CN102463144A - Aluminium oxide slurry for preparing compound carrier coating and preparation method of aluminium oxide slurry - Google Patents
Aluminium oxide slurry for preparing compound carrier coating and preparation method of aluminium oxide slurry Download PDFInfo
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- CN102463144A CN102463144A CN201010552842XA CN201010552842A CN102463144A CN 102463144 A CN102463144 A CN 102463144A CN 201010552842X A CN201010552842X A CN 201010552842XA CN 201010552842 A CN201010552842 A CN 201010552842A CN 102463144 A CN102463144 A CN 102463144A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to aluminium oxide slurry for preparing a compound carrier coating and a preparation method of the aluminium oxide slurry, mainly solving the problems that the conventional aluminium oxide slurry is large in granularity, the abrasive loss rates of the prepared coating and a catalyst are high and the stability of the catalyst is low. The aluminium oxide slurry for preparing the compound carrier coating comprises the following components of water, aluminium sol, aluminium oxide, an organic binding agent, a dispersing agent and a coating adjuvant. The preparation method of the aluminium oxide slurry comprises the following steps of: dissolving the organic binding agent and the dispersing agent into a dilute solution A; sequentially dispersing the dilute solution A, the aluminium sol, the aluminium oxide and the coating adjuvant into water to obtain slurry I; pumping the slurry I into a colloid mill, and milling; reflowing the milled slurry into the slurry I, stirring, and pumping the slurry I into the colloid mill again; and after circulating operation, regulating the viscosity of the slurry to be 10-15Pa.s and controlling the granularity d50 to be less than 5um to obtain the slurry II. By the technical scheme, the problems are solved well; and the aluminium oxide slurry and the preparation method thereof can be applied to the production of the compound carrier coating.
Description
Technical field
The present invention relates to a kind of alumina slurry for preparing the complex carrier coating and preparation method thereof.
Background technology
Noble metal active component catalyst superior performance, but cost is higher.Active component non-uniform Distribution in carrier can reduce the consumption of noble metal, improves the utilization rate of noble metal; Simultaneously, the catalyst of non-uniform Distribution also showed than the better activity of equally distributed catalyst, selectivity and life-span in many reactions.Be to obtain in early days through infusion process, the difficult control but it distributes.This just need provide a kind of special carrier, and this carrier is made up of inert core and coating, has only coating absorption metal and coating layer thickness controlled, Here it is lamellar composite carrier.Just made thickness and the controlled heterogeneity catalyst of distribution flooding catalyst on this carrier, ZL02100598.2 has reported cleaning catalyst for tail gases of automobiles like patent.This invention cleaning catalyst for tail gases of automobiles is first carrier with the cordierite honeycomb ceramic matrix, is second carrier with aluminum oxide coating layer slurries (salic, noble metal).Through with first carrier impregnation in the coating slurries, disposable spray finishing is processed catalyst.In ethylbenzene catalytic dehydrogenation-H 2 selective oxidation process, patent US6177381 and CN1479649A have reported lamellar composite carrier for another example.Carrier has the for example coating gama-alumina for example of Alpha-alumina and an inorganic oxide of a kernel.And for example patent US6858769 and CN1705510A have reported that a kind of is the H 2 selective oxidation catalyst of carrier with the lithium aluminate.This catalyst is a kernel with the cordierite, is coating with the lithium aluminate.
The preparation method of lamellar composite carrier is a lot, and the spraying dip-coating is comparatively common method, and this just needs to improve the slurry of a kind of suitable spraying or dip-coating.Patent CN101491776A provides a kind of prescription and preparation method who prepares coating paste, and this slurry is made up of at the aluminium colloidal sol below 10 microns, activated alumina, organic adhesive, inorganic adhesive, surfactant, pH conditioning agent particle mean size.The preparation method is dissolved in aluminium colloidal sol, organic adhesive, surfactant, pH conditioning agent in the water; Under 500～5000 rev/mins high-speed stirred, mix; Then add inorganic binder, active oxidation aluminium powder; High speed dispersion 10～180 minutes, gained alumina slurry were ground 10 minutes～10 hours in ball mill, sand mill, ball mill or colloid mill again, processed alumina coats pulp.The slurry that makes has improved the stability of coating to a certain extent, has reduced rate of wear, and is abundant inadequately but the pulp particle that this method makes is disperseed; The pulp particle degree is big, and slurry is stable poor, and the pulp preparation cycle is long; The coated carrier of using this slurry to make; Rate of wear is bigger than normal, and the stability of coating and firmness are also relatively poor, and then has influence on the thin-shell type catalyst performance of preparation.Need improve formula of size and preparation method, obtain a manufacturing cycle weak point, high dispersive, the slurry of high stable, thus improve the lamellar composite carrier of preparation and the firmness and the stability of thin-shell type catalyst.
Summary of the invention
One of technical problem to be solved by this invention is that the slurry granularity that exists in the prior art coating and attrition of catalyst rate big, that make are high; The problem of poor catalyst stability; A kind of alumina slurry of new preparation complex carrier coating is provided; This alumina slurry has little, the narrow particle size distribution of granularity, and carrier that makes and attrition of catalyst rate are low, the advantage that catalyst stability is good.Two of technical problem to be solved by this invention provides preparation method a kind of and one of technical solution problem corresponding slurry.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of alumina slurry for preparing the complex carrier coating comprises following component by weight percentage:
A) 1～25% aluminium colloidal sol;
B) 5～50% aluminium oxide;
C) 0.1～5% organic binder bond;
D) 0.01～5% dispersant;
E) 0.5～10% coating aid;
F) 30～90% water;
Wherein: dispersant is selected from organic tannate, gathers carbonic acid, at least a in humic acid, polyacrylic acid, sodium metasilicate, sodium carbonate or the polyphosphate sodium; Coating aid is selected from least a in magnesium phosphate, apatite, basic zirconium phosphate, phosphoric acid silicon, phosphoeptide, phosphorus strontium aluminium stone, animal bone ash or the calcium phosphate; Organic binder bond is selected from least a in polyvinyl alcohol, CMC, hydroxypropyl cellulose, polyethylene glycol, hydroxyethylcellulose or the methylcellulose.
In technique scheme, aluminium colloidal sol consumption preferable range is 5～20% by weight percentage; The aluminium oxide preferred version is γ-Al
2O
3, δ-Al
2O
3Or θ-Al
2O
3In at least a and granularity be controlled at below 10 microns, its consumption is 15～45% by weight percentage; The dispersant preferred version is to be selected from organic tannate, humic acid, polyacrylic acid, to gather at least a in carbonic acid, the polyphosphate sodium, and its consumption is 0.1～1% by weight percentage.The coating aid preferred version is to be selected from least a in magnesium phosphate, apatite, basic zirconium phosphate, phosphorus strontium aluminium stone, animal bone ash or the calcium phosphate, and its consumption is 1～5% by weight percentage.The organic binder bond preferred version is to be selected from a kind of in polyvinyl alcohol, CMC, hydroxypropyl cellulose, polyethylene glycol or the methylcellulose, and its consumption is 0.5～2.5% by weight percentage.The consumption preferable range of water is 40～70% by weight percentage.
For two of technical solution problem, technical scheme provided by the invention is following: a kind of preparation method of alumina slurry of the preparation complex carrier coating that is used for one of technical solution problem may further comprise the steps:
Organic binder bond and dispersant are dissolved into weak solution A, under high-speed stirred successively with A solution, aluminium colloidal sol, aluminium oxide, coating aid be scattered in the deionized water slurry I; Slurry I is transported in the colloid mill through the liquid pump and once grinds, and obtains slurry II; Slurry II flows into once more in the agitator and to stir the back and get into colloid mill through the liquid pump and carry out regrind, and so constantly circulation is carried out, and obtains the slurry III that needs, regulates slurry viscosity at 10～30Pa.s, control granularity d
50Below 5um.
The dissolving of the organic binder bond of requirement is dispersed into weak solution,, under 2000 rev/mins stirring, is well dispersed in the deionized water 30 minutes, obtain slurry I aluminium colloidal sol, aluminium oxide, dispersant, the coating aid of weak solution, requirement; Slurry I is delivered in the colloid mill through the liquid pump and once grinds, and the slurry II after the grinding gets into the stirring system once more, and so circulation is stirred, ground 30～60 minutes, regulates the control slurry viscosity at 15～25Pa.s, pulp particle degree d
50Below 4um, obtain the slurry III that needs.
One aspect of the present invention has been optimized the alumina slurry prescription, and the dispersant of interpolation is that the stable of slurry system provides enough electrostatic repulsion and space bit steric hindrances to repel, and makes that alumina particle disperses more in the slurry body; Apparent particle size is littler; The interpolation of organic binder bond has increased the initial bond strength of coating and carrier kernel, simultaneously also can be to the dispersion and the stable facilitation, the phosphate radical of introducing in the coating aid of playing of particle in the slurry under its high dispersion state; Can with the OH radical reaction; In case the sintering of oxidation aluminium and phase transformation, oxides such as the calcium that its decomposition produces, magnesium, zirconium can be had an effect with aluminium oxide and kernel carrier simultaneously, both can play certain cementation; The firmness that combines of enhancement coating and carrier; Can generate the higher chemical substance of stability again, thereby improve the stability of coating and catalyst, reduce rate of wear.On the other hand; Can guarantee that through timesharing it fully is dispersed with the decentralization and shortening jitter time that is beneficial to the increase alumina particle with organic binder bond and dispersant dilution; Adopt the mode of high-speed stirred and colloidal grinding combined cycle that slurry is all ground at short notice fully; Avoided the inhomogeneities of slurry colloidal grinding, made that the slurry granularity is littler and its particle size distribution is narrower.The slurry that makes is when spraying, because granularity is little, and good dispersion, atomizing effect improves, and can increase the compactness of coating, thereby improves the firmness of coating, the rate of wear of reduction coating.The alumina slurry that uses the inventive method to make, slurry granularity d
50All less than 5um, d90 is less than 10um, and placing 15 days disposed slurry granularities does not have significant change; Make the coated carrier rate of wear less than 0.12% with this slurry; Corresponding attrition of catalyst rate is less than 0.15%, and catalyst was through 800 ℃ of steam treatment 24 hours, and loss late is 0; Be used for the ethylbenzene dehydrogenation H 2 selective oxidation; The oxygen selectivity is about 93%, and the aromatic hydrocarbons loss late is 0.09%, and catalyst is after 24 hours burin-in process of 800 ℃ of steam treatment; It is stable that the oxygen selectivity keeps, and obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
40 gram polyvinyl alcohol, 20 gram polyphosphate sodiums are dissolved in 500 grams make weak solution in the deionized waters, with 1500 gram deionized waters, weak solution; The aluminium colloidal sol of 800 grams 30%, 1200 gram gamma oxidation aluminium powders, 60 gram magnesium phosphates; Add successively and mix 30 minutes in the mixer; Be transported in the colloid mill circular grinding 40 minutes with the liquid pump, the control slurry viscosity is 20, makes slurry A.
[embodiment 2]
With 60 gram CMCs, 4 gram polyacrylic acid are dissolved in the 800 gram deionized waters and make weak solution, with 1000 gram deionized waters; Weak solution, the aluminium colloidal sol of 700 grams 40%, 1500 gram δ-alumina powders; 80 gram calcium phosphate add successively and mix 30 minutes in the mixer, are transported in the colloid mill circular grinding 50 minutes with the liquid pump; The control slurry viscosity is 15, makes slurry B.
[embodiment 3]
With 80 gram polyethylene glycol, 40 gram ammonium polyacrylates are dissolved in the 1000 gram deionized waters and make weak solution, with 1000 gram deionized waters; Weak solution, the aluminium colloidal sol of 1000 grams 40%, 1000 gram θ-alumina powders; 180 gram apatite add successively and mix 30 minutes in the mixer, are transported in the colloid mill circular grinding 45 minutes with the liquid pump; The control slurry viscosity is 22, makes slurry C.
[embodiment 4]
With 120 gram hydroxypropyl celluloses, 25 gram humic acids are dissolved in the 1500 gram deionized waters and make weak solution, with 500 gram deionized waters; Weak solution, the aluminium colloidal sol of 1500 grams 40%, 600 gram θ-alumina powders; 100 gram animal bone ashes add successively and mix 30 minutes in the mixer, are transported in the colloid mill circular grinding 50 minutes with the liquid pump; The control slurry viscosity is 18, makes slurry D.
[embodiment 5]
With 50 gram methylcellulose, 30 grams gather carbonic acid and are dissolved in 700 grams and make weak solution in the deionized waters, with 500 gram deionized waters; Weak solution, the aluminium colloidal sol of 2000 grams 40%, 800 gram δ-alumina powders; 110 gram phosphorus strontium aluminium stones add successively and mix 30 minutes in the mixer, are transported in the colloid mill circular grinding 60 minutes with the liquid pump; The control slurry viscosity is 13, makes slurry E.
[embodiment 6]
With 100 gram FS10, the organic tannic acid ammonium of 20 grams is dissolved in the 1000 gram deionized waters and makes weak solution, with 1000 gram deionized waters; Weak solution, the aluminium colloidal sol of 1000 grams 40%, 500 gram δ-alumina powders; 500 gram gamma oxidation aluminium powders, 150 restrain peganites, add successively to mix 30 minutes in the mixer; Be transported in the colloid mill circular grinding 55 minutes with the liquid pump, the control slurry viscosity is 25, makes slurry F.
[comparative example 1]
With 1000 gram water, the aluminium colloidal sol of 1200 gram concentration 10%, 10 gram PVA, 7.5 gram CMCs; 30 gram sorbester p17s are processed slurries, with 2000 rev/mins of high-speed stirred 30 minutes, add 2.5 ml concns again and be 8% nitric acid, 37.5 gram potassic feldspars; 20 gram diatomite, 1000 gram gamma oxidation aluminium powders; Continue to stir 60 minutes, ball milling 4 hours at room temperature makes alumina slurry G again.
[embodiment 7]
With the slurry A of prepared fresh, B, C, D, E, F, G measures its granule size and distribution with laser particle analyzer, and the result sees table 1.With particle diameter is that 4 millimeters cordierite bead joins in the cylinder, and cylinder is heated to 200 ℃, and the index drum temperature is 200 rev/mins; Slurry A～G is sprayed to respectively on the cordierite bead; Dry in the shade under the room temperature, with 80 ℃ of dryings 2 hours, then be warmed up to 120 ℃ dry 2 hours once more; 1000 ℃ of roastings 12 hours obtain lamellar composite carrier A
0～G
0The rate of wear of carrier the results are shown in Table 2.
The particle diameter of table 1 slurry and distribution
| A | B | C | D | E | F | G | |
| d 50/um | 4.5 | 4.6 | 4.3 | 4.7 | 4.5 | 4.5 | 6.2 |
| d 90/um | 8.9 | 9.1 | 8.6 | 9.3 | 9.0 | 8.7 | 213 |
Can find out that from table 1 the slurry A～F that adopts this patent method to make compares with the slurry G that the method that adopts comparative example 1 obtains, the slurry granularity is littler, d
50Less than 5 microns, the particle size distribution of slurry is narrower, d
90Less than 10um, it is better to explain that the slurry that adopts this patent method to make disperses.Get slurry A and G, place after 15 days the granularity d of slurry A
50Maintain about 5um the granularity d of slurry F
50About 12um, explain that this patent method makes slurry and compares with the slurry that the method that adopts comparative example 1 makes, the dispersion of slurry is more stable.
The physical and chemical performance test result of table 2 carrier
| A 0 | B 0 | C 0 | D 0 | E 0 | F 0 | G 0 | |
| Carrier rate of wear/% | 0.11 | 0.13 | 0.13 | 0.12 | 0.12 | 0.11 | 0.26 |
| Fresh catalyst rate of wear/% | 0.13 | 0.15 | 0.14 | 0.13 | 0.14 | 0.12 | 0.33 |
| 800 degree are handled back loss late/% | / | 0 | / | / | / | 0 | 0.01 |
Can know by table 2, adopt the slurry A～F of this patent method preparation to be prepared into corresponding lamellar composite carrier A
0～F
0Become corresponding complex carrier G with the pulp preparation that adopts comparative example 1 method to make
0Compare complex carrier A
0～F
0Rate of wear lower, rate of wear is all below 0.13%, slightly increases all less than 0.15% but be prepared into behind the corresponding catalyst rate of wear, gets catalyst sample B
0, F
0, G
0After carrying out the processing in 24 hours of 800 degree steam, catalyst B
0, F
0Loss late is 0 basically, and catalyst G
0Loss late be 0.01%, explain that to adopt the complex carrier coating and the catalyst of the pulp preparation that this patent method obtains more firm.
[embodiment 8]
With A
0～G
0Carrier surface dipping Pt, Sn, Li make the corresponding catalyst of catalyst.Elementary analysis shows, with regard to whole catalyst, contains Pt 0.14% according to the mass fraction meter, and Sn 0.16%, and Li 0.72%.Measure the attrition of catalyst rate, get catalyst B
0, F
0, G
0Under 800 degree steam, handled 24 hours, catalyst loss rate before and after measuring, its result sees table 2.Catalyst B with prepared fresh
0, F
0, G
0With through 800 degree steam treatment 24 hours catalyst B
0 *, F
0 *, G
0 *Be used for the reaction that the oxidation of ethyl benzene dehydrogenation preparation of styrene hydrogen selective generates water.Reactor inside diameter is 25 millimeters a stainless steel reaction pipe, in adorn 30 milliliters of catalyst.Reaction pressure is a normal pressure, liquid air speed 3 hours
-1, 580 ℃ of reaction temperatures, the reactant composition is seen table 3, reactivity worth is seen table 4.
The raw material of H 2 selective oxidation is formed in table 3 ethylbenzene dehydrogenation process
| Raw material | Content (molar percentage) |
| Styrene | 2.4 |
| Ethylbenzene | 5.4 |
| Benzene and toluene | 0.08 |
| H 2 | 2.4 |
| O 2 | 1.1 |
| N 2 | 0.11 |
| Water | 88.51 |
The H 2 selective oxidation performance of table 4 catalyst
By table 4, adopt the catalyst B of the pulp preparation one-tenth of this patent method preparation
0, F
0The catalyst G that processes with the slurry of the method preparation of adopting embodiment 1
0Compare, be used for H 2 selective oxidation, B
0, F
0The selectivity of oxygen is higher, and about 93%, the aromatic hydrocarbons loss late is 0.09%, after 24 hours steam treatment of 800 degree, and B
0, F
0Performance does not change, and G
0Slightly reduce, explain that catalyst high temperature is more stable.
Claims (8)
1. alumina slurry for preparing the complex carrier coating comprises following component by weight percentage:
A) 1～25% aluminium colloidal sol;
B) 5～50% aluminium oxide;
C) 0.1～5% organic binder bond;
D) 0.01～5% dispersant;
E) 0.5～10% coating aid;
F) 30～90% water;
Wherein: dispersant is selected from organic tannate, gathers carbonic acid, at least a in humic acid, polyacrylic acid, sodium metasilicate, sodium carbonate or the polyphosphate sodium; Coating aid is selected from least a in magnesium phosphate, apatite, basic zirconium phosphate, phosphoric acid silicon, phosphoeptide, phosphorus strontium aluminium stone, animal bone ash or the calcium phosphate; Organic binder bond is selected from least a in polyvinyl alcohol, CMC, hydroxypropyl cellulose, polyethylene glycol, hydroxyethylcellulose or the methylcellulose.
2. according to the alumina slurry of the said preparation complex carrier of claim 1 coating, it is characterized in that aluminium colloidal sol consumption is 1～25% by weight percentage, be preferably 5～25%.
3. according to the alumina slurry of the said preparation complex carrier of claim 1 coating, it is characterized in that aluminium oxide is γ-Al
2O
3, δ-Al
2O
3Or θ-Al
2O
3In at least a and granularity be controlled at below 10 microns, its consumption is 10～45% by weight percentage.
4. according to the alumina slurry of the said preparation complex carrier of claim 1 coating; It is characterized in that dispersant is selected from organic tannate, humic acid, polyacrylic acid, gathers at least a in carbonic acid or the polyphosphate sodium, its consumption is 0.05～1% by weight percentage.
5. according to the alumina slurry of the said preparation complex carrier of claim 1 coating; It is characterized in that coating aid is at least a in magnesium phosphate, apatite, basic zirconium phosphate, phosphorus strontium aluminium stone, animal bone ash or the calcium phosphate, its consumption is 0.5%～5% by weight percentage.
6. according to the alumina slurry of the said preparation complex carrier of claim 1 coating; It is characterized in that organic binder bond is selected from least a in polyvinyl alcohol, CMC, hydroxypropyl cellulose, polyethylene glycol or the methylcellulose, consumption is 0.5～3% by weight percentage
7. according to the alumina slurry of the said preparation complex carrier of claim 1 coating, it is characterized in that the consumption of water is 40%～80% by weight percentage.
8. the preparation method of the alumina slurry of the described preparation complex carrier of claim 1 coating may further comprise the steps:
Organic binder bond and dispersant are dissolved into weak solution A, under agitation successively with A solution, aluminium colloidal sol, aluminium oxide, coating aid be scattered in the water slurry I; Slurry I is pumped in the colloid mill and grinds, and the grinding disposed slurry flows into and stirs among the slurry I and be pumped into once more in the colloid mill, so circulates and carries out, and regulates slurry viscosity at 10～50Pa.s, control granularity d
50Less than 5um, obtain slurry II.
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|---|---|---|---|
| CN201010552842XA CN102463144B (en) | 2010-11-17 | 2010-11-17 | Aluminium oxide slurry for preparing compound carrier coating and preparation method of aluminium oxide slurry |
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|---|---|---|---|
| CN201010552842XA CN102463144B (en) | 2010-11-17 | 2010-11-17 | Aluminium oxide slurry for preparing compound carrier coating and preparation method of aluminium oxide slurry |
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|---|---|
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| CN102463144B CN102463144B (en) | 2013-09-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496496A (en) * | 2014-12-10 | 2015-04-08 | 中国京冶工程技术有限公司 | Wear-resistant toughener for wet sprayed paint and preparation method thereof |
| CN107352563A (en) * | 2017-07-21 | 2017-11-17 | 江苏万路达环保科技有限公司 | A kind of pretreatment technology of aluminum oxide for catalyst powder body material |
| CN109516831A (en) * | 2018-12-03 | 2019-03-26 | 浙江昕明环境科技有限公司 | A kind of preparation method of aluminum oxide porous material |
| CN112011190A (en) * | 2019-05-31 | 2020-12-01 | 中国石油天然气股份有限公司 | Polymer gel, particle size distribution monodisperse polymer microsphere, preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177381B1 (en) * | 1998-11-03 | 2001-01-23 | Uop Llc | Layered catalyst composition and processes for preparing and using the composition |
| CN1479649A (en) * | 2000-11-27 | 2004-03-03 | �Ʒ� | Layered catalyst composition and process for preparating and using the composition |
| CN1705510A (en) * | 2002-10-18 | 2005-12-07 | 环球油品公司 | A lithium aluminate layered catalyst and a selective oxidation process using the catalyst |
| CN101602016A (en) * | 2008-06-12 | 2009-12-16 | 中国石油化工股份有限公司 | The lamellar composite carrier of hydrothermal stability |
-
2010
- 2010-11-17 CN CN201010552842XA patent/CN102463144B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177381B1 (en) * | 1998-11-03 | 2001-01-23 | Uop Llc | Layered catalyst composition and processes for preparing and using the composition |
| CN1479649A (en) * | 2000-11-27 | 2004-03-03 | �Ʒ� | Layered catalyst composition and process for preparating and using the composition |
| CN1705510A (en) * | 2002-10-18 | 2005-12-07 | 环球油品公司 | A lithium aluminate layered catalyst and a selective oxidation process using the catalyst |
| CN101602016A (en) * | 2008-06-12 | 2009-12-16 | 中国石油化工股份有限公司 | The lamellar composite carrier of hydrothermal stability |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496496A (en) * | 2014-12-10 | 2015-04-08 | 中国京冶工程技术有限公司 | Wear-resistant toughener for wet sprayed paint and preparation method thereof |
| CN104496496B (en) * | 2014-12-10 | 2016-11-09 | 中国京冶工程技术有限公司 | Wet spray material wear-resisting toughener and preparation method thereof |
| CN107352563A (en) * | 2017-07-21 | 2017-11-17 | 江苏万路达环保科技有限公司 | A kind of pretreatment technology of aluminum oxide for catalyst powder body material |
| CN109516831A (en) * | 2018-12-03 | 2019-03-26 | 浙江昕明环境科技有限公司 | A kind of preparation method of aluminum oxide porous material |
| CN112011190A (en) * | 2019-05-31 | 2020-12-01 | 中国石油天然气股份有限公司 | Polymer gel, particle size distribution monodisperse polymer microsphere, preparation and application thereof |
| CN112011190B (en) * | 2019-05-31 | 2022-05-10 | 中国石油天然气股份有限公司 | Polymer gel, particle size distribution monodisperse polymer microsphere, preparation and application thereof |
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| Publication number | Publication date |
|---|---|
| CN102463144B (en) | 2013-09-18 |
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