopped under 90 DEG C of air atmospheres, 0.5~3h is stopped under 330~400 DEG C of non-oxidizing atmospheres, in 250~330 DEG C of oxygen
1~10h is stopped under the property changed atmosphere.
2. according to the method described in claim 1, it is characterised in that the particle diameter of heteropolyacid catalyst powder in the step (2)
For 0.2~10 μm.
3. method according to claim 2, it is characterised in that the particle diameter of heteropolyacid catalyst powder in the step (2)
For 0.5~6 μm.
4. according to the method described in claim 1, it is characterised in that water content≤10wt% in ethanol in the step (3)；Institute
The viscosity for stating heteropolyacid catalyst slurry is 5~500mPas.
5. method according to claim 4, it is characterised in that water content≤5wt% in ethanol in the step (3)；Institute
The viscosity for stating heteropolyacid catalyst slurry is 50~300mPas.
6. according to the method described in claim 1, it is characterised in that the spraying temperature in the step (4) is 40~80 DEG C；Institute
The molecular weight for stating polyvinylpyrrolidone is 40,000~1,300,000；The viscosity of the ethanol solution of the polyvinylpyrrolidone be 5~
500mPa·s。
7. method according to claim 6, it is characterised in that the spraying temperature in the step (4) is 50~70 DEG C；Institute
The molecular weight for stating polyvinylpyrrolidone is 100,000~1,000,000；The viscosity of the ethanol solution of the polyvinylpyrrolidone is 50
~300mPas.
8. according to the method described in claim 1, it is characterised in that roasting comprises the following steps in the step (5)：It is described to apply
Layer catalyst stops 5~10h under 55~80 DEG C of air atmospheres, 1~2h is stopped under 350~380 DEG C of non-oxidizing atmospheres,
2~5h is stopped under 280~320 DEG C of oxidizing atmospheres.
9. coated catalysts prepared by a kind of method according to claim 1, including sphere inert carrier and outer layer activearm
Point, the mass ratio of the sphere inert carrier and outer layer active component is 0.5~2.0:1, described outer layer active component is poly-
Vinylpyrrolidone load using phosphorus, molybdenum, vanadium, copper and arsenic as indispensable element, tellurium, boron, antimony, germanium, tungsten, uranium, bismuth, iron, cobalt, ruthenium and
One or more in nickel are the heteropoly acid of optional elements；The mass ratio of heteropoly acid and polyvinylpyrrolidone is 2~10:1.
10. coated catalysts according to claim 9, it is characterised in that the sphere inert carrier and outer layer activearm
The mass ratio divided is 0.6~1.5:1；The mass ratio of heteropoly acid and polyvinylpyrrolidone is 4~8:1.
11. coated catalysts according to claim 9, it is characterised in that the formula of the heteropoly acid is：
Mo12PaVbCucAsdXeOf·nH2O, wherein, Mo is molybdenum, and P is phosphorus, and V is vanadium, and Cu is copper, and As is arsenic, and O is oxygen；X be selected from tellurium,
One or more elements in boron, antimony, germanium, tungsten, uranium, bismuth, iron, cobalt, ruthenium and nickel；The atomic ratio of various elements is：A=0.5~
3；B=0.1~2；C=0.01~1；D=0.01~2；E=0.01~1；F is the original of oxygen required for meeting each element chemical valence
Sub- ratio.
12. coated catalysts according to claim 11, it is characterised in that the X is selected from tellurium, boron, antimony, tungsten, uranium, bismuth
With one or more elements in iron；The atomic ratio of various elements is：A=1~2；B=0.2~1；C=0.05~0.5；D=
0.05~1；E=0.01~0.5.
13. coated catalysts according to claim 9, it is characterised in that in the outer layer active component aperture be 100~
Pore volume contained by 2000nm hole accounts for the 60~90% of the outer layer active component total pore volume.
14. coated catalysts according to claim 13, it is characterised in that aperture is 100 in the outer layer active component
Pore volume contained by~2000nm hole accounts for the 70~85% of the outer layer active component total pore volume.
15. coated catalysts according to claim 9, it is characterised in that in the outer layer active component aperture be 100~
Pore volume contained by 500nm hole accounts for the 20~50% of the outer layer active component total pore volume.
16. coated catalysts according to claim 15, it is characterised in that aperture is 100 in the outer layer active component
Pore volume contained by~500nm hole accounts for the 30~45% of the outer layer active component total pore volume.
17. it is any in coated catalysts or claim 9~16 prepared by the method according to any one of claim 1~8
Coated catalysts described in prepare the purposes of (methyl) acrylic acid in (methyl) catalytic gas phase oxidation of acrolein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510149553.8A CN104801351B (en) | 2015-04-01 | 2015-04-01 | A kind of preparation method of coated catalysts and the coated catalysts prepared using this method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510149553.8A CN104801351B (en) | 2015-04-01 | 2015-04-01 | A kind of preparation method of coated catalysts and the coated catalysts prepared using this method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104801351A CN104801351A (en) | 2015-07-29 |
| CN104801351B true CN104801351B (en) | 2017-07-21 |
Family
ID=53686794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510149553.8A Active CN104801351B (en) | 2015-04-01 | 2015-04-01 | A kind of preparation method of coated catalysts and the coated catalysts prepared using this method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104801351B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040314B (en) * | 2016-06-13 | 2018-09-18 | 中国科学院过程工程研究所 | The preparation and application of a kind of coated catalysts using ionic liquid as binder |
| US20210053039A1 (en) * | 2018-03-28 | 2021-02-25 | Nippon Kayaku Kabushiki Kaisha | Catalyst for producing unsaturated carboxylic acid |
| CN109331850B (en) * | 2018-10-08 | 2021-07-23 | 万华化学集团股份有限公司 | Core-shell type catalyst carrier and coating catalyst |
| CN112675912A (en) * | 2019-10-18 | 2021-04-20 | 万华化学集团股份有限公司 | Catalyst for producing unsaturated carboxylic acid and preparation method and application thereof |
| CN113083337B (en) * | 2019-12-23 | 2022-04-19 | 万华化学集团股份有限公司 | Catalyst for methacrylic acid production and preparation method and application thereof |
| CN114471644A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Porous heteropolyacid catalyst and preparation method and application thereof |
| CN113198473B (en) * | 2021-04-29 | 2023-02-17 | 清创人和生态工程技术有限公司 | Transition metal oxide Fenton catalyst and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3883755B2 (en) * | 1999-09-17 | 2007-02-21 | 日本化薬株式会社 | Catalyst production method |
| WO2002024328A1 (en) * | 2000-09-21 | 2002-03-28 | Nippon Kayaku Kabushiki Kaisha | Catalyst for methacrylic acid production, coated catalyst, and process for producing the same |
| CN101979138B (en) * | 2010-11-11 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Cobalt-copper Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN103801398A (en) * | 2014-01-02 | 2014-05-21 | 上海东化催化剂有限公司 | Preparation method of catalyst for preparing methacrylic acid |
-
2015
- 2015-04-01 CN CN201510149553.8A patent/CN104801351B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104801351A (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104801351B (en) | A kind of preparation method of coated catalysts and the coated catalysts prepared using this method | |
| JP3834087B2 (en) | Method for producing catalyst, outer shell catalyst, method for producing acrylic acid, acrolein and methacrolein, and method for catalytic gas phase oxidation | |
| US4298763A (en) | Preparation of α,β-olefinically unsaturated aldehydes of 3 or 4 carbon atoms | |
| CN101992093A (en) | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity | |
| CN106040314B (en) | The preparation and application of a kind of coated catalysts using ionic liquid as binder | |
| US7456129B2 (en) | Support for gas-phase oxidation catalyst and process for its production, gas-phase oxidation catalyst, and process for producing acrylic acid | |
| JP6359105B2 (en) | Catalyst for the production of unsaturated carboxylic acids by gas phase oxidation of unsaturated aldehydes. | |
| CN101983174A (en) | Method for producing a nanocrystalline bismuth-molybdenum mixed oxide | |
| CN101690900A (en) | Method for preparing catalyst for acrolein and acrylic acid | |
| JPH09504226A (en) | Process for producing catalytically active composite metal oxide material containing elements V and Mo in the form of oxides as basic components | |
| CN103861640B (en) | A kind of heteropolyacid catalyst and preparation method thereof | |
| JP4119748B2 (en) | Method for producing an annular shell catalyst and use of the catalyst for producing acrolein | |
| KR100234874B1 (en) | Carrier-supported catalyst for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids, and process for preparing the same | |
| CN105209168A (en) | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid, method for manufacturing same, and method for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid | |
| CN101175569A (en) | Method for preparing catalyst for production of methacrylic acid | |
| CN102049261B (en) | Method for preparing catalyst of acrolein by propylene oxidization | |
| CN107848920A (en) | The manufacture method of unsaturated aldehyde and/or unsaturated carboxylic acid | |
| TWI417138B (en) | Oxide catalyst, process for producing acrylic acid and process for producing water-absorbent resin | |
| CN107847922A (en) | The method for preparing the mixed oxide catalyst containing molybdenum and bismuth | |
| WO1997047387A1 (en) | Process for producing a catalyst consisting of a substrate and a catalytically active compound applied to the upper surface of said substrate | |
| CN107774287B (en) | Supported catalyst for preparing maleic anhydride by benzene oxidation and preparation thereof | |
| CN105921154B (en) | A kind of preparation method of more metal composite oxide catalysts and its catalyst of preparation and application thereof | |
| CN106582677B (en) | A kind of preparation method and its usage of more metal composite oxide catalysts | |
| CN103721756B (en) | Catalyst carrier and preparation method thereof, composite oxide catalysts | |
| CN110975903A (en) | Heteropolyacid salt catalyst with high specific surface area and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 264002 Yantai economic and Technological Development Zone, Shandong, Tian Shan Road, No. 17 Applicant after: Wanhua Chemical Group Co.,Ltd. Address before: 264002 Yantai City, Shandong province Zhifu District No. 7 Applicant before: Wanhua Chemical Group Co.,Ltd. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to a preparation method of a coating catalyst and a coating catalyst prepared by the method Effective date of registration: 20211123 Granted publication date: 20170721 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20170721 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |