CN116173993A - Application of noble metal loaded cation doped HAP in VOCs catalytic combustion - Google Patents

Application of noble metal loaded cation doped HAP in VOCs catalytic combustion Download PDF

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CN116173993A
CN116173993A CN202310176124.4A CN202310176124A CN116173993A CN 116173993 A CN116173993 A CN 116173993A CN 202310176124 A CN202310176124 A CN 202310176124A CN 116173993 A CN116173993 A CN 116173993A
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hap
water
catalyst
solution
stirring
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王钰
万继国
黎妍均
王黎
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Wuhan University of Science and Engineering WUSE
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
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    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
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Abstract

The invention belongs to application of noble metal loaded cation doped HAP in VOCs catalytic combustion. The catalyst component comprises: HAP and HAP carrier containing different cation components, wherein the different cation components mainly comprise cerium, titanium, tungsten and vanadium, and the HAP carrier is prepared by adopting a hydrothermal method; and noble metal substances gold, ruthenium, platinum and palladium loaded on the carrier are prepared by adopting a urea precipitation method. The catalyst prepared by the method has stronger heteroatom resistance and chlorine, sulfur and nitrogen atom poisoning resistance; meanwhile, the catalyst has the characteristics of high temperature resistance and sintering resistance, and the structural property of the catalyst is kept stable and is not easy to deactivate under the continuous high temperature. The preparation method is simple, and the chemical properties of the catalyst, such as redox and surface acidity and alkalinity, can be regulated and controlled by changing the proportion of raw materials and technological parameters. The advantages can effectively solve the problems of difficult treatment process, high input cost, short system operation life and the like of the VOCs containing hetero atoms, realize high-efficiency and low-cost degradation, and do not produce secondary pollutants such as dioxin.

Description

Application of noble metal loaded cation doped HAP in VOCs catalytic combustion
Technical Field
The invention belongs to the field of catalyst preparation and environmental protection application, and particularly relates to application of noble metal loaded cation doped HAP in VOCs catalytic combustion.
Background
chlorine-Containing Volatile Organic Compounds (CVOC) are widely available in various fields, such as the mechanical manufacturing, petrochemical, pharmaceutical, and spray coating industries. In addition, the CVOC has strong electronegativity of chlorine element in molecules, is difficult to biodegrade in a free state in the nature, is easy to accumulate in organisms, and has strong three-causing effect.
The purifying and treating technology of CVOC mainly comprises an incineration method, a condensation method, a biological method, a catalytic combustion method and the like. Wherein, the catalytic combustion method is an effective means for treating the chlorine-containing volatile organic compounds, and the CVOC in the waste gas is completely oxidized into CO under the action of a catalyst at a lower temperature 2 /CO、H 2 O、Cl 2 And HC1. The chlorinated organic gas reactant is adsorbed on the surface of the catalyst, so that the activation energy of CVOC is reduced, and the reaction rate is accelerated. Compared with other methods, the catalytic combustion method has the advantages of low operating temperature, low energy consumption, high efficiency, no secondary pollution and the like, and is widely applied to actual production. However, the problems of catalyst chlorine poisoning deactivation, secondary byproducts, and the like are gradually becoming bottlenecks that limit the development of the technology. Development of a novel catalyst with high activity, high selectivity and long service life is an urgent need for application of the catalytic combustion CVOC technology.
Furthermore, the general requirements of catalytic combustion catalysts are: should have a low light-off temperature at a certain fuel/air ratio; the full conversion rate can be maintained under the conditions of the lowest preheating temperature and the maximum mass transfer; the combustion reaction is exothermic, and releases a large amount of heat to make the surface of the catalyst reach a high temperature of 500-1000 ℃, while the catalyst is easy to reduce the activity due to melting, and the catalyst is required to be resistant to high-temperature sintering. Therefore, the core difficulty of catalytic combustion technology is the development of novel catalysts that are resistant to poisoning and sintering.
The transition metal oxide (such as vanadium base, manganese base and the like) has higher catalytic activity, but has the defects of high toxicity or easy occurrence of chlorine poisoning and the like; the catalytic activity of the non-noble metal catalyst is low; noble metal catalysts have high activity for catalytic combustion, but the activity is affected by a number of factors: such as the kind of carrier, particle size, pretreatment of catalyst, loading of active components, etc. In the process of catalytic oxidation of CVOC, noble metal catalysts are easy to react with chlorine species to cause deactivation, even undergo electrophilic chlorination reaction and surface isomerization reaction, and then are converted into oxychloride, and further react with chlorobenzene to generate polychlorinated products with higher toxicity, so that the catalytic activity is reduced, and the stability is poor. The noble metal catalyst is easy to sinter at a higher temperature, and active components are lost due to sublimation, so that the activity is reduced; deactivation by plugging or coking is also possible; there is also a possibility that the activity is lowered due to poisoning. Therefore, it is important to develop a catalyst with high activity, high temperature resistance and high selectivity.
Disclosure of Invention
The invention aims at overcoming the defects of the noble metal catalyst.
The technical scheme adopted by the invention is realized by the following steps:
1. preparation of HAP and HAP vectors of different Metal Components
(1) Mixing a calcium nitrate solution and a diammonium hydrogen phosphate solution to form a milky precipitate solution, and regulating the PH by ammonia water; stirring in water bath for 2-3 h; filtering and washing the obtained suspension, and putting the suspension into an oven for drying at 110-120 ℃ overnight; placing the mixture into a muffle furnace for roasting at 450-550 ℃, wherein 500 ℃ is the optimal temperature, and the roasting time is 4.5-5.5 h, and the roasting time is the optimal time.
In the above embodiment, 14.1g of calcium nitrate, different moles of Ca/P diammonium phosphate, molar ratio Ca: p=1.45, 1.5, 1.55, 1.6, 1.67, 1.7 to explore the most suitable calcium to phosphorus ratio for the best activity of the catalyst.
In the above embodiment, the calcium nitrate is dissolved in a mixed solution of 90ml of water and 90ml of absolute ethanol, and the diammonium phosphate is dissolved in 180ml of water, and the solvent required for the calcium nitrate is a mixed solution of water and absolute ethanol, and the absolute ethanol is added for better dissolution of the calcium nitrate.
In the above embodiment, the pH is adjusted to 9.5 to 12 with ammonia. Is favorable for forming milky white precipitate.
In the embodiment, the temperature of the stirring water bath kettle is 80-90 ℃, and the water is firstly used and then the absolute ethyl alcohol is used for washing, so that the absolute ethyl alcohol is easier to remove impurities.
(2) 1mol/L urea was dissolved in water and pH was adjusted by 6mol/L nitric acid; adding calcium nitrate, diammonium hydrogen phosphate and different metal agents into the solution, and adjusting the PH by nitric acid; stirring for 2-3 h in a water bath, cooling, suction filtering and washing the obtained solution, putting the solution into a hydrothermal kettle, and drying the solution in an oven at 140-180 ℃ for 5-7 h, wherein the optimal hydrothermal condition is 160 ℃ for 6h; cooling, suction filtering and washing the obtained solution, and putting the solution into an oven for drying at 100-110 ℃ overnight; placing the mixture into a muffle furnace for roasting at 450-550 ℃, wherein 500 ℃ is the optimal temperature, and the roasting time is 4.5-5.5 h, and the roasting time is the optimal time.
In the above embodiment, 3.6036g urea and 60ml water are weighed; the pH is regulated to 2-3 by nitric acid.
In the above embodiment, 2.115g of calcium nitrite, 1.407g of diammonium phosphate are weighed; the metal agent is cerium nitrate hexahydrate, titanium sulfate, ammonium paratungstate and ammonium metavanadate; the ratio of doping cations to Ca ranges from 1:9 to 2:9, wherein the optimal ratio is Ce/ca=1:9, ti/ca=1:9, w/ca=1:9, v/ca=1:9.
In the embodiment, the water bath kettle is at normal temperature; the hydrothermal reaction kettle is a reaction container provided by synthesizing chemical substances under certain temperature and certain pressure conditions; the washing process is to use water and then absolute ethyl alcohol, and the absolute ethyl alcohol is easier to remove impurities.
2. Preparation of Au/HAP, ru/HAP, pt/HAP, pd/HAP catalysts
Grinding 2g HAP into powder, and placing into a beaker for water bath stirring; adding 0.02g/ml of tetrachloroauric acid/0.02 g/ml of ruthenium trichloride/0.02 g/ml of chloroplatinic acid/0.02 g/ml of palladium nitrate and urea into the solution, and stirring in a water bath; aging, suction filtering, washing, and drying in a drying oven at 80-90 ℃ for 15-18 h; roasting in a muffle furnace at 350-450 ℃, wherein 400 ℃ is the optimal temperature, and roasting time is 4.5-5.5 h, and wherein roasting time is the optimal time.
In the above embodiment, 2g HAP, 1ml of 0.02g/ml of tetrachloroauric acid, 0.02g/ml of ruthenium trichloride, 0.02g/ml of chloroplatinic acid, 0.02g/ml of palladium nitrate aqueous solution, 1.158g of urea were weighed.
In the above embodiment, 1L of water was placed in the beaker; HAP needs to be ground into very fine powder, which is beneficial to being dissolved in water; the purpose of the water bath agitation is also to better disperse the HAP evenly in the water.
In the above embodiment, the load amount of Au, ru, pt, pd is 1% to 2% of the HAP mass; the molar ratio of urea to doping cations ranges from 120 to 130, 255 to 265, 495 to 505, 215 to 225, wherein the optimal ratio is urea/au=125, urea/ru=260, urea/pt=500, urea/pd=220.
In the above embodiment, the firing in the HAP muffle furnace to which tetrachloroauric acid is added is divided into three temperatures of 200 ℃, 400 ℃,600 ℃.
In the above embodiment, the water bath temperature is 80 to 100 ℃; stirring time is 12-14 h, stirring is carried out for 12-14 h in step (1) to facilitate dispersion of HAP in water, and stirring is carried out for 12-14 h in step (2) to fully load active components on HAP.
In the above embodiment, water is used before absolute ethyl alcohol is used in washing, and the absolute ethyl alcohol is easier to remove impurities; the aging time is 12-16 h.
The hydroxyapatite has the following advantages as a catalyst carrier:
1. the method has strong ion exchange property, and the hydroxyapatite can exchange with most metal ions, so that the high-dispersion and stable supported metal catalyst can be prepared according to the property.
2. Surface acid-base adjustability, in the process of preparing the hydroxyapatite, the acid-base property of the surface of the hydroxyapatite can be adjusted by adjusting the calcium-phosphate ratio so as to meet the requirements of different catalytic reactions.
3. The hydroxyapatite has abundant hydroxyl groups on the surface, has strong adsorptivity, can be modified by organic compounds with polar functional groups, and can better load the organic metal compounds with the polar functional groups.
Au/HAP, ru/HAP, pt/HAP and Pd/HAP have the following advantages as a catalyst:
1. the catalyst has excellent chlorine resistance, can transfer Cl species occupying active sites, has high catalytic performance for chlorine-containing volatile organic compounds (methylene dichloride), and has good tolerance and difficult inactivation.
2. High temperature resistance, high catalytic performance, certain stability and high sintering resistance, and can be sintered at 600 ℃.
3. The catalyst has high activity, higher catalytic efficiency than the traditional catalyst, and has good research significance.
4. The catalyst has good stability and repeatability, can not influence the catalytic effect of the catalyst even if the catalyst is used repeatedly for a long time at a certain temperature, can not reduce the catalytic efficiency, and can be used for a long time.
The method is characterized in that: the catalyst has good catalytic elimination effect on V0C pollutants in the atmosphere, especially on chlorine-containing volatile organic compounds, and compared with other noble metal catalysts, the catalyst has the advantages of simple preparation method, mild reaction conditions, good repeatability in experiments, high catalytic efficiency, high toluene conversion rate of 99.9% at 300 ℃ and DCM conversion rate of 99% at 440 ℃.
Drawings
The following figures are partial sample figures:
FIG. 1 shows Ru/HAP catalytic combustion toluene conversion.
FIG. 2 shows the DCM conversion for Ru/HAP catalytic combustion.
Fig. 3 shows that the catalyst performance was optimal for Ca/p=1.67 at 90% toluene and methylene chloride conversion for different Ca/P.
FIG. 4 shows the conversion of DCM in catalytic combustion with different cations doped with ruthenium, with Ru/Ce-HAP catalyst being optimal.
FIG. 5 shows the conversion of DCM in catalytic combustion with different noble metal doped cerium, with the Pt/Ce-HAP catalyst being optimal.
FIG. 6 is a durability test of Au/HAP-200, au/HAP-600 and Au/Ce/HAP-600 catalysts.
Detailed Description
For further detailed description of the present invention, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1
Taking a beaker, adding 90ml of water and 90ml of absolute ethyl alcohol to form a mixed solution, and dissolving 14.1g of calcium nitrate in the mixed solution to form a solution X; a beaker was taken, 180ml of water was added, and 9.72g of diammonium phosphate was dissolved in water to form solution Y; sucking the Y solution by using a rubber head dropper, gradually dripping the Y solution into a beaker containing the solution X, and putting the beaker into a water bath kettle for stirring in the dripping process to form a milky white solution; absorbing ammonia water by using a rubber head dropper, gradually dripping the ammonia water into a beaker, adjusting the PH, and measuring the PH by using PH test paper until the PH value is about 9.5; heating, stirring at 80deg.C for 2 hr, and sealing the beaker and water bath with preservative film; filtering the obtained suspension, washing twice with deionized water and absolute ethyl alcohol respectively, and drying overnight in an oven at 110 ℃; roasting in a muffle furnace at 500 ℃ for 5 hours to obtain a HAP sample; weighing 2g of HAP, grinding into powder, putting into a beaker containing 1L of water, and stirring at 80 ℃ for about 12 hours; after cooling, 1ml of 0.02g/ml ruthenium trichloride (2 g ruthenium trichloride is dissolved in 100ml of water to form 0.02g/ml ruthenium trichloride aqueous solution, the solution is put into a refrigerator for refrigeration) and 1.158g of urea are added into a beaker, then the beaker is heated, stirred for about 12 hours at a constant temperature in a dark place at 80 ℃, cooled and cooled down to room temperature for aging for 12 hours; filtering the solution containing the precipitate, respectively washing twice with deionized water and absolute ethyl alcohol to remove chloride ions, and drying the obtained sample in an oven at 110 ℃ overnight; roasting in a muffle furnace at 400 ℃ for 5 hours to obtain a Ru/HAP catalyst; 0.75g of the catalyst was weighed and placed in a catalytic combustion furnace, the flow rate of an air injection pump was 500ml/min, the bubbling rate of toluene was 6ml/min, the space velocity of toluene was 40000/h, and the toluene conversion at 350℃was 99.9%.
Example 2
Unlike example 1, 9.399g of diammonium phosphate was weighed out and the toluene conversion was 99.9% at 350 ℃.
Example 3
Unlike example 1, 9.032g of diammonium phosphate was weighed out and the toluene conversion was 99.9% at 350 ℃.
Example 4
Unlike example 1, 8.811g of diammonium phosphate was weighed out and the toluene conversion was 99.9% at 340 ℃.
Example 5
Unlike example 1, 8.442g of diammonium phosphate was weighed out and the toluene conversion was 99.9% at 300 ℃.
Example 6
Unlike example 1, 8.196g of diammonium phosphate was weighed out and the toluene conversion was 99.9% at 310 ℃.
Example 7
Unlike example 1, the VOC was methylene chloride, the methylene chloride bubbling rate was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion was 98% at 520 ℃.
Example 8
Unlike example 1, 9.399g of diammonium phosphate was weighed out, the VOC was methylene chloride, the methylene chloride bubbling rate was 2ml/min, the methylene chloride space velocity was 40000/h, and the conversion was 97.3% at 500 ℃.
Example 9
Unlike example 1, 9.032g of diammonium phosphate was weighed out, the VOC was methylene chloride, the methylene chloride bubbling rate was 2ml/min, the methylene chloride space velocity was 40000/h, and the conversion was 99.4% at 500 ℃.
Example 10
Unlike example 1, 8.811g of diammonium phosphate was weighed out, the VOC was methylene chloride, the methylene chloride bubbling rate was 2ml/min, the methylene chloride space velocity was 40000/h, and the conversion at 490℃was 99.8%.
Example 11
Unlike example 1, 8.4472 g of diammonium phosphate was weighed out, the VOC was methylene chloride, the methylene chloride bubbling rate was 2ml/min, the methylene chloride space velocity was 40000/h, and the 420℃conversion was 98.4%.
Example 12
Unlike example 1, 8.196g of diammonium phosphate was weighed out, the VOC was methylene chloride, the methylene chloride bubbling rate was 2ml/min, the methylene chloride space velocity was 40000/h, and the conversion was 97.7% at 450 ℃.
Example 13
Taking a beaker, adding 60ml of water, dissolving 3.6036g of urea in the water, and sucking 6mol/L nitric acid by using a dropper to adjust the PH to 2; 2.115g of calcium nitrite, 1.407g of diammonium hydrogen phosphate solution and 0.7725g of cerium nitrate hexahydrate are added into the beaker solution for dissolution, and 6mol/L nitric acid is sucked by a dropper to adjust the PH to 2; placing the beaker in a normal-temperature water bath, stirring for 2 hours, carrying out suction filtration on the obtained liquid, respectively washing twice with deionized water and absolute ethyl alcohol, placing the liquid into a hydrothermal kettle, and carrying out drying oven 160 ℃ for 6 hours; filtering the obtained liquid, respectively washing twice with deionized water and absolute ethyl alcohol, and drying overnight in an oven at 110 ℃; roasting in a muffle furnace at 500 ℃ for 5 hours to obtain a HAP sample; weighing 2gCe-HAP, grinding into powder, placing into a beaker containing 1L of water, and stirring at 80 ℃ for about 12 hours; after cooling, 1ml of 0.02g/ml ruthenium trichloride (2 g ruthenium trichloride is dissolved in 100ml of water to form 0.02g/ml ruthenium trichloride aqueous solution, the solution is put into a refrigerator for refrigeration) and 1.158g of urea are added into a beaker, then the beaker is heated, stirred for about 12 hours at a constant temperature in a dark place at 80 ℃, cooled and cooled down to room temperature for aging for 12 hours; filtering the solution containing the precipitate, respectively washing twice with deionized water and absolute ethyl alcohol to remove chloride ions, and drying the obtained sample in an oven at 110 ℃ overnight; and (5) placing the mixture into a muffle furnace to bake for 5 hours at 400 ℃ to obtain the Ru/Ce-HAP catalyst. The VOC was methylene chloride with a methylene chloride bubbling rate of 2ml/min and a methylene chloride space velocity of 40000/h, which gave a conversion of 98% at 340 ℃.
Example 14
Unlike example 13, 0.7725g of cerium nitrate hexahydrate was exchanged for 0.4270g of titanium sulfate to give a Ru/Ti-HAP catalyst. The VOC was methylene chloride with a methylene chloride bubbling rate of 2ml/min and a methylene chloride space velocity of 40000/h, which measured a conversion of 98% at 360 ℃.
Example 15
Unlike example 13, 0.7725g of cerium nitrate hexahydrate was changed to 0.4537g of ammonium paratungstate, resulting in Ru/W-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate was 98% at 380 ℃.
Example 16
Unlike example 13, 0.7725g of cerium nitrate hexahydrate was exchanged for 0.2081g of ammonium metavanadate, yielding a Ru/V-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate was 98% at 380 ℃.
Example 17
Unlike example 13, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml chloroplatinic acid (2 g chloroplatinic acid was dissolved in 100ml water to form 0.02g/ml chloroplatinic acid aqueous solution, and the solution was put into a refrigerator for refrigeration) to obtain a Pt/Ce-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate was 98% at 320 ℃.
Example 18
Unlike example 14, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml chloroplatinic acid, yielding a Pt/Ti-HAP catalyst. The VOC was methylene chloride with a methylene chloride bubbling rate of 2ml/min and a methylene chloride space velocity of 40000/h, which gave a conversion of 98% at 340 ℃.
Example 19
Unlike example 15, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml chloroplatinic acid, yielding a Pt/W-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate was 98% at 350 ℃.
Example 20
Unlike example 16, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml chloroplatinic acid, yielding a Pt/V-HAP catalyst. The VOC was methylene chloride with a methylene chloride bubbling rate of 2ml/min and a methylene chloride space velocity of 40000/h, which measured a conversion of 98% at 360 ℃.
Example 21
Unlike example 13, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml palladium nitrate (2 g palladium nitrate was dissolved in 100ml of water to form 0.02g/ml palladium nitrate aqueous solution, which was put into a refrigerator for refrigeration) to obtain Pd/Ce-HAP catalyst. The VOC was methylene chloride with a methylene chloride bubbling rate of 2ml/min and a methylene chloride space velocity of 40000/h, which measured a conversion of 98% at 360 ℃.
Example 22
Unlike example 14, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml palladium nitrate, yielding a Pd/Ti-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate was 98% at 380 ℃.
Example 23
Unlike example 15, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml palladium nitrate, to obtain a Pd/W-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate was 98% at 380 ℃.
Example 24
Unlike example 16, 1ml of 0.02g/ml ruthenium trichloride was changed to 1ml of 0.02g/ml palladium nitrate, yielding a Pd/V-HAP catalyst. The VOC was methylene chloride, the bubbling rate of methylene chloride was 2ml/min, the space velocity of methylene chloride was 40000/h, and the conversion rate at 390℃was 98% as measured.
Example 25
Taking a beaker, adding 60ml of water, dissolving 3.6036g of urea in the water, and sucking 6mol/L nitric acid by using a dropper to adjust the PH to 2; 2.115g of calcium nitrite, 1.407g of diammonium hydrogen phosphate solution and 0.7725g of cerium nitrate hexahydrate are added into the beaker solution for dissolution, and 6mol/L nitric acid is sucked by a dropper to adjust the PH to 2; placing the beaker in a normal-temperature water bath, stirring for 2 hours, carrying out suction filtration on the obtained liquid, respectively washing twice with deionized water and absolute ethyl alcohol, placing the liquid into a hydrothermal kettle, and carrying out drying oven 160 ℃ for 6 hours; filtering the obtained liquid, respectively washing twice with deionized water and absolute ethyl alcohol, and drying overnight in an oven at 110 ℃; roasting in a muffle furnace at 500 ℃ for 5 hours to obtain a HAP sample; weighing 2gCe-HAP, grinding into powder, placing into a beaker containing 1L of water, and stirring at 80 ℃ for about 12 hours; after cooling, adding 1ml of 0.02g/ml tetrachloroauric acid (2 g of tetrachloroauric acid is dissolved in 100ml of water to form 0.02g/ml tetrachloroauric acid solution, putting the solution into a refrigerator for refrigeration) and 1.158g of urea into a beaker, heating, keeping away from light at 80 ℃ and stirring for about 12 hours at constant temperature, cooling and cooling to room temperature for aging for 12 hours; filtering the solution containing the precipitate, respectively washing twice with deionized water and absolute ethyl alcohol to remove chloride ions, and drying the obtained sample in an oven at 110 ℃ overnight; three samples are taken and put into a muffle furnace to be roasted for 5 hours at 200 ℃, 400 ℃ and 600 ℃ respectively, so as to obtain the Au/Ce-HAP-x catalyst, wherein x represents the roasting temperature. The VOC was methylene dichloride, the bubbling rate of the methylene dichloride was 2ml/min, the space velocity of the methylene dichloride was 40000/h, and the conversion rate of the Au/Ce-HAP-400 catalyst was 98% at 380 ℃. The Au/Ce-HAP-200 catalyst had a conversion of 98% at 420 ℃. The Au/Ce-HAP-600 catalyst had a conversion of 98% at 380 ℃.
Example 26
Taking a beaker, adding 90ml of water and 90ml of absolute ethyl alcohol to form a mixed solution, and dissolving 14.1g of calcium nitrate in the mixed solution to form a solution X; a beaker was taken, 180ml of water was added, and 9.72g of diammonium phosphate was dissolved in water to form solution Y; sucking the Y solution by using a rubber head dropper, gradually dripping the Y solution into a beaker containing the solution X, and putting the beaker into a water bath kettle for stirring in the dripping process to form a milky white solution; absorbing ammonia water by using a rubber head dropper, gradually dripping the ammonia water into a beaker, adjusting the PH, and measuring the PH by using PH test paper until the PH value is about 9.5; heating, stirring at 80deg.C for 2 hr, and sealing the beaker and water bath with preservative film; filtering the obtained suspension, washing twice with deionized water and absolute ethyl alcohol respectively, and drying overnight in an oven at 110 ℃; roasting in a muffle furnace at 500 ℃ for 5 hours to obtain a HAP sample; weighing 2g of HAP, grinding into powder, putting into a beaker containing 1L of water, and stirring at 80 ℃ for about 12 hours; after cooling, adding 1ml of 0.02g/ml tetrachloroauric acid (2 g of tetrachloroauric acid is dissolved in 100ml of water to form 0.02g/ml tetrachloroauric acid solution, putting the solution into a refrigerator for refrigeration) and 1.158g of urea into a beaker, heating, keeping away from light at 80 ℃ and stirring for about 12 hours at constant temperature, cooling and cooling to room temperature for aging for 12 hours; filtering the solution containing the precipitate, respectively washing twice with deionized water and absolute ethyl alcohol to remove chloride ions, and drying the obtained sample in an oven at 110 ℃ overnight; three samples were taken and put into a muffle furnace to be baked at 200 deg.C, 400 deg.C and 600 deg.C for 5 hours, respectively, to obtain Au/HAP-x catalysts, where x represents the baking temperature. The Au-HAP-400 catalyst had a conversion of 98% at 410 ℃. The Au-HAP-200 catalyst had a conversion of 98% at 450 ℃. The Au-HAP-600 catalyst had a conversion of 98% at 430 ℃.

Claims (10)

1. The application of noble metal loaded cation doped HAP in VOCs catalytic combustion is characterized in that:
hydroxyapatite (HAP) and HAP carriers of different cation doping components;
the noble metal species, i.e., the active component, supported on the carrier.
2. A method according to claim 1, characterized in that:
HAP preparation method:
(1) Mixing a calcium nitrate solution and a diammonium hydrogen phosphate solution to form a milky white precipitate solution, and regulating the pH value by ammonia water;
(2) Stirring in water bath for 2-3 h;
(3) Filtering and washing the obtained suspension, and drying for 12-16 h at 110-120 ℃;
(4) Roasting for 4.5-5.5 h at 450-550 ℃.
3. A method according to claim 2, characterized in that:
molar ratio of Ca to P element in calcium nitrate and diammonium phosphate: p=1.45:1 to 1.7:1; the required solvent for the calcium nitrate is a mixed solution of water and absolute ethyl alcohol, wherein the water is as follows: absolute ethanol=1:1 to 1.2:1.
4. A method according to claim 2, characterized in that:
ammonia water is used for regulating the pH value to 9.5-12; the temperature of the water bath kettle is 80-90 ℃; firstly, water is used and then absolute ethyl alcohol is used during washing; roasting at 450-550 deg.c with 500 deg.c being optimal temperature and roasting time of 4.5-5.5 hr, and roasting for 5 hr being optimal condition based on several experiments.
5. A method according to claim 1, characterized in that:
preparing HAP with different cation doping components according to a hydrothermal method:
(1) Dissolving 1mol/L urea in water, and regulating the pH to 2-3 by 6mol/L nitric acid;
(2) Adding calcium nitrate, diammonium hydrogen phosphate and different cation precursors into the solution, and adjusting the pH to 2-3 by nitric acid;
(3) Stirring in water bath for 2-3 h, cooling, suction filtering and washing the obtained solution, further treating by adopting a hydrothermal method, wherein the water temperature is 140-180 ℃ and the time is 5-7 h, and the optimal hydrothermal condition is 160 ℃ and 6h;
(4) Cooling, suction filtering and washing the obtained solution, and drying for 12-16 h at 100-110 ℃;
(5) The precipitate is roasted at 450-550 deg.c with 500 deg.c being optimal temperature and roasting time of 4.5-5.5 hr, and the roasting time of 5 hr being optimal condition based on several experiments.
6. The method according to claim 5, wherein:
adjusting the pH to 2-3 by nitric acid; the temperature of the water bath kettle is 40-60 ℃; the cation precursor can be cerium nitrate hexahydrate, titanium sulfate, ammonium paratungstate and ammonium metavanadate; wherein the ratio of doping cations to Ca ranges from 1:9 to 2:9, wherein the optimal ratio is Ce/ca=1:9, ti/ca=1:9, w/ca=1:9, v/ca=1:9.
7. A method according to claim 1, characterized in that:
the cationic doped HAP catalyst loaded by noble metal is prepared by adopting a urea precipitation method.
8. The method of claim 7, wherein:
(1) Grinding HAP into powder, and placing into a beaker for water bath stirring;
(2) Adding 0.02g/ml of different cation precursors and urea into the solution, and stirring in a water bath;
(3) Aging, suction filtering, washing, and drying in a drying oven at 80-90 ℃ for 14-18 h;
(4) Roasting in a muffle furnace at 350-450 ℃ for 4.5-5.5 h.
9. The method according to claim 8, wherein:
HAP needs to be ground into fine powder, so that the HAP is dissolved in water, and the HAP structure is hard; the purpose of water bath stirring is also to better uniformly disperse and dissolve HAP in water; the cation precursor can be tetrachloroauric acid, ruthenium trichloride, chloroplatinic acid and palladium nitrate, wherein the load of Au, ru, pt, pd is 1-2% of HAP mass; the molar ratio of urea to doping cations ranges from 120 to 130, 255 to 265, 495 to 505, 215 to 225, wherein the optimal ratio is urea/au=125, urea/ru=260, urea/pt=500, urea/pd=220.
10. The method according to claim 8, wherein:
wherein, the baking temperature of the HAP muffle furnace added with tetrachloroauric acid is three temperatures of 200 ℃, 400 ℃ and 600 ℃; roasting at 350-450 ℃, wherein 400 ℃ is the optimal temperature, and the roasting time is 4.5-5.5 h, and the roasting time is 5h which is the optimal condition obtained according to multiple experiments; the water bath temperature is 80-100 ℃; stirring time is 12-14 h, stirring is carried out for 12-14 h in step (1) to ensure that HAP is easier to disperse in water, and stirring is carried out for 12-14 h in step (2) to ensure that active components are all loaded on HAP; the aging time is 12-16 h.
CN202310176124.4A 2023-02-28 2023-02-28 Application of noble metal loaded cation doped HAP in VOCs catalytic combustion Pending CN116173993A (en)

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