CN105402010A - Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter - Google Patents

Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter Download PDF

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CN105402010A
CN105402010A CN201510685730.4A CN201510685730A CN105402010A CN 105402010 A CN105402010 A CN 105402010A CN 201510685730 A CN201510685730 A CN 201510685730A CN 105402010 A CN105402010 A CN 105402010A
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automobile
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孟晓辉
孟雷军
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Suzhou Lianchi Environmental Science & Technology Development Co Ltd
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Suzhou Lianchi Environmental Science & Technology Development Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/101—Three-way catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2250/00—Combinations of different methods of purification
    • F01N2250/12—Combinations of different methods of purification absorption or adsorption, and catalytic conversion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/08—Granular material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/10—Carbon or carbon oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a formula and manufacturing method of an acid and alkali resistant automobile three-way catalytic converter. The formula is characterized in that the formula involves 80-90wt% of porous ceramic, 5-10wt% of an adsorbent and 5-10wt% of a catalyst; the porous ceramic comprises, by weight, 90-100 parts of alumina sol, 40-60 parts of micro-nano-scale alpha-Al2O3, 20-30 parts of a pore-forming agent, 0-5 parts of a binder, 2-5 parts of an adhesive and 250-350 parts of an acid solution with the pH value being 3-4; the adsorbent comprises silica gel. According to the formula and manufacturing method of the acid and alkali resistant automobile three-way catalytic converter, the silica gel is used for replacing traditional aluminum oxide to serve as the adsorbent, and the silica gel is resistant to acid and alkali, still capable of efficiently adsorbing automobile exhaust molecules under strong acid and strong alkali conditions, and stable in adsorption performance.

Description

A kind of acidproof alkaline automobile three-way catalysts formula and preparation method thereof
Technical field
The present invention relates to a kind of acidproof alkaline automobile three-way catalysts formula and preparation method thereof, belong to environment protection catalytic technical field.
Background technique
Ternary catalyzing unit, is mounted in most important outer purifier in automobile exhaust system, and the harmful 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 purification plant, purifying agent 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 harmful gases become innocuous gas, and vehicle exhaust is purified.
The structure of purification plant 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 purifying ability is stronger.The pore former of current carrier is generally organic pore former, as natural fibre, 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 ratio of carrier low, catalytic capability is poor.
In addition, the sorbent in present catalyzer 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 catalyzer after absorption again; But aluminium oxide existence does not tolerate strong acid and strong base, the problem of easy ageing failure under strong acid and strong base environment.
Summary of the invention
The technical problem that the present invention solves is, provide a kind of become adsorption performance is stable under strong, the strong acid and strong base environment of large, the purifying ability of high, the effective adsorption surface area of porosity acidproof alkaline automobile three-way catalysts formula; 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, the preparation method of the acidproof alkaline automobile three-way catalysts that adsorption performance is stable under strong acid and strong base environment.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
An acidproof alkaline automobile three-way catalysts formula, is characterized in that: comprising: the catalyzer of the porous ceramics of 80 ~ 90wt%, the sorbent 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, Bond 0 ~ 5 part, 2 ~ 5 parts, tackiness agent and pH be 3 ~ 4 acidic solution 250 ~ 350 parts; Described pore former is inorganic salts; Described tackiness agent comprises calcium sulfate; Described sorbent comprises silica gel; Described catalyzer comprises metal oxide containing precious metals and rare earth oxide.
Described Bond comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulfate, 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 acidproof alkaline 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 solution, 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 solid 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 solid content Alumina gel of S02, add pore former, Bond and tackiness agent, after heating stirs, inject mould cast molding, then put into vacuum drying oven 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 Furnaces through 1000 ~ 1100 DEG C of sintering at least 1 hour, then cool, obtain post forming pottery;
S05, it is in the acidic 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, silica gel, 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 acidic solution is salpeter solution.
Acid aluminum ratio refers to the ratio of the amount of substance of acidic solution and the amount of substance of boehmite precipitation.
The preparation method of described coating slurry is get silica gel, metal oxide containing precious metals, rare earth oxide and water, and grinding in ball grinder at least 6 hours, the addition of water was 300 ~ 500 times of the total amount of described silica gel, metal oxide containing precious metals and rare earth oxide.
Acidproof alkaline automobile three-way catalysts formula of one provided by the invention and preparation method thereof, replaces traditional aluminium oxide as sorbent with silica gel, and the ability of silica gel absorption vehicle exhaust molecule is stronger, and purifying ability is 1 ~ 2 times of aluminium oxide; Simultaneously the chemical stability of silica gel is better than aluminium oxide, acid-fast alkali-proof, still can efficient adsorption vehicle exhaust molecule under strong acid and strong base condition, and adsorption performance is stablized; 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 surface area are large, catalytic activation site is many, purifying ability is strong; Alumina gel-gel method is in conjunction with the setting of inorganic salts pore former, and the specific surface area further increasing porous ceramics is large, and pore former is uniformly dispersed in high solid 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; Tackiness agent 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 positive ion in adsorbable cleaning boehmite precipitation and negative ion, be convenient to fast that boehmite precipitation cleaning is extremely neutral; In addition, the setting of silica gel, also has guard catalyst not by the effect of sulfur poisoning, further enhancing purifying ability and the working life of ternary catalyzing unit.Acidproof alkaline automobile three-way catalysts formula of one provided by the invention and preparation method thereof, silica gel is adopted to replace traditional aluminium oxide as sorbent, silica gel acid-fast alkali-proof, still can efficient adsorption vehicle exhaust molecule under strong acid and strong base condition, and adsorption performance is stablized.
Embodiment
Below the present invention is further described.
embodiment 1:
An acidproof alkaline automobile three-way catalysts formula, is characterized in that: comprising: the catalyzer of the porous ceramics of 80wt%, the sorbent 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, Bond 0 part, 2 parts, tackiness agent and pH be 3 acidic solution 250 parts; Described pore former is inorganic salts; Described tackiness agent comprises calcium sulfate; Described sorbent comprises silica gel; Described catalyzer comprises metal oxide containing precious metals and rare earth oxide.
Described Bond comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulfate, 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 acidproof alkaline 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 solution, 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 solid 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, Bond and tackiness agent in the high solid content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying oven 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 Furnaces through 1000 DEG C of sintering 1 hour, then cool, obtain post forming pottery;
S05, it is in the acidic 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 silica gel, 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 acidic solution is salpeter solution.
The preparation method of described coating slurry is get silica gel, metal oxide containing precious metals, rare earth oxide and water, and grinding in ball grinder 6 hours, the addition of water was 300 times of the total amount of described silica gel, metal oxide containing precious metals and rare earth oxide.
embodiment 2:
An acidproof alkaline automobile three-way catalysts formula, is characterized in that: comprising: the catalyzer of the porous ceramics of 90wt%, the sorbent 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, Bond 5 parts, 5 parts, tackiness agent and pH be 4 acidic solution 350 parts; Described pore former is inorganic salts; Described tackiness agent comprises calcium sulfate; Described sorbent comprises silica gel; Described catalyzer comprises metal oxide containing precious metals and rare earth oxide.
Described Bond comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulfate, 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 acidproof alkaline 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 solution, 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 solid 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, Bond and tackiness agent in the high solid content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying oven 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 Furnaces through 100 DEG C of sintering 1.5 hours, then cool, obtain post forming pottery;
S05, it is in the acidic 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 silica gel, 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 acidic solution is salpeter solution.
The preparation method of described coating slurry is get silica gel, metal oxide containing precious metals, rare earth oxide and water, and grinding in ball grinder 6.5 hours, the addition of water was 500 times of the total amount of described silica gel, metal oxide containing precious metals and rare earth oxide.
embodiment 3:
An acidproof alkaline automobile three-way catalysts formula, is characterized in that: comprising: the catalyzer of the porous ceramics of 85wt%, the sorbent 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, Bond 2 parts, 3 parts, tackiness agent and pH be 3 acidic solution 300 parts; Described pore former is inorganic salts; Described tackiness agent comprises calcium sulfate; Described sorbent comprises silica gel; Described catalyzer comprises metal oxide containing precious metals and rare earth oxide.
Described Bond comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulfate, 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 acidproof alkaline 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 solution, 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 solid 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, Bond and tackiness agent in the high solid content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying oven 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 Furnaces through 1050 DEG C of sintering 2 hours, then cool, obtain post forming pottery;
S05, it is in the acidic 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 silica gel, 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, then under 480 DEG C of conditions, with hydrogen reducing 5 hours, obtains 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 acidic solution is salpeter solution.
The preparation method of described coating slurry is get silica gel, metal oxide containing precious metals, rare earth oxide and water, and grinding in ball grinder 7 hours, the addition of water was 400 times of the total amount of described silica gel, metal oxide containing precious metals and rare earth oxide.
embodiment 4:
An acidproof alkaline automobile three-way catalysts formula, is characterized in that: comprising: the catalyzer of the porous ceramics of 88wt%, the sorbent 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, Bond 4 parts, 4 parts, tackiness agent and pH be 4 acidic solution 350 parts; Described pore former is inorganic salts; Described tackiness agent comprises calcium sulfate; Described sorbent comprises silica gel; Described catalyzer comprises metal oxide containing precious metals and rare earth oxide.
Described Bond comprises polyvinyl alcohol.
Described pore former comprises one or more in sodium sulfate, 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 acidproof alkaline 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 solution, 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 solid 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, Bond and tackiness agent in the high solid content Alumina gel of S02, injects mould cast molding after heating stirs, and then put into vacuum drying oven 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 Furnaces through 1000 DEG C of sintering 1 hour, then cool, obtain post forming pottery;
S05, it is in the acidic 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, makes coating slurry by silica gel, metal oxide containing precious metals and rare earth oxide, then is flooded 8 minutes in described coating slurry by described porous ceramics, 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 acidic solution is salpeter solution.
The preparation method of described coating slurry is get silica gel, metal oxide containing precious metals, rare earth oxide and water, and grinding in ball grinder 8 hours, the addition of water was 450 times of the total amount of described silica gel, metal oxide containing precious metals and rare earth oxide.
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. an acidproof alkaline automobile three-way catalysts formula, is characterized in that: comprising: the catalyzer of the porous ceramics of 80 ~ 90wt%, the sorbent 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, Bond 0 ~ 5 part, 2 ~ 5 parts, tackiness agent and pH be 3 ~ 4 acidic solution 250 ~ 350 parts; Described pore former is inorganic salts; Described tackiness agent comprises calcium sulfate; Described sorbent comprises silica gel; Described catalyzer comprises metal oxide containing precious metals and rare earth oxide.
2. the acidproof alkaline automobile three-way catalysts formula of one according to claim 1, is characterized in that: described Bond comprises polyvinyl alcohol.
3. the acidproof alkaline automobile three-way catalysts formula of one according to claim 1, is characterized in that: described pore former comprises one or more in sodium sulfate, calcium sulfate, sodium chloride, calcium chloride.
4. the acidproof alkaline automobile three-way catalysts formula of one according to claim 1, is characterized in that: described metal oxide containing precious metals comprises Pt oxide, Pd oxide and Rh oxide.
5. the acidproof alkaline automobile three-way catalysts formula of one 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 acidproof alkaline 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 solution, 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 solid 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 solid content Alumina gel of S02, add pore former, Bond and tackiness agent, after heating stirs, inject mould cast molding, then put into vacuum drying oven 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 Furnaces through 1000 ~ 1100 DEG C of sintering at least 1 hour, then cool, obtain post forming pottery;
S05, it is in the acidic 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, silica gel, 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 acidproof alkaline 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; .
8. the preparation method of a kind of acidproof alkaline 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 acidproof alkaline automobile three-way catalysts according to claim 6, it is characterized in that: the preparation method of described coating slurry is, get silica gel, 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 silica gel, metal oxide containing precious metals and rare earth oxide.
10. the preparation method of a kind of acidproof alkaline automobile three-way catalysts according to claim 6, is characterized in that: described acidic solution is salpeter solution.
CN201510685730.4A 2015-10-22 2015-10-22 Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter Pending CN105402010A (en)

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