CN102463145B - Slurry for hydrogen oxidation catalyst coating and preparation method of slurry - Google Patents
Slurry for hydrogen oxidation catalyst coating and preparation method of slurry Download PDFInfo
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- CN102463145B CN102463145B CN2010105528576A CN201010552857A CN102463145B CN 102463145 B CN102463145 B CN 102463145B CN 2010105528576 A CN2010105528576 A CN 2010105528576A CN 201010552857 A CN201010552857 A CN 201010552857A CN 102463145 B CN102463145 B CN 102463145B
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- oxidation catalyst
- hydrogen oxidation
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Abstract
The invention relates to slurry for a hydrogen oxidation catalyst coating and a preparation method of the slurry, mainly solving the problems that in the prior art, the preparation of the slurry costs a long time and the slurry is large in granularity and low in stability, and thus a catalyst is long in production period and high in cost, the abrasive loss rate of the prepared coating is high, and the performance and the stability of the catalyst are low. The slurry for the hydrogen oxidation catalyst coating comprises the following components of water, aluminium sol, aluminium oxide, a coating adjuvant, a pH regulating agent and a foaming agent. The preparation method of the slurry comprises the following steps of: sequentially adding the water, the aluminium sol, the aluminium oxide andthe coating adjuvant into a colloid mill, and circulating the mixture; regulating the slurry by the pH regulating agent to obtain slurry I; foaming a certain amount of the foaming agent and water by using a foaming machine; and adding foams into the slurry I to obtain slurry II. By the technical scheme, the problems are solved well; and the slurry and the preparation method thereof can be appliedto the industrial production of the catalyst coating slurry.
Description
Technical field
The present invention relates to a kind of slurry for the hydrogen oxidation catalyst coating and preparation method thereof.
Background technology
Noble metal is widely used in chemical industry, oil refining and vehicle exhaust processing as the loaded catalyst of active component at present.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 better active, the selective and life-span of equally distributed catalyst in many reactions.Often reach the effect of non-uniform Distribution by the control to dipping in early days, but often be difficult to control the distribution of catalyst.This just need to provide first a kind of special carrier, and this carrier is comprised of inert core and coating, only has coating adsorbing metal and coating layer thickness controlled, Here it is lamellar composite carrier.Flood catalyst at this carrier and just made thickness and the controlled heterogeneity catalyst of distribution, ZL02100598.2 has reported cleaning catalyst for tail gases of automobiles such as patent.This invention cleaning catalyst for tail gases of automobiles is take the cordierite honeycomb ceramic matrix as the first carrier, take aluminum oxide coating layer slurries (salic, noble metal) as Second support.By with the first carrier impregnation in the coating slurries, the disposable thin-shell catalyst of making.In the H 2 selective oxidation process in the ethylbenzene dehydrogenation, patent US6177381 and CN1479649A have reported the thin-shell catalyst that adopts the lamellar composite carrier preparation, and this catalyst has for example coating gama-alumina for example of Alpha-alumina and an inorganic oxide of kernel.And for example patent US6858769 and CN1705510A have reported a kind of H 2 selective oxidation catalyst take lithium aluminate as carrier.This catalyst is take cordierite as kernel, take lithium aluminate as coating.
The common feature of above-mentioned catalyst is to use on the one hand an inert material, be the kernel of carrier such as ceramic honey comb, cordierite, Alpha-alumina, apply the coating material of one deck bigger serface to enlarge carrier effective surface area, then catalyst activity composition in the load at carrier on the other hand.Influence factor during the preparation coating is a lot, but slurry is undoubtedly one of crucial influence factor.Patent CN101491776A provides a kind of prescription and preparation method who prepares coating paste, and this slurry is comprised of in aluminium colloidal sol, activated alumina, organic adhesive, inorganic adhesive, surfactant, pH adjusting agent below 10 microns particle mean size.The preparation method is dissolved in aluminium colloidal sol, organic adhesive, surfactant, pH adjusting 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, the gained alumina slurry ground 10 minutes～10 hours in ball mill, sand mill, ball mill or colloid mill again, made alumina coats pulp.But this slurry dispersion stabilization is poor, and the slurry preparation process is complicated, and the cycle is long, and the actual production efficient that is used for industrial catalyst is low, and production cost is high.Need to improve slurry preparation method and prescription, enhance productivity, reduce production costs, suitably improve Stability of Slurry simultaneously, improve coating and catalyst performance.
Summary of the invention
One of technical problem to be solved by this invention is that the slurry that exists in the prior art prepares length consuming time, granularity is large, Stability of Slurry is poor, cause that the Catalyst Production cycle is long, cost is high, the coating rate of wear that makes is high, the problem of catalyst performance and poor stability, a kind of new slurry that is used for the hydrogen oxidation catalyst coating is provided, it is short that this slurry has the slurry manufacturing cycle, and the slurry granularity is little, good stability, make the coating rate of wear low, the advantage of catalyst performance and good stability.Two of technical problem to be solved by this invention provides a kind of preparation method of the slurry corresponding with one of technical solution problem.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of slurry for the hydrogen oxidation catalyst coating comprises following component by weight percentage:
A) 1～25% aluminium colloidal sol;
B) 5～50% aluminium oxide;
C) 0.1～10% blowing agent;
D) 0.5～5.0% coating aid;
E) 10～90% deionized water;
F) 0.01～1% pH adjusting agent;
Wherein: coating aid is selected from least a of spodumene, perlite, kaolin, magnesium silicate, calcium silicates, magnesium aluminate, zirconium aluminate or calcium oxide; Blowing agent is selected from least two kinds in PVA, HPC, MC, EMC, tween, sapn or the polyethylene glycol; PH adjusting agent is selected from least a in hydrochloric acid, nitric acid, ammoniacal liquor, aluminium chloride, magnesium chloride, stannic chloride, stannous chloride, the calcium chloride.
In technique scheme, aluminium colloidal sol consumption preferable range is 5～25% 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 5 microns, its consumption preferable range is 10～40% by weight percentage; The blowing agent preferred version is served as reasons and is selected from least a material I among PVA, HPC or the EMC, mix with at least a material II that is selected from tween, sapn or the polyethylene glycol, the part by weight of material I and material II is 1: 0～10: 1, and blowing agent by weight percentage consumption is 0.5～5%; The coating aid preferred version is to be selected from least a in spodumene, perlite, calcium silicates, magnesium aluminate, the calcium oxide, and consumption is 0.5～5% by weight percentage; The pH adjusting agent preferred version is one or more that are selected from hydrochloric acid, ammoniacal liquor, aluminium chloride, stannic chloride, the stannous chloride, and its consumption is 0.05～1% by weight percentage; The consumption preferable range of water is 40%～70% by weight percentage.
Be two of technical solution problem, the technical solution used in the present invention is as follows: a kind of preparation method for the hydrogen oxidation catalyst coating paste may further comprise the steps:
1) by breaking method control aluminium oxide and auxiliary agent particle diameter below 5 microns;
2) water, aluminium colloidal sol, aluminium oxide, coating aid add circular grinding in the circulation colloid mill successively, regulate slurry fluidity with pH adjusting agent, obtain slurry I;
3) after the blowing agent process foaming machine foaming with aequum, join among the slurry I and circulate, regulate slurry pH value at ≈ 4.5 ± 0.3, obtain slurry II.
Aluminium oxide and performance auxiliary agent be selected from by raw material and comminution by gas stream obtains meeting the powder of granularity requirements; Water, aluminium colloidal sol, aluminium oxide, coating aid add successively and carry out circular grinding in the circulation colloid mill, regulate slurry fluidity with pH adjusting agent, obtain slurry I; Blowing agent and water join in the blowing agent and foam, and obtain the foam of requirement and join in the circulating system of slurry I, regulate the pH value at ≈ 4.5 ± 0.3, obtain slurry II.
One aspect of the present invention has been optimized the coating paste prescription: add coating aid, utilize the low melting point of auxiliary agent and the reaction between auxiliary agent and inner nuclear material and the aluminium oxide, increased on the one hand coating and kernel in conjunction with firmness, the stable elements that generates on the other hand is conducive to performance and the stability of coating and catalyst; Blowing agent is by the foaming of foaming machine, can be so that blowing agent disperses more abundant, and the foam quality that obtains is good, bubble diameter is little, the foam yardstick is even, after joining like this among the alumina slurry, a large amount of uniformly vesicle foams have stoped the gathering of alumina particle, the blowing agent of high dispersive can increase intergranular distance at shell of the peripheral formation of particle, has reduced the effect of Van der Waals force, has increased the electro kinetic potential of suspension, again by adding pH adjusting agent, can form good electrostatic stabilization system, can guarantee that by the strict control of pH value size distribution has guaranteed the stability of slurry preparation in the slurry preparation in specific scope; Avoid being unfavorable for simultaneously the too much introducing of the foreign metal of reaction system by the screening of pH adjusting agent, improved catalyst performance and stability.Improve on the other hand the preparation technology of slurry, utilized circulation colloid mill and foaming technique to reduce the slurry preparation section, shortened the slurry preparation time, improved industrial efficient, saved cost.The slurry that uses the inventive method to make, the slurry preparation time has shortened more than 60%, energy efficient and artificial production cost approximately 10%; The slurry granularity is little, d
50For about 3.5um; The slurry distributional stability is placed 30 days d
50Still about 5um; Make the coated carrier rate of wear with this slurry low, rate of wear is about 0.09%.The catalyst that makes is used for the reaction of ethylbenzene dehydrogenation oxidation of hydrogen, oxygen is selectively more than 93%, catalyst through 24 hours degradations of 800 degree steam after, catalyst performance stabilised, oxygen selectively maintains more than 93%, has obtained preferably technique effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 300 gram water, the aluminium colloidal sol of 1200 grams 10%, 800 gram gamma oxidation aluminium powders, 8 gram calcium silicates add successively in the circulation colloid mill and ground 90 minutes, add 20 grams, 20% liquor alumini chloridi and regulate slurry fluidity, get simultaneously 10 gram HPC, 5 gram sapns add water 300 gram and place the foaming machine foaming to make foam, join in the above-mentioned circulation slurry, continue to add 20% aluminium chloride and regulate pH value ≈ 4.70, continue circular grinding 25 minutes, and made the slurry A that needs.
[embodiment 2]
With 500 gram water, the aluminium colloidal sol of 1000 grams 20%, 1200 gram δ-alumina powders, 50 gram calcium oxide, 60 gram magnesium aluminates add successively in the circulation colloid mill and grind 100, add 60 grams, 50% tin chloride solution and regulate slurry fluidity, get 50 gram PVA, 10 gram tweens add water 600 gram and place the foaming machine foaming to make foam, join in the above-mentioned circulation slurry, continue to add 50% stannic chloride and regulate pH value ≈ 4.50, continue circular grinding 20 minutes, and made the slurry B that needs.
[embodiment 3]
With 300 gram water, the aluminium colloidal sol of 2000 grams 40%, 300 gram θ-alumina powders, 30 gram spodumenes add successively in the circulation colloid mill and grind 80, adding 40 gram concentration is 10% magnesium chloride solution, 30 gram concentration are 20% stannous chloride solution, influence liquidity, get 50 gram EMC, 10 gram polyethylene glycol add water 500 gram and place the foaming machine foaming to make foam, join in the above-mentioned circulation slurry, continue to add concentration and be 20% stannous chloride solution and regulate pH value ≈ 4.3, continued circular grinding 30 minutes, make the slurry C of needs.
[embodiment 4]
With 800 gram water, the aluminium colloidal sol of 1000 grams 40%, 300 gram θ-alumina powders, 300 gram gamma oxidation aluminium powders, 20 gram magnesia, 10 gram sodium metasilicate add successively in the circulation colloid mill and grind 70, add the 10% aluminum nitrate solution influence liquidity of 50 grams, get 30 gram HPMC, molten Sha Mujia water 700 grams of 4 gram pools place the foaming machine foaming to make foam, join in the above-mentioned circulation slurry, add nitric acid and ammoniacal liquor and regulate pH ≈ 4.4, continued circular grinding 50 minutes, make slurry D.
[embodiment 5]
With 500 gram water, the aluminium colloidal sol of 1000 grams 40%, 300 gram θ-alumina powders, 10 gram calcium silicates, 5 gram magnesia add successively in the circulation colloid mill and to grind 90 minutes, add the 10% lithium nitrate solution influence liquidity of 50 grams, get 30 gram HPMC, molten Sha Mujia water 700 grams of 4 gram pools place the foaming machine foaming to make foam, join in the above-mentioned circulation slurry, add hydrochloric acid and ammoniacal liquor and regulate pH ≈ 4.6, continue circular grinding 30 minutes, and made slurry E.
[embodiment 6]
With the slurry A of fresh preparation, B, C, D, E spray to respectively on the Alpha-alumina bead of diameter 4mm, dry in the shade under the room temperature, with 80 ℃ of dryings 2 hours, then be warmed up to 120 ℃ dry 2 hours again, 1000 ℃ of roastings 12 hours obtain lamellar composite carrier and are labeled as A
0～E
0The indices of slurry sees Table 1.
[comparative example 1]
Mode according to patent CN101491776 embodiment 3, be that the cyclodextrin solution, 10% CMC, each 10 gram of hydroxypropyl cellulose solution, 1.0 gram softex kws of 25% alumina sol, 30 grams 4% and 1 milliliter 1% hydrochloric acid are made slurries with 35 gram concentration, regulate pH value to 4, with 2000 rev/mins of high-speed stirred 30 minutes.Then in this mixed liquor, add 0.4 gram diatomite, 0.3 gram potassic feldspar, 36 gram particles footpath at the δ-Al below 1 micron
2O
3Powder (160 meters of specific areas
2/ gram), with 2000 rev/mins of high-speed stirred 150 minutes, then slurries is at room temperature carried out colloidal grinding 2 hours, thereby make alumina coats pulp F, make carrier F according to embodiment 6
0The indices of slurry sees Table 1.
Table 1 slurry and coating prepare achievement data
| The slurry title | Fresh slurry d 50/um | Preparation time/min | 1000 turn coating abrasion/% | 30 days disposed slurry d 50/um |
| A | 3.6 | 115 | 0.09 | 5.0 |
| B | 3.5 | 120 | 0.08 | 4.8 |
| C | 3.5 | 115 | 0.09 | 5.1 |
| D | 3.6 | 120 | 0.09 | 5.2 |
| E | 3.5 | 120 | 0.08 | 5.0 |
| F | 8.2 | 300 | 0.15 | 16.8 |
As can be seen from Table 1, the less d of slurry granularity that the slurry that adopts method of the present invention to make makes than employing comparative example 2
50About 3.5um; Slurry is more stable, and slurry is placed 30 days granularities about 5.0um; Adopt this patent method to prepare slurry and compares with the method that adopts comparative example 2, preparation time shortened to about 120 minutes from 300 minutes, had shortened more than 60%, adjusted energy efficient and cost of labor approximately 10%; The slurry that adopts this patent method to make is compared with the slurry that adopts embodiment 1 method to make, be prepared into coated carrier after rate of wear lower, rate of wear is about 0.09%.
[embodiment 7]
With B
0, D
0And F
0Carrier surface dipping Pt, Sn, Li make catalyst C
B, C
D, C
FElementary analysis shows, contains Pt 0.14% according to the mass fraction meter with regard to whole catalyst, and Sn 0.16%, and Li 0.72%.The catalyst for preparing previously is used for the reaction that the oxidation of ethyl benzene dehydrogenation preparation of styrene hydrogen selective generates water.Reactor inside diameter is 25 millimeters stainless steel reaction pipe, in-built 30 milliliters of catalyst.Reaction pressure is normal pressure, liquid air speed 3 hours-1, and 580 ℃ of reaction temperatures, the reactant composition sees Table 2.
The raw material of H 2 selective oxidation forms in table 2 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 |
With C
BAnd C
FCatalyst 800 ℃ through 24 hours steam burin-in process, obtain respectively catalyst C
B *And C
F *, the results are shown in Table 3 for the activity and selectivity of catalyst.Its corresponding catalyst C of slurry that adopts this patent method to make from the result
B, C
D, the catalyst C corresponding with the slurry that adopts the preparation of embodiment 1 method
FCompare, oxygen is selectively higher, and more than 93.5%, 800 ℃ through 24 hours steam burin-in process, its corresponding catalyst C
B *Compare C
F *The oxygen elective reduction still less still maintains more than 93%, shows better stability.
The H 2 selective oxidation performance of table 3 catalyst
Claims (7)
1. slurry that is used for the hydrogen oxidation catalyst coating comprises following component by weight percentage:
A) 1～25% aluminium colloidal sol;
B) 5～50% aluminium oxide;
C) 0.5～10% blowing agent;
D) 0.5～5.0% coating aid;
E) 10～90% deionized water;
F) 0.01～1% pH adjusting agent;
Wherein: coating aid is selected from least a of spodumene, perlite, kaolin, magnesium silicate, calcium silicates, magnesium aluminate, zirconium aluminate or calcium oxide; Blowing agent is mixed with at least a material II that is selected from tween, sapn or the polyethylene glycol by at least a material I that is selected among PVA, HPC or the EMC, and the part by weight of material I and material II is 1: 10～10: 1; PH adjusting agent is selected from least a in hydrochloric acid, nitric acid, the ammoniacal liquor.
2. described slurry for the hydrogen oxidation catalyst coating according to claim 1 is characterized in that aluminium colloidal sol consumption is 5～25% by weight percentage.
3. described slurry for the hydrogen oxidation catalyst coating according to claim 1 is characterized in that aluminium oxide is γ-Al
2O
3, 8-Al
2O
3Or θ-Al
2O
3In at least a and granularity be controlled at below 5 microns, its consumption is 10～40% by weight percentage.
4. described slurry for the hydrogen oxidation catalyst coating according to claim 1 is characterized in that coating aid is to be selected from least a in spodumene, perlite, calcium silicates, magnesium aluminate, the calcium oxide, and consumption is 0.5～5% by weight percentage.
5. described slurry for the hydrogen oxidation catalyst coating according to claim 1 is characterized in that pH adjusting agent is selected from least a in hydrochloric acid, the ammoniacal liquor, and consumption is 0.05～1% by weight percentage.
6. described slurry for the hydrogen oxidation catalyst coating according to claim 1 is characterized in that the consumption of water is 40～80% by weight percentage.
7. the preparation method of the described slurry for the hydrogen oxidation catalyst coating of claim 1 may further comprise the steps:
1) by breaking method control aluminium oxide and auxiliary agent particle diameter below 5 microns;
2) water, aluminium colloidal sol, aluminium oxide, coating aid add in the circulation colloid mill successively, regulate slurry fluidity with pH adjusting agent and obtain slurry I;
3) after the blowing agent process foaming machine foaming with aequum, join among the slurry I and circulate, regulate slurry pH value 4.5 ± 0.3, obtain the slurry for the hydrogen oxidation catalyst coating.
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|---|---|---|---|
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|---|---|---|---|
| CN2010105528576A CN102463145B (en) | 2010-11-17 | 2010-11-17 | Slurry for hydrogen oxidation catalyst coating and preparation method of slurry |
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| CN102463145B true CN102463145B (en) | 2013-09-18 |
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|---|---|---|---|
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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 |
-
2010
- 2010-11-17 CN CN2010105528576A patent/CN102463145B/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 |
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| Publication number | Publication date |
|---|---|
| CN102463145A (en) | 2012-05-23 |
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