CN105289653B - It is a kind of for integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature and preparation method thereof - Google Patents
It is a kind of for integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature and preparation method thereof Download PDFInfo
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- CN105289653B CN105289653B CN201510799745.3A CN201510799745A CN105289653B CN 105289653 B CN105289653 B CN 105289653B CN 201510799745 A CN201510799745 A CN 201510799745A CN 105289653 B CN105289653 B CN 105289653B
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Abstract
The present invention relates to a kind of for integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature and preparation method thereof.The preparation method includes Vehicle element, prepares the steps such as presoma, impregnated transition metal active constituent, dipping noble metal active component.The present invention is handled by aqueous acid, cordierite specific surface area is reached 200m2/ more than g, coating is easier coating, and difficult for drop-off；Two kinds of metal composite oxide coatings are prepared respectively, it is easy to control composite oxides structure and pattern；Effective removal of carbon monoxide can be realized under conditions of low temperature, low CO concentration, high-speed, high aqueous vapor and sulfur-bearing, it is adaptable to CO carbon monoxide at low temperature in gas heater tail gas, gas fired-boiler, the semiclosed space of closing.
Description
【Technical field】
The invention belongs to environmental technology field.More particularly it relates to which one kind is aoxidized for low-temperature catalytic oxidation one
The integral catalyzer of carbon, further relates to the preparation method of the integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature.
【Background technology】
CO is one of major pollutants in air, the imperfect combustion such as coal, natural gas, chemical industry production and machine
Motor-car is discharged using can cause substantial amounts of CO.With social constantly progressive, the continuous improvement of people's living standard, people couple
The requirement of environment is also being improved constantly.Carbon monoxide purification technology is studied, carbon monoxide emission is reduced, with very important meaning
Justice.There are absorption method, catalytic oxidation, plasma technique etc. for the method that carbon monoxide is eliminated at present.And for a large amount of low
The most effective and simple method of carbon monoxide waste gas of concentration is by the way of catalysis oxidation, to be inherently eliminated an oxidation
Carbon, it can convert carbon monoxide into nontoxic carbon dioxide at a lower temperature, environmentally friendly, efficient.
The main preparation methods of Carbon monoxide catalytic oxidation catalyst have traditional infusion process, sol-gal process, coprecipitation,
Precipitate sedimentation, ion-exchange etc..
Industrial simple CO catalytic combustion technologies are relatively simple at present, but the temperature needed is high, and energy consumption is big, but also meeting
Generation explosion accident.And CO low-temperature catalytic oxidations demand then compares many, such as combustion gas tail gas clean-up, closed environment CO are purified, separately
Outer complicated application conditions are also to govern the principal element that CO low-temperature catalytic oxidations realize industrialization.At present, domestic and international CO is low
Warm Catalytic Oxidation is mainly noble metal-based catalysts, although noble metal-based catalysts activity is high, its life-span and stability
There is problem, and the catalyst is especially sensitive to sulphur, steam etc., easy poisoning and deactivation.Therefore develop with high activity, resistance to
The CO low-temperature catalytic oxidation catalyst of sulphur and resistance to steam is crucial, with important economic implications and social effect.
Although considerable research has been carried out to the reaction of CO low-temperature catalytic oxidations, the document published is very
It is few, by furtheing investigate method for preparing catalyst, decentralization, support modification, to improve grinding for the resistance to aqueous vapor of catalyst and Sulfur tolerance
Study carefully document then seldom.In addition, for integral honeycombed catalyst, its difficult point is the coating of coating, it is necessary first to which solution is
Vehicle element problem, pretreatment is not only to remove surface impurity and dirt, and prior improvement surface texture such as expands ratio
In terms of surface, expansion pore volume, aperture.These will also turn into urgent problem.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature.
It is a further object to provide the integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature
Preparation method.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation method of the integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature.The preparation
The step of method, is as follows：
A, Vehicle element
Under conditions of 80~100 DEG C of temperature, cordierite carrier is handled 4~8 hours with acid solution constant temperature, is then washed with water
Wash to neutrality, then be dried；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 0.5~1.0mol/L mixed-salt aqueous solution；Then
Allow the ammonium carbonate solution or concentrated ammonia solution precipitating reagent that described mixed-salt aqueous solution and concentration are 1~5mol/L
Cocurrent is added drop-wise in reactor and is co-precipitated, and the pH of the system of co-precipitation is maintained into 9.8~10.2；
After cocurrent is added dropwise to complete, make whole co-precipitation system ripening 2~4 in 95~105 DEG C of oil baths of temperature small
When, then filter, obtained co-precipitate is washed through deionized water, dried with being calcined, and obtains Ba0.5ZrCe0.5O3Composition metal
Oxide；
Identical mode is prepared according to above-mentioned metal composite oxide, according to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：
0.5：0.5：0.5, La is prepared by lanthanum nitrate, strontium nitrate, nickel nitrate and copper nitrate0.5Sr0.5Ni0.5Cu0.5O3Composition metal
Oxide；Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide according to
Weight compares 1:1~2 mixing, obtains metal composite oxide mixture；
Deionized water is added into the metal composite oxide mixture, stirring is mixed, then ball milling obtains compound gold
Belong to oxide-coated liquid；
The cordierite carrier of processing of step A is allowed to be impregnated 26~34 minutes in the metal composite oxide coating liquid, point
From dipping cordierite is dried up, dried and is calcined, and this processing procedure repeats, until metal composite oxide coating
Measure as the 5~15% of cordierite weight, so obtain a kind of integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in 0.2~0.6mol/L of concentration cobalt nitrate aqueous solution
Impregnate 6~12 hours, separation, drying, then be calcined in air atmosphere at room temperature, its product of roasting contains in terms of cordierite weight
1~10% active component Co3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.1~
Impregnated 6~12 hours in 0.3mol/L platinum acid chloride solution, separation, drying are then calcined, its product of roasting under an inert atmosphere
Containing 0.2~0.5% active component platinum oxide in terms of cordierite weight, this product of roasting is described integral catalyzer.
A preferred embodiment of the invention, in step, the reticular density of the cordierite be 280 structure cells/
Inch2, wall thickness be 0.25mm.
According to another preferred embodiment of the present invention, in step, described acid solution is concentration for by weight
37% aqueous hydrochloric acid solution or 50% oxalic acid aqueous solution.
According to another preferred embodiment of the present invention, in step, the cordierite of washing is in 100~110 DEG C of temperature
Under be dried overnight after, its weight be before processing cordierite weight 70-90%.
According to another preferred embodiment of the present invention, in stepb, obtained co-precipitate is in temperature 100~110
Dry 10~14 hours, be then calcined 3.5~4.5 hours under conditions of 420~480 DEG C of temperature under conditions of DEG C.
According to another preferred embodiment of the present invention, in stepb, deionized water with being combined gold in gram in terms of ml
The ratio for belonging to oxide mixture is 4~5:1.
According to another preferred embodiment of the present invention, in stepb, in temperature 55~65 after dipping cordierite drying
Dry 5.5~6.5 hours, be then calcined 5.5~6.5 hours under conditions of 420~480 DEG C of temperature at DEG C.
According to another preferred embodiment of the present invention, in step C, the presoma of cobalt nitrate aqueous solution is impregnated in temperature
Dried 10~14 hours under conditions of 100~110 DEG C of degree, then be calcined 2~12 at 250~300 DEG C of temperature in air atmosphere
Hour.
According to another preferred embodiment of the present invention, in step D, the presoma of platinum acid chloride solution is impregnated in temperature
Dry 10~14 hours, be then calcined 2~4 hours at 250~300 DEG C of temperature under an inert atmosphere at 100~110 DEG C.
The invention further relates to the integral catalyzer prepared using the preparation method.Described integral catalyzer
Composition it is as follows, by weight
The present invention is described in more detail below.
The present invention relates to a kind of preparation method of the integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature.The preparation
The step of method, is as follows：
A, Vehicle element
Under conditions of 80~100 DEG C of temperature, cordierite carrier is handled 4~8 hours with acid solution constant temperature, is then washed with water
Wash to neutrality, then be dried；
The reticular density for the cordierite that the present invention is used is 280 structure cells/inch2, wall thickness be 0.25mm.
Cordierite is a kind of rich in iron, magnesium, the silicate of aluminiumMineral, magnesium therein can replace by iron or manganese, and partial
Aluminium can also be replaced by iron.Cordierite crystal more be in short cylinder, in crystal occasionally containing sillimanite, spinelle, zircon,Phosphorus ash Stone, mica etc.Inclusion enclave.Therefore, the cordierite carrier that the present invention is used needs to carry out acid treatment, removes the impurity in carrier, together
When carrier is performed etching, increase carrier surface roughness, coating stability and coated weight can be strengthened in applying coating.It is described
Acid solution be concentration for 37% aqueous hydrochloric acid solution or 50% oxalic acid aqueous solution by weight.
The cordierite that the present invention is used is the product sold in the market.
Cordierite needs to be washed with water to neutrality after acid treatment, after being then dried overnight at 100~110 DEG C of temperature,
Its weight is the 70-90% of the cordierite weight of before processing.In the present invention, if the cordierite quality after processing is less than
70%, then can be more little than surface increase due to overtreating, but cordierite honeycomb carrier intensity is seriously reduced, influence is used；
If the cordierite quality after handling is more than 90%, do not handle completely, load surface area per unit volume increase is inadequate, roughness is failed to understand
It is aobvious；Therefore, acid treatment, washing, dried cordierite weight for before processing 70~90% be it is rational, preferably 75
~85%, more preferably 78~83%.
Cordierite by above-mentioned processing is analyzed using conventional surface analytical technology to be determined, its specific surface area reaches
200m2/ more than g.
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 0.5~1.0mol/L mixed-salt aqueous solution；Then
Allow the ammonium carbonate solution or concentrated ammonia solution precipitating reagent that described mixed-salt aqueous solution and concentration are 1~5mol/L
Cocurrent is added drop-wise in reactor and is co-precipitated, and the pH of the system of co-precipitation is maintained into 9.8~10.2.
In the present invention, the main purpose that the pH of co-precipitation system maintains 9.8~10.2 is mixed in the range of this pH
Close the various salt energy deposition sedimentation, therefore sediment component ratio is uniform in salting liquid.
After cocurrent is added dropwise to complete, make whole co-precipitation system ripening 2~4 in 95~105 DEG C of oil baths of temperature small
When, then filter, obtained co-precipitate is washed through deionized water, dried with being calcined, and obtains Ba0.5ZrCe0.5O3Composition metal
Oxide.
In this step, the co-precipitate obtained dries 10~14 hours under conditions of 100~110 DEG C of temperature, so
It is calcined 3.5~4.5 hours under conditions of 420~480 DEG C of temperature afterwards.
Its product of roasting determines that it is Ba through XRF and EDS analyses0.5ZrCe0.5O3Metal composite oxide.
Identical mode is prepared according to above-mentioned metal composite oxide, according to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：
0.5：0.5：0.5, La is prepared by lanthanum nitrate, strontium nitrate, nickel nitrate and copper nitrate0.5Sr0.5Ni0.5Cu0.5O3Composition metal
Oxide, it is determined through XRF and EDS analyses.
Then, by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide is pressed
Compare 1 according to weight:1~2 mixing, obtains metal composite oxide mixture；
Deionized water is added into the metal composite oxide mixture, stirring is mixed, then ball milling obtains compound gold
Belong to oxide-coated liquid；Herein, deionized water and the ratio of metal composite oxide mixture in gram are 4~5 in terms of ml:1.
The cordierite carrier of processing of step A is allowed to be impregnated 26~34 minutes in the metal composite oxide coating liquid, point
From dipping cordierite is dried up, dried and is calcined, and this processing procedure repeats, until metal composite oxide coating
Measure as the 5~15% of cordierite weight, so obtain a kind of integral catalyzer presoma.
In this step, dried 5.5~6.5 hours at 55~65 DEG C of temperature after the drying of dipping cordierite, Ran Hou
It is calcined 5.5~6.5 hours under conditions of 420~480 DEG C of temperature.
In the present invention, if metal composite oxide coated weight is less than the 5% of cordierite weight, carrier can then be played
Very little, consequent activities component load capacity can be than relatively low, while active component surface enrichment, easily occurs crystal grain and increase for the coating of effect
Greatly, activity is bad；If metal composite oxide coated weight be cordierite weight more than 15%, can due to overweight coating,
The firmness of coating is reduced, when being reacted, airflow scouring causes coating and active component to be lost, reduces catalytic activity.Cause
This, metal composite oxide coated weight for cordierite weight 5~15% be it is appropriate, preferably 7~13%, more preferably
It is 9~11%.
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in 0.2~0.6mol/L of concentration cobalt nitrate aqueous solution
Impregnate 6~12 hours, separation, drying, then be calcined in air atmosphere at room temperature, its product of roasting contains in terms of cordierite weight
1~10% active component Co3O4；
In this step, the presoma of dipping cobalt nitrate aqueous solution under conditions of 100~110 DEG C of temperature drying 10~
14 hours, then be calcined 2~12 hours at 250~300 DEG C of temperature in air atmosphere.
The active component Co of its product of roasting3O4It is to be determined using XRD method.
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.1~
Impregnated 6~12 hours in 0.3mol/L platinum acid chloride solution, separation, drying are then calcined, its product of roasting under an inert atmosphere
Containing 0.2~0.5% active component platinum in terms of cordierite weight, this product of roasting is described integral catalyzer.
In this step, the presoma of dipping platinum acid chloride solution is dried 10~14 hours at 100~110 DEG C of temperature,
Then it is calcined 2~4 hours at 250~300 DEG C of temperature under an inert atmosphere.
The active component platinum content of its product of roasting is characterized using XRF and determined.
The invention further relates to the integral catalyzer prepared using the preparation method.
The composition of described integral catalyzer is as follows, by weight
The integral catalyzer of the present invention is with the cobalt (Co with good CO low-temperature catalytic oxidations performance3O4) and platinum for activity
Component, with good water resistance Ba0.5ZrCe0.5O3With the La of Sulfur tolerance0.5Sr0.5Ni0.5Cu0.5O3Composite oxide of metal is
Coating, using honeycomb-like cordierite as carrier, cordierite removes the impurity in carrier, simultaneously by pretreatment in preparation process
Further carrier is performed etching, carrier surface roughness is increased, using conventional Electronic Speculum and Conventional solid surface analysis, it is tied
Fruit is listed in accompanying drawing 1 and accompanying drawing 2；Coated using coating, enhance coating stability and coated weight.Ba0.5ZrCe0.5O3With
La0.5Sr0.5Ni0.5Cu0.5O3Composite oxide of metal coating makes catalyst of the present invention have resistance to steam and resistance to sulphur property, it is adaptable to
The combustion gas tail gas of sulfur-bearing and high steam, while the active metal component loaded on composite oxides can evenly be dispersed in its table
Face, activity is high, and sulfur-bearing that can at a lower temperature, to high-speed, the combustion gas tail gas CO of steam carry out depth elimination；With it is existing
Carbon monoxide catalytic oxidation catalyst compares, the integral catalyzer agent that the present invention is provided, high with resistant to sulfur, moisture-proof and degree of purification
The characteristics of.In 80~140 DEG C of low temperature, low concentration 100ppm, 120000~240000h of high-speed-1, vapour concentration 10%~
15%th, being capable of carbon monoxide oxidation under the conditions of 0.15~0.2ppm of sulfur content, it is adaptable to eliminate the oxygen in combustion gas tail gas
Change carbon, eliminate the Low Level Carbon Monoxides such as confined space.
[beneficial effect]
Compared with prior art, the beneficial effects of the invention are as follows：
1st, after concentrated hydrochloric acid or 50% oxalic acid aqueous solution boiling processing, cordierite specific surface area reaches 200m2/ more than g,
Coating is easier coating, and difficult for drop-off.
2nd, two kinds of metal composite oxide coatings are prepared respectively, it is easy to control composite oxides structure and pattern, aperture point
Analysis shows there is larger distribution (accompanying drawing 2) in the range of 2~6nm and 6~20nm, illustrates that macropore is more, and pore volume is big, profit
In its resistance to steam of holding and resistant to sulfur property；
3rd, at low temperature (80~140 DEG C), low CO concentration (80~100ppm), high-speed (120000~240000h are realized-1), high aqueous vapor (vapour concentration>10%), under sulfur-bearing (0.1~0.2ppm) carbon monoxide effective removing；
4th, good resistance to steam and resistant to sulfur ability, it is adaptable to gas heater tail gas, gas fired-boiler, the semiclosed building of closing
CO low temperature elimination in space.
【Brief description of the drawings】
Fig. 1 is that the present invention is used for the integral catalyzer electron microscope of catalyzing and oxidizing carbon monoxide at low temperature.
Fig. 2 is that the present invention is used for the integral catalyzer graph of pore diameter distribution of catalyzing and oxidizing carbon monoxide at low temperature.
【Embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：The preparation of integral catalyzer of the present invention
The implementation steps of the embodiment are as follows：
A, Vehicle element
Under conditions of 80 DEG C of temperature, 280 structure cells of reticular density/inch2, wall thickness 0.25mm cordierite carrier concentration
Handled 8 hours for by weight 37% aqueous hydrochloric acid solution constant temperature, be then washed with water to neutrality, the cordierite of washing is again in temperature
After being dried overnight at 100 DEG C of degree, its weight is the 70% of the cordierite weight of before processing；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 0.5mol/L mixed-salt aqueous solution；Then
Described mixed-salt aqueous solution is allowed to be added drop-wise to reaction with concentration for 1mol/L ammonium carbonate solution precipitating reagent cocurrent
It is co-precipitated in device, the pH of the system of co-precipitation is maintained 9.8；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 2.0 hours in 95 DEG C of oil baths of temperature are allowed, then
Filtering, obtained co-precipitate is washed three times through deionized water, dried 10 hours under conditions of 100 DEG C of temperature, then in temperature
It is calcined 3.5 hours under conditions of 420 DEG C of degree, obtains Ba0.5ZrCe0.5O3Metal composite oxide；
According to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：0.5：0.5：0.5, metal ion total concentration is prepared for 0.5mol/L
Mixed-salt aqueous solution；Then
Described mixed-salt aqueous solution is allowed to be added drop-wise to reaction with concentration for 4mol/L ammonium carbonate solution precipitating reagent cocurrent
It is co-precipitated in device, the pH of the system of co-precipitation is maintained 9.8；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 3.4 hours in 95 DEG C of oil baths of temperature are allowed, then
Filtering, obtained co-precipitate is washed three times through deionized water, dried 11 hours under conditions of 106 DEG C of temperature, then in temperature
It is calcined 4.0 hours under conditions of 420 DEG C of degree, prepares La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide；
Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide according to
Weight compares 1:1.0 mixing, obtain metal composite oxide mixture；
Deionized water and the ratio of metal composite oxide mixture in gram are 4 in terms of ml:1, toward the composition metal oxygen
Deionized water is added in compound mixture, stirring is mixed, and then ball milling obtains metal composite oxide coating liquid；
Allow the cordierite carrier of processing of step A to be impregnated 26 minutes in the metal composite oxide coating liquid, separate, leaching
Stain cordierite dried up, dry 5.5 hours at 55 DEG C of temperature again, and then roasting 6.2 is small under conditions of 420 DEG C of temperature
When.This processing procedure repeats, until metal composite oxide coated weight is the 12% of cordierite weight, so obtains one
Plant integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in concentration 0.2mol/L cobalt nitrate aqueous solution at room temperature
Dipping 10 hours, separation, the presoma of dipping cobalt nitrate aqueous solution are dried 10 hours under conditions of 100 DEG C of temperature, then in sky
It is calcined 10 hours at 250 DEG C of temperature under gas atmosphere, its product of roasting contains the 6% active component Co in terms of cordierite weight3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.1mol/L's
Impregnated 10 hours in platinum acid chloride solution, separation, the presoma of dipping platinum acid chloride solution are dried 11 hours at 105 DEG C of temperature, are connect
And be calcined 2.6 hours at 300 DEG C of temperature under an inert atmosphere, its product of roasting contains in terms of cordierite weight 0.2% activity
Component platinum oxide, this product of roasting is described integral catalyzer.
Determined using XRF analysis method, described integral catalyzer contains multiple with the overall catalyst weight gauge 12.2%
Close metal oxide, 5.89% cobaltosic oxide and 0.19% platinum oxide.
Embodiment 2：The preparation of integral catalyzer of the present invention
The implementation steps of the embodiment are as follows：
A, Vehicle element
Under conditions of 100 DEG C of temperature, 280 structure cells of reticular density/inch2, wall thickness 0.25mm cordierite carrier with dense
Spend and handled 4 hours for 50% oxalic acid aqueous solution constant temperature, be then washed with water to neutrality, the cordierite of washing is again in temperature 110
After being dried overnight at DEG C, its weight is the 90% of the cordierite weight of before processing；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 1.0mol/L mixed-salt aqueous solution；Then
Described mixed-salt aqueous solution is allowed to be added drop-wise to reaction with concentration for 2mol/L ammonium carbonate solution precipitating reagent cocurrent
It is co-precipitated in device, the pH of the system of co-precipitation is maintained 10.2；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 4.0 hours in 105 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed three times through deionized water, dried 14 hours under conditions of 110 DEG C of temperature, Ran Hou
It is calcined 4.5 hours under conditions of 480 DEG C of temperature, obtains Ba0.5ZrCe0.5O3Metal composite oxide；
According to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：0.5：0.5：0.5, metal ion total concentration is prepared for 1.0mol/L
Mixed-salt aqueous solution；Then
Allow described mixed-salt aqueous solution to be added drop-wise in reactor for concentrated ammonia solution precipitating reagent cocurrent with concentration to be total to
Precipitation, 10.0 are maintained by the pH of the system of co-precipitation；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 3.0 hours in 105 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed three times through deionized water, dried 13 hours under conditions of 105 DEG C of temperature, Ran Hou
It is calcined 3.8 hours under conditions of 460 DEG C of temperature, prepares La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide；
Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide according to
Weight compares 1:2.0 mixing, obtain metal composite oxide mixture；
Deionized water and the ratio of metal composite oxide mixture in gram are 3 in terms of ml:1, toward the composition metal oxygen
Deionized water is added in compound mixture, stirring is mixed, and then ball milling obtains metal composite oxide coating liquid；
Allow the cordierite carrier of processing of step A to be impregnated 28 minutes in the metal composite oxide coating liquid, separate, leaching
Stain cordierite dried up, dry 6.5 hours at 58 DEG C of temperature again, and then roasting 6.0 is small under conditions of 480 DEG C of temperature
When.This processing procedure repeats, until metal composite oxide coated weight is the 5% of cordierite weight, so obtains one
Plant integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in concentration 0.6mol/L cobalt nitrate aqueous solution at room temperature
Dipping 8 hours, separation, the presoma of dipping cobalt nitrate aqueous solution are dried 12 hours under conditions of 105 DEG C of temperature, then in air
It is calcined 2 hours at 280 DEG C of temperature under atmosphere, its product of roasting contains the 8% active component Co in terms of cordierite weight3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.2mol/L's
Impregnated 8 hours in platinum acid chloride solution, separation, the presoma of dipping platinum acid chloride solution dry 13 hours at 110 DEG C of temperature, then
It is calcined 2.0 hours at 280 DEG C of temperature under an inert atmosphere, its product of roasting contains 0.4% activearm in terms of cordierite weight
Divide platinum oxide, this product of roasting is described integral catalyzer.
Determined using XRF analysis method, described integral catalyzer contains multiple with the overall catalyst weight gauge 4.95%
Close metal oxide, 7.97% cobaltosic oxide and 0.38% platinum oxide.
Embodiment 3：The preparation of integral catalyzer of the present invention
The implementation steps of the embodiment are as follows：
A, Vehicle element
Under conditions of 90 DEG C of temperature, 280 structure cells of reticular density/inch2, wall thickness 0.25mm cordierite carrier concentration
Handled 6 hours for by weight 37% aqueous hydrochloric acid solution constant temperature, be then washed with water to neutrality, the cordierite of washing is again in temperature
After being dried overnight at 110 DEG C of degree, its weight is the 78% of the cordierite weight of before processing；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 0.5mol/L mixed-salt aqueous solution；Then
Allow described mixed-salt aqueous solution to be added drop-wise in reactor with concentrated ammonia solution precipitating reagent cocurrent to be co-precipitated, will
The pH of co-precipitation system maintains 10.0；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 3.4 hours in 100 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed four times through deionized water, dried 12 hours under conditions of 106 DEG C of temperature, Ran Hou
It is calcined 4.0 hours under conditions of 450 DEG C of temperature, obtains Ba0.5ZrCe0.5O3Metal composite oxide；
According to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：0.5：0.5：0.5, metal ion total concentration is prepared for 0.5mol/L
Mixed-salt aqueous solution；Then
Allow described mixed-salt aqueous solution to be added drop-wise in reactor with concentrated ammonia solution precipitating reagent cocurrent to be co-precipitated, will
The pH of co-precipitation system maintains 9.8；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 2.6 hours in 100 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed three times through deionized water, dried 10 hours under conditions of 100 DEG C of temperature, Ran Hou
It is calcined 3.5 hours under conditions of 450 DEG C of temperature, prepares La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide；
Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide according to
Weight compares 1:1.6 mixing, obtain metal composite oxide mixture；
Deionized water and the ratio of metal composite oxide mixture in gram are 5 in terms of ml:1, toward the composition metal oxygen
Deionized water is added in compound mixture, stirring is mixed, and then ball milling obtains metal composite oxide coating liquid；
Allow the cordierite carrier of processing of step A to be impregnated 30 minutes in the metal composite oxide coating liquid, separate, leaching
Stain cordierite dried up, dry 6.0 hours at 65 DEG C of temperature again, and then roasting 5.5 is small under conditions of 450 DEG C of temperature
When.This processing procedure repeats, until metal composite oxide coated weight is the 15% of cordierite weight, so obtains one
Plant integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in concentration 0.3mol/L cobalt nitrate aqueous solution at room temperature
Dipping 6 hours, separation, the presoma of dipping cobalt nitrate aqueous solution are dried 14 hours under conditions of 110 DEG C of temperature, then in air
It is calcined 12 hours at 300 DEG C of temperature under atmosphere, its product of roasting contains the 1% active component Co in terms of cordierite weight3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.1mol/L's
Impregnated 6 hours in platinum acid chloride solution, separation, the presoma of dipping platinum acid chloride solution dry 10 hours at 100 DEG C of temperature, then
It is calcined 3.0 hours at 250 DEG C of temperature under an inert atmosphere, its product of roasting contains 0.5% activearm in terms of cordierite weight
Divide platinum oxide, this product of roasting is described integral catalyzer.
Determined using XRF analysis method, described integral catalyzer contains multiple with the overall catalyst weight gauge 14.9%
Close metal oxide, 0.98% cobaltosic oxide and 0.49% platinum oxide.
Embodiment 4：The preparation of integral catalyzer of the present invention
The implementation steps of the embodiment are as follows：
A, Vehicle element
Under conditions of 85 DEG C of temperature, 280 structure cells of reticular density/inch2, wall thickness 0.25mm cordierite carrier concentration
Handled 7 hours for by weight 37% aqueous hydrochloric acid solution constant temperature, each hour changes once the hydrochloric acid solution, is then washed with water
To neutral, after the cordierite of washing is dried overnight at 94 DEG C of temperature again, its weight is the 85% of the cordierite weight of before processing；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 0.8mol/L mixed-salt aqueous solution；Then
Described mixed-salt aqueous solution is allowed to be added drop-wise to reaction with concentration for 4mol/L ammonium carbonate solution precipitating reagent cocurrent
It is co-precipitated in device, the pH of the system of co-precipitation is maintained 9.8；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 3.0 hours in 98 DEG C of oil baths of temperature are allowed, then
Filtering, obtained co-precipitate is washed three times through deionized water, dried 11 hours under conditions of 105 DEG C of temperature, then in temperature
It is calcined 3.8 hours under conditions of 460 DEG C of degree, obtains Ba0.5ZrCe0.5O3Metal composite oxide；
According to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：0.5：0.5：0.5, metal ion total concentration is prepared for 0.8mol/L
Mixed-salt aqueous solution；Then
Described mixed-salt aqueous solution is allowed to be added drop-wise to reaction with concentration for 2mol/L ammonium carbonate solution precipitating reagent cocurrent
It is co-precipitated in device, the pH of the system of co-precipitation is maintained 10.0；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 2.0 hours in 98 DEG C of oil baths of temperature are allowed, then
Filtering, obtained co-precipitate is washed three times through deionized water, dried 14 hours under conditions of 110 DEG C of temperature, then in temperature
It is calcined 4.5 hours under conditions of 480 DEG C of degree, prepares La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide；
Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide according to
Weight compares 1:1.4 mixing, obtain metal composite oxide mixture；
Deionized water and the ratio of metal composite oxide mixture in gram are 43535 in terms of ml:1, toward the compound gold
Deionized water is added in category oxide mixture, stirring is mixed, and then ball milling obtains metal composite oxide coating liquid；
Allow the cordierite carrier of processing of step A to be impregnated 34 minutes in the metal composite oxide coating liquid, separate, leaching
Stain cordierite dried up, dry 5.8 hours under temperature 60 C again, and then roasting 6.5 is small under conditions of 460 DEG C of temperature
When.This processing procedure repeats, until metal composite oxide coated weight is the 8% of cordierite weight, so obtains one
Plant integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in concentration 0.4mol/L cobalt nitrate aqueous solution at room temperature
Dipping 12 hours, separation, the presoma of dipping cobalt nitrate aqueous solution are dried 11 hours under conditions of 105 DEG C of temperature, then in sky
It is calcined 6 hours at 280 DEG C of temperature under gas atmosphere, its product of roasting contains the 10% active component Co in terms of cordierite weight3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.2mol/L's
Impregnated 12 hours in platinum acid chloride solution, separation, the presoma of dipping platinum acid chloride solution are dried 12 hours at 100 DEG C of temperature, are connect
And be calcined 4.0 hours at 280 DEG C of temperature under an inert atmosphere, its product of roasting contains in terms of cordierite weight 0.3% activity
Component platinum oxide, this product of roasting is described integral catalyzer.
Determined using XRF analysis method, described integral catalyzer contains compound with the overall catalyst weight gauge 8.1%
Metal oxide, 9.94% cobaltosic oxide and 0.29% platinum oxide.
Embodiment 5：The preparation of integral catalyzer of the present invention
The implementation steps of the embodiment are as follows：
A, Vehicle element
Under conditions of 92 DEG C of temperature, 280 structure cells of reticular density/inch2, wall thickness 0.25mm cordierite carrier concentration
Handled 5 hours for 50% oxalic acid aqueous solution constant temperature, be then washed with water to neutrality, the cordierite of washing is again at 96 DEG C of temperature
After being dried overnight, its weight is the 80% of the cordierite weight of before processing；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, by barium nitrate, zirconium oxychloride and cerous nitrate prepare metal from
Sub- total concentration is 0.6mol/L mixed-salt aqueous solution；Then
Allow described mixed-salt aqueous solution to be added drop-wise in reactor with concentrated ammonia solution precipitating reagent cocurrent to be co-precipitated, will
The pH of co-precipitation system maintains 10.0；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 2.6 hours in 100 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed three times through deionized water, dried 13 hours under conditions of 108 DEG C of temperature, Ran Hou
It is calcined 4.2 hours under conditions of 450 DEG C of temperature, obtains Ba0.5ZrCe0.5O3Metal composite oxide；
According to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：0.5：0.5：0.5, metal ion total concentration is prepared for 0.6mol/L
Mixed-salt aqueous solution；Then
Allow described mixed-salt aqueous solution to be added drop-wise in reactor with concentrated ammonia solution precipitating reagent cocurrent to be co-precipitated, will
The pH of co-precipitation system maintains 10.0；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 4.0 hours in 102 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed three times through deionized water, dried 12 hours under conditions of 108 DEG C of temperature, Ran Hou
It is calcined 4.2 hours under conditions of 450 DEG C of temperature, prepares La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide；
Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide according to
Weight compares 1:1.8 mixing, obtain metal composite oxide mixture；
Deionized water and the ratio of metal composite oxide mixture in gram are 5 in terms of ml:1, toward the composition metal oxygen
Deionized water is added in compound mixture, stirring is mixed, and then ball milling obtains metal composite oxide coating liquid；
Allow the cordierite carrier of processing of step A to be impregnated 32 minutes in the metal composite oxide coating liquid, separate, leaching
Stain cordierite dried up, dry 6.2 hours under temperature 60 C again, and then roasting 6.0 is small under conditions of 460 DEG C of temperature
When.This processing procedure repeats, until metal composite oxide coated weight is the 10% of cordierite weight, so obtains one
Plant integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in concentration 0.5mol/L cobalt nitrate aqueous solution at room temperature
Dipping 6 hours, separation, the presoma of dipping cobalt nitrate aqueous solution are dried 13 hours under conditions of 110 DEG C of temperature, then in air
It is calcined 8 hours at 300 DEG C of temperature under atmosphere, its product of roasting contains the 4% active component Co in terms of cordierite weight3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma platinum ion concentration 0.3mol/L's
Impregnated 8 hours in platinum acid chloride solution, separation, the presoma of dipping platinum acid chloride solution dry 14 hours at 110 DEG C of temperature, then
It is calcined 3.4 hours at 300 DEG C of temperature under an inert atmosphere, its product of roasting contains 0.4% activearm in terms of cordierite weight
Divide platinum oxide, this product of roasting is described integral catalyzer.
Determined using XRF analysis method, described integral catalyzer contains compound with the overall catalyst weight gauge 11%
Metal oxide, 3.91% cobaltosic oxide and 0.4% platinum oxide.
Comparative example 1~5：Catalyst is prepared using aluminum oxide
Comparative example 1-5 is correspondingly carried out according to embodiment 1-5 embodiments, is simply replaced respectively in reality with aluminum oxide
Apply the metal composite oxide prepared in example 1~5.Below using the embodiment 1-5 integral catalyzers prepared and than embodiment
Catalyst prepared by 1-5 carries out Experimental Comparison.
A, carbon monoxide elimination factor measure
Condition determination：The gas heater used is tested for 13L Haier card Sa Supreme Being's water heater, combustion gas tail gas composition is with body
Product meter CO:81ppm、CO:5%th, oxygen 11%, steam 10%, sulphur 0.1ppm, remaining be N2.100~120 DEG C of outlet temperature, it is empty
Speed is 240000h-1。
CO elimination factor computing formula are as follows：
CO elimination factors=(CO contents after import CO contents-catalysis)/import CO Han Liang ﹡ 100%.
Measurement result after operating 0.5 hour is listed in Table 1 below.
Table 1：Gas heater exports CO content analysis results after operating 0.5 hour
Table 2：Gas heater operates 2.5 hours outlet CO content analysis results
Table 3：After the dehydration desulfurization of combustion gas tail gas, gas heater operates 2.5 hours outlet CO content analysis results
By the table 1-3 result of the tests listed it can be clearly seen that compared with comparative example, prepared by the present invention is used for
The integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature shows good elimination factor, good resistance to steam, Sulfur tolerance.
Claims (10)
1. the preparation method of a kind of integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature, it is characterised in that this method
Step is as follows：
A, Vehicle element
Under conditions of 80~100 DEG C of temperature, cordierite carrier is handled 4~8 hours with acid solution constant temperature, is then washed with water to
Neutrality, then be dried；
B, prepare presoma
According to the atomic ratio 0.5 of barium, zirconium and cerium：1.0：0.5, metal ion is prepared by barium nitrate, zirconium oxychloride and cerous nitrate total
Concentration is 0.5~1.0mol/L mixed-salt aqueous solution；Then
Described mixed-salt aqueous solution and concentration is allowed to be 1~5mol/L ammonium carbonate solution or concentrated ammonia solution precipitating reagent cocurrent
It is added drop-wise in reactor and is co-precipitated, the pH of the system of co-precipitation is maintained 9.8~10.2；
After cocurrent is added dropwise to complete, whole co-precipitation system ripening 2~4 hours in 95~105 DEG C of oil baths of temperature are allowed, connect
Filtering, obtained co-precipitate is washed through deionized water, dried with being calcined, and obtains Ba0.5ZrCe0.5O3Composition metal is aoxidized
Thing；
Identical mode is prepared according to above-mentioned metal composite oxide, according to the atomic ratio 0.5 of lanthanum, strontium, nickel and copper：0.5：
0.5：0.5, La is prepared by lanthanum nitrate, strontium nitrate, nickel nitrate and copper nitrate0.5Sr0.5Ni0.5Cu0.5O3Composition metal is aoxidized
Thing；Then by Ba0.5ZrCe0.5O3Metal composite oxide and La0.5Sr0.5Ni0.5Cu0.5O3Metal composite oxide is according to weight
Than 1:1~2 mixing, obtains metal composite oxide mixture；
Deionized water is added into the metal composite oxide mixture, stirring is mixed, and then ball milling obtains composition metal oxygen
Compound coating liquid；
Allow the cordierite carrier of processing of step A to be impregnated 26~34 minutes in the metal composite oxide coating liquid, separate, leaching
Stain cordierite is dried up, dried and is calcined, and this processing procedure repeats, until metal composite oxide coated weight is violet
The 5~15% of green stone weight, so obtain a kind of integral catalyzer presoma；
C, impregnated transition metal active constituent
Allow integral catalyzer presoma that step B obtains in 0.2~0.6mol/L of concentration cobalt nitrate aqueous solution in room temperature
Lower dipping 6~12 hours, separation, drying, then be calcined in air atmosphere, its product of roasting contains 1 in terms of cordierite weight~
10% active component Co3O4；
D, dipping noble metal active component
At normal temperatures, allow what step C obtained to contain active component Co3O4Presoma 0.1~0.3mol/L's of platinum ion concentration
Impregnated 6~12 hours in platinum acid chloride solution, separation, drying are then calcined, its product of roasting contains blue or green with violet under an inert atmosphere
The active component platinum of stone weight meter 0.2~0.5%, this product of roasting is described integral catalyzer.
2. preparation method according to claim 1, it is characterised in that in step, the reticular density of the cordierite is
280 structure cells/inch2, wall thickness be 0.25mm.
3. preparation method according to claim 1, it is characterised in that in step, described acid solution be concentration be with
The aqueous hydrochloric acid solution of weight meter 37% or 50% oxalic acid aqueous solution.
4. preparation method according to claim 1, it is characterised in that in step, the cordierite of washing temperature 100~
After being dried overnight at 110 DEG C, its weight is the 70-90% of before processing cordierite weight.
5. preparation method according to claim 1, it is characterised in that in stepb, obtained co-precipitate is in temperature 100
Dry 10~14 hours, be then calcined 3.5~4.5 hours under conditions of 420~480 DEG C of temperature under conditions of~110 DEG C.
6. preparation method according to claim 1, it is characterised in that in stepb, in terms of ml deionized water with gram
The ratio of metal composite oxide mixture is 4~5:1.
7. preparation method according to claim 1, it is characterised in that in stepb, in temperature after dipping cordierite drying
Dry 5.5~6.5 hours, be then calcined 5.5~6.5 hours under conditions of 420~480 DEG C of temperature at 55~65 DEG C.
8. preparation method according to claim 1, it is characterised in that in step C, impregnates the forerunner of cobalt nitrate aqueous solution
Body is dried 10~14 hours under conditions of 100~110 DEG C of temperature, then is calcined in air atmosphere at 250~300 DEG C of temperature
2~12 hours.
9. preparation method according to claim 1, it is characterised in that in step D, impregnates the presoma of platinum acid chloride solution
Dry 10~14 hours at 100~110 DEG C of temperature, then roasting 2~4 is small at 250~300 DEG C of temperature under an inert atmosphere
When.
10. the integral catalyzer that the preparation method according to any one of claim 1-9 claim is prepared, it is special
Levy be it composition it is as follows, by weight
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