CN101249444B - Method for preparing nitrous oxides selectivity reduction catalyst on metal alloy carrier - Google Patents
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Abstract
The invention belongs to a field of diesel-engined car tail gas cleaning and relates to a method for preparing a catalyst with optimized performance on metal alloy support for selectively reducing nitrogen oxide. The method includes preparing nickel nitrate solution, manganese nitrate solution, copper nitrate solution, cobalt nitrate solution, ferric nitrate solution, cerium nitrate solution and chromium nitrate solution with the distilled water as solvent; selecting 2-4 kinds of solutions from the solutions and mixing with silver nitrate solution or palladium nitrate of equivalent volume to prepare catalyst solution; dip-coating the catalyst solution on a glass ceramic coating of metal alloy support by; air-drying the coated metal carrier at room temperature; drying at 120-180 DEG C; repeating the coating and the drying for 5-8 times; and calcining at 600-1,000 DEG C for 1-5h to activate and mold. The method has the advantages of low cost, good initiation and catalytic characteristic effect.
Description
Technical field
The invention belongs to the diesel car tail gas refining field, relate to the method for the nitrous oxides selectivity reduction catalyst of a kind of performance optimization of preparation on metal alloy carrier
Background technology
Along with being on the rise of atmosphere pollution, environmental protection has worldwide caused people's great attention, and the control technology that exhaust gas from diesel vehicle pollutes is the important environmental problem that air conservation must solve.The pollutant NO of emission of diesel engine
XBe a kind of pernicious gas that atmospheric environment is produced severe contamination, it can form photochemical fog under photoinduction, and the respiratory system of harmful to human destroys the high-altitude ozone layer, also is one of important origin cause of formation of acid rain simultaneously.Therefore, for NO in the diesel vehicle
XCatalytic purification be the focus of motor vehicle tail-gas purifying research.As the most promising post-processing technology, SCR (Selective Catalytic Reduction) technology has NO
XThe reduction efficiency height generates the advantage of the few and safety non-toxic of accessory substance, becomes the focus that the researcher pays close attention in recent years.The key issue of SCR technology is to select good catalyst, selected catalyst should have the following advantages: high activity, good mechanical strength, mar proof, have suitable operation interval and anti-poisoning capability strong, such catalyst just can be applied to actual art production process.The catalyst of research has noble metal catalyst, metal oxide catalyst and molecular sieve catalyst etc. at present.But the noble metal catalyst active temperature windows is narrower, and selectivity is relatively poor relatively, N in the course of reaction
2The O growing amount is more; Single metal oxide type catalyst high temperature is unstable down, and catalytic activity is not high; The anti-H of molecular sieve catalyst
2O and SO
2Ability, and cost an arm and a leg and be not suitable for suitability for industrialized production and use.All there is shortcoming separately in above-mentioned catalyst, is difficult to satisfy needs of production, the present invention is directed to above problem, and to go out a kind of initiation temperature low, active high and have a production technology of SCR catalyst in the active temperature interval of broad with practical exploration by producing.
Summary of the invention
The objective of the invention is with the metal alloy is carrier, adopts unique carrier preprocess method, efficiently and with metallic carrier the preparation method of the nitrous oxides selectivity reduction catalyst of binding ability is by force arranged thereby provide a kind of.Method of the present invention can solve present diesel vehicle SCR (Selective Catalytic Reduction SCR) catalyst initiation temperature height, the relatively poor problem of clean-up effect.
The metal alloy carrier that SCR catalyst of the present invention is chosen is the resistant to elevated temperatures Ni-Cr-Fe alloy material that the Beijing North Metallurgical Functional Materials Co., Ltd sells, wherein Ni mass content 35%, Cr mass content 20%, Fe mass content 45%; And Ni-Cr alloy material, wherein Ni mass content 80%, Cr mass content 20%.The metal alloy carrier surface applies glass ceramic coating through after the preliminary treatment, and the glass ceramic coating material of main part is to be decomposed into after selecting to heat to have enamel characteristic Al
2O
3Aluminum nitrate, and be decomposed into after the heating have high temperature ductility, wearability and corrosion resistance SiO
2Ethyl orthosilicate, add the little metal oxide again to optimize the performance of coating.Catalyst is main active component with the metal oxide, suitably adds a small amount of rare earth oxide and noble metal and improves catalytic performance.
Selective catalytic reduction catalysts preparation method of the present invention the steps include:
With distilled water is solvent, the preparation mass concentration is 10～15% nickel nitrate solution, 10～20% manganese nitrate solution, 10～12% copper nitrate solution, 12～20% cobalt nitrate solution, 10～15% iron nitrate solution, 12～20% cerous nitrate solution and 15～20% chromium nitrate solution, choose wherein 2～4 kinds of solution and mass concentration and be 2～5% liquor argenti nitratis ophthalmicus or mass concentration and be 0.1～0.5% palladium nitrate solution equal-volume and mix the preparation catalyst solution; Then catalyst solution is adopted on the glass ceramic coating of the metal alloy carrier that the mode of dip coating is coated on, after the coating with metallic carrier at normal temperatures gentle breeze dry up, then in 120 ℃～180 ℃ oven dry down; Repeat the process of 5～8 above-mentioned coatings and oven dry, activated typing in 1～5 hour in 600 ℃～1000 ℃ following constant temperature calcinings at last and handle.
Metal alloy carrier surface preparation process described in the said method is:
1) volume ratio that metal alloy carrier is immersed fully ammoniacal liquor, hydrogen peroxide and deionized water is that ultrasonic wave cleaned 1～4 hour in 1: 2: 6 the mixed solution, and the greasy dirt of metal surface is removed in alkali cleaning, thereafter oven dry;
2) volume ratio that above-mentioned metal alloy carrier is immersed fully again hydrochloric acid, hydrogen peroxide and deionized water is that the pickling time is 1～30 minute in 1: 2: 6 the mixed solution, and the oxide of metal carrier surface, oven dry are thereafter removed in the residual alkali lye pickling simultaneously that neutralizes;
3) above-mentioned metal alloy carrier is immersed in the deionized water fully, ultrasonic wave cleaned 1～4 hour, flush away remained on surface acid ion etc., oven dry thereafter;
4) above-mentioned metal alloy carrier is immersed in the absolute ethyl alcohol fully, ultrasonic wave cleaned 1～4 hour, strengthened the dispersibility on metal alloy carrier surface, made the coating of coating more even, thereafter oven dry;
5) with above-mentioned alloying metal carrier under air conditions 500 ℃～1000 ℃ following roastings 1～3 hour, room temperature cooling.
The metal alloy carrier surface applies glass ceramic coating through after the preliminary treatment, be to be cut into long 12 centimetres wide strips of 5 centimetres through pretreated metal alloy carrier, put into the glass coating gel solution, apply 3～5 times, whenever be coated with to take out for one time and dry up with hair-dryer after drying in the shade 15～30 minutes under the room temperature, last is all over utilizing absorbent cotton that it is dried in the shade under room temperature in air, then in air, under 120～180 ℃, in drying baker, dried 3～5 hours, take out with stove cooling back, under 500～800 ℃ temperature, in high temperature furnace, calcined 1～5 minute then, quench under the room temperature, then obtain applying uniform glass ceramic coating on metal alloy carrier, thickness is 5～20 microns.
The preparation process of glass coating gel solution is:
1) with distilled water be solvent, the preparation mass concentration is 5～38% nine water aluminum nitrate (Al (NO
3)
39H
2O) solution, 5～40% nitrate trihydrate copper (Cu (NO
3)
23H
2O) solution, 5～50% six water nickel nitrate (Ni (NO
3)
26H
2O) solution and 5～50% six water manganese nitrate (Mn (NO
3)
26H
2O) solution, equal-volume mixes then; Prepare mass concentration again and be 5%～20% BAS, then 10～30g nitrate mixed solution is mixed with 10～20g BAS, under 20～60 ℃ temperature, stirred 1～3 hour, dissolve fully up to all salt;
2) taking by weighing mass concentration is that 85～99% 1～10 milliliter of 4～20 milliliters of ethanol, distilled water and mass concentration are 0.1～0.3 milliliter in 65% nitric acid, three kinds of solution are mixed and evenly stirring, making the pH value of solution value is 1～5, take by weighing 10～40 milliliters teos solution again, slowly ethyl orthosilicate is poured in the mixed solution of this step with the speed of per 1 minute 3～5ml and powerful the stirring, finally formed transparent clear solutions;
3) get 10～30g step 2) solution, slowly be injected in the solution of 20～40g step 1), powerful simultaneously the stirring, the glass coating gel solution is made in ageing 8～15 hours.
Technique effect of the present invention is:
Catalyst of the present invention can improve the bond strength between metallic carrier and the Catalytic Layer, have not only that initiation temperature is low, high activity, the anti-poisoning and the catalytic conversion efficiency advantages of higher, and preparation technology is simple, cost is low, can be widely used in light, heavy-duty diesel vehicle and other miniature diesel car tail gas catalytic purification.Compare with catalyst commonly used in the prior art and to have the following advantages:
1) be carrier with mechanical strength height, hot melt is little, thermal conductivity is high metal alloy, improve the uniformity of carrier inside Temperature Distribution, improve the rate of heat addition of SCR catalysis system when cold-starting automobile, thus when improving cold start-up to the clean-up effect of tail gas.
2) adopt unique carrier preprocess method, improve the microstructure of metal alloy carrier, increased the bond strength of carrier and catalyst layer, can effectively improve the problem of peeling off, as Fig. 1.
3) glass coating of function admirable has better chemical stability and heat endurance, not only can strengthen the binding ability of catalyst and metallic carrier, but also can provide bigger specific area, increased the load capacity of catalyst greatly, and the chemical constituent in the coating can also play the effect of SCR catalyst promoter, the raising activity of such catalysts.
4) result of combined catalyst rerum natura sign screens active component optimization catalyst formulation, catalyst mainly adopts metal oxide, cost is relatively low, suitably add heat endurance and the oxygen storage capacity that a small amount of rare earth oxide and noble metal can improve catalyst, make catalyst have higher low temperature light off characteristics and catalytic conversion efficiency.It is extremely even to illustrate that this SCR catalyst disperses by the SEM power spectrum, as Fig. 2.
5) the catalyst initiation temperature is low, the transformation efficiency height.When temperature reached 150 ℃, the NOx conversion ratio can reach more than 40%, and promptly catalyst under very low temperature catalytic reaction takes place, when temperature reached 200 ℃, conversion ratio had reached 90%, arrived 450 ℃ when temperature continues to rise, conversion ratio still can remain on about 80%, as Fig. 3.
In sum as can be seen: selective catalytic reduction catalysts of the present invention is except that compared with prior art having the tangible novelty on prescription and preparation method, and it is with low cost, show good light off characteristics and catalysis characteristics, have significant technological progress and outstanding substantive distinguishing features, can produce good economic and social benefit.
Description of drawings
Fig. 1: SEM (ESEM) photo of 800 ℃ of roastings after the preliminary treatment of Ni-Cr-Fe metal alloy carrier;
The SEM of manganese element (ESEM) can spectrogram behind coating catalyst on the transition zone among Fig. 2: the embodiment 2;
Fig. 3: sample continuous temperature empirical curve among the embodiment.
The specific embodiment
This patent is to set forth the present invention with specific embodiments; rather than limitation of the present invention; every can being used on the SCR tail gas refining processor; the method that on metal alloy carrier, prepares selective catalytic reduction catalysts; every relating to the metal oxide is key component or associated nonmetal oxide, rare earth oxide; and Zhi Bei catalyst is our rights protection scope in this way.
The selection of coating ingredients:
Nine water aluminum nitrate (Al
2(NO
3)
39H
2O): 5～38%
Six water manganese nitrate (Mn (NO
3)
26H
2O): 5～50%
Six water nickel nitrate (Ni (NO
3)
26H
2O): 5～50%
Nitrate trihydrate copper (Cu (NO
3)
23H
2O): 5～40%
The selection of catalytic component presoma:
Salt compounds such as six water nickel nitrates, six water manganese nitrates, nitrate trihydrate copper, cobalt nitrate hexahydrate, nine water ferric nitrates, six water cerous nitrates, nine water chromic nitrates.
Noble metal is selected the salt compounds of silver, palladium for use.
Embodiment 1:
With mass concentration is that 25% ammoniacal liquor, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume, and metal alloy carrier is immersed in the mixed solution fully, and ultrasonic wave cleaned 1 hour, thereafter oven dry; Be that 35% hydrochloric acid, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume again with mass concentration, carrier immersed in the mixed solution fully that the pickling time is 5 minutes, thereafter oven dry; Metal alloy carrier after the pickling is immersed in the deionized water fully, and ultrasonic wave cleaned 1 hour, flush away remained on surface acid ion etc., oven dry thereafter; At last above-mentioned metal alloy carrier is immersed in the absolute ethyl alcohol fully, ultrasonic wave cleaned 1 hour, thereafter oven dry.Burnt 2 hours the room temperature cooling down at 800 ℃.
The nitrate adding distil water of each material in the sol-gel solution is mixed with certain mass concentration mixed solution, wherein Al (NO
3)
39H
2The concentration of O is 38%, Mn (NO
3)
26H
2The concentration of O is 50%, Ni (NO
3)
26H
2The concentration of O is 30%, Cu (NO
3)
23H
2The concentration of O is 30%, and equal-volume mixes.Secondly, prepare mass concentration again and be 20% boric acid aqueous solution, the mixed solution 20g with above-mentioned nitrate mixes with BAS 18g then, and stirring is 2 hours under 20 ℃ temperature, dissolves fully up to all salt; Once more, take by weighing mass concentration and be 85% 5 milliliters of 20 milliliters of ethanol, distilled water and concentration and be 0.2 milliliter in 65% nitric acid, three kinds of solution are mixed and evenly stirring, recording the pH value by pH meter is 2, take by weighing 30 milliliters teos solution again, pour ethyl orthosilicate in the mixed solution for preparing powerful the stirring with the speed of per 1 minute 5ml slowly, the transparent clear solutions of final formation, from wherein get the 20g solution mixed solution that joins 38g nitrate and boric acid slowly, ageing obtained gel solution in 12 hours.To be cut into long 12 centimetres wide strips of 5 centimetres through pretreated metal alloy carrier, put into above-mentioned glass coating solution, apply 5 times, whenever be coated with to take out for one time and dry up with hair-dryer after drying in the shade 15 minutes under the room temperature, last is all over utilizing absorbent cotton that it is dried in the shade under room temperature in air, then in air, under 180 ℃ of temperature, in drying baker, dried 3 hours, take out with stove cooling back, under 500 ℃ temperature, in high temperature furnace, calcined 2 minutes then, quench under the room temperature, obtain applying uniform thickness and be about 10 microns glass coating.
It is 20% 6 water manganese nitrate solution, 12% nitrate trihydrate copper solution, 12% 6 water nickel nitrate, 0.5% palladium nitrate solution that catalytic component is chosen mass concentration, the solution equal-volume is evenly mixed, the carrier that applies glass coating is dipped in the mixed solution for preparing applies once more, whenever dried in the shade 1 hour after being coated with once, the back in baking oven in air 120 ℃ of oven dry, repeat the process of 5 above-mentioned coatings and oven dry, in air, cool off with stove after 4 hours again, both got finished product at 600 ℃ of constant temperature calcinings.
Embodiment 2:
With mass concentration is that 25% ammoniacal liquor, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume, and metal alloy carrier is immersed in the mixed solution fully, and ultrasonic wave cleaned 1 hour, thereafter oven dry; Be that 35% hydrochloric acid, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume again with mass concentration, carrier immersed in the mixed solution fully that the pickling time is 5 minutes, thereafter oven dry; Metal alloy carrier after the pickling is immersed in the deionized water fully, and ultrasonic wave cleaned 1 hour, flush away remained on surface acid ion etc., oven dry thereafter; At last above-mentioned metal alloy carrier is immersed in the absolute ethyl alcohol fully, ultrasonic wave cleaned 1 hour, thereafter oven dry.Burnt 2 hours the room temperature cooling down at 900 ℃.
The nitrate adding distil water of each material in the sol-gel solution is mixed with certain mass concentration mixed solution, wherein Al (NO
3)
39H
2The concentration of O is 35%, Mn (NO
3)
26H
2The concentration of O is 30%, Ni (NO
3)
26H
2The concentration of O is 40%, Cu (NO
3)
23H
2The concentration of O is 30%, and equal-volume mixes.Secondly, prepare mass concentration again and be 8% boric acid aqueous solution, the mixed solution 18g with above-mentioned nitrate mixes with BAS 18g then, and stirring is 1 hour under 20 ℃ temperature, dissolves fully up to all salt; Once more, take by weighing mass concentration and be 95% 7 milliliters of 15 milliliters of ethanol, distilled water and concentration and be 0.1 milliliter in 65% nitric acid, three kinds of solution are mixed and evenly stirring, recording the pH value by pH meter is 3, take by weighing 35 milliliters teos solution again, pour ethyl orthosilicate in the mixed solution for preparing powerful the stirring with the speed of per 1 minute 5ml slowly, the transparent clear solutions of final formation, from wherein take out the 17g solution mixed solution that joins 36g nitrate and boric acid slowly, ageing obtained gel solution in 10 hours.To be cut into long 12 centimetres wide strips of 5 centimetres through pretreated metal alloy carrier, put into above-mentioned glass coating solution, apply 5 times, whenever be coated with to take out for one time and dry up with hair-dryer after drying in the shade 15 minutes under the room temperature, last is all over utilizing absorbent cotton that it is dried in the shade under room temperature in air, then in air, under 160 ℃, in drying baker, dried 3 hours, take out with stove cooling back, under 550 ℃ temperature, in high temperature furnace, calcined 2 minutes then, quench under the room temperature, obtain applying uniform thickness and be about 10 microns glass coating.
It is 15% 6 water nickel nitrate solution, 12% nitrate trihydrate copper solution, 10% 9 water iron nitrate solution, 0.3% palladium nitrate solution that catalytic component is chosen mass concentration, the solution equal-volume is evenly mixed, the carrier that applies glass coating is dipped in the mixed solution for preparing applies once more, whenever dried in the shade 1 hour after being coated with once, the back in baking oven in air 120 ℃ of oven dry, repeat the process of 5 above-mentioned coatings and oven dry, in air, cool off with stove after 4 hours again, both got finished product at 600 ℃ of constant temperature calcinings.
Embodiment 3:
With mass concentration is that 25% ammoniacal liquor, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume, and metal alloy carrier is immersed in the mixed solution fully, and ultrasonic wave cleaned 1 hour, thereafter oven dry; Be that 35% hydrochloric acid, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume again with mass concentration, carrier immersed in the mixed solution fully that the pickling time is 5 minutes, thereafter oven dry; Metal alloy carrier after the pickling is immersed in the deionized water fully, and ultrasonic wave cleaned 1 hour, flush away remained on surface acid ion etc., oven dry thereafter; At last above-mentioned metal alloy carrier is immersed in the absolute ethyl alcohol fully, ultrasonic wave cleaned 1 hour, thereafter oven dry.Burnt 1 hour the room temperature cooling down at 900 ℃.
The nitrate adding distil water of each material in the sol-gel solution is mixed with certain mass concentration mixed solution, wherein Al (NO
3)
39H
2The concentration of O is 30%, Mn (NO
3)
26H
2The concentration of O is 40%, Ni (NO
3)
26H
2The concentration of O is 50%, Cu (NO
3)
23H
2The concentration of O is 40%, and equal-volume mixes.Secondly, prepare mass concentration again and be 12% boric acid aqueous solution, the mixed solution 20g with above-mentioned nitrate mixes with BAS 17g then, and stirring is 2 hours under 20 ℃ temperature, dissolves fully up to all salt; Once more, take by weighing mass concentration and be 95% 6 milliliters of 13 milliliters of ethanol, distilled water and concentration and be 0.15 milliliter in 65% nitric acid, three kinds of solution are mixed and evenly stirring, recording the pH value by pH meter is 1, take by weighing 30 milliliters teos solution again, pour ethyl orthosilicate in the mixed solution for preparing powerful the stirring with the speed of per 1 minute 5ml slowly, the transparent clear solutions of final formation, from wherein take out the 21g solution mixed solution that joins 37g nitrate and boric acid slowly, ageing obtained gel solution in 12 hours.To be cut into long 12 centimetres wide strips of 5 centimetres through pretreated metal alloy carrier, put into above-mentioned glass coating solution, apply 5 times, whenever be coated with to take out for one time and dry up with hair-dryer after drying in the shade 15 minutes under the room temperature, last is all over utilizing absorbent cotton that it is dried in the shade under room temperature in air, then in air, under 120 ℃, in drying baker, dried 3 hours, take out with stove cooling back, under 650 ℃ temperature, in high temperature furnace, calcined 1 minute then, quench under the room temperature, obtain applying uniform thickness and be about 10 microns glass coating.
It is 20% 6 water manganese nitrate solution, 20% 6 water cerous nitrate solution, 10% nitrate trihydrate copper solution, 0.2% palladium nitrate solution that catalytic component is chosen mass concentration, the solution equal-volume is evenly mixed, the carrier that applies glass coating is dipped in the mixed solution for preparing applies once more, whenever dried in the shade 1 hour after being coated with once, the back in baking oven in air 120 ℃ of oven dry, repeat the process of 5 above-mentioned coatings and oven dry, in air, cool off with stove after 4 hours again, both got finished product at 600 ℃ of constant temperature calcinings.
Embodiment 4:
With mass concentration is that 25% ammoniacal liquor, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume, and metal alloy carrier is immersed in the mixed solution fully, and ultrasonic wave cleaned 1 hour, thereafter oven dry; Be that 35% hydrochloric acid, mass concentration are that 30% hydrogen peroxide and deionized water are mixing in 1: 2: 6 by volume again with mass concentration, carrier immersed in the mixed solution fully that the pickling time is 5 minutes, thereafter oven dry; Metal alloy carrier after the pickling is immersed in the deionized water fully, and ultrasonic wave cleaned 1 hour, flush away remained on surface acid ion etc., oven dry thereafter; At last above-mentioned metal alloy carrier is immersed in the absolute ethyl alcohol fully, ultrasonic wave cleaned 1 hour, thereafter oven dry.Burnt 1 hour the room temperature cooling down at 1000 ℃.
The nitrate adding distil water of each material in the sol-gel solution is mixed with certain mass concentration mixed solution, wherein Al (NO
3)
39H
2The concentration of O is 25%, Mn (NO
3)
26H
2The concentration of O is 30%, Ni (NO
3)
26H
2The concentration of O is 50%, Cu (NO
3)
23H
2The concentration of O is 40%, and equal-volume mixes.Secondly, prepare mass concentration again and be 15% boric acid aqueous solution, the mixed solution 20g with above-mentioned nitrate mixes with BAS 15g then, and stirring is 2 hours under 20 ℃ temperature, dissolves fully up to all salt; Once more, take by weighing mass concentration and be 85% 10 milliliters of 20 milliliters of ethanol, distilled water and concentration and be 0.2 milliliter in 65% nitric acid, three kinds of solution are mixed and evenly stirring, recording the pH value by pH meter is 3, take by weighing 30 milliliters teos solution again, pour ethyl orthosilicate in the mixed solution for preparing powerful the stirring with the speed of per 1 minute 5ml slowly, the transparent clear solutions of final formation, from wherein get the mixed solution that 18g solution slowly joins 35g nitrate and boric acid, ageing obtained gel solution in 15 hours.To be cut into long 12 centimetres wide strips of 5 centimetres through pretreated metal alloy carrier, put into above-mentioned glass coating solution, apply 5 times, whenever be coated with to take out for one time and dry up with hair-dryer after drying in the shade 15 minutes under the room temperature, last is all over utilizing absorbent cotton that it is dried in the shade under room temperature in air, then in air, under 120 ℃, in drying baker, dried 3 hours, take out with stove cooling back, under 600 ℃ temperature, in high temperature furnace, calcined 2 minutes then, quench under the room temperature, obtain applying uniform thickness and be about 10 microns glass coating.
It is 15% 6 water manganese nitrate solution, 20% cobalt nitrate hexahydrate solution, 5% liquor argenti nitratis ophthalmicus that catalytic component is chosen concentration, the solution equal-volume is evenly mixed, the carrier that applies glass coating is dipped in the mixed solution for preparing applies once more, whenever dried in the shade 1 hour after being coated with once, the back in baking oven in air 120 ℃ of oven dry, repeat the process of 5 above-mentioned coatings and oven dry, in air, cool off with stove after 4 hours again, both got finished product at 600 ℃ of constant temperature calcinings.
By platform experiment test, it is low that above-mentioned catalyst all has an initiation temperature, the premium properties that transformation efficiency is high.When temperature reaches 150 ℃, the NOx conversion ratio can reach more than 40%, be that catalyst under very low temperature catalytic reaction takes place, when temperature reaches 200 ℃, conversion ratio has reached 90%, arrives 450 ℃ when temperature continues to rise, and conversion ratio still can remain on about 80%, wherein the performance with example 3 is the most outstanding, as Fig. 3.
Claims (5)
1. the method that on metal alloy carrier, prepares nitrous oxides selectivity reduction catalyst, it is characterized in that: be solvent with distilled water, the preparation mass concentration is 10～15% nickel nitrate solution, 10～20% manganese nitrate solution, 10～12% copper nitrate solution, 12～20% cobalt nitrate solution, 10～15% iron nitrate solution, 12～20% cerous nitrate solution and 15～20% chromium nitrate solution, choose wherein 2～4 kinds of solution and mass concentration and be 2～5% liquor argenti nitratis ophthalmicus or mass concentration and be 0.1～0.5% palladium nitrate solution equal-volume and mix the preparation catalyst solution; Then catalyst solution is adopted the mode of dip coating to be coated on the glass ceramic coating of metal alloy carrier, after the coating with metallic carrier at normal temperatures gentle breeze dry up, then in 120 ℃～180 ℃ down oven dry; Repeat the process of 5～8 above-mentioned coatings and oven dry, activated typing in 1～5 hour in 600 ℃～1000 ℃ constant temperature calcinings at last and handle.
2. the method that on metal alloy carrier, prepares nitrous oxides selectivity reduction catalyst as claimed in claim 1, it is characterized in that: metal alloy carrier is Ni-Cr-Fe alloy or Ni-Cr alloy, and the metal alloy carrier surface applies glass ceramic coating through after the preliminary treatment.
3. the method for preparing nitrous oxides selectivity reduction catalyst on metal alloy carrier as claimed in claim 2 is characterized in that: metal alloy carrier surface preparation process is,
1) volume ratio that metal alloy carrier is immersed fully ammoniacal liquor, hydrogen peroxide and deionized water is that ultrasonic wave cleaned 1～4 hour, thereafter oven dry in 1: 2: 6 the mixed solution;
2) volume ratio that above-mentioned metal alloy carrier is immersed fully again hydrochloric acid, hydrogen peroxide and deionized water is that the pickling time is 1～30 minute, thereafter oven dry in 1: 2: 6 the mixed solution;
3) above-mentioned metal alloy carrier is immersed in the deionized water fully, ultrasonic wave cleaned 1～4 hour, thereafter oven dry;
4) above-mentioned metal alloy carrier is immersed in the absolute ethyl alcohol fully, ultrasonic wave cleaned 1～4 hour, thereafter oven dry;
5) with above-mentioned alloying metal carrier under air conditions 500 ℃～1000 ℃ following roastings 1～3 hour, room temperature cooling.
4. the method that on metal alloy carrier, prepares nitrous oxides selectivity reduction catalyst as claimed in claim 3, it is characterized in that: the metal alloy carrier surface applies glass ceramic coating through after the preliminary treatment, be to be cut into strip through pretreated metal alloy carrier, put into the glass coating gel solution, apply 3～5 times, whenever be coated with to take out for one time and dry up with hair-dryer after drying in the shade 15～30 minutes under the room temperature, last is all over utilizing absorbent cotton that it is dried in the shade under room temperature in air, then in air, under 120～180 ℃, in drying baker, dried 3～5 hours, take out with stove cooling back, under 500～800 ℃ temperature, in high temperature furnace, calcined 1～5 minute then, quench under the room temperature, then obtain applying uniform glass ceramic coating on metal alloy carrier, thickness is 5～20 microns.
5. the method for preparing nitrous oxides selectivity reduction catalyst on metal alloy carrier as claimed in claim 4 is characterized in that: the preparation process of glass coating gel solution is,
1) with distilled water be solvent, the preparation mass concentration is 5～38% nine water aluminum nitrate Al (NO
3)
39H
2O solution, 5～40% nitrate trihydrate copper Cu (NO
3)
23H
2O solution, 5～50% six water nitric acid nickel (NO
3)
26H
2O solution and 5～50% six water manganese nitrate Mn (NO
3)
26H
2O solution, equal-volume mixes then; Prepare mass concentration again and be 5%～20% BAS, then 10～30g nitrate mixed solution is mixed with 10～20g BAS, under 20～60 ℃ temperature, stirred 1～3 hour, dissolve fully up to all salt;
2) taking by weighing mass concentration is that 85～99% 1～10 milliliter of 4～20 milliliters of ethanol, distilled water and mass concentration are 0.1～0.3 milliliter in 65% nitric acid, three kinds of solution are mixed and evenly stirring, take by weighing 10～40 milliliters teos solution again, slowly ethyl orthosilicate is poured in the mixed solution of this step with the speed of per 1 minute 3～5ml and powerful the stirring, finally formed transparent clear solutions;
3) get 10～30g step 2) solution, slowly be injected in the solution of 20～40g step 1), powerful simultaneously the stirring, the glass coating gel solution is made in ageing 8～15 hours.
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|---|---|---|---|---|
| CN108786839A (en) * | 2018-01-18 | 2018-11-13 | 合肥小小作为信息科技有限公司 | A kind of preparation method of metallic carrier for catalyst |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861613A (en) * | 2012-12-14 | 2014-06-18 | 上海郎特汽车净化器有限公司 | Metal soft carrier gasoline vehicle tail gas cleaning catalyst |
| CN103861614A (en) * | 2012-12-14 | 2014-06-18 | 上海郎特汽车净化器有限公司 | Metal soft carrier ternary catalyst with firm carrying layer |
| CN104451731B (en) * | 2014-11-28 | 2017-06-20 | 中国科学院金属研究所 | Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy |
| CN107029750A (en) * | 2017-05-14 | 2017-08-11 | 蒋春霞 | A kind of preparation method of the long-acting high activity denitrating catalyst of self refresh |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786839A (en) * | 2018-01-18 | 2018-11-13 | 合肥小小作为信息科技有限公司 | A kind of preparation method of metallic carrier for catalyst |
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