CN110449181A - A kind of molecular sieve catalytic coating remaining slurry repetition reuse method and its application in SCR - Google Patents
A kind of molecular sieve catalytic coating remaining slurry repetition reuse method and its application in SCR Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
Abstract
A kind of molecular sieve catalytic coating remaining slurry of the invention repeats reuse method and its application in SCR, including the pulping process by remaining catalyst coatings slurry and additive a, additive b and auxiliary agent according to mass ratio 10-40:5-30:5-40:0.1-10；The additive a is inorganic oxide that is with fixed structure carrier good combination to be coated and facilitating molecular sieve catalyst dispersion and catalytic performance promotion；The additive b is the hydrophilic organic matter binding agent for having multiple hydroxy or carboxy.The molecular sieve catalytic coating remaining slurry repeats reuse method, and method is easy, easily operated, and is significantly reduced industrial solid wastes, realizes resource reutilization, industrial application value with higher；And repeat the coating type molecular sieve catalyst initiation temperature T recycled50Lower than 180 DEG C, temperature window T90Range is more than 200 DEG C.
Description
Technical field
The present invention relates to a kind of molecular sieve catalytic coating remaining slurries to repeat reuse method and its application in SCR,
Belong to monoblock type (coating type) molecular sieve catalyst preparation field.
Background technique
It is shown according to " Chinese automotive environment manages annual report (2018) " data, four kinds of major pollutants carbon monoxide of motor vehicle
(CO), hydrocarbon (HC), nitrogen oxides (NOx), particulate matter (PM) total emission volumn reach 4359.7 ten thousand tons.Wherein, an oxygen
Change 3327.3 ten thousand tons of carbon (CO), 407.1 ten thousand tons of hydrocarbon (HC), 574.3 ten thousand tons of nitrogen oxides (NOx), particulate matter (PM)
50.9 ten thousand tons.Pollutant of the nitrogen oxides (NOx) as the more difficult removal of exhaust gas from diesel vehicle is to cause acid rain and photochemical fog dirt
One of the arch-criminal of dye problem, or induce the major pollutants of haze weather.Therefore, emission of diesel engine nitrogen oxides pollution is solved
Problem is prerequisite and the basis of " winning blue sky defended war ".
Ammonia selective catalytic reduction (NH3- SCR) technology is NO in the oxygen-enriched tail gas of internationally recognized high-efficient purificationXMainstream
Technology.By high activity, highly selective and high stability catalyst, which has NOXHigh conversion rate, at low cost etc. are excellent
Gesture.Monoblock type (coating type) catalyst was mainly used as one of the core of the technology and key in state in six discharge standard stages
Be molecular sieve catalyst.Integral catalyzer preparation process includes catalyst powder preparation, slurrying, coating, drying and roasting
Etc. multiple links.Wherein, slurrying and coating are the committed step that catalyst powder and honeycomb ceramic carrier are combined closely, direct shadow
Ring the activity of integral catalyzer.In actual application, the coating of catalyst coat slurry is generally carried out using infusion process.The mistake
Journey is often associated with abundant residues slurry, while resulting in waste of resources, also will form solid waste, pollutes ambient enviroment.Currently, about
The technology and correlative study that waste catalyst coating paste recycles are less.Coating method disclosed in patent CN104998697A is not adopted
With organic additive and dispersing agent, only with water as dispersing agent, boehmite is as thickener and additive；It is not ugly
Out, which lacks organic additive and dispersing agent will lead to Stability of Slurry variation, directly affects the equal of applying coating
Even property.Organics additive and dispersing agent, especially polyhydroxy organic matter, to molecular sieve catalyst Stability of Slurry and coating with
Combination between carrier is most important.
Summary of the invention
In view of the foregoing, the present invention discloses a kind of molecular sieve catalytic coating remaining slurry repetition reuse method, will receive
Discarded molecular sieve catalyst slurry after collection first passes through alkali process, removes the part silicon-containing compound in remaining slurry, then with
Additive a and additive b, auxiliary agent, deionized water mix co-ground slurrying, realize that molecular sieve catalyst slurry recycles.With
This simultaneously, immersion coating is prepared into monoblock type (coating type) catalyst, for eliminating the nitrogen oxides in tail gas.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of molecular sieve catalytic coating remaining slurry repetition reuse method, including by remaining catalyst coatings slurry and add
Agent a, additive b and auxiliary agent according to mass ratio 10-40:5-30:5-40:0.1-10 pulping process；
The additive a be with fixed structure carrier good combination to be coated and facilitate molecular sieve catalyst dispersion and
The inorganic oxide that catalytic performance is promoted；
The additive b is the hydrophilic organic matter binding agent for having multiple hydroxy or carboxy.
Further, which includes high speed ball milling step, and the purpose is to promote while grinding slurry particle
Chemical coupling reaction occurs for surface group, and suitable particle size range is 0.1-15 μm, and suitable pH value range is 2.0-6.5.
Further, the molecular sieve for being coated on fixed structure carrier that the remaining catalyst coatings slurry refers to is urged
The remaining coating paste of agent.Herein, molecular sieve catalyst refers to using molecular sieve as catalyst activity component or chief active group
/ mono- catalyst；Molecular sieve catalyst coating paste is for molecular sieve catalyst is coated on honeycomb ceramic carrier and is used for
It prepares integral catalyzer and is formed by slurry, wherein slurry includes molecular sieve catalyst, binder, dispersing agent, auxiliary agent and water
Deng；Survival sieve catalyst coating paste is that obtained solid, main component are point after remaining slurries drying after coating
Sub- sieve catalyst, silica, aluminum oxide, titanium dioxide etc..
Further, the molecular sieve catalyst be CHA structure molecular sieve catalyst, RHO structural molecule sieve catalyst,
One of BEA structural molecule sieve catalyst, MFI structure molecular sieve catalyst, and preferably CHA structure molecular sieve catalyst, and
Cu/SSZ-13 molecular sieve catalyst in more preferable CHA structure molecular sieve catalyst.
Further, the fixed structure carrier is cordierite honeycomb ceramic carrier, silicon carbide honeycomb ceramics carrier, metal bee
At least one of nest ceramic monolith.
Further, the additive a is γ-Al2O3、SiO2, TiO2, at least one of cerium zirconium powder.
Further, the additive b be polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, disodium ethylene diamine tetraacetate,
Fatty alcohol polyoxyethylene ether, ethylene glycol, polyacrylic acid, carboxyethyl cellulose, sesbania powder, glycerine, at least one in citric acid
Kind.
Further, the auxiliary agent is alkaline earth, rare earth, the ion of transition metal and/or the oxide containing above-mentioned metal.
Further, the ion of the metal is Cu2+、Ce4+、Ba2+、Mn4+At least one of；The oxide of the metal
For MnO2、CeO2、CuO2、CuO-MnO2At least one of.
Further, further include preprocessing process, alkali treatment, the alkali process are included at least in the preprocessing process
Refer to and above-mentioned remainder catalyst coating paste is immersed in alkaline solution, removes the impurity on molecular sieve catalyst surface and promotion
Molecular sieve catalyst disperses each other；Binder, dispersing agent and auxiliary agent etc. in above-mentioned molecular sieve catalyst coating paste make molecule
Sieve catalyst is bonded to one another and is attached to molecular sieve catalyst surface, suitable alkali process pH value 10-12 with impurity；To ensure
Molecular sieve catalyst structure in lye is not destroyed, and suitable alkali process time range is 2-24h, suitable alkali purification temp
Lower than 100 DEG C.
Further, the stir process which is related to is 12h, and the purpose is to allow remaining slurry sufficiently and alkali
Liquid contacts to remove molecular sieve catalyst surface impurity and to promote agglomerated particle rapid dispersion.
It repeats to recycle coating type molecular sieve catalyst in eliminating vehicle exhaust the present invention also provides as described above
The application of nitrogen oxide pollutant.Compared with fresh sample, it is in NH under the same test conditions3The ignition showed in-SCR reaction
Temperature T50(NOXConversion ratio reaches 50% temperature) it does not reduce, temperature window T90(NOXConversion ratio reaches 90% temperature) range
Deterioration rate is no more than 15%.
Above-mentioned fresh sample refers to that the molecular sieve catalyst coating paste before recycling coats the coating type of preparation for the first time and urges
Agent.The molecular sieve catalyst coating paste is passed through by molecular sieve catalyst powder, binder, auxiliary agent and solvent materials
Mixing, grinding, stirring and etc. preparation uniform slurries, main purpose is that molecular sieve catalyst is firmly attached to carrier
On, motor-vehicle tail-gas emission reduction is realized by the ability of the selective catalysis nitrogen oxides reduction of molecular sieve catalyst.
It is that molecular sieve catalytic coating of the present invention is remaining that above-mentioned molecular sieve catalyst slurry, which coats remaining slurries,
Slurry.
Above-mentioned temperature window T90Range refers to NOXConversion ratio is more than 90% temperature range absolute value.
Above-mentioned deterioration rate calculation formula is as follows: deterioration rate=(fresh sample temperature window T90Range-repetition recycles sample
Temperature window T90Range)/fresh sample temperature window T90Range × 100%.
Compared with the prior art, molecular sieve catalytic coating remaining slurry of the present invention repeat reuse method have with
Lower advantage:
(1) molecular sieve catalyst table is removed in alkaline solution environment to survival sieve catalyst coatings slurry pretreatment
Face promotes the molecular sieve catalyst being sticked together to disperse each other containing impurity such as Si, Al under stirring, to repeat to recycle
It creates conditions.
(2) it repeats to recycle and feeds intake middle addition additive a and additive b, the two mutually cooperate with.The effect of additive a it
First is that providing carrier supported for molecular sieve catalyst and auxiliary agent, promote above-mentioned catalyst and auxiliary agent evenly dispersed, and close therewith
In conjunction with；In addition, effect second is that, promote the combination between catalyst coatings each component and coating and carrier after roasting.Have multiple
The effect of the hydrophilic organics additive b of hydroxy or carboxy is to grind each other in aqueous solvent with catalyst, auxiliary agent, additive a
Mill forms slurry stable, uniform and with caking property.
(3) the molecular sieve catalytic coating remaining slurry repeats reuse method, and method is easy, easily operated, and greatly
Reduction industrial solid wastes, realize resource reutilization, industrial application with higher value.
(4) compared with fresh sample, the coating type molecular sieve catalyst initiation temperature T recycled is repeated50Lower than 180 DEG C, temperature
Spend window T90Range is more than 200 DEG C.
Detailed description of the invention
Fig. 1 is embodiment 1 and fresh sample in NH3NO in-SCR reactionXConversion rate curve.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
In embodiments of the present invention, coating load rate refers to that coating front and back is of poor quality than quality before coating；Coating shedding rate
Refer to that catalyst coatings reduction amount is than upper catalyst coatings gross mass in coating temperature test experiments.
The preparation process for the molecular sieve catalyst slurry (fresh sample) used in the embodiment of the present invention is as follows:
Successively by Cu/SSZ-13 molecular sieve catalyst powder, silane coupling agent KH-560, polyethylene glycol, cerous nitrate according to
Mass ratio 1:0.1:0.02:0.005 is added in deionized water, is prepared into mass content 20% by mixing, stirring, grinding and starches
Liquid.
18*18*20cm (long * wide * high) cordierite honeycomb ceramic carrier sample suitable for SCR is taken, molecular sieve is immersed in
It in catalyst coat slurry, is coated, dip time 15s, falls leftover slurry with compressed air purging after taking-up, 120 DEG C
Drying；After drying, above-mentioned coating step is repeated, carries out the second secondary coating coating；After coating, 120 DEG C of dryings, 550
DEG C roasting 6h, obtains molecular sieve catalyst sample, remaining slurry is labeled as remaining molecular sieve catalyst slurry.
Below in conjunction with embodiment come the present invention will be described in detail create.
Embodiment 1
(1) it pre-processes
It will be dried under the conditions of 120 DEG C of remaining molecular sieve catalyst slurry, be prepared into powder using super fine grinder, soaked
Not in the sodium hydroxide solution of 0.1N, stir process 12h；After treatment, filtration washing to neutrality, filter cake is in 120 DEG C of items
It is dried under part；
(2) pulping process
By above-mentioned pretreated slurry, SiO2, carboxymethyl cellulose, citric acid, sesbania powder and Gerhardite press
Deionized water is added in mass ratio=30:25:20:10:10:5, is uniformly mixed and is configured to 350ml slurries, in high speed ball mill
With 25Hz milled processed 40min, it is made and repeats to recycle catalyst coatings slurry, analyzed using 3000 type laser particle analyzer of Malvern
Obtaining average grain diameter is 1.3 μm, and measuring pH value using plum Teller-portable pH meter of support benefit FG3 type is 4.8.
(3) coating procedure
18*18*20cm (long * wide * high) cordierite honeycomb ceramic carrier sample suitable for SCR is taken, is immersed in above-mentioned heavy
It in the molecular sieve catalyst coating paste recycled again, is coated, dip time 15s uses compressed air purging after taking-up
Fall leftover slurry, 120 DEG C of drying；After drying, above-mentioned coating step is repeated, carries out the second secondary coating coating；Coating terminates
Afterwards, 120 DEG C of dryings, 550 DEG C of roasting 6h obtain the molecular sieve catalyst sample for repeating to recycle, and coating load rate reaches
30.52%, expulsion rate 1.08%.
Embodiment 2
Pretreatment, coating procedure are same as Example 1, and difference is the type and addition of additive a, b in pulping process
Amount is different.Pulping process is specifically distinguished: by pretreated slurry, Al2O3、SiO2, polyethylene glycol, polyacrylic acid, glycerine,
50% manganese nitrate aqueous solution and cerous nitrate in mass ratio=30:10:22:9:7:20:1:1, deionized water is added, is uniformly mixed and matches
350ml slurries are made, with 25Hz milled processed 40min in high speed ball mill, is made and repeats to recycle catalyst coatings slurry, survey
Obtain average grain diameter, pH value is shown in Table 1；The molecular sieve catalyst sample for repeating to recycle is obtained, coating load rate and expulsion rate are shown in Table
1。
Embodiment 3
Pretreatment, coating procedure are same as Example 1, and difference is the type and addition of additive a, b in pulping process
Amount is different.Pulping process is specifically distinguished: by pretreated slurry, SiO2, cerium zirconium powder, fatty alcohol polyoxyethylene ether, polypropylene
Acid, carboxymethyl cellulose, glucose, CeO2 in mass ratio=30:20:12:8:8:10:10:1, deionized water is added, mixing is equal
It is even to be configured to 350ml slurries, with 25Hz milled processed 40min in high speed ball mill, it is made and repeats to recycle catalyst coatings slurry
Material, measures average grain diameter, pH value is shown in Table 1；Obtain the molecular sieve catalyst sample for repeating to recycle, coating load rate and expulsion rate
It is shown in Table 1.
Embodiment 4
Pretreatment, coating procedure are same as Example 1, and difference is the type and addition of additive a, b in pulping process
Amount is different.Pulping process is specifically distinguished: by pretreated slurry, SiO2, polyethylene glycol, ethylene glycol, citric acid, ZrO2,
CeO2 in mass ratio=30:30:8:25:5:1:1, be added deionized water, be uniformly mixed be configured to 350ml slurries, in clipping the ball
With 25Hz milled processed 40min in grinding machine, it is made and repeats to recycle catalyst coatings slurry, measure average grain diameter, pH value is shown in Table 1；
The molecular sieve catalyst sample for repeating to recycle is obtained, coating load rate and expulsion rate are shown in Table 1.
Comparative example 1
Substance classes, feed ratio, preparation method, control parameter and the technique and implementation that pulping process and coating procedure are related to
Example 1 is identical, and difference is not pre-process leftover slurry, the repetition of preparation recycle catalyst coatings slurry average particle size with
PH value is shown in Table 1, and the coating load rate and expulsion rate for the molecular sieve catalyst sample that the repetition of preparation recycles are shown in Table 1.
Comparative example 2
Pretreatment, coating procedure are same as Example 1, and difference place is to be added without additive a in pulping process, feed intake
Than pretreated slurry, carboxymethyl cellulose, citric acid, sesbania powder and Gerhardite in mass ratio=30:20:10:
10:5, addition deionized water, which is uniformly mixed, is configured to 350ml slurries, and the repetition of preparation recycles catalyst coatings slurry average particle size
It is shown in Table 1 with pH value, the coating load rate and expulsion rate for the molecular sieve catalyst sample that the repetition of preparation recycles are shown in Table 1.
Comparative example 3
Pretreatment, coating procedure are same as Example 1, and difference place is to be added without additive b in pulping process, feed intake
Than pretreated slurry, SiO2With Gerhardite in mass ratio=6:5:1, be added deionized water be uniformly mixed is configured to
350ml slurries, the repetition of preparation recycle catalyst coatings slurry average particle size and pH value to be shown in Table 1, what the repetition of preparation recycled
The coating load rate and expulsion rate of molecular sieve catalyst sample are shown in Table 1.
Comparative example 4
Pretreatment, coating procedure are same as Example 1, and difference place is to be added without additive b in pulping process and add
Add agent b, the pretreated slurry of feed ratio and Gerhardite in mass ratio=6:1, deionized water is added and is uniformly mixed and matches
350ml slurries are made, the repetition of preparation recycles catalyst coatings slurry average particle size and pH value to be shown in Table 1, and the repetition of preparation is sharp again
The coating load rate and expulsion rate of molecular sieve catalyst sample are shown in Table 1.
Comparative example 5
Pretreatment, coating procedure are same as Example 1, and difference place is to be added without auxiliary agent in pulping process, feed ratio
Pretreated slurry, SiO2, carboxymethyl cellulose, citric acid, sesbania powder in mass ratio=30:25:20:10:10, addition goes
Ionized water, which is uniformly mixed, is configured to 350ml slurries, and the repetition of preparation recycles catalyst coatings slurry average particle size to be shown in Table with pH value
1, the coating load rate and expulsion rate for the molecular sieve catalyst sample that the repetition of preparation recycles are shown in Table 1.
Table 1
| Embodiment | Average particle size/μm | PH value | Load factor/% | Expulsion rate/% |
| Embodiment 1 | 1.3 | 4.8 | 30.52 | 1.08 |
| Embodiment 2 | 1.4 | 3.9 | 28.68 | 0.96 |
| Embodiment 3 | 1.3 | 3.8 | 31.34 | 1.27 |
| Embodiment 4 | 2.1 | 4.5 | 29.77 | 1.29 |
| Comparative example 1 | 5.8 | 4.8 | 37.13 | 2.31 |
| Comparative example 2 | 0.5 | 4.8 | 19.01 | 12.35 |
| Comparative example 3 | 1.9 | 6.3 | 7.39 | 32.14 |
| Comparative example 4 | 0.3 | 6.3 | 7.14 | 35.43 |
| Comparative example 5 | 1.5 | 4.8 | 29.85 | 1.67 |
Verify embodiment
The embodiment of the present invention 1~4 and comparative example 1~5 are coated to the whole sample for being prepared into 13*13*15 (length, width and height), In
NH is carried out on the micro fixed-bed reactor of laboratory self assembly3- SCR catalytic performance test, and compared with fresh sample.Make
Crystal reaction tube is having a size of 15mm, 5 DEG C/min of evaluation test heating rate.Form content are as follows: 500ppm NO, 500ppm
NH3, 5%O2, N2For Balance Air, total flow 1800ml/min, reaction velocity 54000h-1。
This example is that Examples 1 to 4 and comparative example 1-5 remove NOXEvaluation result (being shown in Table 2).
Table 2
By data in Tables 1 and 2 as it can be seen that compared with comparative example 1, the leftover slurry in embodiment 1 is due to having carried out pre- place
Reason, has abolished leftover slurry and has been adhered, and facilitates catalyst coatings dispersion, repeats to recycle the slurry partial size of preparation smaller；Separately
On the one hand, pretreatment helps to remove that molecular sieve catalyst surface is siliceous, aluminium element impurity in alkaline environment, is conducive to catalysis and lives
Property center exposure, show more good cryogenic property and active temperature windows.
Compared with comparative example 2,3,4, repeat that slurrying is recycled to joined additive a and additive b, the two in embodiment 1
Act synergistically each other, formed stablize, stablize, uniformly and with appropriate caking property slurry, after roasting with catalyst, auxiliary agent and violet
Green stone carrier forms close, stable catalyst coatings, therefore coating load rate is higher, and expulsion rate is lower.
It repeats that slurrying is recycled to joined auxiliary agent compared with comparative example 5, in embodiment 1, the effect of auxiliary agent is to promote catalysis
Activity, therefore show broader operation temperature window.
It is compared with fresh sample, repetition prepared by the embodiment of the present invention 1 recycles coating type molecular sieve catalyst temperature window
Deterioration rate is less than.
In conclusion molecular sieve catalytic coating remaining slurry provided by the invention repeats reuse method and catalyst, it is real
The repetition of existing waste residual slurry recycles, in NH3Good cryogenic property and operation temperature window are shown in-SCR reaction.
Lacking pretreatment, additive a, additive b and auxiliary agent can not achieve low temperature, high temperature NOXEfficient removal.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of molecular sieve catalytic coating remaining slurry repeats reuse method, which is characterized in that including by remaining catalyst coatings
Slurry is with additive a, additive b and auxiliary agent according to the pulping process of mass ratio 10-40:5-30:5-40:0.1-10；
The additive a is with fixed structure carrier good combination to be coated and facilitates molecular sieve catalyst dispersion and catalysis
The inorganic oxide of performance boost；
The additive b is the hydrophilic organic matter binding agent for having multiple hydroxy or carboxy.
2. a kind of molecular sieve catalytic coating remaining slurry according to claim 1 repeats reuse method, which is characterized in that
The remaining coating for the molecular sieve catalyst for being coated on fixed structure carrier that the remaining catalyst coatings slurry refers to
Slurry.
3. a kind of molecular sieve catalytic coating remaining slurry according to claim 1 repeats reuse method, which is characterized in that
The fixed structure carrier is cordierite honeycomb ceramic carrier, silicon carbide honeycomb ceramics carrier, in metal beehive ceramic monolith
It is at least one.
4. a kind of molecular sieve catalytic coating remaining slurry according to claim 1 repeats reuse method, which is characterized in that
The additive a is γ-Al2O3、SiO2, TiO2, at least one of cerium zirconium powder.
5. a kind of molecular sieve catalytic coating remaining slurry according to claim 1 repeats reuse method, which is characterized in that
The additive b is polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, disodium ethylene diamine tetraacetate, aliphatic alcohol polyethenoxy
At least one of ether, ethylene glycol, polyacrylic acid, carboxyethyl cellulose, sesbania powder, glycerine, citric acid.
6. a kind of molecular sieve catalytic coating remaining slurry according to claim 1 repeats reuse method, which is characterized in that
The auxiliary agent is alkaline earth, rare earth, the ion of transition metal and/or the oxide containing above-mentioned metal.
7. a kind of molecular sieve catalytic coating remaining slurry according to claim 6 repeats reuse method, which is characterized in that
The ion of the metal is Cu2+、Ce4+、Ba2+、Mn4+At least one of；The oxide of the metal is MnO2、CeO2、CuO2、
CuO-MnO2At least one of.
8. a kind of molecular sieve catalytic coating remaining slurry according to claim 6 repeats reuse method, which is characterized in that
The molecular sieve catalyst is CHA structure molecular sieve catalyst, RHO structural molecule sieve catalyst, the catalysis of BEA structure molecular screen
One of agent, MFI structure molecular sieve catalyst.
9. a kind of molecular sieve catalytic coating remaining slurry according to claim 1 repeats reuse method, which is characterized in that
Further include preprocessing process, alkali treatment, the pH value 10-12 of the alkali process, at alkali are included at least in the preprocessing process
Time range 2-24h is managed, suitable alkali purification temp is lower than 100 DEG C.
10. the molecular sieve catalyst obtained according to any the method for right 1-9 is in catalytic purification NOXIn application.
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| Publication number | Priority date | Publication date | Assignee | Title |
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