CN109364905B - Alumina containing auxiliary agent, preparation method thereof and catalyst containing alumina - Google Patents

Alumina containing auxiliary agent, preparation method thereof and catalyst containing alumina Download PDF

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CN109364905B
CN109364905B CN201811206959.5A CN201811206959A CN109364905B CN 109364905 B CN109364905 B CN 109364905B CN 201811206959 A CN201811206959 A CN 201811206959A CN 109364905 B CN109364905 B CN 109364905B
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catalyst
alumina
auxiliary agent
acid
solution
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CN109364905A (en
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陈淼
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Ningbo Haibo New Material Technology Co.,Ltd.
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Ningbo Yingnuo New Material Technology Co ltd
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01J35/63—Pore volume
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
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Abstract

The invention provides an alumina containing an auxiliary agent, which is subjected to air roasting treatment at 1000 ℃ for 1-6h, and the total pore volume measured by low-temperature nitrogen adsorption is not less than 1.0cm3(ii) in terms of/g. The invention also provides a preparation method of the alumina and a catalyst using the alumina as a carrier. The alumina containing the auxiliary agent prepared by the invention has better high temperature resistance and larger pore volume. The catalyst prepared by using the catalyst as a carrier has higher activity and correspondingly prolonged service life.

Description

Alumina containing auxiliary agent, preparation method thereof and catalyst containing alumina
Technical Field
The invention relates to the technical field of modified catalysts, in particular to alumina containing an auxiliary agent, a preparation method of the alumina containing the auxiliary agent and a catalyst containing the alumina containing the auxiliary agent.
Background
In the field of high-temperature catalysis, alumina containing auxiliaries is generally used as a catalyst carrier. The carrier needs to provide a certain surface loading of the active component, and the active component is well dispersed uniformly on the carrier, which puts high demands on the pore structure of the carrier. The pores of the alumina support can be divided into three types: 1) primary particle inter-grain pores are mainly dehydration pores of alumina raw material grains and are basically gaps between parallel plate surfaces with the size of 1-2 nm; 2) the pores among the secondary particles of the alumina raw material are changed along with the escape of moisture and the change of a crystal phase during calcination and are pores more than tens of nanometers; 3) defective pores and macropores which are generated when the pore-forming agent and the carrier are formed. Therefore, the proportion of alumina raw materials of different types and particle sizes, the amount of pore-forming agent, the forming mode and the calcining system, etc. all affect the pore structure and physical properties of the catalyst carrier, and further affect the performance of the catalyst.
However, the existing commercial alumina material containing the auxiliary agent is often too quickly deactivated due to the large collapse of the specific surface and pore channels during the reaction and the covering or sintering of the main active component of the catalyst because of insufficient specific surface area and pore volume or poor high temperature resistance under high temperature. Therefore, it is necessary to use an alumina containing auxiliary agent, which still has a large pore volume at high temperature, as a catalyst carrier, so that the catalyst prepared by the alumina containing auxiliary agent has good catalytic activity and a long service life.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide alumina containing an auxiliary agent, which is high temperature resistant and has larger pore volume.
The second purpose of the invention is to provide a preparation method of the alumina containing the auxiliary agent.
The third object of the present invention is to provide a catalyst comprising the alumina containing a promoter.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an alumina containing a promoter comprising alumina and a promoter, wherein:
the mass percentage of the alumina is more than or equal to 50 percent, and the balance is auxiliary agent;
the auxiliary agent is selected from one or more of the following oxides of elements in any ratio: ge. P, As, Sb, Bi, Ni, Cu, Zr, Hf, Si, Nb, Ta, Fe, La, Ce, Nd, Sm, Pr, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, In, Ti;
after the alumina containing the auxiliary agent is roasted at the high temperature of 1000 ℃ for 1-6h, the total pore volume measured by low-temperature nitrogen adsorption is still more than or equal to 1.0cm3/g。
The invention also relates to a preparation method of the alumina containing the auxiliary agent, which comprises the following steps:
(1) dissolving soluble aluminum salt in water to obtain a precursor solution, adding a precursor of an auxiliary agent and a precipitator into the precursor solution at the temperature of 10-90 ℃ to generate an aluminum hydroxide precipitate containing the auxiliary agent precursor, controlling the pH value to be 5.0-9.0 in the precipitation process, and then filtering and washing the precipitate to obtain a filter cake, namely a solid material A;
(2) dissolving organic amine in water to obtain a solution B, wherein the molar ratio of the organic amine to the soluble aluminum salt is (0.06-0.2): 1;
(3) fully dispersing the solid material A in the step (1) in the solution B in the step (2), stirring for 30-240min, and filtering to obtain a filter cake, namely a solid material C;
(4) and (4) drying the solid material C in the step (3), and roasting at 400-1200 ℃ for 1-24h to obtain the alumina containing the auxiliary agent.
Preferably, in step (1), the precursor of the auxiliary agent is an oxide, a hydroxide, a complex, an acid, a salt or an organic ester corresponding to the element contained in the auxiliary agent. When the precursor of the auxiliary agent is an oxide or hydroxide containing the element of the auxiliary agent, the precursor may be in the form of a solid, nanoparticle dispersion or colloidal solution of the oxide or hydroxide.
Preferably, in step (1), the soluble aluminum salt is selected from at least one of sodium aluminate, potassium aluminate, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum-containing alkoxide.
Preferably, in the step (1), the precipitant is an acid solution or an alkali solution; the acid solution is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, citric acid, perchloric acid, oxalic acid and carbonic acid;
the alkali liquor is at least one of sodium hydroxide, potassium hydroxide, ammonia water, ammonium carbonate and ammonium bicarbonate.
Preferably, in the step (1), the precipitant contains a pore-forming agent. The pore-forming agent is a combustible carbon-containing material and is selected from at least one of petroleum coke, carbon powder, graphite, polyethylene, polypropylene, rosin and vaseline, preferably the petroleum coke, the graphite or the vaseline, more preferably the petroleum coke, and most preferably the petroleum coke with the particle size of 0-200 mu m. The mass ratio of the pore-forming agent to the soluble aluminum salt is 1 (10-100).
Preferably, in the step (2), the organic amine is at least one selected from trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, n-butylamine, pyrrolidine and hexamethylenediamine.
Preferably, in the step (2), a lower alcohol is further added to the organic amine, and the mass ratio of the organic amine to the lower alcohol is (57-375) to (10-110).
Preferably, the lower alcohol is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and n-pentanol.
Preferably, in the step (2), polyethylene glycol is further added to the organic amine, and the mass ratio of the organic amine to the polyethylene glycol is (57-375) to (20-50).
Preferably, the polyethylene glycol has a molecular weight of 1000-.
Preferably, in the step (3), after stirring, hydrothermal treatment is further carried out for 1-24h at the conditions of 150-250 ℃ and 2-15 atm.
Preferably, in the step (4), the roasting is carried out at a higher temperature and a lower temperature, the higher temperature Th is 700-1100 ℃ and the temperature is kept for 1-12 hours, preferably 800-900 ℃; the lower temperature Tl is 50-70% of Th and the temperature is kept for 1-12 hours, preferably the temperature Tl is 400-550 ℃.
The invention also relates to a catalyst comprising at least:
1) high temperature resistant macroporous alumina containing an adjuvant as described previously or alumina containing an adjuvant as prepared according to the foregoing method;
2) a main active ingredient combined on the alumina containing the auxiliary agent, wherein the main active ingredient comprises at least one or more of the following elements in any ratio: pd, Pt, Rh, Ru, Ir, Au, Ag, Fe, Co, Ni, Cu, Zn, Cr, V, Mn, W, Mo, Zr, La, Sm, Ce, Nd, Ba, Y, Mg, Na, K, Ca, Cs, Sn, In, Ga, Nb, Tc.
Preferably, the catalyst is an automotive exhaust catalyst comprising: gasoline vehicle tail gas catalyst, diesel vehicle tail gas catalyst, motorcycle tail gas catalyst, compressed natural gas locomotive tail gas catalyst.
Preferably, the gasoline vehicle exhaust catalyst includes: three-way catalysts (TWC), four-way catalysts (FWC).
Preferably, the diesel exhaust catalyst comprises: diesel Oxidation Catalyst (DOC), Catalyzed Soot Filter (CSF), Lean Nox Trap (LNT), ammonia oxidation catalyst (AMOX).
Preferably, the catalyst is a Volatile Organic Compounds (VOCs) purification catalyst.
Preferably, the catalyst is a hydrocracking catalyst.
The invention has the beneficial effects that:
compared with the commercial product, the alumina containing the auxiliary agent prepared by the invention has better high temperature resistance and larger pore volume. The catalyst prepared by using the catalyst as a catalyst carrier has higher activity and correspondingly prolonged service life.
In the preferred scheme, a higher temperature and a lower temperature are selected to be matched for roasting, and the roasting is carried out at the higher temperature to crystallize the alumina containing the auxiliary agent, wherein the alumina containing the auxiliary agent can be used but has poor performance. However, the performance of the alumina containing the auxiliary agent can be improved by arranging one time of roasting at a lower temperature before and after roasting at a higher temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to alumina containing an auxiliary agent, which comprises alumina and the auxiliary agent, wherein:
the mass percentage of the alumina is more than or equal to 50 percent, and the balance is the auxiliary agent, wherein the mass percentage of the alumina is the mass percentage of the alumina in the total mass of the alumina containing the auxiliary agent.
The auxiliary agent is selected from one or more of the following oxides of elements in any ratio: ge. P, As, Sb, Bi, Ni, Cu, Zr, Hf, Si, Nb, Ta, Fe, La, Ce, Nd, Sm, Pr, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, In, Ti.
After the alumina containing the auxiliary agent is subjected to high-temperature roasting treatment for 1-6h at 1000 ℃, the total pore volume measured by low-temperature nitrogen adsorption is still more than or equal to 1.0cm3/g。
Under normal conditions, gamma alumina is transformed into delta and theta alumina at more than 800 ℃, the specific surface and the pore volume are collapsed to a certain extent, and after being further roasted at 1000-<0.60cm3(iv)/g, the original activity of the catalyst was not maintained well. The alumina containing the auxiliary agent still has larger pore volume after being roasted at 1000 ℃, and can meet the application requirement of a catalytic process.
The embodiment of the invention also relates to a preparation method of the alumina containing the auxiliary agent, which comprises the following steps:
step (1): dissolving soluble aluminum salt in water to obtain a precursor solution, and adding the precursor of the auxiliary agent and a precipitator into the precursor solution at the temperature of 10-90 ℃ to generate aluminum hydroxide precipitate containing the auxiliary agent precursor. The precursor of the auxiliary agent and the precipitating agent can be added in sequence, or the precursor of the auxiliary agent and the precipitating agent can be added simultaneously. Controlling the pH value to be 5.0-9.0 in the precipitation process, and then filtering and washing the precipitate to obtain a filter cake, namely the solid material A.
Further, the soluble aluminum salt is selected from at least one of sodium aluminate, potassium aluminate, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum-containing alkoxide.
Furthermore, the precursor of the auxiliary agent is an oxide, a hydroxide, a complex, an acid, a salt or an organic ester corresponding to the element contained in the auxiliary agent. When the precursor of the auxiliary agent is an oxide or hydroxide containing the element of the auxiliary agent, the precursor may be in the form of a solid, nanoparticle dispersion or colloidal solution of the oxide or hydroxide.
Further, the precipitator is acid liquor or alkali liquor. Wherein the acid solution is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, citric acid, perchloric acid, oxalic acid and carbonic acid. The alkali liquor is at least one of sodium hydroxide, potassium hydroxide, ammonia water, ammonium carbonate and ammonium bicarbonate.
Further, in the step (1), the assistant precursor, the pore-forming agent and the precipitant may be mixed, and then the mixture may be added dropwise to the aluminum salt solution to form the aluminum hydroxide precipitate. Wherein the pore-forming agent is a combustible carbon-containing material and is selected from at least one of petroleum coke, carbon powder, graphite, polyethylene, polypropylene, rosin and vaseline, preferably petroleum coke, graphite or vaseline, more preferably petroleum coke, and most preferably petroleum coke with the particle size of 0-200 μm. The pore-forming agent has the functions of oxidizing in the roasting process, generating gas to escape, and forming macropores in the alumina containing the auxiliary agent so as to enable the alumina to have a proper pore structure and specific surface. The mass ratio of the pore-forming agent to the soluble aluminum salt is 1 (10-100).
Step (2): dissolving organic amine in water to obtain solution B, wherein the molar ratio of the organic amine to the soluble aluminum salt is (0.06-0.2): 1.
Further, the organic amine is at least one selected from trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, n-butylamine, pyrrolidine, and hexamethylenediamine.
Further, in the step (2), a low carbon alcohol can be added into the organic amine, so that the specific surface area and the pore volume of the alumina containing the auxiliary agent can be further improved. The lower alcohol is at least one selected from ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and n-pentanol. The mass ratio of the organic amine to the lower alcohol is (57-375) to (10-110).
Further, polyethylene glycol can be added into organic amine in the step (2) to improve the specific surface area and pore volume of the alumina containing the auxiliary agent. The mass ratio of the organic amine to the polyethylene glycol is (57-375) to (20-50), and the molecular weight of the polyethylene glycol is 1000-10000.
And (3): and (3) fully dispersing the solid material A obtained in the step (1) in the solution B obtained in the step (2), stirring for 30-240min, and filtering to obtain a filter cake, namely the solid material C.
Further, in the step (3), after stirring, hydrothermal treatment is carried out for 1-24h at the temperature of 150-250 ℃ and under the pressure of 2-15atm to promote the forming of the alumina containing the auxiliary agent.
(4) And (4) drying the solid material C obtained in the step (3), and roasting at 400-1200 ℃ for 1-24h to obtain the alumina containing the auxiliary agent.
Further, it is preferable to perform the second baking by using a combination of a higher temperature and a lower temperature.
It should be noted that the temperature for the second calcination is required to meet specific requirements, because too high a temperature will affect the activity and selectivity of the resulting catalyst, and too low a calcination temperature will result in poor strength of the alumina containing the promoter. Specifically, the temperature of the second roasting is selected from a higher temperature and a lower temperature, namely: if the first roasting adopts higher temperature, the second roasting can adopt lower temperature; conversely, if a lower temperature is used for the first firing, a higher temperature may be used for the second firing. Wherein the higher temperature Th is in the range of 700-1100 ℃ and is kept for 1-12 hours, preferably 800-900 ℃. The lower temperature Tl is 50-70% of Th and the temperature is kept for 1-12 hours, preferably the temperature Tl is 400-550 ℃.
If both are calcined at lower temperatures, the alumina containing the promoter cannot undergo phase transformation. And selecting higher temperatures twice would obviously consume more energy and would not be necessary. Therefore, the invention selects a higher temperature and a lower temperature to match, and the alumina containing the auxiliary agent is roasted at the higher temperature to complete crystal transformation, and the alumina containing the auxiliary agent can be used as a carrier but has poor performance. However, the performance of the carrier can be greatly improved by arranging one time of roasting at a lower temperature before and after roasting at a higher temperature.
For example, the solid material C may be calcined at 400 ℃, and the alumina containing the auxiliary agent is a transition phase, so that the performance is poor and the solid material C cannot be used for preparing the catalyst. Then roasting at 900 ℃, and the obtained alumina containing the auxiliary agent has better crushing strength, and the catalyst prepared by using the alumina as a carrier has stable performance and higher activity.
Embodiments of the present invention also relate to a catalyst, comprising at least:
1) the alumina containing the auxiliary agent or the alumina containing the auxiliary agent prepared by the method is used as a catalyst carrier;
2) a main active component combined on the alumina carrier containing the auxiliary agent, wherein the main active component contains at least one or more of the following elements in combination in any proportion: pd, Pt, Rh, Ru, Ir, Au, Ag, Fe, Co, Ni, Cu, Zn, Cr, V, Mn, W, Mo, Zr, La, Sm, Ce, Nd, Ba, Y, Mg, Na, K, Ca, Cs, Sn, In, Ga, Nb, Tc.
Further, the catalyst may be a motor vehicle exhaust catalyst comprising: gasoline vehicle tail gas catalyst, diesel vehicle tail gas catalyst, motorcycle tail gas catalyst, compressed natural gas locomotive tail gas catalyst.
Further, the gasoline car exhaust catalyst includes: three-way catalysts (TWC), four-way catalysts (FWC).
Further, the diesel vehicle exhaust catalyst includes: diesel Oxidation Catalyst (DOC), Catalyzed Soot Filter (CSF), Lean Nox Trap (LNT), ammonia oxidation catalyst (AMOX).
In addition, the catalyst can also be a Volatile Organic Compounds (VOCs) purification catalyst or a hydrocracking catalyst in petrochemical industry.
Preparation examples 1-1 to 1-7 are the preparation of alumina containing an assistant.
Preparation examples 1 to 1
The preparation example provides lanthanum-containing alumina, which is prepared by the following method:
(1) dissolving 90 parts by weight of sodium aluminate in 600 parts by weight of deionized water, placing the solution in a constant-temperature water bath at 10 ℃ for stirring, and firstly dropwise adding 70.2mL of LaCl3Solution (LaCl)3The concentration is 50g/L), then HCl solution with the concentration of 1mol/L is dripped dropwise until the precipitation is complete, and the pH value is controlled to be 8.0; the precipitate is then filtered and washed with deionized water, whereuponObtaining a filter cake which is a solid material A;
(2) weighing 20 parts by weight of hexamethylenediamine and 2.5 parts by weight of ethanol, and dissolving in 600 parts by weight of deionized water to prepare a solution B;
(3) mixing the solid material A with the aqueous solution B, fully stirring and dispersing the solid material A to obtain a suspension, strongly and mechanically stirring the suspension at the speed of 500r/min for 240min, transferring the material into a polytetrafluoroethylene hydrothermal reaction kettle with a stainless steel outer liner, carrying out hydrothermal treatment at the temperature of 150 ℃ and the pressure of 5atm for 12h, taking out the mixture, and filtering to obtain a solid C;
(4) drying the solid material C at 150 ℃ for 2h, and roasting at 800 ℃ for 3h to obtain the lanthanum (La) containing2O3Content 4 wt.%) of finished alumina in a fresh state.
Preparation examples 1 to 2
The preparation example provides silicon-containing alumina, which is prepared by the following method:
(1) dissolving 110 parts by weight of aluminum chloride hexahydrate and 6.1 parts by weight of silica sol dispersion (the content of silica is 20 wt%) in 500 parts by weight of deionized water, placing the mixture in a constant-temperature water bath at 90 ℃ for stirring, and then dropwise adding a NaOH solution with the concentration of 4mol/L until the precipitation is complete, wherein the pH value is 8.5; then filtering the precipitate, and washing with deionized water to obtain a filter cake, namely a solid material A;
(2) dissolving 5 parts by weight of trimethylamine, 1.2 parts by weight of polyethylene glycol with the molecular weight of 10000 and 0.6 part by weight of isopropanol in 350 parts by weight of deionized water to prepare solution B;
(3) mixing the solid material A with the solution B, fully stirring and dispersing the solid material A to obtain a suspension, strongly and mechanically stirring the suspension at the speed of 200r/min for 240min, transferring the material to a polytetrafluoroethylene hydrothermal reaction kettle with a stainless steel outer liner, carrying out hydrothermal treatment for 24h at the temperature of 250 ℃ and the pressure of 15atm, taking out the material after the hydrothermal treatment, and filtering to obtain a solid material C;
(4) drying the solid material C at 80 ℃ for 48h, and roasting at 800 ℃ for 3h to obtain silicon-containing (SiO)2Content 5 wt.%) alumina in a fresh state.
Preparation examples 1 to 3
Other operating conditions and the amounts of the raw materials in this preparation example were the same as in preparation example 1-1, except that: and (2) adding petroleum coke into the step (1), and adding the petroleum coke and the HCl solution into the sodium aluminate solution together.
Preparation examples 1 to 4
Other operating conditions and the amounts of the raw materials in this preparation example were the same as in preparation example 1-1, except that:
and (2) adding petroleum coke into the step (1), and adding the petroleum coke and the HCl solution into the sodium aluminate solution together.
Roasting twice in the step (4), namely: and drying the solid material C at 80 ℃ for 48h, roasting at 400 ℃ for 2h, and then roasting at 800 ℃ for 3h to obtain the finished product of aluminum oxide.
Preparation examples 1 to 5
Other operating conditions and the amounts of the raw materials in the preparation examples were the same as those in preparation examples 1 to 2 except that:
and (2) adding petroleum coke into the step (1), and adding the petroleum coke and the NaOH solution into the aluminum chloride solution together.
Roasting twice in the step (4), namely: and drying the solid material C at 80 ℃ for 48h, roasting at 400 ℃ for 2h, and then roasting at 800 ℃ for 3h to obtain the finished product of aluminum oxide.
Preparation examples 1 to 6
The preparation example provides barium-containing alumina, which is prepared by the following method:
(1) dissolving 588 weight parts of aluminum sulfate octadecahydrate into 1000 weight parts of deionized water, placing the solution in a constant-temperature water bath at 30 ℃ for stirring, firstly dropwise adding a barium hydroxide aqueous solution (5.6 weight parts of barium hydroxide are dissolved in 200 weight parts of deionized water), then dropwise adding a NaOH solution with the concentration of 2mol/L until the precipitation is complete, and controlling the pH value to be 7.5; then filtering the precipitate, and washing with deionized water to obtain a filter cake, namely a solid material A;
(2) weighing 10 parts by weight of triethylamine and 2 parts by weight of n-propanol, and dissolving the triethylamine and the n-propanol in 800 parts by weight of deionized water to prepare a solution B;
(3) mixing the solid material A with the aqueous solution B, fully stirring the solid material A to obtain a suspension, strongly and mechanically stirring the suspension at the speed of 200r/min for 240min, taking out the material, and filtering to obtain a solid material C;
(4) and drying the solid material C at 110 ℃ for 10h, and roasting at 800 ℃ for 3h to obtain a finished product of aluminum oxide containing barium (10 wt% of BaO), wherein the finished product is in a fresh state.
Preparation examples 1 to 7
The preparation example provides alumina containing zirconium and lanthanum, which is prepared by the following method:
(1) taking 62 parts by weight of sodium aluminate and 100 parts by weight of (ZrO)2Content 10 wt.%) of a dispersion of zirconia nanoparticles (ZrO)2Average particle diameter of 20nm) in 600 parts by weight of deionized water, stirring in a 30 ℃ constant temperature water bath, and dropwise adding LaCl3Solution (3.42g LaCl)3·7H2Dissolving O in 20mL of deionized water), then dropwise adding 1mol/L HCl solution until the precipitation is complete, and controlling the pH value to be 7.5; then filtering the precipitate, and washing with deionized water to obtain a filter cake, namely a solid material A;
(2) weighing 15 parts by weight of tri-n-propylamine and 2 parts by weight of isopropanol, and dissolving the tri-n-propylamine and the isopropanol in 600 parts by weight of deionized water to prepare a solution B;
(3) mixing the solid material A with the aqueous solution B, fully stirring and dispersing the solid material A to obtain a suspension, strongly and mechanically stirring the suspension at the speed of 200r/min for 240min, transferring the material into an autoclave, keeping the material at the temperature of 200 ℃ for 12h under the condition of 4atm, taking out the material, and filtering to obtain a solid material C;
(4) drying the solid material C at 120 ℃ for 12h, and roasting at 800 ℃ for 3h to obtain the zirconium (ZrO) containing material220 wt%) and lanthanum (La)2O3Content 3 wt.%) of finished alumina in a fresh state.
Example 1
Preparation of TWC catalyst
200g of the alumina powders obtained in production examples 1 to 4 and 150g of a Ce-Zr oxide solid solution powder (containing CeO)240mol％，ZrO2 60mol%) and then added to 500g of a deionized water solution in which 60g of lanthanum nitrate and 10g of barium nitrate were dissolved. Under continuous stirring, 12g of palladium nitrate solution (Pd mass concentration 15%), [ Rh (NH) was added3)6](NO3)33g of solution (Rh mass concentration is 5 percent), continuously stirring for 1.5 hours with strong force to prepare TWC catalyst slurry, and then grinding the slurry by a grinder until the granularity D90 is 4-6 mu m.
After immersing small strips of cordierite carrier (pore density 600cpsi, wall thickness 4.3mil, diameter 3cm, length 8cm) in the above catalyst slurry, taking out and blowing excess slurry with a wind gun, then drying the slurry coated carrier in an oven at 100 ℃ for 12h and calcining at 400 ℃ for 4h under air conditions. The total noble metal loading of the obtained catalyst is 80g/ft3。
Before the activity test, the catalyst was placed in a muffle furnace and aged at 1025 ℃ for 12 hours (atmosphere of 10% steam, 2% CO, 3% propylene, 1% toluene, 2% NO, 82% air) as an aging treatment process for the catalyst. The aged catalyst was subjected to evaluation of the activity of gasoline engine exhaust gas treatment according to the NEDC test cycle.
Example 2
Preparation of DOC catalyst
10g of citric acid and 14g of ethylene glycol were added to 500g of deionized water, and 15.6g of an aqueous platinum nitrate solution (Pt mass concentration 15%) and 7.8g of a palladium nitrate solution (Pd mass concentration 15%) were added to the above solution. Then 200g of the alumina powder obtained in preparation examples 1 to 5 and 120g H-. beta.molecular sieve powder were added to the above mixed solution, followed by vigorous stirring for 1.5 hours to obtain a catalyst slurry, and the slurry was further milled by a mill until the particle size D90 became 4 to 6 μm.
After immersing small strips of cordierite support (pore density 600cpsi, wall thickness 4.3mil, diameter 3cm, length 8cm) into the catalyst slurry, taking out and blowing excess slurry with a wind gun, then drying the slurry coated support in an oven at 100 ℃ for 12h and calcining at 400 ℃ for 4h in air.
Before the activity test, the catalyst is placed in a muffle furnace and is calcined for 6 hours at 750 ℃ in an air atmosphere, and the calcination process is used as an aging treatment process for the catalyst. The aged catalyst was evaluated for diesel exhaust treatment activity according to NEDC test cycles.
Example 3
Preparation of FWC catalyst
200g of the alumina powders obtained in production examples 1 to 6 and 170g of a Ce-Zr oxide solid solution powder (containing CeO)245mol％，ZrO255 mol%) were mixed and added to 500g of a deionized water solution in which 55g of lanthanum nitrate was dissolved. Under continuous stirring, 20g of palladium nitrate solution (Pd mass concentration 15%), [ Rh (NH) was added3)6](NO3)36g of solution (Rh mass concentration is 5%), 36g of zirconium acetate solution (mass concentration is 25%) and 20g of alumina sol (mass concentration is 10%), continuously stirring strongly for 1.5h to prepare FWC catalyst slurry, and then grinding the slurry by a grinder until the granularity D90 is 4-6 μm.
After immersing small strips of cordierite carrier (pore density 300cpsi, wall thickness 4.3mil, diameter 1inch, length 3inch) in the above catalyst slurry, taking out and blowing excess slurry with a wind gun, then placing the slurry-coated carrier in an oven at 100 ℃ for drying for 12h and calcining at 500 ℃ for 4h in air. The total noble metal loading of the obtained catalyst is 60g/ft3。
Before the activity test, the catalyst was placed in a tube furnace and aged at 1050 ℃ for 12 hours (atmosphere of 10% steam, 2% CO, 3% propylene, 1% toluene, 2% NO, 82% air) as an aging treatment process for the catalyst. The aged catalyst was subjected to evaluation of the activity of the gasoline locomotive in FWC tail gas treatment according to NEDC test cycles.
Example 4
Preparation of CSF catalyst
200g of the alumina powder obtained in production examples 1 to 5 was added to 450g of a deionized water solution in which 18g of barium nitrate was dissolved. Under continuous stirring, 7.5g of platinum nitrate aqueous solution (Pt mass concentration is 15%) and 3.2g of palladium nitrate solution (Pd mass concentration is 15%) are added, 20g of zirconium acetate solution (mass concentration is 25%) is added, strong stirring is continued for 1.5h, CSF catalyst slurry is prepared, and the slurry is ground to the granularity D90 of 4-6 μm by a grinding machine.
Small strips (hole density) of silicon carbide material carrier300cpsi, 58% porosity, 22 μm pore size, 1inch diameter, 3 inches long) was immersed in the catalyst slurry described above, removed and the excess slurry was blown with a wind gun, and the slurry coated support was then dried in an oven at 100 ℃ for 12h and calcined at 400 ℃ for 4h in air. The total noble metal loading of the catalyst obtained was 10g/ft3。
Before the activity test, the catalyst was placed in a tube furnace and aged at 750 ℃ for 4 hours (atmosphere of 10% water vapor, 90% air) as an aging treatment process for the catalyst. The aged catalyst was evaluated for diesel locomotive CSF tail gas treatment activity according to NEDC test cycle.
Example 5
Preparation of AMOX catalyst
350g of the aluminum oxide powders obtained in preparation examples 1 to 4 were added to 600g of deionized water. Under continuous stirring, 25g of palladium nitrate solution (Pd mass concentration is 15%) and 40g of zirconium acetate solution (mass concentration is 25%) are added, the pH value is adjusted to 4.6 by glacial acetic acid, strong stirring is continued for 1.5h, AMOX catalyst slurry is prepared, and the slurry is ground by a grinder until the granularity D90 is 4-6 μm.
After immersing small strips of cordierite carrier (pore density 200cpsi, wall thickness 4.3mil, diameter 1inch, length 3inch) in the above catalyst slurry, taking out and blowing excess slurry with a wind gun, then placing the slurry-coated carrier in an oven at 100 ℃ for drying for 12h and calcining at 500 ℃ for 5h under air conditions. The total noble metal loading of the catalyst obtained was 35g/ft3。
Before the activity test, the catalyst is placed in a muffle furnace and aged for 4 hours at 750 ℃ in an air atmosphere, and the aging process is taken as an aging treatment process for the catalyst. The activity evaluation of the AMOX tail gas treatment of the aged catalyst is carried out on laboratory simulation test equipment, and the atmosphere conditions are as follows: 40ppm NH330ppm NO, 50ppm propylene, 15% O2，5％H2O, the balance of balance gas is nitrogen, and the space velocity is 20000h-1。
Example 6
Preparation of LNT catalyst
150g of the alumina powder obtained in production examples 1 to 4, 80g of barium carbonate powder and 120g of cerium oxide powder were added to 700g of deionized water. Under the condition of continuous stirring, 25g of platinum nitrate aqueous solution (Pt mass concentration is 15%) and 5g of palladium nitrate solution (Pd mass concentration is 15%), 40g of magnesium acetate solution (mass concentration is 15%) and 30g of zirconium acetate solution (mass concentration is 25%) are continuously stirred strongly for 1.5h to prepare LNT catalyst slurry, and then the slurry is ground to the granularity D90 of 4-6 mu m by a grinding machine.
After immersing small strips of cordierite carrier (pore density 400cpsi, wall thickness 4.3mil, diameter 1inch, length 3inch) in the above catalyst slurry, taking out and blowing excess slurry with a wind gun, then placing the slurry-coated carrier in an oven at 100 ℃ for drying for 12h and calcining at 500 ℃ for 5h under air conditions. The total noble metal loading of the obtained catalyst is 60g/ft3。
Before the activity test, the catalyst is placed in a tubular furnace and aged for 4 hours at 800 ℃ under the atmosphere of 10% of water vapor and 90% of air, and the aging process is taken as the aging process procedure of the catalyst. LNT catalysts were tested for stored NO under a NEDC cyclexCapability.
Example 7
Preparation of motorcycle exhaust catalyst
150g of the alumina powders obtained in production examples 1 to 7 and 200g of a Ce-Zr oxide solid solution powder (containing CeO)250mol％，ZrO250 mol%) were mixed and added to 600g of a deionized water solution in which 8g of lanthanum nitrate, 4g of neodymium nitrate and 25g of nickel nitrate were dissolved. Under continuous stirring, 20g of palladium nitrate solution (Pd mass concentration 15%), [ Rh (NH) was added3)6](NO3)38g of the solution (Rh mass concentration is 5%) and 20g of the zirconium acetate solution (mass concentration is 25%), strong stirring is continued for 1.5h to prepare motorcycle catalyst slurry, and the slurry is ground by a grinder until the granularity D90 is 4-6 μm.
After immersing small strips of cordierite carrier (pore density 400cpsi, wall thickness 4.3mil, diameter 1inch, length 3inch) in the above catalyst slurry, taking out and blowing excess slurry with a wind gun, then placing the slurry-coated carrier in an oven at 100 ℃ for drying for 12h and calcining at 500 ℃ for 4h in air. The total noble metal loading of the obtained catalyst is 60g/ft3。
Before the activity test, the catalyst is placed in a tubular furnace and aged for 4 hours at 600 ℃ under the atmosphere of 10% of water vapor and 90% of air, and the aging process is taken as the aging process procedure of the catalyst. The tail gas treatment capability of the motorcycle catalyst was tested using the Euro V test protocol.
Example 8
Preparation of tail gas catalyst for compressed natural gas engine
12g of citric acid and 10g of ethylene glycol were added to 500g of deionized water, and to the above solution were added 14.3g of an aqueous platinum nitrate solution (Pt mass concentration 15%), 7.2g of a palladium nitrate solution (Pd mass concentration 15%) and 6g of barium nitrate. After sufficiently stirring, dissolving and dispersing, 220g of the alumina powder obtained in preparation examples 1 to 5 and 120g of the cerium oxide powder were added to the above mixed solution, followed by vigorous stirring for 1.5 hours to obtain a catalyst slurry, and the slurry was further milled by a mill until the particle size D90 became 4 to 6 μm.
After immersing small strips of cordierite carrier (pore density 600cpsi, wall thickness 4.3mil, diameter 1inch, length 3inch) into the above catalyst slurry, taking out and blowing excess slurry with a wind gun, then placing the slurry coated carrier in an oven at 100 ℃ for drying for 12h and calcining for 2h at 500 ℃ under air conditions. The total noble metal loading of the obtained catalyst is 50g/ft3。
Before the activity test, the catalyst is placed in a muffle furnace and is roasted for 6 hours at 650 ℃ in an air atmosphere, and the aging treatment process is carried out on the catalyst. The aged catalyst is evaluated for the methane ignition activity on laboratory simulation test equipment, the temperature is increased from 25 ℃ to 650 ℃ at 5 ℃/min, the concentration change of methane is recorded in real time by mass spectrum, and the test atmosphere is as follows: 1.5% CO, 1500ppm methane, 1000ppm NO, 5% oxygen, the balance being nitrogen.
EXAMPLE 9VOCs clean-up catalyst
100g of copper nitrate, 320g of manganese nitrate and 40g of zirconium nitrate were dissolved in 220g of deionized water, and after stirring uniformly, the solution was dropwise added to 800g of the alumina powder obtained in preparation examples 1 to 5 while continuously stirring the powder, and dry impregnation was performed.
And putting the powder impregnated by the dry method into 1L of deionized water, fully stirring to form slurry, and grinding the slurry by a grinder until the granularity D90 is 4-6 mu m.
Small strips of cordierite support (pore density 600cpsi, 4.3mil wall thickness, 3cm diameter, 8cm length) were immersed in the catalyst slurry, removed, and excess slurry was blown with a blower gun, and the slurry coated support was dried in a 110 ℃ oven for 12h and calcined at 550 ℃ in air for 4 h.
Before the activity test, the catalyst is placed in a muffle furnace and is roasted for 6 hours at 750 ℃ in an air atmosphere to serve as an aging treatment process for the VOCs catalyst.
The aged catalyst was subjected to a toluene combustion test under the following conditions:
5 ℃/min from 25 ℃ to 500 ℃, the toluene concentration change was recorded in real time by mass spectrometry, space velocity: 10000h-1The atmosphere was 0.1% toluene and the balance air.
Example 10 hydrocracking catalyst
320g of the alumina powder obtained in preparation examples 1 to 4, 380g of ultrastable Y molecular sieve (USY) and 20g of sesbania powder are mixed, extruded into a cylindrical shape with the diameter of 6mm, dried at 110 ℃ for 6h, and roasted at 600 ℃ for 6h in an air atmosphere to obtain a roasted carrier strip.
After the carrier is cooled, 100g of carrier strip is dipped in aqueous solution which is prepared by 51g of ammonium metatungstate, 10g of nickel nitrate, 10.5g of citric acid and 84g of water. And after the impregnation is finished, drying for 6 hours at 180 ℃, and taking out to obtain the hydrocracking catalyst.
Analytical pure tetrahydronaphthalene was used as a raw material, and the hydrocracking activity was evaluated on a mini-fixed bed reactor. The catalyst loading is 10g, the reaction temperature is 350 ℃ and 400 ℃, and the pressure is 3.3-3.9 MPa.
Comparative example 1
The other conditions were the same as in example 1, and only in the preparation of TWC catalyst slurry, alumina was replaced with fresh commercially available alumina powder (Sasol Corp., La-containing Co.)2O3 4wt％)。
Comparative example 2
The remaining conditions were the same as in example 2, and only during the preparation of DOC catalyst slurry, the alumina was replaced with fresh oneCommercially available alumina powder (Sasol Corp., SiO-containing)2 5wt％)
Comparative example 3
The remaining conditions were the same as in example 3 except that during the preparation of the FWC catalyst slurry, the alumina was replaced with a fresh commercial alumina powder (Sasol Corp., BaO 10 wt%)
Comparative example 4
The remaining conditions were the same as in example 4, and only during the preparation of CSF catalyst slurry, the alumina was replaced with fresh commercial alumina powder (Sasol Corp., SiO-containing Co.)2 5wt％)
Comparative example 5
The remaining conditions were the same as in example 3, and only during the preparation of the AMOX catalyst slurry, the alumina was replaced with fresh commercial alumina powder (Sasol corporation, La-containing)2O3 4wt％)
Comparative example 6
The other conditions were the same as in example 4, and only during the preparation of LNT catalyst slurry, the alumina was replaced with fresh commercial alumina powder (Sasol Corp., La-containing, Co., Ltd.)2O3 4wt％)
Comparative example 7
The other conditions were the same as in example 3 except that the alumina was replaced with a fresh commercially available alumina powder (Sasol Corp., ZrO-containing) only in the preparation of the motorcycle exhaust catalyst slurry2 20wt％，La2O3 3wt％)
Comparative example 8
The remaining conditions were the same as in example 4, and only in the preparation of the catalyst slurry for compressed natural locomotive, the alumina was replaced with a fresh commercially available alumina powder (Sasol Corp., SiO-containing powder)2 5wt％)
Comparative example 9
The other conditions were the same as in example 3, and only during the preparation of the VOCs purifying catalyst slurry, the alumina was replaced with fresh commercial alumina powder (Sasol Corp., SiO-containing powder)2 5wt％)
Comparative example 10
The other conditions were the same as in example 4, except that the hydrocracking catalyst was supported on a carrierDuring the preparation of the bodies, the alumina was replaced by fresh commercial alumina powder (Sasol Corp., La-containing)2O3 4wt％)
The fresh alumina prepared above, and the specific surface and pore volume properties after being respectively subjected to baking aging at 1000 ℃ for 4 hours are shown in Table 1. The results of the activity tests of the catalysts are shown in Table 2. (the low temperature nitrogen adsorption tester is Tristar II 3020 from McMac USA)
TABLE 1
Figure GDA0003064125720000181
TABLE 2
Figure GDA0003064125720000182
Figure GDA0003064125720000191
As can be seen from the comparison in Table 1, the catalyst carrier used was alumina having a large pore volume and a high temperature resistance, and had a larger pore volume and a larger specific surface area than those of the alumina commercially available from Sasol company under both fresh conditions and high temperature conditions, and the pore volume was 1.0cm after calcination and aging at 1000 ℃ for 4 hours3More than g. Comparing the aluminas prepared in preparation examples 1-3 to 1-5 with those of preparation examples 1-1 and 1-2, it is understood that the specific surface area and pore volume can be further improved by using a pore-forming agent and by employing a secondary calcination during the preparation.
As can be seen from table 2, the catalyst carrier obtained by applying the catalyst carrier to TWC, DOC, FWC, CSF, AMOX, LNT, motorcycle catalyst, compressed natural gas locomotive catalyst, purification of VOCs, and hydrocracking reaction also has a better catalytic conversion effect. Specifically, examples 1, 2, 3, 4 had less pollutant emissions than comparative examples 1, 2, 3, 4, examples 5, 7 had higher pollutant conversions than comparative examples 5, 7, and example 6 had higher NO than comparative example 6xThe capacity of storing and discharging the pollutants,examples 8 and 9 have lower contaminant conversion temperatures than comparative examples 8 and 9, and example 10 has higher substrate conversion and longer catalyst life than comparative example 10. The advantages of the activity are derived from the fact that the alumina carrier containing the auxiliary agent has better heat resistance and good specific surface and pore canal properties at high temperature, so that the main active component of the catalyst still has good dispersity at high temperature, and meanwhile, macromolecular hydrocarbon substances can be well diffused in alumina pores, and the reaction is promoted to continue.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (6)

1. An alumina containing auxiliary agent, which comprises alumina and auxiliary agent, is characterized in that,
the mass percentage of the alumina is more than or equal to 50 percent, and the balance is auxiliary agent;
the auxiliary agent is selected from one or more of the following oxides of elements in any ratio: ge. P, As, Sb, Bi, Ni, Cu, Zr, Hf, Si, Nb, Ta, Fe, La, Ce, Nd, Sm, Pr, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, In, Ti;
the total pore volume measured by low-temperature nitrogen adsorption is more than or equal to 1.0cm after the alumina containing the auxiliary agent is roasted for 1-6h at 1000 DEG C3/g；
The preparation method of the alumina containing the auxiliary agent comprises the following steps:
(1) dissolving soluble aluminum salt in water to obtain a precursor solution, adding a precursor of an auxiliary agent and a precipitator into the precursor solution at the temperature of 10-90 ℃ to generate an aluminum hydroxide precipitate containing the auxiliary agent precursor, controlling the pH value to be 5.0-9.0 in the precipitation process, and then filtering and washing the precipitate to obtain a filter cake, namely a solid material A;
the precipitator contains a pore-forming agent, and the pore-forming agent is a combustible carbon-containing material and is selected from at least one of petroleum coke, carbon powder, graphite, polyethylene, polypropylene, rosin and vaseline; the mass ratio of the pore-forming agent to the soluble aluminum salt is 1 (10-100);
(2) dissolving organic amine in water to obtain a solution B, wherein the molar ratio of the organic amine to the soluble aluminum salt is (0.06-0.2): 1; the organic amine is selected from at least one of trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, n-butylamine, pyrrolidine and hexamethylenediamine;
adding a lower alcohol into the organic amine, wherein the mass ratio of the organic amine to the lower alcohol is (57-375) to (10-110); the low-carbon alcohol is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and n-pentanol;
polyethylene glycol is also added into the organic amine, the mass ratio of the organic amine to the polyethylene glycol is (57-375) to (20-50), and the molecular weight of the polyethylene glycol is 1000-10000;
(3) fully dispersing the solid material A in the step (1) in the solution B in the step (2), stirring for 30-240min, carrying out hydrothermal treatment for 1-24h at the temperature of 150-;
(4) drying and roasting the solid material C obtained in the step (3) to obtain the alumina containing the auxiliary agent;
the roasting is carried out at a higher temperature Th of 700-; the lower temperature Tl is 50-70% of Th and the temperature is kept for 1-12 hours.
2. The alumina according to claim 1, wherein in step (1), the assistant precursor is an oxide, a hydroxide, a complex, an acid, a salt or an organic ester corresponding to the element contained in the assistant;
the soluble aluminum salt is selected from at least one of sodium aluminate, potassium aluminate, aluminum chloride, aluminum nitrate, aluminum sulfate and aluminum-containing alkoxide;
the precipitator is acid liquor or alkali liquor; the acid solution is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, citric acid, perchloric acid, oxalic acid and carbonic acid;
the alkali liquor is at least one of sodium hydroxide, potassium hydroxide, ammonia water, ammonium carbonate and ammonium bicarbonate.
3. A catalyst comprising at least:
1) the alumina containing an auxiliary according to claim 1 or 2;
2) a main active ingredient combined on the alumina containing the auxiliary agent, wherein the main active ingredient comprises at least one or more of the following elements in any ratio: pd, Pt, Rh, Ru, Ir, Au, Ag, Fe, Co, Ni, Cu, Zn, Cr, V, Mn, W, Mo, Zr, La, Sm, Ce, Nd, Ba, Y, Mg, Na, K, Ca, Cs, Sn, In, Ga, Nb, Tc.
4. The catalyst of claim 3, wherein the catalyst is an automotive exhaust catalyst comprising: gasoline vehicle tail gas catalyst, diesel vehicle tail gas catalyst, motorcycle tail gas catalyst, compressed natural gas locomotive tail gas catalyst.
5. The catalyst according to claim 4, wherein the gasoline vehicle exhaust catalyst comprises: three-way catalysts, four-way catalysts;
the diesel vehicle exhaust catalyst includes: diesel oxidation catalysts, catalyzed soot filters, lean nitrogen oxide traps, ammonia oxidation catalysts.
6. The catalyst according to claim 4 or 5, wherein the catalyst is a volatile organic compound purification catalyst or a hydrocracking catalyst.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4671497A (en) * 1984-02-15 1987-06-09 Klockner-Humboldt-Deutz Aktiengesellschaft Apparatus and method for the continuous calcination of aluminum hydroxide
CN101468322A (en) * 2007-12-27 2009-07-01 中国石油化工股份有限公司 Alumina supporter and preparation method thereof
CN102413904A (en) * 2009-05-18 2012-04-11 尤米科尔股份公司及两合公司 High Pd content diesel oxidation catalyst with improved hydrothermal durability
CN102631917A (en) * 2012-04-09 2012-08-15 福州大学 Oxidation catalyst for purifying tail gas of diesel vehicle and preparation method for oxidation catalyst
CN103459017A (en) * 2011-03-24 2013-12-18 优美科触媒日本有限公司 Catalyst for exhaust gas purification, method for producing same, and exhaust gas purification method using same
CN103922373A (en) * 2014-04-14 2014-07-16 浙江大学 Preparation method of alumina porous microsphere
CN105948089A (en) * 2016-05-03 2016-09-21 许杰 High-temperature-resistant and large-specific-surface-area aluminum oxide and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4671497A (en) * 1984-02-15 1987-06-09 Klockner-Humboldt-Deutz Aktiengesellschaft Apparatus and method for the continuous calcination of aluminum hydroxide
CN101468322A (en) * 2007-12-27 2009-07-01 中国石油化工股份有限公司 Alumina supporter and preparation method thereof
CN102413904A (en) * 2009-05-18 2012-04-11 尤米科尔股份公司及两合公司 High Pd content diesel oxidation catalyst with improved hydrothermal durability
CN103459017A (en) * 2011-03-24 2013-12-18 优美科触媒日本有限公司 Catalyst for exhaust gas purification, method for producing same, and exhaust gas purification method using same
CN102631917A (en) * 2012-04-09 2012-08-15 福州大学 Oxidation catalyst for purifying tail gas of diesel vehicle and preparation method for oxidation catalyst
CN103922373A (en) * 2014-04-14 2014-07-16 浙江大学 Preparation method of alumina porous microsphere
CN105948089A (en) * 2016-05-03 2016-09-21 许杰 High-temperature-resistant and large-specific-surface-area aluminum oxide and preparation method thereof

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