CN105289653A - Monolithic catalyst for low temperature catalytic oxidation of carbon monoxide and preparation method thereof - Google Patents
Monolithic catalyst for low temperature catalytic oxidation of carbon monoxide and preparation method thereof Download PDFInfo
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- CN105289653A CN105289653A CN201510799745.3A CN201510799745A CN105289653A CN 105289653 A CN105289653 A CN 105289653A CN 201510799745 A CN201510799745 A CN 201510799745A CN 105289653 A CN105289653 A CN 105289653A
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Abstract
The invention relates to a monolithic catalyst for low temperature catalytic oxidation of carbon monoxide and a preparation method thereof. The preparation method comprises carrier pretreatment, precursor preparation, immersion in a transition metal active component and immersion in a precious metal active component. Through acid aqueous solution treatment, an iolite specific surface area is 200m<2>/g or more and the coating can be easily formed and does not fall off easily. Two composite metal oxide coatings are respectively prepared and composite oxide structure and morphology are controlled easily. The monolithic catalyst can realize effective removal of carbon monoxide under conditions of a low temperature, a low CO concentration, a high air speed, high moisture and sulfur content and is suitable for low temperature elimination of carbon monoxide in combustion gas water heater tail gas, a combustion gas boiler and enclosed and semiclosed building spaces.
Description
[technical field]
The invention belongs to environmental technology field.More specifically, the present invention relates to a kind of integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature, also relate to the described preparation method for the integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature.
[background technology]
CO is one of major pollutants in air, and the imperfect combustion such as coal, natural gas, chemical industry production and motor vehicle use and all can cause a large amount of CO discharges.Along with society's constantly progress, people's living standard improves constantly, and people are also improving constantly the requirement of environment.Research carbon monoxide purification technology, reduces carbon monoxide emission, has very important significance.The method eliminated for carbon monoxide at present has absorption method, catalytic oxidation, plasma technique etc.And for the carbon monoxide waste gas of large volume low-concentration, the most effective and simple method is the mode adopting catalytic oxidation, and fundamentally eliminate carbon monoxide, monoxide conversion can be become nontoxic carbon dioxide by a lower temperature, environmental protection, efficient.
The main preparation methods of Carbon monoxide catalytic oxidation catalyst has traditional infusion process, sol-gal process, coprecipitation, precipitation sedimentation, ion-exchange etc.
Current industrial simple CO catalytic combustion technology is comparatively simple, but the temperature needed is high, and energy consumption is large, but also accident of blasting.CO low-temperature catalytic oxidation demand is then many, and as combustion gas tail gas clean-up, closed environment CO purify, application conditions complicated in addition is also govern the principal element that CO low-temperature catalytic oxidation realizes industrialization.At present, domestic and international CO low-temperature catalytic oxidation research is mainly noble metal-based catalysts, although noble metal-based catalysts activity is high, its life-span and stability all have problems, and this catalyst is responsive especially to sulphur, steam etc., easy poisoning and deactivation.Therefore it is crucial for developing the CO low-temperature catalytic oxidation catalyst with high activity, resistant to sulfur and resistance to steam, has important economic implications and social effect.
Although carried out considerable research to the reaction of CO low-temperature catalytic oxidation, the document published is little, and by further investigation method for preparing catalyst, decentralization, support modification, the Research Literature improving the resistance to aqueous vapor of catalyst and Sulfur tolerance is then little.In addition, for integral honeycombed catalyst, its difficult point is the coating of coating, what first need solution is Vehicle element problem, pretreatment is not only removing surface impurity and dirt, priorly improves surface texture, as expanded specific surface, expanding the aspect such as pore volume, aperture.These also will become urgent problem.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature.
Another object of the present invention is to provide the described preparation method for the integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature.
[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 step of this preparation method is as follows:
A, Vehicle element
Under the condition of temperature 80 ~ 100 DEG C, cordierite carrier acid solution constant temperature process 4 ~ 8 hours, is then washed with water to neutrality, then carries out drying;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.5 ~ 1.0mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution of 1 ~ 5mol/L or concentrated ammonia solution precipitating reagent and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 9.8 ~ 10.2;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2 ~ 4 hours in temperature 95 ~ 105 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water washing, dry and roasting, obtain Ba
0.5zrCe
0.5o
3composite metal oxide;
Prepare identical mode according to above-mentioned composite metal oxide, according to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare La by lanthanum nitrate, strontium nitrate, nickel nitrate and copper nitrate
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide; Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide mixes according to weight ratio 1:1 ~ 2, obtains composite metal oxide mixture;
In described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
The cordierite carrier of processing of step A is allowed to flood 26 ~ 34 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, drying and roasting, this processing procedure repeats, until composite metal oxide coated weight is 5 ~ 15% of cordierite weight, obtain a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 6 ~ 12 hours in the cobalt nitrate aqueous solution of concentration 0.2 ~ 0.6mol/L, be separated, dry, roasting in air atmosphere again, its product of roasting contains with cordierite weighing scale 1 ~ 10% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 6 ~ 12 hours in the platinum acid chloride solution of platinum ion concentration 0.1 ~ 0.3mol/L, be separated, dry, then roasting under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.2 ~ 0.5% active component platinum oxide, and this product of roasting is described integral catalyzer.
A preferred embodiment of the invention, in step, the reticular density of described cordierite is 280 structure cells/inch
2, wall thickness is 0.25mm.
According to another kind of preferred embodiment of the present invention, in step, described acid solution to be concentration the be aqueous hydrochloric acid solution of 37% or the oxalic acid aqueous solution of 50% by weight.
According to another kind of preferred embodiment of the present invention, in step, the cordierite of washing is at temperature 100 ~ 110 DEG C after dried overnight, and its weight is the 70-90% of cordierite weight before process.
According to another kind of preferred embodiment of the present invention, in stepb, the coprecipitate obtained is dried 10 ~ 14 hours under the condition of temperature 100 ~ 110 DEG C, then roasting 3.5 ~ 4.5 hours under the condition of temperature 420 ~ 480 DEG C.
According to another kind of preferred embodiment of the present invention, in stepb, in ml deionized water be 4 ~ 5:1 in the ratio of gram composite metal oxide mixture.
According to another kind of preferred embodiment of the present invention, in stepb, dry 5.5 ~ 6.5 hours at temperature 55 ~ 65 DEG C after dipping cordierite dries up, then roasting 5.5 ~ 6.5 hours under the condition of temperature 420 ~ 480 DEG C.
According to another kind of preferred embodiment of the present invention, in step C, the presoma of dipping cobalt nitrate aqueous solution is dried 10 ~ 14 hours under the condition of temperature 100 ~ 110 DEG C, then roasting 2 ~ 12 hours at temperature 250 ~ 300 DEG C in air atmosphere.
According to another kind of preferred embodiment of the present invention, in step D, the presoma of dipping platinum acid chloride solution is dried 10 ~ 14 hours at temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours at temperature 250 ~ 300 DEG C under an inert atmosphere.
The invention still further relates to the integral catalyzer adopting described preparation method to prepare.Described integral catalyzer composed as follows, by weight
In more detail the present invention will be described 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 step of this preparation method is as follows:
A, Vehicle element
Under the condition of temperature 80 ~ 100 DEG C, cordierite carrier acid solution constant temperature process 4 ~ 8 hours, is then washed with water to neutrality, then carries out drying;
The reticular density of the cordierite that the present invention uses is 280 structure cells/inch
2, wall thickness is 0.25mm.
Cordierite is a kind of silicate being rich in iron, magnesium, aluminium
mineral, magnesium wherein can be replaced by iron or manganese, and the aluminium of part also can be replaced by iron.Cordierite crystal is many in short cylinder, in crystal occasionally containing sillimanite, spinelle, zircon,
apatite, mica etc.
inclusion enclave.Therefore, the cordierite carrier that the present invention uses needs to carry out acid treatment, and the impurity in removing carrier, etches carrier simultaneously, increases carrier surface roughness, can strengthen coating stability and coated weight when applying coating.Described acid solution to be concentration the be aqueous hydrochloric acid solution of 37% or the oxalic acid aqueous solution of 50% by weight.
The cordierite that the present invention uses is product sold in the market.
Cordierite needs to be washed with water to neutrality after acid treatment, and then at temperature 100 ~ 110 DEG C after dried overnight, its weight is the 70-90% of cordierite weight before treatment.In the present invention, if the cordierite quality after process is lower than 70%, then can due to overtreating, specific surface increases little, but cordierite honeycomb carrier intensity seriously reduces, and impact uses; If the cordierite quality after process is greater than 90%, then do not process completely, the increase of carrier specific surface is inadequate, roughness is not obvious; Therefore, the weight of acid treatment, washing, dried cordierite is before treatment 70 ~ 90% is rational, preferably 75 ~ 85%, more preferably 78 ~ 83%.
Cordierite through above-mentioned process adopts the analysis of conventional surface analytical technology to determine, its specific area reaches 200m
2/ more than g.
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.5 ~ 1.0mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution of 1 ~ 5mol/L or concentrated ammonia solution precipitating reagent and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 9.8 ~ 10.2.
In the present invention, the pH of co-precipitation system maintains the main purpose of 9.8 ~ 10.2 is that the various salt within the scope of this pH in mixing salt solution are energy deposition sedimentation all, and therefore a sediment component ratio is even.
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2 ~ 4 hours in temperature 95 ~ 105 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water washing, dry and roasting, obtain Ba
0.5zrCe
0.5o
3composite metal oxide.
In this step, the coprecipitate obtained is dried 10 ~ 14 hours under the condition of temperature 100 ~ 110 DEG C, then roasting 3.5 ~ 4.5 hours under the condition of temperature 420 ~ 480 DEG C.
Its product of roasting is analyzed through XRF and EDS and is determined, it is Ba
0.5zrCe
0.5o
3composite metal oxide.
Prepare identical mode according to above-mentioned composite metal oxide, according to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare La by lanthanum nitrate, strontium nitrate, nickel nitrate and copper nitrate
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide, it is analyzed through XRF and EDS and determines.
Then, by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide mixes according to weight ratio 1:1 ~ 2, obtains composite metal oxide mixture;
In described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid; Here, in ml deionized water be 4 ~ 5:1 in the ratio of gram composite metal oxide mixture.
The cordierite carrier of processing of step A is allowed to flood 26 ~ 34 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, drying and roasting, this processing procedure repeats, until composite metal oxide coated weight is 5 ~ 15% of cordierite weight, obtain a kind of integral catalyzer presoma like this.
In this step, dry 5.5 ~ 6.5 hours at temperature 55 ~ 65 DEG C after dipping cordierite dries up, then roasting 5.5 ~ 6.5 hours under the condition of temperature 420 ~ 480 DEG C.
In the present invention, if composite metal oxide coated weight is less than 5% of cordierite weight, then can then play the coating of carrier function very little, consequent activities component load capacity can be lower, simultaneously active component surface enrichment, crystal grain easily occurs and increases, active bad; If composite metal oxide coated weight is more than 15% of cordierite weight, then due to overweight coating, can reduce the firmness of coating, when reacting, airflow scouring, causes coating and active component loss, reduces catalytic activity.Therefore, composite metal oxide coated weight is 5 ~ 15% of cordierite weight is appropriate, preferably 7 ~ 13%, more preferably 9 ~ 11%.
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 6 ~ 12 hours in the cobalt nitrate aqueous solution of concentration 0.2 ~ 0.6mol/L, be separated, dry, roasting in air atmosphere again, its product of roasting contains with cordierite weighing scale 1 ~ 10% active component Co
3o
4;
In this step, the presoma of dipping cobalt nitrate aqueous solution is dried 10 ~ 14 hours under the condition of temperature 100 ~ 110 DEG C, then roasting 2 ~ 12 hours at temperature 250 ~ 300 DEG C in air atmosphere.
The active component Co of its product of roasting
3o
4xRD method is adopted to determine.
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 6 ~ 12 hours in the platinum acid chloride solution of platinum ion concentration 0.1 ~ 0.3mol/L, be separated, dry, then roasting under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.2 ~ 0.5% active component platinum, and 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 temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours at temperature 250 ~ 300 DEG C under an inert atmosphere.
The active component platinum content of its product of roasting adopts XRF sign to determine.
The invention still further relates to the integral catalyzer adopting described preparation method to prepare.
Described integral catalyzer composed as follows, by weight
Integral catalyzer of the present invention is to have the cobalt (Co of good CO low-temperature catalytic oxidation performance
3o
4) and platinum be active component, to have good water resistance Ba
0.5zrCe
0.5o
3with the La of Sulfur tolerance
0.5sr
0.5ni
0.5cu
0.5o
3composite oxide of metal is coating, take honeycomb-like cordierite as carrier, in preparation process, cordierite passes through pretreatment, remove the impurity in carrier, further carrier is etched simultaneously, increase carrier surface roughness, adopt conventional Electronic Speculum and Conventional solid surface analysis, it the results are shown in accompanying drawing 1 with accompanying drawing 2; Utilize coating to apply, enhance coating stability and coated weight.Ba
0.5zrCe
0.5o
3and La
0.5sr
0.5ni
0.5cu
0.5o
3composite oxide of metal coating makes catalyst of the present invention have resistance to steam and resistance to sulphur property, be applicable to the combustion gas tail gas of sulfur-bearing and high steam, the active metal component energy of load on composite oxides is simultaneously evenly be dispersed in its surface, active high, degree of depth elimination can be carried out at a lower temperature, to the sulfur-bearing of high-speed, the combustion gas tail gas CO of steam; Compare with existing Carbon monoxide catalytic oxidation catalyst, integral catalyzer agent provided by the invention, has the advantages that resistant to sulfur, moisture-proof and degree of purification are high.In low temperature 80 ~ 140 DEG C, low concentration 100ppm, high-speed 120000 ~ 240000h
-1, vapour concentration 10% ~ 15%, can carbon monoxide oxidation under sulfur content 0.15 ~ 0.2ppm condition, be applicable to eliminate the carbon monoxide in combustion gas tail gas, eliminate the Low Level Carbon Monoxides such as confined space.
[beneficial effect]
Compared with prior art, the invention has the beneficial effects as follows:
1, after concentrated hydrochloric acid or 50% oxalic acid aqueous solution boiling process, cordierite specific area reaches 200m
2/ more than g, coating more easily applies, and difficult drop-off.
2, two kinds of composite metal oxide coatings are prepared respectively, be easy to control composite oxides structure and pattern, pore analysis shows, larger distribution (accompanying drawing 2) is had in the scope of 2 ~ 6nm and 6 ~ 20nm, explanation macropore is more, pore volume is large, is beneficial to and keeps its resistance to steam and resistant to sulfur character;
3, at low temperature (80 ~ 140 DEG C), low CO concentration (80 ~ 100ppm) is realized, high-speed (120000 ~ 240000h
-1), carbon monoxide effectively removes under high aqueous vapor (vapour concentration >10%), sulfur-bearing (0.1 ~ 0.2ppm);
4, good resistance to steam and resistant to sulfur ability, be applicable to the low temperature elimination of CO in gas heater tail gas, gas fired-boiler, closed semiclosed space.
[accompanying drawing explanation]
Fig. 1 is the integral catalyzer Electronic Speculum figure of the present invention for catalyzing and oxidizing carbon monoxide at low temperature.
Fig. 2 is the integral catalyzer graph of pore diameter distribution of the present invention for catalyzing and oxidizing carbon monoxide at low temperature.
[detailed description of the invention]
The present invention can be understood better by following embodiment.
Embodiment 1: the preparation of integral catalyzer of the present invention
The implementation step of this embodiment is as follows:
A, Vehicle element
Under the condition of temperature 80 DEG C, reticular density 280 structure cells/inch
2, wall thickness 0.25mm cordierite carrier concentration be by weight 37% aqueous hydrochloric acid solution constant temperature process 8 hours, then neutrality is washed with water to, the cordierite of washing is again at temperature 100 DEG C after dried overnight, and its weight is 70% of cordierite weight before treatment;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.5mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution precipitating reagent of 1mol/L and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 9.8;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2.0 hours in temperature 95 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, dry 10 hours under the condition of temperature 100 DEG C, then roasting 3.5 hours under the condition of temperature 420 DEG C, obtains Ba
0.5zrCe
0.5o
3composite metal oxide;
According to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare the mixed-salt aqueous solution that metal ion total concentration is 0.5mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution precipitating reagent of 4mol/L and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 9.8;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 3.4 hours in temperature 95 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 106 DEG C dry 11 hours, then roasting 4.0 hours under the condition of temperature 420 DEG C, prepares La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide;
Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide, according to weight ratio 1:1.0 mixing, obtains composite metal oxide mixture;
In ml deionized water be 4:1 in the ratio of gram composite metal oxide mixture, in described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
Allow the cordierite carrier of processing of step A flood 26 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, dries 5.5 hours at temperature 55 DEG C, then roasting 6.2 hours under the condition of temperature 420 DEG C.This processing procedure repeats, until composite metal oxide coated weight is 12% of cordierite weight, obtains a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 10 hours in the cobalt nitrate aqueous solution of concentration 0.2mol/L, the presoma being separated, flooding cobalt nitrate aqueous solution is dried 10 hours under the condition of temperature 100 DEG C, roasting 10 hours at temperature 250 DEG C in air atmosphere again, its product of roasting contains with cordierite weighing scale 6% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 10 hours in the platinum acid chloride solution of platinum ion concentration 0.1mol/L, the presoma being separated, flooding platinum acid chloride solution is dried 11 hours at temperature 105 DEG C, then roasting 2.6 hours at temperature 300 DEG C under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.2% active component platinum oxide, and this product of roasting is described integral catalyzer.
Adopt XRF analysis method to determine, described integral catalyzer contains with this overall catalyst weight gauge 12.2% composite metal oxide, 5.89% cobaltosic oxide and 0.19% platinum oxide.
Embodiment 2: the preparation of integral catalyzer of the present invention
The implementation step of this embodiment is as follows:
A, Vehicle element
Under the condition of temperature 100 DEG C, reticular density 280 structure cells/inch
2, wall thickness 0.25mm cordierite carrier concentration be 50% oxalic acid aqueous solution constant temperature process 4 hours, be then washed with water to neutrality, the cordierite of washing is again at temperature 110 DEG C after dried overnight, and its weight is 90% of cordierite weight before treatment;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 1.0mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution precipitating reagent of 2mol/L and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 10.2;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 4.0 hours in temperature 105 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 110 DEG C dry 14 hours, then roasting 4.5 hours under the condition of temperature 480 DEG C, obtains Ba
0.5zrCe
0.5o
3composite metal oxide;
According to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare the mixed-salt aqueous solution that metal ion total concentration is 1.0mol/L; Then
Allow described mixed-salt aqueous solution and concentration be concentrated ammonia solution precipitating reagent and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 10.0;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 3.0 hours in temperature 105 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 105 DEG C dry 13 hours, then roasting 3.8 hours under the condition of temperature 460 DEG C, prepares La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide;
Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide, according to weight ratio 1:2.0 mixing, obtains composite metal oxide mixture;
In ml deionized water be 3:1 in the ratio of gram composite metal oxide mixture, in described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
Allow the cordierite carrier of processing of step A flood 28 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, dries 6.5 hours at temperature 58 DEG C, then roasting 6.0 hours under the condition of temperature 480 DEG C.This processing procedure repeats, until composite metal oxide coated weight is 5% of cordierite weight, obtains a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 8 hours in the cobalt nitrate aqueous solution of concentration 0.6mol/L, the presoma being separated, flooding cobalt nitrate aqueous solution is dried 12 hours under the condition of temperature 105 DEG C, roasting 2 hours at temperature 280 DEG C in air atmosphere again, its product of roasting contains with cordierite weighing scale 8% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 8 hours in the platinum acid chloride solution of platinum ion concentration 0.2mol/L, the presoma being separated, flooding platinum acid chloride solution is dried 13 hours at temperature 110 DEG C, then roasting 2.0 hours at temperature 280 DEG C under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.4% active component platinum oxide, and this product of roasting is described integral catalyzer.
Adopt XRF analysis method to determine, described integral catalyzer contains with this overall catalyst weight gauge 4.95% composite metal oxide, 7.97% cobaltosic oxide and 0.38% platinum oxide.
Embodiment 3: the preparation of integral catalyzer of the present invention
The implementation step of this embodiment is as follows:
A, Vehicle element
Under the condition of temperature 90 DEG C, reticular density 280 structure cells/inch
2, wall thickness 0.25mm cordierite carrier concentration be by weight 37% aqueous hydrochloric acid solution constant temperature process 6 hours, then neutrality is washed with water to, the cordierite of washing is again at temperature 110 DEG C after dried overnight, and its weight is 78% of cordierite weight before treatment;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.5mol/L; Then
Allow described mixed-salt aqueous solution and concentrated ammonia solution precipitating reagent drip be added in reactor and carry out co-precipitation, the pH of co-precipitation system is maintained 10.0;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 3.4 hours in temperature 100 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash four times, under the condition of temperature 106 DEG C dry 12 hours, then roasting 4.0 hours under the condition of temperature 450 DEG C, obtains Ba
0.5zrCe
0.5o
3composite metal oxide;
According to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare the mixed-salt aqueous solution that metal ion total concentration is 0.5mol/L; Then
Allow described mixed-salt aqueous solution and concentrated ammonia solution precipitating reagent drip be added in reactor and carry out co-precipitation, the pH of co-precipitation system is maintained 9.8;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2.6 hours in temperature 100 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 100 DEG C dry 10 hours, then roasting 3.5 hours under the condition of temperature 450 DEG C, prepares La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide;
Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide, according to weight ratio 1:1.6 mixing, obtains composite metal oxide mixture;
In ml deionized water be 5:1 in the ratio of gram composite metal oxide mixture, in described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
Allow the cordierite carrier of processing of step A flood 30 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, dries 6.0 hours at temperature 65 DEG C, then roasting 5.5 hours under the condition of temperature 450 DEG C.This processing procedure repeats, until composite metal oxide coated weight is 15% of cordierite weight, obtains a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 6 hours in the cobalt nitrate aqueous solution of concentration 0.3mol/L, the presoma being separated, flooding cobalt nitrate aqueous solution is dried 14 hours under the condition of temperature 110 DEG C, roasting 12 hours at temperature 300 DEG C in air atmosphere again, its product of roasting contains with cordierite weighing scale 1% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 6 hours in the platinum acid chloride solution of platinum ion concentration 0.1mol/L, the presoma being separated, flooding platinum acid chloride solution is dried 10 hours at temperature 100 DEG C, then roasting 3.0 hours at temperature 250 DEG C under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.5% active component platinum oxide, and this product of roasting is described integral catalyzer.
Adopt XRF analysis method to determine, described integral catalyzer contains with this overall catalyst weight gauge 14.9% composite metal oxide, 0.98% cobaltosic oxide and 0.49% platinum oxide.
Embodiment 4: the preparation of integral catalyzer of the present invention
The implementation step of this embodiment is as follows:
A, Vehicle element
Under the condition of temperature 85 DEG C, reticular density 280 structure cells/inch
2, wall thickness 0.25mm cordierite carrier concentration be by weight 37% aqueous hydrochloric acid solution constant temperature process 7 hours, each hour changes once this hydrochloric acid solution, then neutrality is washed with water to, the cordierite of washing is again at temperature 94 DEG C after dried overnight, and its weight is 85% of cordierite weight before treatment;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.8mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution precipitating reagent of 4mol/L and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 9.8;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 3.0 hours in temperature 98 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, dry 11 hours under the condition of temperature 105 DEG C, then roasting 3.8 hours under the condition of temperature 460 DEG C, obtains Ba
0.5zrCe
0.5o
3composite metal oxide;
According to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare the mixed-salt aqueous solution that metal ion total concentration is 0.8mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution precipitating reagent of 2mol/L and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 10.0;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2.0 hours in temperature 98 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 110 DEG C dry 14 hours, then roasting 4.5 hours under the condition of temperature 480 DEG C, prepares La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide;
Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide, according to weight ratio 1:1.4 mixing, obtains composite metal oxide mixture;
In ml deionized water be 43535:1 in the ratio of gram composite metal oxide mixture, in described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
Allow the cordierite carrier of processing of step A flood 34 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, dries 5.8 hours under temperature 60 C, then roasting 6.5 hours under the condition of temperature 460 DEG C.This processing procedure repeats, until composite metal oxide coated weight is 8% of cordierite weight, obtains a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 12 hours in the cobalt nitrate aqueous solution of concentration 0.4mol/L, the presoma being separated, flooding cobalt nitrate aqueous solution is dried 11 hours under the condition of temperature 105 DEG C, roasting 6 hours at temperature 280 DEG C in air atmosphere again, its product of roasting contains with cordierite weighing scale 10% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 12 hours in the platinum acid chloride solution of platinum ion concentration 0.2mol/L, the presoma being separated, flooding platinum acid chloride solution is dried 12 hours at temperature 100 DEG C, then roasting 4.0 hours at temperature 280 DEG C under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.3% active component platinum oxide, and this product of roasting is described integral catalyzer.
Adopt XRF analysis method to determine, described integral catalyzer contains with this overall catalyst weight gauge 8.1% composite metal oxide, 9.94% cobaltosic oxide and 0.29% platinum oxide.
Embodiment 5: the preparation of integral catalyzer of the present invention
The implementation step of this embodiment is as follows:
A, Vehicle element
Under the condition of temperature 92 DEG C, reticular density 280 structure cells/inch
2, wall thickness 0.25mm cordierite carrier concentration be 50% oxalic acid aqueous solution constant temperature process 5 hours, be then washed with water to neutrality, the cordierite of washing is again at temperature 96 DEG C after dried overnight, and its weight is 80% of cordierite weight before treatment;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.6mol/L; Then
Allow described mixed-salt aqueous solution and concentrated ammonia solution precipitating reagent drip be added in reactor and carry out co-precipitation, the pH of co-precipitation system is maintained 10.0;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2.6 hours in temperature 100 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 108 DEG C dry 13 hours, then roasting 4.2 hours under the condition of temperature 450 DEG C, obtains Ba
0.5zrCe
0.5o
3composite metal oxide;
According to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare the mixed-salt aqueous solution that metal ion total concentration is 0.6mol/L; Then
Allow described mixed-salt aqueous solution and concentrated ammonia solution precipitating reagent drip be added in reactor and carry out co-precipitation, the pH of co-precipitation system is maintained 10.0;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 4.0 hours in temperature 102 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water wash three times, under the condition of temperature 108 DEG C dry 12 hours, then roasting 4.2 hours under the condition of temperature 450 DEG C, prepares La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide;
Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide, according to weight ratio 1:1.8 mixing, obtains composite metal oxide mixture;
In ml deionized water be 5:1 in the ratio of gram composite metal oxide mixture, in described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
Allow the cordierite carrier of processing of step A flood 32 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, dries 6.2 hours under temperature 60 C, then roasting 6.0 hours under the condition of temperature 460 DEG C.This processing procedure repeats, until composite metal oxide coated weight is 10% of cordierite weight, obtains a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 6 hours in the cobalt nitrate aqueous solution of concentration 0.5mol/L, the presoma being separated, flooding cobalt nitrate aqueous solution is dried 13 hours under the condition of temperature 110 DEG C, roasting 8 hours at temperature 300 DEG C in air atmosphere again, its product of roasting contains with cordierite weighing scale 4% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 8 hours in the platinum acid chloride solution of platinum ion concentration 0.3mol/L, the presoma being separated, flooding platinum acid chloride solution is dried 14 hours at temperature 110 DEG C, then roasting 3.4 hours at temperature 300 DEG C under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.4% active component platinum oxide, and this product of roasting is described integral catalyzer.
Adopt XRF analysis method to determine, described integral catalyzer contains with this overall catalyst weight gauge 11% composite metal oxide, 3.91% cobaltosic oxide and 0.4% platinum oxide.
Comparative example 1 ~ 5: use alumina preparation catalyst
Comparative example 1-5 correspondingly carries out according to embodiment 1-5 embodiment, just replaces the composite metal oxide of preparation in embodiment 1 ~ 5 respectively with aluminium oxide.The integral catalyzer adopting embodiment 1-5 to prepare below carries out Experimental Comparison with the catalyst prepared than embodiment 1-5.
The mensuration of A, carbon monoxide elimination factor
Condition determination: the gas heater that test adopts is 13L Haier card Sa Supreme Being water heater, combustion gas tail gas consist of by volume CO:81ppm, CO:5%, oxygen 11%, steam 10%, sulphur 0.1ppm, all the other are for N2.Outlet temperature 100 ~ 120 DEG C, air speed is 240000h
-1.
CO elimination factor computing formula is as follows:
CO elimination factor=(after import CO content-catalysis CO content)/import CO Han Liang ﹡ 100%.
List in table 1 in the measurement result of running after 0.5 hour.
Table 1: gas heater exports CO content analysis result after operating 0.5 hour
Table 2: gas heater operates and exports CO content analysis result for 2.5 hours
Table 3: after combustion gas tail gas dehydration desulfurization, gas heater operates and exports CO content analysis result for 2.5 hours
The result of the test listed by table 1-3 can clearly be seen that, compared with comparative example, the integral catalyzer for catalyzing and oxidizing carbon monoxide at low temperature prepared by the present invention shows good elimination factor, good resistance to steam, Sulfur tolerance.
Claims (10)
1., for a preparation method for the integral catalyzer of catalyzing and oxidizing carbon monoxide at low temperature, it is characterized in that the step of the method is as follows:
A, Vehicle element
Under the condition of temperature 80 ~ 100 DEG C, cordierite carrier acid solution constant temperature process 4 ~ 8 hours, is then washed with water to neutrality, then carries out drying;
B, prepare presoma
According to the atomic ratio 0.5:1.0:0.5 of barium, zirconium and cerium, prepare by barium nitrate, zirconium oxychloride and cerous nitrate the mixed-salt aqueous solution that metal ion total concentration is 0.5 ~ 1.0mol/L; Then
Allow described mixed-salt aqueous solution and concentration be the ammonium carbonate solution of 1 ~ 5mol/L or concentrated ammonia solution precipitating reagent and drip is added in reactor and carries out co-precipitation, the pH of co-precipitation system is maintained 9.8 ~ 10.2;
Until and after stream is added dropwise to complete, allow whole co-precipitation system ripening 2 ~ 4 hours in temperature 95 ~ 105 DEG C of oil baths, then filter, the coprecipitate obtained through deionized water washing, dry and roasting, obtain Ba
0.5zrCe
0.5o
3composite metal oxide;
Prepare identical mode according to above-mentioned composite metal oxide, according to the atomic ratio 0.5:0.5:0.5:0.5 of lanthanum, strontium, nickel and copper, prepare La by lanthanum nitrate, strontium nitrate, nickel nitrate and copper nitrate
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide; Then by Ba
0.5zrCe
0.5o
3composite metal oxide and La
0.5sr
0.5ni
0.5cu
0.5o
3composite metal oxide mixes according to weight ratio 1:1 ~ 2, obtains composite metal oxide mixture;
In described composite metal oxide mixture, add deionized water, be uniformly mixed, then ball milling obtains composite metal oxide coating liquid;
The cordierite carrier of processing of step A is allowed to flood 26 ~ 34 minutes in described composite metal oxide coating liquid, be separated, dipping cordierite carries out drying up, drying and roasting, this processing procedure repeats, until composite metal oxide coated weight is 5 ~ 15% of cordierite weight, obtain a kind of integral catalyzer presoma like this;
C, impregnated transition metal active constituent
The integral catalyzer presoma allowing step B obtain at room temperature floods 6 ~ 12 hours in the cobalt nitrate aqueous solution of concentration 0.2 ~ 0.6mol/L, be separated, dry, roasting in air atmosphere again, its product of roasting contains with cordierite weighing scale 1 ~ 10% active component Co
3o
4;
D, dipping noble metal active component
At normal temperatures, what allow step C obtain contains active component Co
3o
4presoma flood 6 ~ 12 hours in the platinum acid chloride solution of platinum ion concentration 0.1 ~ 0.3mol/L, be separated, dry, then roasting under an inert atmosphere, its product of roasting contains with cordierite weighing scale 0.2 ~ 0.5% active component platinum, and this product of roasting is described integral catalyzer.
2. preparation method according to claim 1, is characterized in that in step, and the reticular density of described cordierite is 280 structure cells/inch
2, wall thickness is 0.25mm.
3. preparation method according to claim 1, is characterized in that in step, described acid solution to be concentration the be aqueous hydrochloric acid solution of 37% or the oxalic acid aqueous solution of 50% by weight.
4. preparation method according to claim 1, is characterized in that in step, and the cordierite of washing is at temperature 100 ~ 110 DEG C after dried overnight, and its weight is the 70-90% of cordierite weight before process.
5. preparation method according to claim 1, is characterized in that in stepb, and the coprecipitate obtained is dried 10 ~ 14 hours under the condition of temperature 100 ~ 110 DEG C, then roasting 3.5 ~ 4.5 hours under the condition of temperature 420 ~ 480 DEG C.
6. preparation method according to claim 1, is characterized in that in stepb, in ml deionized water be 4 ~ 5:1 in the ratio of gram composite metal oxide mixture.
7. preparation method according to claim 1, is characterized in that in stepb, dries 5.5 ~ 6.5 hours, then roasting 5.5 ~ 6.5 hours under the condition of temperature 420 ~ 480 DEG C after dipping cordierite dries up at temperature 55 ~ 65 DEG C.
8. integral catalyzer according to claim 1, it is characterized in that in step C, the presoma of dipping cobalt nitrate aqueous solution is dried 10 ~ 14 hours under the condition of temperature 100 ~ 110 DEG C, then roasting 2 ~ 12 hours at temperature 250 ~ 300 DEG C in air atmosphere.
9. integral catalyzer according to claim 1, is characterized in that in step D, and the presoma of dipping platinum acid chloride solution is dried 10 ~ 14 hours at temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours at temperature 250 ~ 300 DEG C under an inert atmosphere.
10. the integral catalyzer that described in claim, preparation method prepares any one of claim 1-9, is characterized in that the composed as follows of it, by weight
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Cited By (6)
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| CN107308954A (en) * | 2017-06-22 | 2017-11-03 | 浙江工业大学 | A kind of monoblock type combustion catalyst with dynamics model |
| CN107983366A (en) * | 2016-10-26 | 2018-05-04 | 中国科学院大连化学物理研究所 | A kind of resistance to hydro-thermal resistant to sulfur overall structure combustion catalyst and preparation method thereof |
| CN110116009A (en) * | 2019-05-30 | 2019-08-13 | 陕西省煤化工工程技术研究中心 | Containing wet VOCs catalysis oxidation integral catalyzer and its preparation method and application |
| CN112675846A (en) * | 2020-12-22 | 2021-04-20 | 安徽稞馨环境科技有限公司 | Preparation method and application of noble metal monolithic catalyst for removing carbon monoxide at room temperature by catalytic oxidation method |
| CN114210335A (en) * | 2021-12-31 | 2022-03-22 | 上海复翼环保科技有限公司 | Low-temperature water-resistant sulfur-resistant non-noble metal catalyst for removing carbon monoxide |
| CN117839773A (en) * | 2024-03-04 | 2024-04-09 | 北京科技大学 | Monolithic carbon monoxide catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983366A (en) * | 2016-10-26 | 2018-05-04 | 中国科学院大连化学物理研究所 | A kind of resistance to hydro-thermal resistant to sulfur overall structure combustion catalyst and preparation method thereof |
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| CN110116009A (en) * | 2019-05-30 | 2019-08-13 | 陕西省煤化工工程技术研究中心 | Containing wet VOCs catalysis oxidation integral catalyzer and its preparation method and application |
| CN112675846A (en) * | 2020-12-22 | 2021-04-20 | 安徽稞馨环境科技有限公司 | Preparation method and application of noble metal monolithic catalyst for removing carbon monoxide at room temperature by catalytic oxidation method |
| CN114210335A (en) * | 2021-12-31 | 2022-03-22 | 上海复翼环保科技有限公司 | Low-temperature water-resistant sulfur-resistant non-noble metal catalyst for removing carbon monoxide |
| CN117839773A (en) * | 2024-03-04 | 2024-04-09 | 北京科技大学 | Monolithic carbon monoxide catalyst and preparation method and application thereof |
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