CN105214622A - A kind of high activity automobile three-way catalysts formula and preparation method thereof - Google Patents
A kind of high activity automobile three-way catalysts formula and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high activity automobile three-way catalysts formula and preparation method thereof, it is characterized in that: comprising: the catalyst of the porous ceramics of 80 ~ 90wt%, the adsorbent of 5 ~ 10wt% and 5 ~ 10wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 90 ~ 100 parts, micro/nano level α-Al
2o
3?40 ~ 60 parts, pore former 20 ~ 30 parts, binding agent 0 ~ 5 part, 2 ~ 5 parts, adhesive and pH be 3 ~ 4 acid solution 250 ~ 350 parts; Described adsorbent comprises magnetic chitosan nanoparticles.A kind of high activity automobile three-way catalysts formula provided by the invention and preparation method thereof, magnetic chitosan nanoparticles is adopted to replace traditional aluminium oxide as adsorbent, the ability of magnetic chitosan nanoparticles adsorption vehicle tail gas molecule is stronger, detergent power is 5 ~ 10 times of aluminium oxide, the iron on shitosan surface has desulphurizing activated, effectively avoids ternary catalyzing unit sulfur poisoning.
Description
Technical field
The present invention relates to a kind of high activity automobile three-way catalysts formula and preparation method thereof, belong to environment protection catalytic technical field.
Background technology
Ternary catalyzing unit, is mounted in most important outer purifier in automobile exhaust system, and the pernicious gases such as CO, HC and NOx that vehicle exhaust can be discharged by it change harmless carbon dioxide, water and nitrogen into by oxidation and reduction.When the vehicle exhaust of high temperature is by purifier, cleanser in ternary catalyzing unit will strengthen the activity of CO, HC and NOx tri-kinds of gases, impel it to carry out certain oxidationreduction chemical reaction, wherein CO is at high temperature oxidized into colourless, nontoxic carbon dioxide; HC compound is at high temperature oxidized to water and carbon dioxide; NOx is reduced into nitrogen and oxygen.Three kinds of pernicious gases become innocuous gas, and vehicle exhaust is purified.
The structure of purifier comprises carrier (i.e. porous ceramics) and load at supported catalyst, and the hole of carrier is more much more even, then effective adsorption surface area of carrier is larger, and detergent power is stronger.The pore former of current carrier is generally organic pore former, as natural fiber, high molecular polymer and organic acid etc., organic pore former is decomposed under far below carrier sintering temperature, hole is left after decomposition, these holes, especially some apertures, easily close when high temperature sintering is below shaping, cause the porosity of carrier low, catalytic capability is poor.
In addition, the adsorbent in present catalyst generally selects aluminium oxide, and the adsorbable Small molecular polar compound of aluminium oxide, as CO, HC and NOx, changes CO, HC and NOx into harmless carbon dioxide, water and nitrogen by catalyst after absorption again; The problems such as it is more weak that but aluminium oxide exists adsorption capacity, and aluminum particulate easily spreads rearrangement, easy sulfur poisoning.
Summary of the invention
The present invention solve technical problem be, provide a kind of become high, the effective adsorption surface area of porosity large, detergent power is strong, absorption property is strong, overcome the high activity automobile three-way catalysts formula of sulfur poisoning problem; Further, the invention provides a kind of sol-gel process that adopts to prepare, adopt Small molecular inorganic salts pore-forming simultaneously, become porosity high, pore-forming is even, and Alumina gel solid content is high, absorption property strong, overcome the preparation method of the high activity automobile three-way catalysts of sulfur poisoning problem.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A high activity automobile three-way catalysts formula, is characterized in that: comprising: the catalyst of the porous ceramics of 80 ~ 90wt%, the adsorbent of 5 ~ 10wt% and 5 ~ 10wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 90 ~ 100 parts, micro/nano level α-Al
2o
340 ~ 60 parts, pore former 20 ~ 30 parts, binding agent 0 ~ 5 part, 2 ~ 5 parts, adhesive and pH be 3 ~ 4 acid solution 250 ~ 350 parts; Described pore former is inorganic salts; Described adhesive comprises calcium sulfate; Described adsorbent comprises magnetic chitosan nanoparticles; Described catalyst comprises metal oxide containing precious metals and rare earth oxide.
Described binding agent comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulphate, calcium sulfate, sodium chloride, calcium chloride.
Described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
Described rare earth oxide comprises one or more in the oxide of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y.
A preparation method for high activity automobile three-way catalysts, is characterized in that: comprise the following steps:
S01, the preparation of Alumina gel:
S01-1, the preparation of sodium aluminate solution: be dissolved in ultra-pure water by NaOH solid and be mixed with 5%NaOH solution, then be added in 5%NaOH solution by aluminium powder, aluminium powder adds weight: 5%NaOH liquor capacity is 4 ~ 5:100; Filter after stirring and dissolving, obtain sodium aluminate solution;
S01-2, the preparation of boehmite precipitation: by NaHCO
3solid is dissolved in ultra-pure water and gathers the NaHCO being mixed with 4 ~ 4.5%
3solution, described NaHCO
3the volume of solution is at least 3 times amount of sodium aluminate solution volume, by described NaHCO
3solution is added in described sodium aluminate solution while stirring, and after having added, heating is also stirred at least after 30min simultaneously, filters, obtains boehmite precipitation;
S01-3, cleaning boehmite precipitation: after ultra-pure water cleaning, boehmite precipitation is put into ultra-pure water, add Cation adsorption resin adsorption at least after 10min, ultra-pure water cleans, then boehmite precipitation is put into ultra-pure water, add Anion-adsorption resin adsorption at least after 10min, ultra-pure water cleaning is neutral to cleaning fluid, dry;
S01-4, acid adding prepares Alumina gel: join in the salpeter solution of 1mol/L by dried boehmite precipitation, and heating stirring and dissolving obtains Alumina gel, and sour aluminum ratio is 0.08 ~ 0.20;
S02, the preparation of high solids content Alumina gel: add micro/nano level α-Al in the Alumina gel of S01-4
2o
3, after heating for dissolving, obtain the Alumina gel that solid content reaches 60 ~ 65%;
S03, in the high solids content Alumina gel of S02, add pore former, binding agent and adhesive, after heating stirs, inject mould cast molding, then put into vacuum drying chamber vacuum outgas and drying, obtain preliminary forming ceramic, vacuum drying temperature is 50 ~ 70 DEG C;
S04, unsticking and sintering: by described just one-step forming ternary catalyzing unit in atmosphere through 500 ~ 600 DEG C of unstickings at least 1 hour, then put into high temperature furnace through 1000 ~ 1100 DEG C of sintering at least 1 hour, then cool, obtain post forming pottery;
S05, it is in the acid solution of 3 ~ 4 that described post forming pottery is put into pH, adds thermal response at least 3 hours, then takes out, and ultra-pure water cleaning, to neutral, dried, obtained porous ceramics;
S06, magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide are made coating slurry, again described porous ceramics is flooded 3 ~ 10 minutes in described coating slurry, roasting 3 ~ 5 hours at 700 ~ 800 DEG C after drying, again under 450 ~ 500 DEG C of conditions, with hydrogen reducing at least 4 hours, obtain ternary catalyzing unit.
In S01-2, heating-up temperature is 80 ~ 85 DEG C.
The addition of described Cation adsorption resin and Anion-adsorption resin is 1/10 of at least boehmite precipitation weight.
Described sour aluminum ratio is 0.10 ~ 0.12.
Heating-up temperature in S02 is 50 ~ 70 DEG C.
Described acid solution is salpeter solution.
Acid aluminum ratio refers to the ratio of the amount of substance of acid solution and the amount of substance of boehmite precipitation.
The preparation method of described coating slurry is, get magnetic chitosan nanoparticles, metal oxide containing precious metals, rare earth oxide and water, grinding in ball grinder at least 6 hours, the addition of water was 300 ~ 500 times of the total amount of described magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide.
The preparation method of described magnetic chitosan nanoparticles is: add in there-necked flask by the chitosan-acetic acid solution of 0.3 ~ 0.5wt%, under nitrogen protection, add mixed molysite solution, after slowly dropping concentrated ammonia liquor is 5 ~ 6,50 ~ 60 DEG C of reaction 5 ~ 15min to pH under rapid stirring, be warming up to 65 ~ 70 DEG C, drip epoxychloropropane, react and stir, reaction terminates acetum and the ultrapure water extremely neutrality of rear use 0.5%, and magnetic field is separated to obtain described magnetic chitosan nanoparticles; Acetic acid content in described chitosan-acetic acid solution is 0.1 ~ 0.2%; The addition of described mixed molysite solution is 1/4 ~ 1/5 of the volume of described chitosan-acetic acid solution; Containing the FeCl of 0.2 ~ 0.3g/mL in described mixed molysite solution
36H
2the FeCl of O and 0.05 ~ 0.1g/mL
24H
2o; The addition of described epoxychloropropane is 1/3 ~ 1/2 of the volume of described mixed molysite solution.
A kind of high activity automobile three-way catalysts formula provided by the invention and preparation method thereof, replace traditional aluminium oxide as adsorbent with magnetic chitosan nanoparticles, the ability of magnetic chitosan nanoparticles adsorption vehicle tail gas molecule is stronger, and detergent power is 5 ~ 10 times of aluminium oxide; Simultaneously the chemical stability of magnetic chitosan nanoparticles is better than aluminium oxide, acid-fast alkali-proof, still can efficient adsorption vehicle exhaust molecule under strong acid and strong base condition, and absorption property is stablized; Due to iron shitosan disperseing magnetic, iron has desulphurizing activated, avoids ternary catalyzing unit sulfur poisoning; Pore former is the setting of inorganic salts, and inorganic salts fusing point is high, also can not melt when high temperature sintering, rear acid dissolve inorganic salts are sintered, obtain porous ceramics, the porous ceramics prepared with inorganic salts, even pore distribution, specific area are large, catalytic activation site is many, detergent power is strong; Alumina gel-gel method is in conjunction with the setting of inorganic salts pore former, and the specific area further increasing porous ceramics is large, and pore former is uniformly dispersed in high solids content Alumina gel, even pore distribution during pore-forming, becomes porosity up to 60%; Micro/nano level α-Al
2o
3interpolation, make Alumina gel solid content high and easily flow; Adhesive is the setting of calcium sulfate, makes porous ceramics form acidic alumina in the process of preparation, is applicable to decomposing pore former in acid condition, thus forms porous ceramics; The setting of Cation adsorption resin and Anion-adsorption resin, the cation in adsorbable cleaning boehmite precipitation and anion, be convenient to fast that boehmite precipitation cleaning is extremely neutral; In addition, the setting of magnetic chitosan nanoparticles, also has guard catalyst not by the effect of sulfur poisoning, further enhancing detergent power and the service life of ternary catalyzing unit.A kind of high activity automobile three-way catalysts formula provided by the invention and preparation method thereof, magnetic chitosan nanoparticles is adopted to replace traditional aluminium oxide as adsorbent, the ability of magnetic chitosan nanoparticles adsorption vehicle tail gas molecule is stronger, detergent power is 5 ~ 10 times of aluminium oxide, and the iron on shitosan surface also has desulphurizing activated, effectively avoid ternary catalyzing unit sulfur poisoning.
Detailed description of the invention
Below the present invention is further described.
embodiment 1:
A high activity automobile three-way catalysts formula, is characterized in that: comprising: the catalyst of the porous ceramics of 80wt%, the adsorbent of 10wt% and 10wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 90 parts, micro/nano level α-Al
2o
340 parts, pore former 20 parts, binding agent 0 part, 2 parts, adhesive and pH be 3 acid solution 250 parts; Described pore former is inorganic salts; Described adhesive comprises calcium sulfate; Described adsorbent comprises magnetic chitosan nanoparticles; Described catalyst comprises metal oxide containing precious metals and rare earth oxide.
Described binding agent comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulphate, calcium sulfate, sodium chloride, calcium chloride.
Described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
Described rare earth oxide comprises one or more in the oxide of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y.
A preparation method for high activity automobile three-way catalysts, is characterized in that: comprise the following steps:
S01, the preparation of Alumina gel:
S01-1, the preparation of sodium aluminate solution: be dissolved in ultra-pure water by NaOH solid and be mixed with 5%NaOH solution, then be added in 5%NaOH solution by aluminium powder, aluminium powder adds weight: 5%NaOH liquor capacity is 4:100; Filter after stirring and dissolving, obtain sodium aluminate solution;
S01-2, the preparation of boehmite precipitation: by NaHCO
3solid is dissolved in ultra-pure water and gathers the NaHCO being mixed with 4%
3solution, described NaHCO
3the volume of solution is 3 times amount of sodium aluminate solution volume, by described NaHCO
3solution is added in described sodium aluminate solution while stirring, and after having added, heating also, after stirring 30min simultaneously, is filtered, obtained boehmite precipitation;
S01-3, cleaning boehmite precipitation: after ultra-pure water cleaning, boehmite precipitation is put into ultra-pure water, after adding Cation adsorption resin adsorption 10min, ultra-pure water cleans, then boehmite precipitation is put into ultra-pure water, after adding Anion-adsorption resin adsorption 10min, ultra-pure water cleaning is neutral to cleaning fluid, dry;
S01-4, acid adding prepares Alumina gel: join in the salpeter solution of 1mol/L by dried boehmite precipitation, and heating stirring and dissolving obtains Alumina gel, and sour aluminum ratio is 0.08;
S02, the preparation of high solids content Alumina gel: add micro/nano level α-Al in the Alumina gel of S01-4
2o
3, after heating for dissolving, obtain the Alumina gel that solid content reaches 60%;
S03, adds pore former, binding agent and adhesive in the high solids content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying chamber vacuum outgas and drying, obtain preliminary forming ceramic, vacuum drying temperature is 50 DEG C;
S04, unsticking and sintering: by described just one-step forming ternary catalyzing unit in atmosphere through 500 DEG C of unstickings 1 hour, then put into high temperature furnace through 1000 DEG C of sintering 1 hour, then cool, obtain post forming pottery;
S05, it is in the acid solution of 3 that described post forming pottery is put into pH, adds thermal response at least 3 hours, then takes out, and ultra-pure water cleaning, to neutral, dried, obtained porous ceramics;
S06, makes coating slurry by magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide, then is flooded 3 minutes in described coating slurry by described porous ceramics, roasting 3 hours at 700 DEG C after drying, again under 450 DEG C of conditions, with hydrogen reducing 4 hours, obtain ternary catalyzing unit.
In S01-2, heating-up temperature is 80 DEG C.
The addition of described Cation adsorption resin and Anion-adsorption resin is 1/10 of boehmite precipitation weight.
Heating-up temperature in S02 is 50 DEG C.
Described acid solution is salpeter solution.
The preparation method of described coating slurry is, get magnetic chitosan nanoparticles, metal oxide containing precious metals, rare earth oxide and water, grinding in ball grinder 6 hours, the addition of water was 300 times of the total amount of described magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide.
The preparation method of described magnetic chitosan nanoparticles is: add in there-necked flask by the chitosan-acetic acid solution of 0.3wt%, under nitrogen protection, add mixed molysite solution, after slowly dropping concentrated ammonia liquor is 5,50 DEG C of reaction 5min to pH under rapid stirring, be warming up to 65 DEG C, drip epoxychloropropane, react and stir, reaction terminates acetum and the ultrapure water extremely neutrality of rear use 0.5%, and magnetic field is separated to obtain described magnetic chitosan nanoparticles; Acetic acid content in described chitosan-acetic acid solution is 0.1%; The addition of described mixed molysite solution is 1/4 of the volume of described chitosan-acetic acid solution; Containing the FeCl of 0.2g/mL in described mixed molysite solution
36H
2the FeCl of O and 0.05g/mL
24H
2o; The addition of described epoxychloropropane is 1/3 of the volume of described mixed molysite solution.
embodiment 2:
A high activity automobile three-way catalysts formula, is characterized in that: comprising: the catalyst of the porous ceramics of 90wt%, the adsorbent of 5wt% and 5wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 100 parts, micro/nano level α-Al
2o
360 parts, pore former 30 parts, binding agent 5 parts, 5 parts, adhesive and pH be 4 acid solution 350 parts; Described pore former is inorganic salts; Described adhesive comprises calcium sulfate; Described adsorbent comprises magnetic chitosan nanoparticles; Described catalyst comprises metal oxide containing precious metals and rare earth oxide.
Described binding agent comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulphate, calcium sulfate, sodium chloride, calcium chloride.
Described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
Described rare earth oxide comprises one or more in the oxide of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y.
A preparation method for high activity automobile three-way catalysts, is characterized in that: comprise the following steps:
S01, the preparation of Alumina gel:
S01-1, the preparation of sodium aluminate solution: be dissolved in ultra-pure water by NaOH solid and be mixed with 5%NaOH solution, then be added in 5%NaOH solution by aluminium powder, aluminium powder adds weight: 5%NaOH liquor capacity is 5:100; Filter after stirring and dissolving, obtain sodium aluminate solution;
S01-2, the preparation of boehmite precipitation: by NaHCO
3solid is dissolved in ultra-pure water and gathers the NaHCO being mixed with 4.5%
3solution, described NaHCO
3the volume of solution is 3.5 times amount of sodium aluminate solution volume, by described NaHCO
3solution is added in described sodium aluminate solution while stirring, and after having added, heating also, after stirring 40min simultaneously, is filtered, obtained boehmite precipitation;
S01-3, cleaning boehmite precipitation: after ultra-pure water cleaning, boehmite precipitation is put into ultra-pure water, after adding Cation adsorption resin adsorption 15min, ultra-pure water cleans, then boehmite precipitation is put into ultra-pure water, after adding Anion-adsorption resin adsorption 15min, ultra-pure water cleaning is neutral to cleaning fluid, dry;
S01-4, acid adding prepares Alumina gel: join in the salpeter solution of 1mol/L by dried boehmite precipitation, and heating stirring and dissolving obtains Alumina gel, and sour aluminum ratio is 0.20;
S02, the preparation of high solids content Alumina gel: add micro/nano level α-Al in the Alumina gel of S01-4
2o
3, after heating for dissolving, obtain the Alumina gel that solid content reaches 65%;
S03, adds pore former, binding agent and adhesive in the high solids content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying chamber vacuum outgas and drying, obtain preliminary forming ceramic, vacuum drying temperature is 0 DEG C;
S04, unsticking and sintering: by described just one-step forming ternary catalyzing unit in atmosphere through 600 DEG C of unstickings 1.5 hours, then put into high temperature furnace through 100 DEG C of sintering 1.5 hours, then cool, obtain post forming pottery;
S05, it is in the acid solution of 4 that described post forming pottery is put into pH, adds thermal response 4 hours, then takes out, and ultra-pure water cleaning, to neutral, dried, obtained porous ceramics;
S06, makes coating slurry by magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide, then is flooded 10 minutes in described coating slurry by described porous ceramics, roasting 5 hours at 800 DEG C after drying, again under 500 DEG C of conditions, with hydrogen reducing 4.5, obtain ternary catalyzing unit.
In S01-2, heating-up temperature is 85 DEG C.
The addition of described Cation adsorption resin and Anion-adsorption resin is 1/8 of boehmite precipitation weight.
Heating-up temperature in S02 is 70 DEG C.
Described acid solution is salpeter solution.
The preparation method of described coating slurry is, get magnetic chitosan nanoparticles, metal oxide containing precious metals, rare earth oxide and water, grinding in ball grinder 6.5 hours, the addition of water was 500 times of the total amount of described magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide.
The preparation method of described magnetic chitosan nanoparticles is: add in there-necked flask by the chitosan-acetic acid solution of 0.5wt%, under nitrogen protection, add mixed molysite solution, after slowly dropping concentrated ammonia liquor is 6,60 DEG C of reaction 15min to pH under rapid stirring, be warming up to 70 DEG C, drip epoxychloropropane, react and stir, reaction terminates acetum and the ultrapure water extremely neutrality of rear use 0.5%, and magnetic field is separated to obtain described magnetic chitosan nanoparticles; Acetic acid content in described chitosan-acetic acid solution is 0.2%; The addition of described mixed molysite solution is 1/5 of the volume of described chitosan-acetic acid solution; Containing the FeCl of 0.3g/mL in described mixed molysite solution
36H
2the FeCl of O and 0.1g/mL
24H
2o; The addition of described epoxychloropropane is 1/2 of the volume of described mixed molysite solution.
embodiment 3:
A high activity automobile three-way catalysts formula, is characterized in that: comprising: the catalyst of the porous ceramics of 85wt%, the adsorbent of 5wt% and 10wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 95 parts, micro/nano level α-Al
2o
350 parts, pore former 25 parts, binding agent 2 parts, 3 parts, adhesive and pH be 3 acid solution 300 parts; Described pore former is inorganic salts; Described adhesive comprises calcium sulfate; Described adsorbent comprises magnetic chitosan nanoparticles; Described catalyst comprises metal oxide containing precious metals and rare earth oxide.
Described binding agent comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulphate, calcium sulfate, sodium chloride, calcium chloride.
Described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
Described rare earth oxide comprises one or more in the oxide of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y.
A preparation method for high activity automobile three-way catalysts, is characterized in that: comprise the following steps:
S01, the preparation of Alumina gel:
S01-1, the preparation of sodium aluminate solution: be dissolved in ultra-pure water by NaOH solid and be mixed with 5%NaOH solution, then be added in 5%NaOH solution by aluminium powder, aluminium powder adds weight: 5%NaOH liquor capacity is 4.5:100; Filter after stirring and dissolving, obtain sodium aluminate solution;
S01-2, the preparation of boehmite precipitation: by NaHCO
3solid is dissolved in ultra-pure water and gathers the NaHCO being mixed with 4.2%
3solution, described NaHCO
3the volume of solution is 4 times amount of sodium aluminate solution volume, by described NaHCO
3solution is added in described sodium aluminate solution while stirring, and after having added, heating also, after stirring 50min simultaneously, is filtered, obtained boehmite precipitation;
S01-3, cleaning boehmite precipitation: after ultra-pure water cleaning, boehmite precipitation is put into ultra-pure water, after adding Cation adsorption resin adsorption 20min, ultra-pure water cleans, then boehmite precipitation is put into ultra-pure water, after adding Anion-adsorption resin adsorption 20min, ultra-pure water cleaning is neutral to cleaning fluid, dry;
S01-4, acid adding prepares Alumina gel: join in the salpeter solution of 1mol/L by dried boehmite precipitation, and heating stirring and dissolving obtains Alumina gel, and sour aluminum ratio is 0.10;
S02, the preparation of high solids content Alumina gel: add micro/nano level α-Al in the Alumina gel of S01-4
2o
3, after heating for dissolving, obtain the Alumina gel that solid content reaches 63%;
S03, adds pore former, binding agent and adhesive in the high solids content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying chamber vacuum outgas and drying, obtain preliminary forming ceramic, vacuum drying temperature is 60 DEG C;
S04, unsticking and sintering: by described just one-step forming ternary catalyzing unit in atmosphere through 550 DEG C of unstickings 2 hours, then put into high temperature furnace through 1050 DEG C of sintering 2 hours, then cool, obtain post forming pottery;
S05, it is in the acid solution of 3 that described post forming pottery is put into pH, adds thermal response 5 hours, then takes out, and ultra-pure water cleaning, to neutral, dried, obtained porous ceramics;
S06, makes coating slurry by magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide, more described porous ceramics is flooded 5 clocks in described coating slurry, after drying when 750 roasting 4, again under 480 DEG C of conditions, with hydrogen reducing 5 hours, obtain ternary catalyzing unit.
In S01-2, heating-up temperature is 82 DEG C.
The addition of described Cation adsorption resin and Anion-adsorption resin is 1/10 of boehmite precipitation weight.
Heating-up temperature in S02 is 60 DEG C.
Described acid solution is salpeter solution.
The preparation method of described coating slurry is, get magnetic chitosan nanoparticles, metal oxide containing precious metals, rare earth oxide and water, grinding in ball grinder 7 hours, the addition of water was 400 times of the total amount of described magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide.
The preparation method of described magnetic chitosan nanoparticles is: add in there-necked flask by the chitosan-acetic acid solution of 0.4wt%, under nitrogen protection, add mixed molysite solution, after slowly dropping concentrated ammonia liquor is 5,55 DEG C of reaction 10min to pH under rapid stirring, be warming up to 68 DEG C, drip epoxychloropropane, react and stir, reaction terminates acetum and the ultrapure water extremely neutrality of rear use 0.5%, and magnetic field is separated to obtain described magnetic chitosan nanoparticles; Acetic acid content in described chitosan-acetic acid solution is 0.15%; The addition of described mixed molysite solution is 1/5 of the volume of described chitosan-acetic acid solution; Containing the FeCl of 0.25g/mL in described mixed molysite solution
36H
2the FeCl of O and 0.08g/mL
24H
2o; The addition of described epoxychloropropane is 1/3 of the volume of described mixed molysite solution.
embodiment 4:
A high activity automobile three-way catalysts formula, is characterized in that: comprising: the catalyst of the porous ceramics of 88wt%, the adsorbent of 6wt% and 6wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 92 parts, micro/nano level α-Al
2o
345 parts, pore former 28 parts, binding agent 4 parts, 4 parts, adhesive and pH be 4 acid solution 350 parts; Described pore former is inorganic salts; Described adhesive comprises calcium sulfate; Described adsorbent comprises magnetic chitosan nanoparticles; Described catalyst comprises metal oxide containing precious metals and rare earth oxide.
Described binding agent comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulphate, calcium sulfate, sodium chloride, calcium chloride.
Described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
Described rare earth oxide comprises one or more in the oxide of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y.
A preparation method for high activity automobile three-way catalysts, is characterized in that: comprise the following steps:
S01, the preparation of Alumina gel:
S01-1, the preparation of sodium aluminate solution: be dissolved in ultra-pure water by NaOH solid and be mixed with 5%NaOH solution, then be added in 5%NaOH solution by aluminium powder, aluminium powder adds weight: 5%NaOH liquor capacity is 4:100; Filter after stirring and dissolving, obtain sodium aluminate solution;
S01-2, the preparation of boehmite precipitation: by NaHCO
3solid is dissolved in ultra-pure water and gathers the NaHCO being mixed with 4.3%
3solution, described NaHCO
3the volume of solution is 3.2 times amount of sodium aluminate solution volume, by described NaHCO
3solution is added in described sodium aluminate solution while stirring, and after having added, heating also, after stirring 60min simultaneously, is filtered, obtained boehmite precipitation;
S01-3, cleaning boehmite precipitation: after ultra-pure water cleaning, boehmite precipitation is put into ultra-pure water, after adding Cation adsorption resin adsorption 25min, ultra-pure water cleans, then boehmite precipitation is put into ultra-pure water, after adding Anion-adsorption resin adsorption 25min, ultra-pure water cleaning is neutral to cleaning fluid, dry;
S01-4, acid adding prepares Alumina gel: join in the salpeter solution of 1mol/L by dried boehmite precipitation, and heating stirring and dissolving obtains Alumina gel, and sour aluminum ratio is 0.12;
S02, the preparation of high solids content Alumina gel: add micro/nano level α-Al in the Alumina gel of S01-4
2o
3, after heating for dissolving, obtain the Alumina gel that solid content reaches 64%;
S03, adds pore former, binding agent and adhesive in the high solids content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying chamber vacuum outgas and drying, obtain preliminary forming ceramic, vacuum drying temperature is 65 DEG C;
S04, unsticking and sintering: by described just one-step forming ternary catalyzing unit in atmosphere through 600 DEG C of unstickings 1 hour, then put into high temperature furnace through 1000 DEG C of sintering 1 hour, then cool, obtain post forming pottery;
S05, it is in the acid solution of 4 that described post forming pottery is put into pH, adds thermal response 6 hours, then takes out, and ultra-pure water cleaning, to neutral, dried, obtained porous ceramics;
S06, magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide are made coating slurry, again described porous ceramics is flooded 8 minutes in described coating slurry, roasting 3.5 hours at 780 DEG C after drying, again under 460 DEG C of conditions, with hydrogen reducing 6 hours, obtain ternary catalyzing unit.
In S01-2, heating-up temperature is 85 DEG C.
The addition of described Cation adsorption resin and Anion-adsorption resin is 1/10 of boehmite precipitation weight.
Heating-up temperature in S02 is 70 DEG C.
Described acid solution is salpeter solution.
The preparation method of described coating slurry is, get magnetic chitosan nanoparticles, metal oxide containing precious metals, rare earth oxide and water, grinding in ball grinder 8 hours, the addition of water was 450 times of the total amount of described magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide.
The preparation method of described magnetic chitosan nanoparticles is: add in there-necked flask by the chitosan-acetic acid solution of 0.35wt%, under nitrogen protection, add mixed molysite solution, after slowly dropping concentrated ammonia liquor is 6,54 DEG C of reaction 8min to pH under rapid stirring, be warming up to 66 DEG C, drip epoxychloropropane, react and stir, reaction terminates acetum and the ultrapure water extremely neutrality of rear use 0.5%, and magnetic field is separated to obtain described magnetic chitosan nanoparticles; Acetic acid content in described chitosan-acetic acid solution is 0.18%; The addition of described mixed molysite solution is 1/4 of the volume of described chitosan-acetic acid solution; Containing the FeCl of 0.22g/mL in described mixed molysite solution
36H
2the FeCl of O and 0.06g/mL
24H
2o; The addition of described epoxychloropropane is 1/2 of the volume of described mixed molysite solution.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a high activity automobile three-way catalysts formula, is characterized in that: comprising: the catalyst of the porous ceramics of 80 ~ 90wt%, the adsorbent of 5 ~ 10wt% and 5 ~ 10wt%; Described porous ceramics comprises the raw material of following weight portion: Alumina gel 90 ~ 100 parts, micro/nano level α-Al
2o
340 ~ 60 parts, pore former 20 ~ 30 parts, binding agent 0 ~ 5 part, 2 ~ 5 parts, adhesive and pH be 3 ~ 4 acid solution 250 ~ 350 parts; Described pore former is inorganic salts; Described adhesive comprises calcium sulfate; Described adsorbent comprises magnetic chitosan nanoparticles; Described catalyst comprises metal oxide containing precious metals and rare earth oxide.
2. a kind of high activity automobile three-way catalysts formula according to claim 1, is characterized in that: described binding agent comprises polyvinyl alcohol.
3. a kind of high activity automobile three-way catalysts formula according to claim 1, is characterized in that: described pore former comprises one or more in sodium sulphate, calcium sulfate, sodium chloride, calcium chloride.
4. a kind of high activity automobile three-way catalysts formula according to claim 1, is characterized in that: described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
5. a kind of high activity automobile three-way catalysts formula according to claim 1, is characterized in that: described rare earth oxide comprises one or more in the oxide of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, scandium Sc and yttrium Y.
6. the preparation method of a kind of high activity automobile three-way catalysts according to any one of claim 1 ~ 5, is characterized in that: comprise the following steps:
S01, the preparation of Alumina gel:
S01-1, the preparation of sodium aluminate solution: be dissolved in ultra-pure water by NaOH solid and be mixed with 5%NaOH solution, then be added in 5%NaOH solution by aluminium powder, aluminium powder adds weight: 5%NaOH liquor capacity is 4 ~ 5:100; Filter after stirring and dissolving, obtain sodium aluminate solution;
S01-2, the preparation of boehmite precipitation: by NaHCO
3solid is dissolved in ultra-pure water and gathers the NaHCO being mixed with 4 ~ 4.5%
3solution, described NaHCO
3the volume of solution is at least 3 times amount of sodium aluminate solution volume, by described NaHCO
3solution is added in described sodium aluminate solution while stirring, and after having added, heating is also stirred at least after 30min simultaneously, filters, obtains boehmite precipitation;
S01-3, cleaning boehmite precipitation: after ultra-pure water cleaning, boehmite precipitation is put into ultra-pure water, add Cation adsorption resin adsorption at least after 10min, ultra-pure water cleans, then boehmite precipitation is put into ultra-pure water, add Anion-adsorption resin adsorption at least after 10min, ultra-pure water cleaning is neutral to cleaning fluid, dry;
S01-4, acid adding prepares Alumina gel: join in the salpeter solution of 1mol/L by dried boehmite precipitation, and heating stirring and dissolving obtains Alumina gel, and sour aluminum ratio is 0.08 ~ 0.20;
S02, the preparation of high solids content Alumina gel: add micro/nano level α-Al in the Alumina gel of S01-4
2o
3, after heating for dissolving, obtain the Alumina gel that solid content reaches 60 ~ 65%;
S03, in the high solids content Alumina gel of S02, add pore former, binding agent and adhesive, after heating stirs, inject mould cast molding, then put into vacuum drying chamber vacuum outgas and drying, obtain preliminary forming ceramic, vacuum drying temperature is 50 ~ 70 DEG C;
S04, unsticking and sintering: by described just one-step forming ternary catalyzing unit in atmosphere through 500 ~ 600 DEG C of unstickings at least 1 hour, then put into high temperature furnace through 1000 ~ 1100 DEG C of sintering at least 1 hour, then cool, obtain post forming pottery;
S05, it is in the acid solution of 3 ~ 4 that described post forming pottery is put into pH, adds thermal response at least 3 hours, then takes out, and ultra-pure water cleaning, to neutral, dried, obtained porous ceramics;
S06, magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide are made coating slurry, again described porous ceramics is flooded 3 ~ 10 minutes in described coating slurry, roasting 3 ~ 5 hours at 700 ~ 800 DEG C after drying, again under 450 ~ 500 DEG C of conditions, with hydrogen reducing at least 4 hours, obtain ternary catalyzing unit.
7. the preparation method of a kind of high activity automobile three-way catalysts according to claim 6, is characterized in that: in S01-2, heating-up temperature is 80 ~ 85 DEG C; Heating-up temperature in S02 is 50 ~ 70 DEG C; Described sour aluminum ratio is 0.10 ~ 0.12; Described acid solution is salpeter solution.
8. the preparation method of a kind of high activity automobile three-way catalysts according to claim 6, is characterized in that: the addition of described Cation adsorption resin and Anion-adsorption resin is 1/10 of at least boehmite precipitation weight.
9. the preparation method of a kind of high activity automobile three-way catalysts according to claim 6, it is characterized in that: the preparation method of described coating slurry is, get magnetic chitosan nanoparticles, metal oxide containing precious metals, rare earth oxide and water, grinding in ball grinder at least 6 hours, the addition of water was 300 ~ 500 times of the total amount of described magnetic chitosan nanoparticles, metal oxide containing precious metals and rare earth oxide.
10. the preparation method of a kind of high activity automobile three-way catalysts according to claim 6, it is characterized in that: the preparation method of described magnetic chitosan nanoparticles is: add in there-necked flask by the chitosan-acetic acid solution of 0.3 ~ 0.5wt%, under nitrogen protection, add mixed molysite solution, slowly dripping concentrated ammonia liquor under rapid stirring is 5 ~ 6 to pH, after 50 ~ 60 DEG C of reaction 5 ~ 15min, be warming up to 65 ~ 70 DEG C, drip epoxychloropropane, react and stir, reaction terminates acetum and the ultrapure water extremely neutrality of rear use 0.5%, magnetic field is separated to obtain described magnetic chitosan nanoparticles, acetic acid content in described chitosan-acetic acid solution is 0.1 ~ 0.2%, the addition of described mixed molysite solution is 1/4 ~ 1/5 of the volume of described chitosan-acetic acid solution, containing the FeCl of 0.2 ~ 0.3g/mL in described mixed molysite solution
36H
2the FeCl of O and 0.05 ~ 0.1g/mL
24H
2o, the addition of described epoxychloropropane is 1/3 ~ 1/2 of the volume of described mixed molysite solution.
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