CN104415745A - Perovskite structure substance and preparation method thereof - Google Patents
Perovskite structure substance and preparation method thereof Download PDFInfo
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- CN104415745A CN104415745A CN201310371206.0A CN201310371206A CN104415745A CN 104415745 A CN104415745 A CN 104415745A CN 201310371206 A CN201310371206 A CN 201310371206A CN 104415745 A CN104415745 A CN 104415745A
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Abstract
The invention provides a perovskite structure substance and a preparation method thereof. The preparation method comprises: dropwise adding titanium tetrachloride into deionized water, adding ammonia water to adjust the pH value, washing off chlorine ion in the obtained colloid material by using deionized water, mixing with V2O5, and grinding at a certain temperature after mixing, so as to obtain the perovskite structure substance. The perovskite structure substance is applicable to prepare a SCR catalyst used for processing diesel-engine exhaust gas NOx, and improves the uniformity of V2O5 and the selectivity of a catalytic reaction.
Description
Technical field
The present invention relates to diesel engine vent gas process field, relate to a kind of perovskite structure material and preparation method thereof specifically.
Background technology
Over nearly 20 years, in the face of the increasingly exhausted pressure brought to social development of world petroleum resource, in the face of automobile pollution sharp increase is on the impact of environment, world car is ceaselessly finding the solution realizing auto industry sustainable development, in continuous technical development, people have had renewal to diesel engine for automobile and diesel vehicle, more deep understanding, diesel engine compared with gasoline engine economical, under the prerequisite that dynamic property is superior, pollution for environment brings certain negative, along with the deterioration of environmental quality, to the limit value also increasingly stringent of the moving source pollution emissions such as vehicle, nitrogen oxide (the NO of one of environmental quality assessment index especially as a whole
x).Have research display, it not only can cause acid rain, photochemical fog etc. to destroy the series of problems of ball ecological environment, but also the health of human body in serious harm.Therefore, how effectively to remove nitrogen oxide and become the important topic that in current field of Environment Protection, attracts people's attention.Ammonia selective catalytic reduction (selective catalyticreduction, SCR) is due to ripe and efficient and become the denitration technology of main flow, and its key problem is just the development of catalyst and the adaptability of catalyst and various operating mode.Chinese scholars has carried out going deep into systematic research, as V to many catalyst systems
2o
5-WO
3/ TiO
2, MnO
2/ TiO
2, FeO
x/ TiO
2, CuO/TiO
2, Cr
2o
3/ TiO
2and CeO
2/ TiO
2deng.At present, the NH of industrial applications
3-SCR catalyst, mainly with TiO
2for carrier, then upload a certain amount of V
2o
5, WO
3, M
0o
3deng.For this reason, people are deepening constantly the research of denitration catalyst technology, to seek the wider denitrating catalyst of the scope of application, adapt to various operating mode with this.
CN201110389934 mono-kind for the preparation method of the SCR vanadium catalyst series of exhaust gas from diesel vehicle denitration, a kind of preparation method of the SCR vanadium catalyst series for exhaust gas from diesel vehicle denitration of this disclosure of the invention.Catalyst adopts simple infusion process to introduce active component, then by carrying out different temperature calcination process to catalyst carrier or catalyst, the SCR vanadium catalyst series obtained like this has outstanding catalytic performance to be improved, and considerably increase catalytic activity, catalyst strength also increases greatly.Vanadium series denitrating catalyst provided by the invention has higher denitration efficiency and wider temperature window, and what be applicable to exhaust gas from diesel vehicle nitrogen oxide removes field.Adopting laboratory simulation exhaust gas from diesel vehicle evaluation display, is 500ppm, H when air speed is 30000h-1, NO content
2o content is under the condition of 4%, the temperature range of 170-460 DEG C, uses the SCR vanadium catalyst series prepared of the inventive method to the removal efficiency of NOx more than 90%.There is life-span short defect in SCR catalyst prepared by this employing infusion process, on the durability of catalyst with impact.
CN201210055163.0 low-temperature SCR catalyst for diesel car tail gas refining and preparation method thereof, this invention relates to a kind of low-temperature SCR catalyst for diesel car tail gas refining and preparation method thereof, and object has high thermal stability and better low-temperature catalytic activity; This catalyst components content is by weight percentage: silica alumina ratio Si/Al is molecular sieve HZSM-5:40 ~ 80% of 38 ~ 50; Ammonium molybdate (NH
4) 6Mo
7o
244H
2o:0 ~ 12.1%; Anhydrous FeCl
3: 0.1 ~ 10.7%; Manganese acetate: 0.1 ~ 19.9%; Cerous nitrate: 0.1 ~ 17.0%; The purity of each component is pure for analyzing; Its preparation method adds ammonium molybdate (NH in deionized water
4) 6Mo
7o
244H
2o and anhydrous FeCl
3, add molecular sieve HZSM-5 again after stirring and dissolving, keep homogeneous temperature to stir, until moisture distilled-to-dryness; Dry 12h at 110 ~ 130 DEG C of temperature, then at 500 ~ 700 DEG C of temperature lower calcination 3 ~ 6h, obtain intermediate products; Manganese acetate and cerous nitrate are mixed with these intermediate products, adds deionized water and stirring, regulate pH value to 12 ~ 13 with ammoniacal liquor, continue to stir 2h, vacuum filtration, washing; Freeze-day with constant temperature 12h at 110 DEG C, then at 350 ~ 550 DEG C roasting 5h.There is life-span short defect in SCR catalyst prepared by this method, on the durability of catalyst with impact.
CN201110425117 electrospray SCR diesel engine tail gas catalyst, this disclosure of the invention be a kind of electrospray SCR diesel engine tail gas catalyst.The present invention starts with in nature from Diesel engine, in conjunction with each composition CO/HC/NO of diesel engine emissions tail gas
x/ NH
3the character of gas, carries out catalytic purification to the pernicious gas in exhaust emissions, and takes measure targetedly, is coated with modified RE oxide catalyst coatings, catalyst activity component coating and catalyst activity component solution is respectively coated with stain to carrier.The present invention needs to make reducing agent in conjunction with urea water when being used in Diesel engine tail gas catalyzed, and by urea pyrolysis, hydrolysis of urea, NOx reduces, the series reaction such as ammonia oxidation, could tail gas catalytic purification the most at last.The present invention proves by experiment, and to the tail gas catalytic purification effect of Diesel engine, preparation cost is cheap, effective.
CN1101584992A urea scr catalyst and manufacture method thereof, this invention relates to a kind of selective reduction catalyst: wherein substantially along the longitudinal, and half catalyst (entrance) scribbles Mn/TiO
2, and second half catalyst (outlet) scribbles Fe-zeolite/ZSM, and prepare finishing coat by adding cerous carbonate, thus in finishing coat, form hole by the decomposition in roasting process, and increase the active surface sum effectiveness of performance of catalyst.The feature of this aspect is the preparation method of this selective reduction catalyst.The defect of denitration catalyst agent material prepared by this employing impregnation method is that service life is short, can not adapt with various operating mode.
CN101954281A is used for the cerium copper titanium compound oxide catalyst of denitrating flue gas and preparation method, and this disclosure of the invention a kind of cerium copper titanium compound oxide catalyst for denitrating flue gas and preparation method, the component of this catalyst comprises CeO
2, CuO and TiO
2.Catalyst preparing adopts coprecipitation, can reach desirable denitration effect.The advantage of this catalyst is: 1) have higher activity to the catalytic reduction of nitrogen oxides in effluent; 2) the adaptive temperature window of catalyst is wider, in 150 ~ 450 DEG C of whole temperature ranges, all have certain activity; 3) effectively can improve the runnability of catalyst under SO2 and H2O condition, to the bad working environments under sulfur dioxide and water etc. exist, there is stronger adaptability, exercisable wider; 4) raw materials is easy to get, preparation technology is simple, and catalyst cost is lower, and the defect of denitration catalyst agent material prepared by this employing coprecipitation is that service life is short, can not adapt with various operating mode.
SCR technology is as removing diesel engine NO
xmainstream technology, the especially selective catalytic reduction catalysts of vanadium titanium series, has higher NO
xremoval efficiency, preferably sulfur resistance, longer service life, the in addition national condition of Chinese oil product, SCR is Chinese Diesel machine NO
xdischarge optimal a kind of technology path.But owing to finding in the use of traditional catalyst, selective strong during reaction, the defects such as service life is short.
Summary of the invention
The present invention provide firstly a kind of perovskite structure material, and it prepares by the following method:
Titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 5 ~ 30%, add ammoniacal liquor and regulate pH value 7 ~ 8, gained colloidal material is spent deionized water, by the material after washing and V
2o
5mixing, wherein vanadium is 0.5 ~ 1:1 ~ 5 with the ratio of the amount of substance of titanium, and the temperature of grinding is 300 ~ 500 DEG C, and milling time 1 ~ 16h, obtains perovskite structure material after grinding.
Wherein purity >=99.9% of titanium tetrachloride.
Present invention also offers the method preparing above-mentioned perovskite structure material:
Titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 5 ~ 30%, add ammoniacal liquor and regulate pH value 7 ~ 8, gained colloidal material is spent deionized water, by the material after washing and V
2o
5mixing, wherein vanadium is 0.5 ~ 1:1 ~ 5 with the ratio of the amount of substance of titanium, and the temperature of grinding is 300 ~ 500 DEG C, and milling time 1 ~ 16h, obtains perovskite structure material after grinding.
Present invention also offers a kind of titanium tungsten powder, it prepares by the following method:
Configuration weight percent concentration is the ammonium metatungstate solution of 5 ~ 10%, add citric acid, (adopting citric acid as cosolvent), in above-mentioned solution, add weight percent concentration is 5 ~ 10% cerous nitrates (as coagents), again anatase titanium dioxide is joined in above-mentioned solution and stir, wherein the weight ratio of titanium dioxide and solution is 40 ~ 60:50 ~ 70, finally carry out drying and calcining, baking temperature is 100 ~ 200 DEG C, drying time is 1 ~ 24h, calcining heat is 400 ~ 600 DEG C, calcination time is 1 ~ 24h, obtains required titanium tungsten powder;
Wherein the addition of citric acid is 1 ~ 10% of ammonium metatungstate solution weight.
The specific area of wherein said anatase titanium dioxide is more than or equal to 300m
2/ g, median is less than or equal to 0.1 μm; Purity>=99.9% of described ammonium metatungstate.
Object feature of the present invention is: 1. this technique adopts titanium tetrachloride to synthesize the perovskite structure material containing vanadium as presoma, be added drop-wise in deionized water by titanium tetrachloride, add ammoniacal liquor and regulate pH value, gained colloidal material is spent after deionized water chlorion with V
2o
5mixing, carry out grinding after mixing at a certain temperature and obtain perovskite structure material, this perovskite structure material improves V
2o
5the uniformity and catalytic reaction selective, ammonium metatungstate is carried out modification to the titanium dioxide powder of anatase structures and obtains titanium tungsten powder, adopt citric acid as cosolvent; Adopt cerous nitrate as the coagent in synthesis titanium tungsten powder, obtain titanium tungsten powder through super-dry and calcining, improve the sulfur resistance of catalyst and the service life of catalyst; 2. perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol and water stir, and are prepared coating colloid under high speed shear emulsification condition, selective when this active component adds catalyst reaction with the mode that respective matrix disperses; 3. the ceramic honeycomb that ultrasonic cleaning is good is placed in coating colloid and carries out immersion load coating; 4. the ceramic honeycomb carrier of starching is put into Muffle furnace and carry out drying and roasting.The catalyst that drying of the present invention and roasting obtain treated application 8L co-rail diesel machine frame cleaning test shows, gas reaction temperature still keeps nitrogen oxide to have the transformation efficiency of 95% at 180 ~ 420 DEG C, product is after stand quick aging, gas reaction temperature still keeps nitrogen oxide to have the transformation efficiency of 85% at 180 ~ 420 DEG C, can meet Europe IV/V and above Abgasgesetz.
Detailed description of the invention
A kind of perovskite structure material of the present invention, it prepares by the following method:
Titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 5 ~ 30%, add ammoniacal liquor and regulate pH value 7 ~ 8, gained colloidal material is spent deionized water, by the material after washing and V
2o
5mixing, wherein vanadium is 0.5 ~ 1:1 ~ 5 with the ratio of the amount of substance of titanium, and the temperature of grinding is 300 ~ 500 DEG C, and milling time 1 ~ 16h, obtains perovskite structure material after grinding.
Wherein purity >=99.9% of titanium tetrachloride.
Present invention also offers the method preparing above-mentioned perovskite structure material:
Titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 5 ~ 30%, add ammoniacal liquor and regulate pH value 7 ~ 8, gained colloidal material is spent deionized water, by the material after washing and V
2o
5mixing, wherein vanadium is 0.5 ~ 1:1 ~ 5 with the ratio of the amount of substance of titanium, and the temperature of grinding is 300 ~ 500 DEG C, and milling time 1 ~ 16h, obtains perovskite structure material after grinding.
Present invention also offers the method preparing above-mentioned titanium tungsten powder:
Configuration weight percent concentration is the ammonium metatungstate solution of 5 ~ 10%, add citric acid, (adopting citric acid as cosolvent), in above-mentioned solution, add weight percent concentration is 5 ~ 10% cerous nitrates (as coagents), again anatase titanium dioxide is joined in above-mentioned solution and stir, wherein the weight ratio of titanium dioxide and solution is 40 ~ 60:50 ~ 70, finally carry out drying and calcining, baking temperature is 100 ~ 200 DEG C, drying time is 1 ~ 24h, calcining heat is 400 ~ 600 DEG C, calcination time is 1 ~ 24h, obtains required titanium tungsten powder.
Above-mentioned titanium tungsten powder is uniformly dispersed, specific area is high, and titanium dioxide anatase structures remain unchanged, material or the impurity of all the other crystalline structures can not be generated, during for making catalyst, contribute to increase catalytic reaction time selective, the lifting of the sulfur resistance of catalyst is greatly improved.
The purposes of above-mentioned perovskite structure material and titanium tungsten powder is for the preparation of process diesel engine vent gas NO
xsCR catalyst.
Present invention also offers a kind of for the treatment of diesel engine vent gas NO
xsCR catalyst, this SCR catalyst prepares by the following method:
(1) coating colloid is prepared
Above-mentioned perovskite structure material, titanium tungsten powder and aluminium glue are mixed, adds polyvinyl alcohol and deionized water stirs, under high speed shear emulsification condition, be prepared coating colloid;
The weight ratio of described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, deionized water is 10 ~ 30:60 ~ 80:1 ~ 5:0.1 ~ 2:100 ~ 150;
The above-mentioned perovskite structure material containing vanadium, have the effect of high degree of dispersion between vanadium titanium, titanium itself, as the matrix material of SCR catalyst, is partly introduced in this step, is also V
2o
5to carry out pre-dispersed in the matrix material of whole catalyst.
(2) slurry ageing
Above-mentioned coating colloid is added humic acid potassium and carries out ageing, the addition of humic acid potassium is 0.1 ~ 1.5% of coating adhesive body weight;
(3) carrier starching:
The ceramic honeycomb that ultrasonic cleaning is good is placed in the coating colloid after ageing and carries out immersion load starching, the load capacity of coating is 100-160g/L;
(4) drying and roasting:
The ceramic honeycomb carrier of starching is put into Muffle furnace and carries out drying and roasting, obtain SCR catalyst.
Wherein in step (), described high-speed shearing machine is prepared colloid, and cutter rotating speed is 100 ~ 200r/min, and preparation time is 2 ~ 10h; The weight ratio of perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol and deionized water is 24:70:3:0.5:120.
Wherein in step (two), the humic acid potassium that described coating colloid adds 0.1 ~ 1.5% carries out ageing, and digestion time is 5 ~ 30 days; Purity >=99.9% of described humic acid potassium.
Wherein in step (three), the ceramic honeycomb that ultrasonic cleaning is good is placed in the coating colloid after ageing and carries out immersion load starching, the load capacity of coating is 100-160g/L.
Wherein in step (four), baking temperature controls at 80 ~ 150 DEG C, and drying time is 1 ~ 5h, and sintering temperature controls 400 ~ 600 DEG C, roasting time 1 ~ 10h.
Present invention also offers a kind of for the treatment of diesel engine vent gas NO
xthe preparation method of SCR catalyst, it is characterized in that method comprises the steps:
(1) coating colloid is prepared
Perovskite structure material, titanium tungsten powder and aluminium glue are mixed, adds polyvinyl alcohol and deionized water stirs, under high speed shear emulsification condition, be prepared coating colloid;
The weight ratio of described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, deionized water is 10 ~ 30:60 ~ 80:1 ~ 5:0.1 ~ 2:100 ~ 150;
(2) slurry ageing
Above-mentioned coating colloid is added humic acid potassium and carries out ageing, the addition of humic acid potassium is 0.1 ~ 1.5% of coating adhesive body weight;
(3) carrier starching:
The ceramic honeycomb that ultrasonic cleaning is good is placed in the coating colloid after ageing and carries out immersion load starching, the load capacity of coating is 100-160g/L;
(4) drying and roasting:
The ceramic honeycomb carrier of starching is put into Muffle furnace and carries out drying and roasting, obtain SCR catalyst.
The one that the present invention sets up is used for diesel engine vent gas process NO
xsCR catalyst and preparation method, synthesize in the preparation process of catalyst and prepared the material containing the perovskite structure of vanadium, synthesize and prepared titanium tungsten powder, the active component of catalyst is made to be dispersed in respective matrix material respectively, add the selective of catalytic reaction, what also extend the sulfur resistance of catalyst and catalyst benefits from the life-span, through the SCR catalyst performance adaptation condition wide ranges that this technique is obtained, and the advantages such as long service life.
Embodiment 1:
Containing the synthesis and preparation of the perovskite structure material of vanadium, comprise following sequential steps:
Titanium tetrachloride is synthesized perovskite structure material containing vanadium as presoma, be added drop-wise in deionized water with the titanium tetrachloride that weight percent concentration is 20%, add ammoniacal liquor and regulate pH value 8, gained colloidal material is spent deionized water chlorion, by the material after above-mentioned washing and V
2o
5mixing, wherein the ratio of the amount of substance of vanadium titanium is 1:1, and the temperature of grinding is 450 DEG C, and milling time 12h, obtains perovskite structure material after grinding.
The synthesis and preparation of titanium tungsten powder, comprises following sequential steps:
By weight percent concentration be 7% ammonium metatungstate modification carried out to the titanium dioxide powder of anatase structures obtain titanium tungsten powder, first configuring weight percent concentration is the ammonium metatungstate solution of 7%, adopt citric acid as cosolvent, the percentage by weight of citric acid is 8%, in above-mentioned solution, add weight percent concentration is that 6% cerous nitrate is as coagent, again anatase titanium dioxide is joined in above-mentioned solution and stir, wherein the weight ratio of titanium dioxide and solution is 45:65, finally carry out drying and calcining, baking temperature is 120 DEG C, drying time is 12h, calcining heat is 550 DEG C, calcination time is 4h, obtain required titanium tungsten powder.
The preparation of catalyst:
Step 1: preparation coating colloid:
By above-mentioned perovskite structure material, titanium tungsten powder, aluminium glue, add appropriate polyvinyl alcohol and appropriate deionized water stirs, under high speed shear emulsification condition, be prepared coating colloid.
The weight ratio of described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, deionized water is 24:70:3:0.5:120.
Described high-speed shearing machine is prepared colloid, and cutter rotating speed is 150r/min, and preparation time is 4h.
Step 2: slurry ageing
The humic acid potassium that described coating colloid adds 1.0% is carried out ageing, and digestion time is 20 days.
Purity requirement >=99.9% of described humic acid potassium.
Step 3: carrier starching:
To be of a size of Φ 267mm × 152mm, hole count is 62/cm
2cordierite ceramic honeycomb be placed in ultrasonic washing instrument and carry out ultrasonic cleaning, and add hydrofluoric acid and regulate cleaning fluid PH=2, wherein the frequency of ultrasonic washing instrument is 50HZ, power is 100W, and the ultrasonic cleaning time is 120min.
The ceramic honeycomb that ultrasonic cleaning is good is placed in coating colloid and carries out immersion load starching, the load capacity of coating is 120g/L.
Step 4: drying and roasting:
The ceramic honeycomb carrier of starching is put into Muffle furnace and carries out drying and roasting, wherein baking temperature controls at 120 DEG C, and drying time is 2h, and sintering temperature controls 590 DEG C, roasting time 6h.
Embodiment 2:
Containing the synthesis and preparation of the perovskite structure material of vanadium, comprise following sequential steps:
Titanium tetrachloride is synthesized perovskite structure material containing vanadium as presoma, titanium tetrachloride is added drop-wise in deionized water, be configured to the colloid that weight percent concentration is 25%, add ammoniacal liquor and regulate pH value 8, gained colloidal material is spent deionized water chlorion, by the material after above-mentioned washing and V
2o
5mixing, wherein the ratio of the amount of substance of vanadium titanium is 1:1.2, and the temperature of grinding is 460 DEG C, and milling time 14h, obtains perovskite structure material after grinding.
The synthesis and preparation of titanium tungsten powder, comprises following sequential steps:
By weight ratio be 8% ammonium metatungstate modification carried out to the titanium dioxide powder of anatase structures obtain titanium tungsten powder, first configuring weight concentration is the ammonium metatungstate solution of 8%, adopt citric acid as cosolvent, the percentage by weight of citric acid is 8%, in above-mentioned solution, add weight percent concentration is that 7% cerous nitrate is as coagent, again anatase titanium dioxide is joined in above-mentioned solution and stir, wherein the weight of titanium dioxide and solution is 44:66, finally carry out drying and calcining, baking temperature is 120 DEG C, drying time is 13h, calcining heat is 560 DEG C, calcination time is 5h, obtain required titanium tungsten powder.
The preparation of catalyst comprises following sequential steps:
Step 1: preparation coating colloid:
By above-mentioned perovskite structure material, titanium tungsten powder, aluminium glue, add appropriate polyvinyl alcohol and appropriate deionized water stirs, under high speed shear emulsification condition, be prepared coating colloid.
The weight ratio of described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, deionized water is 23:74:3:0.5:125.
Described high-speed shearing machine is prepared colloid, and cutter rotating speed is 150r/min, and preparation time is 4h.
Step 2: slurry ageing
The coating colloid prepared is added humic acid potassium and carries out ageing.
The humic acid potassium that described coating colloid adds 1.2% carries out ageing, and digestion time is 20 days.
Purity requirement >=99.9% of described humic acid potassium.
Step 3: carrier starching:
To be of a size of Φ 267mm × 152mm, hole count is 62/cm
2cordierite ceramic honeycomb be placed in ultrasonic washing instrument and carry out ultrasonic cleaning, and add hydrofluoric acid, cleaning fluid PH=2, wherein the frequency of ultrasonic washing instrument is 50HZ, power is 100W, and the ultrasonic cleaning time is 130min.
The ceramic honeycomb that ultrasonic cleaning is good is placed in coating colloid and carries out immersion load, the load capacity of coating is 140g/L.
Step 4: drying and roasting:
The ceramic honeycomb carrier of starching is put into Muffle furnace and carries out drying and roasting, wherein baking temperature controls at 120 DEG C, and drying time is 2h, and sintering temperature controls 600 DEG C, roasting time 6h.
Embodiment 3:
Containing the synthesis and preparation of the perovskite structure material of vanadium, comprise following sequential steps:
Titanium tetrachloride is synthesized perovskite structure material containing vanadium as presoma, be added drop-wise in deionized water with the titanium tetrachloride that weight ratio is 15%, add ammoniacal liquor and regulate pH value 8, gained colloidal material is spent deionized water chlorion, by the material after above-mentioned washing and V
2o
5mixing, wherein the ratio of the amount of substance of vanadium titanium is 1.2:1, and the temperature of grinding is 400 DEG C, and milling time 10h, obtains perovskite structure material after grinding.
The synthesis and preparation of titanium tungsten powder, comprises following sequential steps:
By weight ratio be 6% ammonium metatungstate modification carried out to the titanium dioxide powder of anatase structures obtain titanium tungsten powder, first configuring weight concentration is the ammonium metatungstate solution of 6%, adopt citric acid as cosolvent, the percentage by weight of citric acid is 8%, in above-mentioned solution, add weight ratio is that 5% cerous nitrate is as coagent, again anatase titanium dioxide is joined in above-mentioned solution and stir, wherein the weight of titanium dioxide and solution is 46:62, finally carry out drying and calcining, baking temperature is 120 DEG C, drying time is 12h, calcining heat is 500 DEG C, calcination time is 4h, obtain required titanium tungsten powder.
The preparation of catalyst comprises following sequential steps:
Step 1: preparation coating colloid:
By above-mentioned perovskite structure material, titanium tungsten powder, aluminium glue, add appropriate polyvinyl alcohol and appropriate deionized water stirs, under high speed shear emulsification condition, be prepared coating colloid.
The weight ratio of described perovskite structure material, titanium tungsten powder, aluminium glue, polyvinyl alcohol, deionized water is 20:75:3:0.5:120.
Described high-speed shearing machine is prepared colloid, and cutter rotating speed is 150r/min, and preparation time is 4h.
Step 2: slurry ageing
The coating colloid prepared is added humic acid potassium and carries out ageing.
The humic acid potassium that described coating colloid adds 0.6% carries out ageing, and digestion time is 20 days.
Purity requirement >=99.9% of described humic acid potassium.
Step 3: carrier starching:
To be of a size of Φ 267mm × 152mm, hole count is 62 holes/cm
2cordierite ceramic honeycomb be placed in ultrasonic washing instrument and carry out ultrasonic cleaning, and add hydrofluoric acid, cleaning fluid PH=2, wherein the frequency of ultrasonic washing instrument is 50HZ, power is 100W, and the ultrasonic cleaning time is 100min.
The ceramic honeycomb that ultrasonic cleaning is good is placed in coating colloid and carries out immersion load, the load capacity of coating is 100g/L.
Step 4: drying and roasting:
The ceramic honeycomb carrier of starching is put into Muffle furnace and carries out drying and roasting, wherein baking temperature controls at 120 DEG C, and drying time is 2h, and sintering temperature controls 500 DEG C, roasting time 6h.
According to the SCR catalyst that embodiment 1 is obtained, product size is 267mm × 152mm, and quantity is 2, and catalyst hole count is 62 holes/cm
2, inwall wall thickness is 0.11mm.Active component WO contained by catalyst
3content 5.0%, V
2o
5content 1.0%.The density of product is 500g/l, carried out installing by catalyst cascade and carry out engine rig test, diesel fuel injection system is high-pressure common rail, and waste gas purification technology path is DOC+SCR, fresh state and aging state emission result are respectively in table 1, table 2, and the aging 100h experimental condition of stand carries out.Remarks: (aging condition: HJ451-2008 People's Republic of China (PRC) state environment protecting standard " environmental protection product technical requirement-diesel engine truck exhaust after-treatment device ".）
The fresh state testing result of table 1
The durable state testing result of table 2 stand 100h quick aging
Claims (2)
1. a perovskite structure material, is characterized in that it prepares by the following method:
Titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 5 ~ 30%, add ammoniacal liquor and regulate pH value 7 ~ 8, gained colloidal material is spent deionized water, by the material after washing and V
2o
5mixing, wherein vanadium is 0.5 ~ 1:1 ~ 5 with the ratio of the amount of substance of titanium, and the temperature of grinding is 300 ~ 500 DEG C, and milling time 1 ~ 16h, obtains perovskite structure material after grinding.
2. prepare a method for perovskite structure material described in claim 1, it is characterized in that the method is:
Titanium tetrachloride is added in deionized water, is configured to the colloid that weight percent concentration is 5 ~ 30%, add ammoniacal liquor and regulate pH value 7 ~ 8, gained colloidal material is spent deionized water, by the material after washing and V
2o
5mixing, wherein vanadium is 0.5 ~ 1:1 ~ 5 with the ratio of the amount of substance of titanium, and the temperature of grinding is 300 ~ 500 DEG C, and milling time 1 ~ 16h, obtains perovskite structure material after grinding.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076356A (en) * | 2016-06-16 | 2016-11-09 | 上海净球环保科技有限公司 | A kind of titanium tungsten powder and its production and use |
| CN106111117A (en) * | 2016-06-16 | 2016-11-16 | 上海净球环保科技有限公司 | One is used for processing diesel engine vent gas NOxsCR catalyst and preparation method thereof |
| CN106111116A (en) * | 2016-06-16 | 2016-11-16 | 上海净球环保科技有限公司 | A kind of perovskite structure material and its production and use |
| CN113578303A (en) * | 2021-08-03 | 2021-11-02 | 安徽元琛环保科技股份有限公司 | Preparation method of SCR denitration catalyst with ultralow vanadium load by taking perovskite type composite oxide as carrier and prepared catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273628A (en) * | 1992-05-11 | 1993-12-28 | Gas Research Institute | Mixed ionic-electronic conductors for oxygen separation and electrocatalysis |
| US20030024389A1 (en) * | 2001-07-23 | 2003-02-06 | Flippo Belynda G. | Method for carbon monoxide reduction during thermal/wet abatement of organic compounds |
| CN1498128A (en) * | 2001-03-19 | 2004-05-19 | 高级技术材料公司 | Oxygen-enhanced CDA modification to CDO integrated scrubber |
| CN101757907A (en) * | 2008-12-26 | 2010-06-30 | 晶锐瓷业（北京）有限公司 | Titanium dioxide powder containing tungsten for preparing honeycomb SCR DeNOx catalyst and preparation method thereof |
-
2013
- 2013-08-22 CN CN201310371206.0A patent/CN104415745A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273628A (en) * | 1992-05-11 | 1993-12-28 | Gas Research Institute | Mixed ionic-electronic conductors for oxygen separation and electrocatalysis |
| CN1498128A (en) * | 2001-03-19 | 2004-05-19 | 高级技术材料公司 | Oxygen-enhanced CDA modification to CDO integrated scrubber |
| US20030024389A1 (en) * | 2001-07-23 | 2003-02-06 | Flippo Belynda G. | Method for carbon monoxide reduction during thermal/wet abatement of organic compounds |
| CN101757907A (en) * | 2008-12-26 | 2010-06-30 | 晶锐瓷业（北京）有限公司 | Titanium dioxide powder containing tungsten for preparing honeycomb SCR DeNOx catalyst and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076356A (en) * | 2016-06-16 | 2016-11-09 | 上海净球环保科技有限公司 | A kind of titanium tungsten powder and its production and use |
| CN106111117A (en) * | 2016-06-16 | 2016-11-16 | 上海净球环保科技有限公司 | One is used for processing diesel engine vent gas NOxsCR catalyst and preparation method thereof |
| CN106111116A (en) * | 2016-06-16 | 2016-11-16 | 上海净球环保科技有限公司 | A kind of perovskite structure material and its production and use |
| CN113578303A (en) * | 2021-08-03 | 2021-11-02 | 安徽元琛环保科技股份有限公司 | Preparation method of SCR denitration catalyst with ultralow vanadium load by taking perovskite type composite oxide as carrier and prepared catalyst |
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