CN102861594A - Coating slurry, preparation method and application thereof - Google Patents
Coating slurry, preparation method and application thereof Download PDFInfo
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- CN102861594A CN102861594A CN2011101884326A CN201110188432A CN102861594A CN 102861594 A CN102861594 A CN 102861594A CN 2011101884326 A CN2011101884326 A CN 2011101884326A CN 201110188432 A CN201110188432 A CN 201110188432A CN 102861594 A CN102861594 A CN 102861594A
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Abstract
The invention discloses a coating slurry, a preparation method and an application thereof. The solid content of the coating slurry is 20%-50%, and its pH is 2.5-6.5. According to the solid content, the coating slurry contains the following components of: by weight, 40-80 wt% of pseudoboehmite, 5-40 wt% of zirconium oxide and cerium oxide, 5-40 wt% of lanthanum oxide, 1-15 wt% of nanometer titania, 1-10 wt% of copper nitrate, 0.5-15 wt% of manganese nitrate and 1-10 wt% of aluminum nitrate. The preparation method of the coating slurry comprises the following steps of: weighing an appropriate amount of pseudoboehmite, cerium-zirconium oxide or nitrate, nano-sized TiO2, copper, manganese and aluminum nitrate, putting into a ball milling tank for ball milling so as to obtain an uniform slurry; taking out the slurry which has undergone ball milling, adding concentrated nitric acid and stirring to prepare the coating slurry. The application of the coating slurry comprises the following steps of: immersing a cordierite carrier into the coating slurry for 10-30 min, taking out, blowing off residual liquid in pore canal, drying at the temperature of 90-130 DEG C for 5-7 hours, and roasting in the air of 500-600 DEG C, so as to prepare a coating-containing catalytic combustion catalyst carrier. The coating slurry provided by the invention has high solid content, is easy to coat, and has strong adhesion with a carrier and high specific surface area.
Description
Technical field
The present invention relates to a kind of coating slurries and its preparation method and application, specifically relate to coating slurries and preparation and the application of the high catalyst for catalytic combustion of a kind of solid content.
Background technology
The coating slurries are mixtures of a kind of solid and uniform liquid mixing and stable in properties, are the important predecessors of preparation catalyst for catalytic combustion.In the preparation process of catalyst, the coating slurries need to be coated on the cordierite carrier, purpose is to improve the specific area of catalyst carrier, thereby makes the active material high dispersive in its surface.Good coating slurries should have the following advantages: first, higher coating specific area, specific area is an important indicator of evaluate catalysts, its size all has obvious impact to catalyst coat macroscopic property, adsorption capacity, chemical stability etc., and the specific area that increases catalyst coat can effectively increase the quantity and the distribution situation of improving reactive metal of catalyst active center; The second, coating adhesive strength preferably, honeycomb catalyst wearing and tearing in use mainly come from the erosion of exhaust-gas flow, and the adhesive strength that improves coating is extending catalyst service life effectively.
CN1415410 discloses a kind of catalyst for catalytic combustion and preparation method thereof, and the coating slurries preparation method that this catalyst adopts is as follows: the coating according to honeycomb ceramic carrier forms, and is active A l by weight percentage
2O
320%～80%, TiO
210%～40%, CeO25%～30%, ZrO25%～20% calculates and takes by weighing each material, add distilled water and mix, be modulated into moisture thin pulp, the distilled water of adding is 10-50:1 with the ratio of solid gross mass, described coating slurries have coating easily, be difficult for stopping up the advantage in duct, but the solid content of these coating slurries is not high, the coating specific area is low and poor with the adhesive strength of honeycomb ceramic carrier.CN101439290 discloses a kind of cellular ceramic type catalyst for catalytic combustion of perovskite and preparation and application, comprising the preparation of slurries, gets an amount of γ-Al
2O
3, Ce
mZr
1-mO
2, LaMnAl
11O
19, BaMnAl
11O
19Or Sr
12Al
14O
21Metal oxide and citric acid and deionized water mix and blend make stable suspension, coating slurries namely, wherein solid content is about 5-50%, this slurry constituents is complicated, the coating specific area is low, need repeatedly to apply easily to cause coating shedding.
The character of coating slurries is most important for the high performance catalyst for catalytic combustion of preparation, the activity of catalyst, stable all relevant with it.Yet the report that prior art is scrutinized for the coating slurries but seldom.The part prior art is not detailed aspect introducing in the preparation of slurries, can't repeat to make, or can't form mixed uniformly slurries at all.Therefore, develop high solids content, good in conjunction with firmness, be easy to apply and to have catalyst for catalytic combustion coating slurries of higher coating specific area significant.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of coating slurries and its preparation method and application, these coating slurries have higher solid content, are easy to apply and high with strong adhesion, the coating specific area of carrier.
A kind of coating slurries, solid content is that 20%～50%(solid content is the mass percent that coating slurries remainder after 120 ℃ of oven dry accounts for total amount), pH is 2.5～6.5, by weight percentage, contain the boehmite of 40wt%～80wt% in the solid content, the zirconia of 5wt%～40wt% and cerium oxide, the lanthana of 5wt%～40wt%, the nano titanium oxide of 1wt%～15wt%, the copper nitrate of 1wt%～10wt%, the manganese nitrate of 0.5wt%～15wt%, the aluminum nitrate of 1wt%～10wt%.
A kind of preparation method of coating slurries comprises the steps:
(1) takes by weighing an amount of boehmite, cerium Zirconium oxide or nitrate, lanthanum nitrate, nano-TiO
2, aluminum nitrate, manganese nitrate and copper nitrate put into tank, ball milling becomes uniform slurries;
(2) slurries behind the taking-up ball milling add red fuming nitric acid (RFNA) and stirring, leave standstill, and make the coating slurries.
Ball-milling Time in the inventive method step 1 is 2～16 hours, preferred 4～8 hours.Spheroid in the ball grinder is 0.3～2.2 with the slurry weight ratio.
Mixing time in the inventive method step 2 is 2～16 hours, preferred 4～8 hours, and 500～800 rev/mins of mixing speeds, time of repose is 1～2 hour.
Add an amount of carbonate, bicarbonate or urea in the coating slurries that can also make to step (2) in the inventive method, add thermal agitation and make the coating slurries, these coating slurries are compared the pH value raising 0.3-1.5 of the coating slurries that step (2) makes.Described mixing time is 20～40 minutes, 600～1000 rev/mins of mixing speeds, and keeping the coating slurry temperature in the whipping process is 20 ℃～40 ℃.
The application of above-mentioned coating slurries in preparation catalyst for catalytic combustion carrier: cordierite carrier is dipped in the coating slurries 10-30 minute, take out the residual liquid in the after-blow clear opening road, 90-130 ℃ of lower oven dry 5-7 hour, at 500-600 ℃ of air roasting 4-6 hour, make the catalyst for catalytic combustion carrier that contains coating.
The research discovery, the solid content of coating slurries, component, viscosity, acid-base value and preparation method thereof have direct relation to the coating effect of coating slurries, and mutually work in coordination with, cooperatively interact between each factor.The inventive method is by adding an amount of nano-TiO in slurries
2, zirconium cerium oxide or nitrate, lanthana and copper manganese aluminium nitrate and control slurries solid content, adjust the acidity of slurries, the coating slurries that make compared with prior art, have be easy to apply and with strong adhesion, the coating specific area advantages of higher of carrier.After having adjusted acidity, in slurries, weakly alkaline carbonate, bicarbonate or urea have been added in the inventive method, under the condition of heating, generate gas with the nitric acid effect, slurries are played better peptizaiton, simultaneously can consume slowly a small amount of nitric acid, the acidity of slurries is carried out slowly, made more high performance coating slurries after the fine setting dynamically.The inventive method preparation process is simple, and the coating slurries of preparation for a long time retention properties do not change, and satisfy the requirement of follow-up use.Have very high specific area and good bond strength by the prepared catalyst coat of these coating slurries, in the service life of having improved catalyst, economic benefit is obvious.
The specific embodiment
Further specify effect of the present invention and effect below in conjunction with embodiment, but described embodiment should not be construed as the restriction of the scope of the invention.
Embodiment 1
Take by weighing boehmite 46g, cerium oxide 10g, zirconia 8g, lanthanum nitrate 21g, nano-TiO
25g, copper nitrate 2g, manganese nitrate 2.8g and aluminum nitrate 2.7g are dissolved in the 100g deionized water, stir a little in the rear immigration ball grinder with glass bar, behind the ball milling 5 hours, the slurries that obtain are poured into add while stirring red fuming nitric acid (RFNA) 0.3ml in the beaker, mixing speed is 600 rev/mins, mixing time is 4 hours, leaves standstill 2 hours, and the pH that the coating slurries are finished in preparation is 6.2, solids content approximately 45%, the boehmite that contains 56wt% in the solid content, the zirconia of 19wt% and cerium oxide, the lanthana of 10wt%, the nano titanium oxide of 6.0wt%, the copper nitrate of 2.4wt%, the manganese nitrate of 3.4wt%, the aluminum nitrate of 3.2wt%.
Embodiment 2
Take by weighing boehmite 22g, cerous nitrate 7.5g, zirconium nitrate 8.2g, lanthanum nitrate 26.6g, nano-TiO
20.8g, copper nitrate 0.8g, manganese nitrate 1.2g and aluminum nitrate 3g are dissolved in the 100g deionized water, stir a little in the rear immigration ball grinder with glass bar, behind the ball milling 4 hours, the slurries that obtain are poured into add while stirring red fuming nitric acid (RFNA) 0.6ml in the beaker, mixing speed is 800 rev/mins, mixing time is 6 hours, leave standstill and add 4g sodium acid carbonate and strong stirring 40min after 2 hours, 1000 rev/mins of mixing speeds, 30 ℃ of temperature, the pH that the coating slurries are finished in preparation is 5.0, solids content approximately 30%, the boehmite that contains 50wt% in the solid content, the zirconia of 14wt% and cerium oxide, the lanthana of 23wt%, the nano titanium oxide of 1.8wt%, the copper nitrate of 1.8wt%, the manganese nitrate of 2.7wt%, the aluminum nitrate of 6.7wt%.
Embodiment 3
Take by weighing boehmite 19.2g, cerium zirconium powder 4.7g, lanthanum nitrate 6.3g, nano-TiO
21.2g, copper nitrate 1.6g, manganese nitrate 2.4g and and aluminum nitrate 2.1g be dissolved in the 100g deionized water, stir a little in the rear immigration ball grinder with glass bar, behind the ball milling 8 hours, the slurries that obtain are poured into add while stirring red fuming nitric acid (RFNA) 0.8ml in the beaker, mixing speed is 500 rev/mins, mixing time is 2 hours, leave standstill and add 2.5g urea and strong stirring 30min after 1 hour, 800 rev/mins of mixing speeds, 35 ℃ of temperature, the pH that the coating slurries are finished in preparation is 3.8, solids content approximately 25%, the boehmite that contains 57wt% in the solid content, the zirconia of 14wt% and cerium oxide, the lanthana of 7.2wt%, the nano titanium oxide of 3.6wt%, the copper nitrate of 4.8wt%, the manganese nitrate of 7.1wt%, the aluminum nitrate of 6.3wt%.
Embodiment 4
Take by weighing boehmite 22g, cerium zirconium powder 16g, lanthanum nitrate 17.8g, nano-TiO
23.6g, copper nitrate 1.6g, manganese nitrate 2.4g and aluminum nitrate 2.2g are dissolved in the 100g deionized water, stir a little in the rear immigration ball grinder with glass bar, behind the ball milling 6 hours, the slurries that obtain are poured into add while stirring red fuming nitric acid (RFNA) 0.3ml in the beaker, mixing speed is 600 rev/mins, mixing time is 4 hours, leaves standstill 2 hours, and the pH that the coating slurries are finished in preparation is 5.5, solids content approximately 35%, the boehmite that contains 40wt% in the solid content, the zirconia of 30wt% and cerium oxide, the lanthana of 12wt%, the nano titanium oxide of 6.6wt%, the copper nitrate of 3.0wt%, the manganese nitrate of 4.4wt%, the aluminum nitrate of 4.0wt%.
Comparative Examples 1
Prepare the coating slurries by the CN1415410 method, take by weighing 70g γ-Al
2O
3Powder, 14g Detitanium-ore-type TiO
2Powder, 10gCeO
2Powder, 6gZrO
2Powder mixes rear adding 1.4L distilled water, carefully grinds to form moisture thin pulp, and solid content is about 7%.
The application of coating slurries in preparation catalyst for catalytic combustion carrier: make the coating slurries according to embodiment and Comparative Examples, the cordierite carrier that cuts into fritter is dipped in the coating slurries 20 minutes, blow off residual liquid in the inner duct with compress wind after taking out, 110 ℃ of lower oven dry 6 hours, 550 ℃ of air roastings 5 hours, make the catalyst carrier sample that contains coating.Investigate carrier coating specific area, coating intensity and the coating of coating slurries in conjunction with firm degree, following experiment be set:
Experiment 1: the record carrier sample applies the weight after front and the roasting, sees Table 1.
Table 1 support samples weightening finish ratio.
| Test number | The former weight of carrier (g) | Weight (g) after the carrier coating roasting | Weightening finish is than (%) |
| Embodiment 1 | 12.24 | 13.25 | 8.25 |
| Embodiment 2 | 11.56 | 12.69 | 9.78 |
| Embodiment 3 | 12.14 | 13.25 | 9.14 |
| Embodiment 4 | 13.32 | 14.26 | 7.06 |
| Comparative Examples 1 | 11.88 | 12.23 | 2.94 |
Annotate: weightening finish ratio=(weight after the roasting-carrier original weight)/carrier original weight * 100%.
Can be found out by above data, the support samples coating solid increment of embodiment 1～4 is more than 7%.
Experiment 2: the sampling support samples, sample presentation analytic sample specific area the results are shown in Table 2.
Table 2 support samples specific surface test data.
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 |
| BET area (m 2/g） | 19.17 | 23.26 | 22.84 | 18.23 | 11.15 |
Can be found out by above data, the support samples specific area of embodiment 1～4 exceeds Comparative Examples 2 specific areas more than 40%.
Experiment 3: the sample after the sample presentation analysis was put into the microwave oscillation cleaning machine 5 hours, load-bearing before and after the concussion, the coating combination of investigation sample is degree firmly, and data see Table 3.
Table 3 support samples microwave oscillation data.
| Test number | Coated carrier weight (g) | Weight behind the microwave oscillation (g) | Loss of weight is than (%) |
| Embodiment 1 | 7.232 | 7.134 | 1.355 |
| Embodiment 2 | 7.456 | 7.363 | 1.247 |
| Embodiment 3 | 6.582 | 6.496 | 1.306 |
| Embodiment 4 | 7.124 | 7.113 | 1.544 |
| Comparative Examples 1 | 6.863 | 6.716 | 2.142 |
Annotate: loss of weight ratio=(weight after coated carrier weight-concussion)/coated carrier weight * 100%, in order to guarantee to calculate accurately the loss of weight ratio, the selection weighing precision is that the electronic balance of 0.001g carries out weighing.
Can be found out by above data, the support samples expulsion rate of embodiment 1～4 is lower, illustrates that it has better coating firmness.
As seen, the prepared catalyst coat slurries of this patent method are having obvious advantage aspect specific area, coating firmness and the slurries solids content.
The above only is this patent preferred embodiment, be not that this patent is done any pro forma restriction, the professional can be changed and be revised as the case may be, still, does not everyly break away from the simple modification that the technical solution of the present invention content carries out and still belongs in the scope of technical solution of the present invention.
Claims (8)
1. coating slurries, it is characterized in that: solid content is 20%～50%, the pH value is 2.5～6.5, in the solid content by weight percentage: the boehmite that contains 40wt%～80wt%, the zirconia of 5wt%～40wt% and cerium oxide, the lanthana of 5wt%～40wt%, the nano titanium oxide of 1wt%～15wt%, the aluminum nitrate of the copper nitrate of 1wt%～10wt%, the manganese nitrate of 0.5wt%～15wt% and 1wt%～10wt%.
2. the preparation method of the described coating slurries of claim 1 is characterized in that: comprise the steps:
(1) takes by weighing an amount of boehmite, cerium Zirconium oxide or nitrate, lanthanum nitrate, nano-TiO
2, copper nitrate, manganese nitrate and aluminum nitrate put into the ball grinder endosphere and wear into uniform slurries;
(2) slurries behind the taking-up ball milling add red fuming nitric acid (RFNA) and stirring, leave standstill, and make the coating slurries.
3. method according to claim 2, it is characterized in that: the Ball-milling Time in the described step 1 is 2～16 hours.
4. method according to claim 2, it is characterized in that: the spheroid in the described ball grinder is 0.3～2.2 with the slurry weight ratio.
5. method according to claim 2, it is characterized in that: the mixing time in the described step 2 is 2～16 hours, 500～800 rev/mins of mixing speeds, time of repose is 1～2 hour.
6. method according to claim 2, it is characterized in that: add carbonate, bicarbonate or urea in the coating slurries that make to step (2), add thermal agitation and make the coating slurries, the pH value that these coating slurries are compared the coating slurries that step (2) makes improves 0.3-1.5.
7. method according to claim 6, it is characterized in that: described mixing time is 20～40 minutes, 600～1000 rev/mins of mixing speeds, keeping the coating slurry temperature in the whipping process is 20 ℃～40 ℃.
8. the application of the described coating slurries of claim 1 in preparation catalyst for catalytic combustion carrier: cordierite carrier is dipped in the coating slurries 10-30 minute, take out the residual liquid in the after-blow clear opening road, 90-130 ℃ of lower oven dry 5-7 hour, at 500-600 ℃ of air roasting 4-6 hour, make the catalyst for catalytic combustion carrier that contains coating.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497644A (en) * | 2014-11-28 | 2015-04-08 | 石江潭 | High-temperature-resistant inorganic catalytic coating and porous honeycomb metal burning board coated with same |
| CN106732576A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN109364903A (en) * | 2018-10-23 | 2019-02-22 | 江西科技师范大学 | A kind of high-specific area nano optically catalytic TiO 2 coating and preparation method |
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| CN1436594A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process of waste gas purifying catalyst containing noble metal |
| CN1461672A (en) * | 2002-05-31 | 2003-12-17 | 中国石油化工股份有限公司 | Method for coating active component cellular carrier |
| CN101209425A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Method for preparing slurry containing aluminum oxide |
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2011
- 2011-07-07 CN CN201110188432.6A patent/CN102861594B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1436594A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process of waste gas purifying catalyst containing noble metal |
| CN1461672A (en) * | 2002-05-31 | 2003-12-17 | 中国石油化工股份有限公司 | Method for coating active component cellular carrier |
| CN101209425A (en) * | 2006-12-30 | 2008-07-02 | 比亚迪股份有限公司 | Method for preparing slurry containing aluminum oxide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497644A (en) * | 2014-11-28 | 2015-04-08 | 石江潭 | High-temperature-resistant inorganic catalytic coating and porous honeycomb metal burning board coated with same |
| CN106732576A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN106732576B (en) * | 2015-11-19 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN109364903A (en) * | 2018-10-23 | 2019-02-22 | 江西科技师范大学 | A kind of high-specific area nano optically catalytic TiO 2 coating and preparation method |
| CN109364903B (en) * | 2018-10-23 | 2021-05-25 | 江西科技师范大学 | High-specific-surface-area nano titanium dioxide photocatalytic coating and preparation method thereof |
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