CN113842913A - Catalyst for low-temperature catalytic oxidation of CO and C3H8Preparation and use of the catalyst - Google Patents
Catalyst for low-temperature catalytic oxidation of CO and C3H8Preparation and use of the catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
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Abstract
The invention discloses a method for low-temperature catalytic oxidation of CO and C3H8The preparation and application of the catalyst; the invention provides a homogeneous hydrothermal method for preparing ZrxTi1‑xO2Method for preparing/GE composite oxide, and loading Ru by using composite oxide as carrier and adopting impregnation method to obtain novel Ru/ZrxTi1‑xO2The catalyst has low price compared with noble metal catalysts such as platinum, palladium, rhodium and the like, effectively ensures and improves the catalytic oxidation efficiency, and has better toxicity resistance.
Description
Technical Field
The invention relates to a preparation method and application of a catalyst, in particular to a catalyst for low-temperature catalytic oxidation of CO and C3H8The preparation and application of the catalyst.
Background
With the rapid increase of the number of motor vehicles in China year by year, the motor vehicles bring convenience to the life of people, and the exhaust gas discharged by the motor vehicles also brings serious air pollution problems. Traditional automobiles use mineral oil such as gasoline and diesel oil as fuel, and tail gas components are complex, mainly including carbon monoxide (CO), Hydrocarbon (HC) and Nitrogen Oxide (NO)x) And Particulate Matter (PM), and the like. Carbon monoxide is a colorless, odorless, suffocating, toxic gas caused by incomplete combustion of hydrocarbons in the fuel during cold start or neutral operation of an automobile. Nitrogen oxides produced by oxidation of small amounts of nitrogen at high temperatures and pressures with increased load on the engine, NOxEnvironmental problems such as photochemical smog and acid rain can be caused after entering the atmosphere. The carbon ammonia compound is also mainly generated due to incomplete combustion, is a carcinogenic substance and can cause damage to human bodies. Because automobile exhaust contains various toxic and harmful substances, the ecological environment is damaged, and the human health is threatened, so that the effective control of automobile exhaust pollution is an urgent worldwide problem to be solved.
The diesel vehicle has high fuel efficiency and high stability and is concerned, but the pollution caused by the diesel vehicle cannot be ignored. The emission limit of light automobile pollutants and the standard of a measuring method (the sixth stage of China) issued by the ministry of environmental protection in 11 months in 2016, clear limits are made on the emission of the tail gas of the diesel vehicle, and the tail gas treatment system of the diesel vehicle meeting the emission requirements of the country VI comprises an oxidation catalyst (DOC), a particulate matter trap (DPF) and a Selective Catalytic Reduction (SCR) technology. Wherein DOC can oxidize CO, HC, NO and other harmful gases in the tail gas into CO2、H2O and NO2And meanwhile, most of soluble organic matters (SOF) in the tail gas are efficiently converted, thereby being beneficial to the subsequent tail gas treatment process flow.
DOC catalysts are mostly supported catalysts, and noble metal active components such as platinum (Pt), palladium (Pd), ruthenium (Ru) and the like are supported on SiO2、TiO2、CeO2And the like on the carrier, and a certain catalytic effect is obtained. It has been found through studies that the choice of carrier is critical to maximize the activity of the active ingredient. TiO 22Commonly used as catalyst, adsorbent, sensor, etc., but pure TiO2There are obvious disadvantages as carriers: small specific surface area and poor thermal stability. Thus, it was sought to retain TiO2The focus of the researchers is the carrier which can overcome the existing shortcomings. Found by research on TiO2Other metal ions doped in the catalyst have good thermal stability on a carrier and noble metals with high surface dispersion. ZrO (ZrO)2The catalyst is one of the commonly used catalyst carriers, and has the advantages of high thermal stability, good chemical stability, high mechanical strength, strong ion migration capability, acid and alkali corrosion resistance and the like. Zhang et al are Zr4+Doping to anatase TiO2Solid solution is formed in the crystal lattice, the surface area, the pore volume and the surface acidity and alkalinity are all superior to those of a single component, and defects are formed on the surface of the carrier and are used as grafting sites of the active component. In addition, the cold start tail gas temperature of the diesel vehicle is low, and the existing catalyst catalyzes and oxidizes CO and C3H8The temperature is higher.
Therefore, in order to solve the above technical problems, the present invention adopts a homogeneous hydrothermal precipitation method to prepare ZrxTi1-xO2the/GE carrier is prepared by loading noble metal Ru by an ultrasonic impregnation method to prepare Ru/Zr with different Zr/Ti ratios and different GE doping amountsxTi1- xO2the/GE catalyst is used for researching low-temperature catalytic oxidation of CO and HC.
Disclosure of Invention
The invention aims to provide a catalyst for low-temperature catalytic oxidation of CO and C3H8The preparation method and the application of the catalyst. The invention provides a homogeneous hydrothermal method for preparing ZrxTi1-xO2Method for preparing/GE composite oxide, and loading Ru by using composite oxide as carrier and adopting impregnation method to obtain novel Ru/ZrxTi1-xO2The catalyst has the advantages of low price compared with noble metal catalysts such as platinum (Pt), palladium (Pd) and rhodium (Rh), equivalent catalytic oxidation efficiency, even higher catalytic oxidation efficiency, and better toxicity resistance.
The technical scheme of the invention is as follows: catalyst for low-temperature catalytic oxidation of CO and C3H8The preparation method of the catalyst comprises the following steps：
(1) Preparing graphene oxide by a modified Hummers method;
(2)ZrxTi1-xO2preparation of/GE composite oxide support:
ultrasonically dispersing 10-30mg of graphene oxide prepared in the step (1) into 40mL of deionized water according to the following proportion to obtain a solution A;
dissolving titanium sulfate in deionized water to obtain solution B;
dissolving the zirconium oxychloride octahydrate in the deionized water to obtain solution C, wherein the sum of the concentration of the titanium sulfate in the solution B and the concentration of the zirconium oxychloride octahydrate in the solution C is 1.4-1.8 mol/L;
adding 20ml of the solution B and 20ml of the solution C into the solution A under the stirring state, and continuously stirring for 20-40min to obtain a mixed solution;
adding urea with the molar weight 10-30 times of the total metal molar weight into the mixed solution, adding deionized water with the volume 0.4-0.6 times of the mixed solution, heating in a water bath to 70-90 ℃, and continuously stirring for reaction for 3-5 hours to obtain a reaction solution;
sixthly, adding the reaction solution into a polytetrafluoroethylene lining hydrothermal kettle, heating to 110-;
seventhly, centrifuging and washing the suspension, drying at 70-90 ℃, roasting at 500-700 ℃, and grinding to obtain ZrxTi1-xO2a/GE composite oxide support powder, and 0<x<1；
(3) Preparation of Ru/ZrxTi1-xO2The catalyst is as follows: to RuCl3Adding Zr into the solutionxTi1-xO2(ii) a/GE composite oxide support powder with RuCl3Controlling the total load mass of the active components to be 0.5-2% of the carrier powder, carrying out ultrasonic treatment for 0.5-1.5h, drying at 70-90 ℃, then heating to 300-500 ℃ at 2-4 ℃/min, roasting, keeping the temperature for 1-3h, and grinding to obtain Ru/ZrxTi1-xO2A GE catalyst, and 0<x<1。
In the step I, 20mg of graphene oxide prepared in the step (1) is ultrasonically dispersed in 40mL of deionized water according to the following proportion to obtain a solution A.
In the third step, the sum of the concentration of the titanium sulfate in the liquid B and the concentration of the zirconium oxychloride octahydrate in the liquid C is 1.6 mol/L.
And in the fourth step, adding the solution B and the solution C into the solution A under the stirring state, and continuously stirring for 30min to obtain a mixed solution.
In the fifth step, adding urea with the molar weight 20 times of the total metal molar weight and deionized water with the volume 0.5 times of the mixed solution into the mixed solution, heating the mixed solution in a water bath to 80 ℃, and continuously stirring and reacting the mixed solution for 4 hours to obtain reaction liquid.
In the step (sixthly), the temperature is raised to 120 ℃ for reaction for 24 hours.
In the step (c), drying at 80 ℃ and roasting at 600 ℃; said ZrxTi1-xO2The molar ratio of zirconium to titanium in the/GE composite oxide support powder is selected from any one of Zr and Ti, 1:3, 1:2, 1:1, 2:1 or 3: 1.
Said ZrxTi1-xO2The molar ratio of zirconium to titanium in the/GE composite oxide carrier powder is Zr to Ti which is 2 to 1.
In the step (3), RuCl3Volume of solution and ZrxTi1-xO2The volume mass ratio of the/GE composite oxide carrier powder is more than 2.5 mL: 1g of a compound; in the step (3), RuCl is used3Controlling the total load mass of the active components to be 1% of the carrier powder, carrying out ultrasonic treatment for 1h, drying at 80 ℃, then heating to 400 ℃ at the speed of 3 ℃/min, roasting, and keeping the temperature for 2 h.
Ru/Zr prepared by the methodxTi1-xO2the/GE catalyst is used in DOC reaction system to react CO and C3H8Conversion to non-toxic and pollution-free CO2And H2O, the reaction temperature is 80-320 ℃, the total flow of the gas is controlled to be 1L/min, and the space velocity is 60000h-1And the CO conversion rate is more than or equal to 90 percent.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares Zr by a homogeneous hydrothermal methodxTi1-xO2The Ru/Zr is obtained by loading metal Ru on a/GE (x is a molar weight) composite oxide carrier by adopting an impregnation methodxTi1-xO2a/GE low temperature DOC catalyst. Wherein the Zr/Ti ratio is adjustable, and the catalyst has higher CO and C at low temperature3H8Oxidation performance. The results show that Ru/Zr2Ti1O2T for CO oxidation by GE catalyst50％The conversion rate of CO is up to 91% at 125 ℃ and 280 ℃, and C is oxidized3H8T of50％ At 226 ℃ C, complete conversion of C at 440 ℃3H8Is superior to most noble metal catalysts such as Pt, Pd and the like, has better sulfur resistance stability, and is introduced with 100ppm SO at 280 DEG C2The activity of the catalyst is basically unchanged after reaction for 3h, which shows that the Ru/Zr2Ti1O2the/GE catalyst has higher oxidation activity and poison-resistant stability.
Ru/ZrxTi1-xO2the/GE catalyst improves the active surface area, the oxidation reduction capability and the like of the catalyst possibly due to the introduction of Graphene (GE), thereby improving the catalytic oxidation of CO and C by the catalyst3H8The performance of (c). 100ppm SO was passed at 280 ℃2Reaction for 3h, Ru/ZrxTi1-xO2CO conversion of the/GE catalyst did not drop significantly, and C3H8The conversion of (A) is improved, indicating that the catalyst is suitable for use at lower exhaust temperatures and contains SO2And the like, which has a toxic effect on the activity of the catalyst.
The following is a comparison of the catalytic performance of the present invention with that of existing conventional materials.
TABLE 1 comparison of the catalytic Activity of different catalysts
As can be seen from Table 1, the catalyst prepared according to the invention catalyzes the conversion CXHYAnd T of CO50The catalyst has low sulfur resistance and good sulfur resistance, and is a good DOC catalyst.
Graphene (GE) materials have many excellent physical and chemical properties and are often used as reinforcing and functional phases in composites. The graphene may also beThe load of noble metal Ru is effectively reduced, so that the cost is reduced, and the introduction of Graphene (GE) improves Ru/ZrxTi1-xO2Performance of the/GE catalyst.
Experiments prove that:
Ru/Zr obtained in examples 1-5xTi1-xO2Use of/GE catalysts (Zr: Ti ═ 1:3, 1:2, 1:1, 2:1, 3:1) for the catalytic oxidation of CO and C3H8. 1g of CO and C are weighed3H8The catalyst is put into a quartz tube of a fixed bed reactor with the diameter of 20mm, the total gas flow is controlled to be 1L/min, the steel cylinder gas simulates the tail gas of a diesel vehicle, and the volume ratio of CO to C is 0.1 percent3H80.05% and O25％，N2The space velocity is 60000h for balancing gas-1Introducing N before the reaction2Pretreating the catalyst, adjusting the temperature of the reaction tube during reaction to measure the activity of the catalyst under different temperature conditions, and detecting the tail gas by using a flue gas analyzer KM 9106).
Introducing N before reaction2The catalyst is pretreated, and a temperature controller is adjusted to measure the activity of the catalyst at different temperatures during reaction. CO and C3H8The conversion (X) of (2) is obtained by the following formula (1):
in the formula, CinAs initial concentration, CoutIs the instantaneous concentration at a certain temperature. By T50％Evaluation of the Low temperature Effect of the catalyst, T50％Conversion of 50% of CO and C for the catalyst3H8The corresponding temperature.
Different Zr/Ti ratio Ru/ZrxTi1-xO2Catalytic oxidation of CO and C by GE catalyst3H8The efficiencies are shown in FIG. 1 and FIG. 2, respectively, for Ru/Zr2Ti1O2the/GE catalyst showed the best activity, T of CO50％The corresponding temperature is as low as 125 ℃, the conversion rate at 280 ℃ is as high as more than 90 percent, and C3H8Oxidized T50％As low as 226 c,realization of C at 440 DEG C3H8And (4) complete conversion. SO (SO)2The effect on CO conversion is shown in FIG. 3, with 100ppm SO at 280 ℃ C2Reaction for 3h, Ru/Zr2Ti1O2The CO conversion of the/GE catalyst is only reduced by 1%. SO (SO)2To C3H8The effect of conversion is shown in FIG. 4, Ru/Zr2Ti1O2C of/GE catalyst3H8The conversion rate is introduced with SO2Then sharply increased, basically kept unchanged for 3 hours, and stopped introducing SO2Rear C3H8The conversion rate is restored to the initial level, which shows that the catalyst has better stability against sulfur.
In conclusion, the invention provides a homogeneous hydrothermal method for preparing ZrxTi1-xO2Method for preparing/GE composite oxide, and loading Ru by using composite oxide as carrier and adopting impregnation method to obtain novel Ru/ZrxTi1-xO2The catalyst/GE is applied to the DOC catalysis field, has low price compared with noble metal catalysts of platinum (Pt), palladium (Pd) and rhodium (Rh), effectively ensures and improves the catalytic oxidation efficiency, and has better toxicity resistance.
Drawings
FIG. 1 shows Ru/Zr in examples 1 to 5 of the present inventionxTi1-xO2A performance curve diagram of catalytic oxidation CO of a GE catalyst;
FIG. 2 shows Ru/Zr in examples 1 to 5 of the present inventionxTi1-xO2Catalytic oxidation of C with GE catalyst3H8Performance graph of (a);
FIG. 3 shows Ru/Zr according to the present invention2Ti1O2Sulfur resistance performance curve diagram of the GE catalyst for CO oxidation;
FIG. 4 shows Ru/Zr according to the present invention2Ti1O2Oxidation of GE catalyst C3H8Curve diagram of sulfur resistance.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example 1: Ru/Zr1Ti3O2Preparation of/GE catalysts
Ultrasonically dispersing 10mgGO (graphene oxide prepared by a modified Hummers method) in 40mL of deionized water to obtain solution A; 5.760g of Ti (SO) were taken4)2Dissolving in 20mL of deionized water to obtain solution B; 2.578g ZrOCl2·8H2O20 mL of deionized water to obtain solution C; rapidly adding the solution B and the solution C into the solution A under vigorous stirring, and continuously stirring for 20min to fully and uniformly mix the solution B and the solution C to obtain a mixed solution; adding urea with the molar weight 10 times of the total metal molar weight and deionized water with the volume 0.4 times of the mixed solution into the mixed solution, heating the mixed solution in a water bath to 70 ℃, and continuously stirring for reaction for 3 hours to slowly decompose the urea to obtain a reaction solution; transferring the reaction solution into a 250mL polytetrafluoroethylene lining hydrothermal kettle, heating to 110 ℃ for reaction for 20h, and centrifugally washing the suspension after reaction by using deionized water and ethanol until Ag (NO)3)3Detecting no white precipitate, drying the obtained solid at 70 ℃, roasting at 500 ℃, and grinding to obtain Zr1Ti3O2a/GE composite oxide support powder; 10mL of RuCl was taken31g of Zr was added to the solution1Ti3O2The total load mass of active components is controlled to be 0.5 percent of that of the carrier powder (taking RuCl as the basis)3Metering), ultrasonic treatment for 0.5h, drying at 70 ℃, then heating to 300 ℃ at the speed of 2 ℃/min, roasting, keeping the temperature for 1h, and grinding to obtain Ru/Zr1Ti3O2a/GE catalyst.
Example 2: Ru/Zr1Ti2O2Preparation of/GE catalysts
Ultrasonically dispersing 20mgGO (graphene oxide prepared by a modified Hummers method) in 40mL of deionized water to obtain solution A; 5.119g of Ti (SO) was taken4)2Dissolving in 20mL of deionized water to obtain solution B; 3.438g ZrOCl2·8H2O20 mL of deionized water to obtain solution C; rapidly adding the solution B and the solution C into the solution A under vigorous stirring, and continuously stirring for 30min to fully and uniformly mix the solution B and the solution C to obtain a mixed solution; adding urea with the molar weight 20 times of the total metal molar weight and deionized water with the volume 0.5 times of the mixed solution into the mixed solution, and then adding the mixture into the reactorHeating in water bath to 80 ℃, and continuously stirring for reacting for 4 hours to slowly decompose urea to obtain reaction liquid; transferring the reaction solution into a 250mL polytetrafluoroethylene lining hydrothermal kettle, heating to 120 ℃ for reaction for 24h, and centrifugally washing the suspension after reaction by using deionized water and ethanol until Ag (NO)3)3Detecting no white precipitate, drying the obtained solid at 80 deg.C, roasting at 600 deg.C, and grinding to obtain Zr1Ti2O2a/GE composite oxide support powder; 10mL of RuCl was taken31g of Zr was added to the solution1Ti2O2The total load mass of active components is controlled to be 1 percent of the total load mass of the carrier (taking RuCl as a reference)3Metering), ultrasonic treatment for 1h, drying at 80 ℃, then heating to 400 ℃ at the speed of 3 ℃/min, roasting, keeping the temperature for 2h, and grinding to obtain Ru/Zr1Ti2O2a/GE catalyst.
Example 3: Ru/Zr1Ti1O2Preparation of/GE catalysts
Ultrasonically dispersing 20mgGO (graphene oxide prepared by a modified Hummers method) in 40mL of deionized water to obtain solution A; 3.840g of Ti (SO) are taken4)2Dissolving in 20mL of deionized water to obtain solution B; 5.156g ZrOCl2·8H2O20 mL of deionized water to obtain solution C; rapidly adding the solution B and the solution C into the solution A under vigorous stirring, and continuously stirring for 30min to fully and uniformly mix the solution B and the solution C to obtain a mixed solution; adding urea with the molar weight 20 times of the total metal molar weight and deionized water with the volume 0.5 times of the mixed solution into the mixed solution, heating the mixed solution in a water bath to 80 ℃, and continuously stirring for reaction for 4 hours to slowly decompose the urea to obtain a reaction solution; transferring the reaction solution into a 250mL polytetrafluoroethylene lining hydrothermal kettle, heating to 120 ℃ for reaction for 24h, and centrifugally washing the suspension after reaction by using deionized water and ethanol until Ag (NO)3)3Detecting no white precipitate, drying the obtained solid at 80 deg.C, roasting at 600 deg.C, and grinding to obtain Zr1Ti1O2a/GE composite oxide support powder; 10mL of RuCl was taken31g of Zr was added to the solution1Ti1O2The total load mass of active components is controlled to be 1 percent of the total load mass of the carrier (taking RuCl as a reference)3Metering), ultrasonic treatment for 1h, drying at 80 ℃, then heating to 400 ℃ at the speed of 3 ℃/min, roasting, keeping the temperature for 2h, and grinding to obtain Ru/Zr1Ti1O2a/GE catalyst.
Example 4: Ru/Zr2Ti1O2Preparation of/GE catalysts
Ultrasonically dispersing 20mgGO (graphene oxide prepared by a modified Hummers method) in 40mL of deionized water to obtain solution A; 2.561g of Ti (SO) was taken4)2Dissolving in 20mL of deionized water to obtain solution B; 6.873g ZrOCl2·8H2O20 mL of deionized water to obtain solution C; rapidly adding the solution B and the solution C into the solution A under vigorous stirring, and continuously stirring for 30min to fully and uniformly mix the solution B and the solution C to obtain a mixed solution; adding urea with the molar weight 20 times of the total metal molar weight and deionized water with the volume 0.5 times of the mixed solution into the mixed solution, heating the mixed solution in a water bath to 80 ℃, and continuously stirring for reaction for 4 hours to slowly decompose the urea to obtain a reaction solution; transferring the reaction solution into a 250mL polytetrafluoroethylene lining hydrothermal kettle, heating to 120 ℃ for reaction for 24h, and centrifugally washing the suspension after reaction by using deionized water and ethanol until Ag (NO)3)3Detecting no white precipitate, drying the obtained solid at 80 deg.C, roasting at 600 deg.C, and grinding to obtain Zr2Ti1O2Taking 10mL RuCl from the/GE composite oxide carrier powder31g of Zr was added to the solution2Ti1O2The total load mass of active components is controlled to be 1 percent of the total load mass of the carrier (taking RuCl as a reference)3Metering), ultrasonic treatment for 1h, drying at 80 ℃, then heating to 400 ℃ at the speed of 3 ℃/min, roasting, keeping the temperature for 2h, and grinding to obtain Ru/Zr2Ti1O2a/GE catalyst.
Example 5: Ru/Zr3Ti1O2Preparation of/GE catalysts
Ultrasonically dispersing 30mgGO (graphene oxide prepared by a modified Hummers method) in 40mL of deionized water to obtain solution A; 1.920g of Ti (SO) was taken4)2Dissolving in 20mL of deionized water to obtain solution B; 7.734g ZrOCl2·8H2O20 mL of deionized water to obtain solution C; mixing solution B and solution C under vigorous stirringQuickly adding the urea into the solution A, continuously stirring for 40min to fully and uniformly mix the urea, the urea and the deionized water, wherein the molar weight of the urea is 30 times of that of the total metal, and the deionized water is 0.6 times of the volume of the mixed solution; the reaction solution is transferred to a 250mL polytetrafluoroethylene lining hydrothermal kettle and heated to 130 ℃ for reaction for 28 h. The suspension after reaction is centrifugally washed by deionized water and ethanol until Ag (NO)3)3Detecting no white precipitate, drying the obtained solid at 90 deg.C, roasting at 700 deg.C, and grinding to obtain Zr3Ti1O2Taking 10mL RuCl from the/GE composite oxide carrier powder31g of Zr was added to the solution3Ti1O2The total load mass of active components is controlled to be 2 percent of the carrier (taking RuCl as a reference)3Metering), ultrasonic treatment for 1.5h, drying at 90 ℃, then heating to 500 ℃ at 4 ℃/min, roasting, keeping the temperature for 3h, and grinding to obtain Ru/Zr3Ti1O2a/GE catalyst.
Claims (10)
1. Catalyst for low-temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: the method comprises the following steps:
(1) preparing graphene oxide by a modified Hummers method;
(2)ZrxTi1-xO2preparation of/GE composite oxide support:
ultrasonically dispersing 10-30mg of graphene oxide prepared in the step (1) into 40mL of deionized water according to the following proportion to obtain a solution A;
dissolving a proper amount of titanium sulfate in deionized water to obtain solution B;
dissolving a proper amount of zirconium oxychloride octahydrate in deionized water to obtain solution C, wherein the sum of the concentration of titanium sulfate in the solution B and the concentration of the zirconium oxychloride octahydrate in the solution C is 1.4-1.8 mol/L;
adding 20mlB solution and 20ml C solution into the A solution under stirring, and continuing stirring for 20-40min to obtain mixed solution;
adding urea with the molar weight 10-30 times of the total metal molar weight into the mixed solution, adding deionized water with the volume 0.4-0.6 times of the mixed solution, heating in a water bath to 70-90 ℃, and continuously stirring for reaction for 3-5 hours to obtain a reaction solution;
sixthly, adding the reaction solution into a polytetrafluoroethylene lining hydrothermal kettle, heating to 110-;
seventhly, centrifuging and washing the suspension, drying at 70-90 ℃, roasting at 500-700 ℃, and grinding to obtain ZrxTi1-xO2a/GE composite oxide support powder, and 0<x<1；
(3) Preparation of Ru/ZrxTi1-xO2The catalyst is as follows: to RuCl3Adding Zr into the solutionxTi1-xO2(ii) a/GE composite oxide support powder with RuCl3Controlling the total load mass of the active components to be 0.5-2% of the carrier powder, carrying out ultrasonic treatment for 0.5-1.5h, drying at 70-90 ℃, then heating to 300-500 ℃ at 2-4 ℃/min, roasting, keeping the temperature for 1-3h, and grinding to obtain Ru/ZrxTi1-xO2A GE catalyst, and 0<x<1。
2. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: in the step I, 20mg of graphene oxide prepared in the step (1) is ultrasonically dispersed in 40mL of deionized water according to the following proportion to obtain a solution A.
3. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: in the third step, the sum of the concentration of the titanium sulfate in the liquid B and the concentration of the zirconium oxychloride octahydrate in the liquid C is 1.6 mol/L.
4. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: and in the fourth step, adding the solution B and the solution C into the solution A under the stirring state, and continuously stirring for 30min to obtain a mixed solution.
5. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: in the fifth step, adding urea with the molar weight 20 times of the total metal molar weight into the mixed solution, adding deionized water with the volume 0.5 times of the mixed solution, heating in water bath to 80 ℃, and continuously stirring for reaction for 4 hours to obtain the reaction solution.
6. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: in the step (sixthly), the temperature is raised to 120 ℃ for reaction for 24 hours.
7. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: in the step (c), drying at 80 ℃ and roasting at 600 ℃; said ZrxTi1-xO2The molar ratio of zirconium to titanium in the/GE composite oxide support powder is selected from any one of Zr and Ti, 1:3, 1:2, 1:1, 2:1 or 3: 1. .
8. The process of claim 7 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: said ZrxTi1-xO2The molar ratio of zirconium to titanium in the/GE composite oxide support powder is selected from Zr to Ti to 2 to 1.
9. The process of claim 1 for the low temperature catalytic oxidation of CO and C3H8The method for preparing the catalyst of (1), which is characterized in that: in the step (3), RuCl3Volume of solution and ZrxTi1-xO2The volume mass ratio of the/GE composite oxide carrier powder is more than 2.5 mL: 1g of a compound; in the step (3), RuCl is used3Controlling the total load mass of the active components to be 1% of the carrier powder, carrying out ultrasonic treatment for 1h, drying at 80 ℃, then heating to 400 ℃ at the speed of 3 ℃/min, roasting, and keeping the temperature for 2 h.
10. Ru/Zr prepared by the method according to any one of claims 1-9xTi1-xO2the/GE catalyst is used in a DOC reaction system, the reaction temperature is 80-320 ℃, the total flow of gas is controlled to be 1L/min, and the space velocity is 60000h-1The conversion rate of CO is more than or equal to 90 percent3H8Conversion to non-toxic and pollution-free CO2And H2O。
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