CN115770618A - Supported vanadium phosphorus oxo heteropoly acid catalyst and preparation method and application thereof - Google Patents
Supported vanadium phosphorus oxo heteropoly acid catalyst and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a supported vanadium phosphorus oxo heteropoly acid catalyst and a preparation method and application thereof, belonging to the field of atmospheric pollution treatment. The catalyst takes vanadium-phosphorus-oxygen as an active component and adopts N-doped modified TiO 2 Is used as a carrier, and the mass of the active component is 7-15% of the total mass of the catalyst. The preparation method of the catalyst comprises the following steps: vanadium pentoxide is used as an active precursor, and C is used 6 H 12 O 6 Reducing pentavalent vanadium into tetravalent vanadium as a reducing agent, adding phosphoric acid, mixing, synthesizing an active component vanadium-phosphorus-oxygen by a hydrothermal method, and loading the active component on nitrogen-doped modified TiO 2 Obtained on a carrier. The conversion rate of toluene of the catalyst can reach more than 90 percent at 225 ℃, and the conversion rate of toluene can reach more than 99.9 percent at 250 ℃; meanwhile, the catalyst shows stronger sulfur resistance. The supported vanadium phosphorus oxapolyacid catalyst can be effectively extracted at low temperatureHigh activity and toluene purifying efficiency, simple preparation process, wide material source and low cost.
Description
Technical Field
The invention relates to the field of atmospheric pollution treatment, in particular to a supported vanadium phosphorus oxo heteropoly acid catalyst, a preparation method thereof and application thereof in removing VOCs.
Background
Volatile Organic Compounds (VOCs) are a major class of atmospheric pollutants and are O 3 The important precursor is an important factor causing secondary aerosol (SOA) pollution, plays an important role in composite atmospheric pollution such as haze and ozone and can cause serious harm to human health and environment. VOCs are an important part of atmospheric combined pollution, and the pollution of VOCs becomes a new problem of atmospheric pollution in China, so that the treatment of VOCs in China is very slow.
In recent years, researchers in various countries have been working on technologies for catalytic oxidation of VOCs to remove VOCs using different catalysts. The commercial V-W/Ti catalyst has low efficiency of catalyzing and oxidizing VOCs at low temperature, the optimal temperature window is generally 500-700 ℃, and the efficiency of the V-W/Ti catalyst modified by doping transition metal is higherThe optimum temperature window is generally 350-450 ℃. The higher reaction temperature necessitates the placement of the SCR reactor bed in front of the air preheater, dust collector and desulfurization unit, which exposes the catalyst to high SO concentrations 2 And high dust fume, the removal rate of the catalyst on VOCs and the service life of the catalyst are seriously influenced. Therefore, the development of low-temperature and efficient VOCs removing catalysts is critical.
In the existing VOCs catalytic oxidation technology, a catalyst is the core of the technology. According to the difference of catalyst carrier and active component, the catalyst is mainly divided into four classes of noble metal, metal oxide, carbon-based material and molecular sieve. Because the VOCs are various in types and the characteristic that the ring opening of the benzene ring is difficult is considered, toluene is taken as a representative pollutant of the VOCs in the research. Researches show that the precious metal catalyst has a good effect of removing volatile organic compounds, the low-temperature efficiency can reach 100%, but the precious metal is expensive and difficult to obtain, and large-scale engineering application cannot be realized. There have also been some studies on the preparation of catalysts using transition metals, and although the cost is reduced, the optimum active temperature window is still high. In addition, most of the studies on the catalytic oxidation of toluene did not explore SO 2 The effect on the catalyst.
For example, chinese patent CN114100607A discloses a Pd-based catalyst, a preparation method and use thereof, wherein the conversion efficiency of the catalyst in toluene at 200 ℃ can reach more than 90%, and the efficiency at 230 ℃ can reach 100%. Guo Na et al (journal of environmental engineering, 2022, 16 (6): 1853-1861) found in their studies that RuCe/ZSM-5 catalyst Ru (1.0)/CZ catalyst exhibited excellent low-temperature catalytic performance, CO 2 Selectivity and stability, and can convert 90% of toluene at 210 ℃. Although the noble metal catalysts (palladium and ruthenium) have high conversion efficiency to toluene at low temperature, the noble metals are difficult to obtain and very expensive, and are difficult to be produced and used on a large scale in industry, and the research does not consider SO 2 Competitive adsorption with the catalyst.
For example, chinese patent CN113019368A discloses a cobalt-containing mesoporous silica nanosphere catalyst, and a preparation method and application thereof, wherein divalent cobalt oxide is used as an important active component, and the catalyst is prepared at 291The toluene purification rate can reach 99.9% at the temperature of DEG C. WeiLiu et al (Fuel 312 (2022) 122975) found in the study CuO/MnO 2 The conversion rate of the composite metal oxide catalyst in toluene at 240 ℃ can reach 90%, and the conversion rate of toluene at 270 ℃ can reach 99.9%. The optimum activity temperature windows of the two catalysts are both higher, and no consideration is given to the easy reaction of the transition metal oxide and SO 2 The reaction produces sulfate species that compete with toluene for adsorption effects.
In summary, although there have been some significant results in recent years on the research of catalysts for catalytic oxidation of VOCs, the problems in terms of low temperature and cost have not been solved well. Therefore, the catalyst which has good low-temperature activity, low cost, strong sulfur resistance and great industrial application value is researched and developed, the service life of the catalyst is prolonged, the cost of removing VOCs is reduced, and the catalyst has important significance in theoretical and engineering application.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defects that the catalytic activity of the existing catalyst for catalyzing and oxidizing VOCs is poor at low temperature and the optimal activity temperature window is high, and provides a supported catalyst for catalyzing and oxidizing VOCs by using vanadium, phosphorus and oxygen and a preparation method thereof, so that the optimal reaction temperature window for catalyzing and oxidizing VOCs can be reduced, and the catalyst has high catalytic activity and catalytic efficiency and high sulfur resistance under the low-temperature condition.
2. Technical scheme
In order to solve the technical problems, the invention is realized by the following technical scheme.
The invention provides a supported vanadium phosphorus oxapolyacid catalyst, which takes vanadium phosphorus oxygen as an active component and N-doped modified TiO 2 Is a carrier, and the mass of the active component is 7-15% of the total mass of the catalyst.
The invention also provides a preparation method of the supported vanadium phosphorus oxygen heteropoly acid catalyst, which comprises the following steps:
the method comprises the following steps: preparation of the active ingredient
(1) Will C 6 H 12 O 6 And V 2 O 5 According to a molar ratio of 0.2-0.5: 1, dissolving in water, stirring uniformly, heating at the high temperature of 180 ℃ for 12 hours to obtain a mixed solution, centrifuging the mixed solution to obtain a solid, drying the solid, and grinding to obtain powder;
(2) Dissolving the powder obtained in the step (1) in a phosphoric acid solution, heating for 24 hours at a high temperature of 160 ℃ to obtain a mixed solution, and then centrifuging, drying and grinding to obtain an active component precursor, wherein H is 3 PO 4 Phosphorus and V 2 O 5 The molar ratio of vanadium in the vanadium is 0.2-2.0;
(3) Roasting the active component precursor obtained in the step (2) in a nitrogen atmosphere to obtain active component powder;
step two: preparation of the catalyst
(1) Dissolving the active component obtained in the step one in distilled water, and then adding TiO 2 The carrier enables the mass percentage of the active component in the catalyst to be 7-15%;
(2) And (2) stirring the mixed solution in the step (1), then sequentially carrying out constant-temperature water bath, drying and roasting, and then grinding to obtain a target product, namely supported vanadium-phosphorus oxapolyacid catalyst powder.
Further, the TiO is 2 The carrier is nitrogen-doped modified anatase TiO 2 And (3) a carrier.
Further, the stirring in the first step and the second step means: stirring for 1-3 h at room temperature, raising the temperature to 70-85 ℃, and then stirring in a thermostatic water bath until the mixture is evaporated to dryness.
Further, the drying temperature in the first step is 80 ℃, the drying time is 10-12 h, the drying temperature in the second step is 100-110 ℃, and the drying time is 3-6 h.
Furthermore, the roasting temperature in the first step and the roasting temperature in the second step are both 300-450 ℃, and the roasting time is 3-5 h.
Further, the molar ratio of phosphorus to vanadium in the first step is 0.2, and the mass percentage of the active component in the catalyst in the second step is 10%.
The supported vanadium phosphorus oxygen heteropoly acid catalyst can be applied to catalytic oxidation of VOCs.
Further, the VOCs is toluene.
3. Advantageous effects
Compared with the prior art, the invention has the following technical effects:
(1) The supported vanadium phosphorus oxa-polyacid catalyst takes vanadium phosphorus oxygen as an active component, and the vanadium phosphorus oxygen belongs to heteropoly acid, so that the heteropoly acid has strong electron transport capacity and redox property, and has strong surface acidity, high activity lattice oxygen and other characteristics, and the vanadium phosphorus oxygen is taken as the active component, so that the surface acidity position of the catalyst and the redox property of the catalyst can be increased, the activity of the catalyst can be effectively improved under the low-temperature condition, and the vanadium phosphorus oxygen is strong in sulfur resistance.
(2) The invention relates to a supported vanadium phosphorus oxapolyacid catalyst, which is anatase TiO 2 The urea is used as a carrier and is modified by adding a proper amount of urea, so that the dispersity of active particles is improved, the specific surface area and acid sites of the catalyst are increased, the low-temperature activity and the stability of the catalytic activity of the catalyst are improved, the sulfur poisoning resistance of the catalyst is further enhanced, and the use temperature window of the catalyst is enlarged.
(3) According to the preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst, vanadium phosphorus oxo is used as the catalyst, so that the oxidation-reduction performance of the catalyst is enhanced, and the chemical adsorption oxygen (O) is increased α ) The amount of lattice oxygen which is continuously supplemented and consumed promotes the increase of B acid and L acid on the surface of the catalyst, so the catalyst has better effect of removing toluene at low temperature.
(4) According to the preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst, the ratio of each reaction raw material and each reaction process parameter, such as the phosphorus-vanadium molar ratio, the reaction temperature, the roasting temperature and the like, are strictly controlled, so that the catalytic activity and the sulfur resistance of the catalyst can be optimally matched, and the preparation process is simple, the raw material source is wide, the cost is low, and the application value is high; when the molar ratio of phosphorus to vanadium is 0.2.
Drawings
FIG. 1 is an activity diagram of the sulfur resistance of the supported vanadium phosphoheteropolyacid catalyst of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific examples, but the present invention is not limited to the examples.
The invention relates to a supported vanadium phosphorus oxapolyacid catalyst, which takes vanadium phosphorus oxygen as an active component and is supported on nitrogen-doped modified anatase TiO 2 Loading active component H on the carrier by adopting an impregnation method 3 PO 4 And V 2 O 5 (ii) a The molar ratio of P to V in the catalyst is (0.2-2) to 1. The preparation process of the catalyst comprises the following steps: will V 2 O 5 Sequentially dissolve in C 6 H 12 O 6 Heating the solution (fructose solution or glucose solution) and phosphoric acid solution at high temperature to obtain a mixed solution, centrifuging the mixed solution to obtain a precipitate, and drying, roasting and grinding the precipitate to obtain vanadium-phosphorus-oxygen active component powder. The catalytic activity and the sulfur resistance of the catalyst can be optimally matched by strictly controlling the proportion of each reaction raw material and each reaction process parameter (heating temperature, sintering temperature, drying time, sintering time, stirring time and the like).
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment comprises the following steps:
the method comprises the following steps: preparation of the active ingredient
(1) Will V 2 O 5 And C 6 H 12 O 6 Dissolving a reducing agent in water, uniformly stirring, heating at the high temperature of 180 ℃ for 12 hours to obtain a mixed solution, centrifuging the mixed solution to obtain a solid, drying the solid, and grinding to obtain powder;
(2) Dissolving the powder obtained in the step (1) in a phosphoric acid solution, heating the solution at the high temperature of 160 ℃ for 24 hours to obtain a mixed solution, and then adding the mixed solutionCentrifuging, drying, and grinding to obtain active component precursor, wherein V 2 O 5 Neutralization of vanadium and H 3 PO 4 The mole ratio of the middle phosphorus (0.2-2.0) is 1;
(3) Calcining the active component precursor obtained in the step (2) at 400 ℃ in a nitrogen atmosphere to obtain active component powder;
step two: preparation of the catalyst
(1) Weighing a certain amount of the active components obtained in the step one, dissolving the active components in distilled water, and adding nitrogen-doped modified TiO 2 The carrier enables the mass percentage of the active component in the catalyst to be 7-15%;
(2) And (2) stirring the mixed solution obtained in the step (1) at room temperature for 1-3 h, then sequentially carrying out constant-temperature water bath, drying and roasting, and then grinding to obtain a target product, namely supported vanadium-phosphorus oxapolyacid catalyst powder. Wherein the temperature of the constant-temperature water bath is 80-95 ℃, and the time is 3-8 h; the drying temperature is 100-110 ℃, and the drying time is 3-6 h; the roasting temperature is 300-450 ℃, and the roasting time is 3-5 h.
In the technology of catalytic oxidation of VOCs, the redox performance, the acid site and the oxygen vacancy of the catalyst play an important role in the reaction process. Heteropolyacids, which are oxygen-containing polyacids composed of heteroatoms (such as P, si, fe, co, etc.) and polyatomic atoms (such as Mo, W, V, nb, ta, etc.) bridged by coordination of oxygen atoms in a certain structure, have the advantages of uniform-strength protonic acid, redox property, low-temperature activity, "pseudo-liquid phase" behavior, and adjustment of acid strength and redox property by changing the molecular composition thereof, are used in the field of catalysis. However, few studies on the catalytic oxidation of VOCs by using a heteropoly acid catalyst are currently conducted, and most studies are conducted on oxidative desulfurization or organic compound preparation by using a heteropoly acid catalyst.
For example, chinese patent CN111100137A, the name of the invention is: the patent relates to a method for catalyzing and oxidizing dicyclopentadiene by using supported heteropolyacid, which adopts a process for catalyzing and oxidizing dicyclopentadiene by using the supported heteropolyacid, and prepares dicyclopentadiene dioxide by using dicyclopentadiene as a raw material and hydrogen peroxide as an oxidant.
Based on the above problems, the present applicationThe inventors of the present invention have found through extensive experiments that volatile organic compounds are mainly oxidized by lattice oxygen, resulting in a decrease in the amount of lattice oxygen. Meanwhile, chemisorbed oxygen with higher mobility can provide consumed lattice oxygen through a series of migration and transformation. Because the heteropoly acid has stronger electron transmission capability and redox property and has stronger surface acidity and high-activity lattice oxygen and other characteristics, vanadium phosphorus oxygen is used as an active component, so that the redox property of the catalyst is enhanced, and the chemical adsorption oxygen (O) is increased α ) The amount of the catalyst also promotes the increase of B acid and L acid on the surface of the catalyst, so that the adsorption capacity of the catalyst and the effect of purifying toluene at low temperature can be effectively improved, and the catalyst also has stronger sulfur resistance.
Simultaneously, loading active component vanadium phosphorus oxygen on N-TiO 2 In addition, the specific surface area of the catalyst is increased, and the dispersibility of active particles is enhanced, so that the total number of active sites on the surface of the catalyst is increased, and the sulfur poisoning resistance of the catalyst can be effectively enhanced. Specifically, the specific analysis principle of the present invention is as follows:
firstly, the vanadium phosphorus oxygen of the invention belongs to heteropoly acid, and the heteropoly acid has stronger electron transmission capability and oxidation reduction property, and simultaneously has stronger surface acidity and characteristics of high active lattice oxygen and the like, so the vanadium phosphorus oxygen as an active component not only has stronger oxidation reduction property and surface acidity, but also can increase chemisorption oxygen (O) α ) Amount, oxidation of toluene to CO 2 Therefore, the catalyst has better effect of purifying toluene at low temperature.
Secondly, SO is generated during the reaction of low-temperature catalytic oxidation of VOCs 2 Is an important factor affecting the activity of the catalyst. SO 2 On the one hand occupying the active sites by competitive adsorption and on the other hand SO 2 Is oxidized into SO 3 Sulfate is formed, resulting in irreversible deactivation of the catalyst. SO (SO) 2 Belonging to the group of acid gases, SO can be suppressed by enhancing the surface acidity of the catalyst 2 Adsorption and surface sulfate formation. VPO itself contains a large amount of B acid and L acid sites, and V element forms B acid sites (V-OH) on one hand and VO formed by partial V element on the other hand 2+ Ions promote the formation of L acid sites, thereby improving the SO resistance of the catalyst 2 Of the cell.
For a further understanding of the present invention, reference will now be made in detail to the present embodiments of the invention.
Example 1
The preparation method of the supported vanadium phosphorus oxapolyacid catalyst of the embodiment is as follows:
the method comprises the following steps: preparation of the active ingredient
In the first step, 0.445g of fructose and 1.5gV were weighed 2 O 5 (C 6 H 12 O 6 /V 2 O 5 = 0.3) dissolving in 50mL of distilled water, stirring at normal temperature for 2h to obtain a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, heating at 180 ℃ for reaction for 12h, cooling the autoclave to room temperature, and centrifugally filtering to separate a black solid (V) 2 O 4 ) Then dried overnight at 80 ℃ and ground to a powder; and step two, according to the molar ratio of phosphorus to vanadium of 0.2:1 ratio of V to 2 O 4 Adding into phosphoric acid solution, stirring at room temperature for 2 hr to obtain mixed solution, adding into high pressure reactor, heating at 160 deg.C for 24 hr, cooling to room temperature, centrifuging, filtering to obtain blue solid, drying at 80 deg.C overnight, and grinding into powder; a third step of converting the powder obtained in the second step into N flowing at a temperature of 400 DEG C 2 (100mLmin -1 ) After calcining for 12h, an active component VPO is obtained and is marked as VPO (0.3) -P (0.2) 。
Step two: preparation of the support
First step, with CO (NH) 2 ) 2 As nitrogen source, according to TiO 2 And a N molar ratio of 98:2 ratio of anatase TiO 2 Dissolving urea in distilled water, stirring for 2h, evaporating to dryness in water bath at 85 deg.C, calcining in muffle furnace at 400 deg.C for 3h, and grinding into powder; secondly, cleaning the powder obtained in the first step by using dilute sulfuric acid and distilled water, and then drying the powder for 4 hours in a drying oven at the temperature of 105 ℃ to obtain a nitrogen modified titanium dioxide carrier which is marked as N-TiO 2 。
Step three: preparation of the catalyst
First, the VPO-P prepared in the first step (0.2) Dissolving the powder in distilled water, adding carrier N-TiO according to the ratio of the mass of the active component to the mass of the catalyst of 10 percent 2 (ii) a Secondly, stirring the solution obtained in the first step at room temperature for 1h, continuously stirring in a water bath at the temperature of 85 ℃ for 3h, drying at the temperature of 105 ℃ for 3h, finally calcining at the temperature of 350 ℃ for 3h, cooling and grinding into catalyst powder, which is recorded as 10VPO (0.3) -P (0.2) /N-TiO 2-350 。
Comparative example 1
The procedure of this comparative example is essentially the same as example 1 except that: the carrier adopts anatase TiO 2 The urea is not added for modification, and the preparation method comprises the following steps:
the method comprises the following steps: preparation of the active ingredient
First, 0.445g of fructose and 1.5g of V are weighed 2 O 5 (C 6 H 12 O 6 /V 2 O 5 = 0.3) dissolving in 50mL of distilled water, stirring at normal temperature for 2h to obtain a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, heating at 180 ℃ for reaction for 12h, cooling the autoclave to room temperature, and centrifugally filtering to separate a black solid (V) 2 O 4 ) Then dried overnight at 80 ℃ and ground into a powder; and step two, according to the molar ratio of phosphorus to vanadium of 0.2:1 ratio will be a certain amount of V 2 O 4 Adding into phosphoric acid solution, stirring at room temperature for 2 hr to obtain mixed solution, adding into high pressure reactor, heating at 160 deg.C for 24 hr, cooling to room temperature, centrifuging, filtering to obtain blue solid, drying at 80 deg.C overnight, and grinding into powder; a third step of converting the powder obtained in the second step into N which flows at a temperature of 400 DEG C 2 (100mLmin -1 ) Calcining for 12h to obtain active component VPO, and marking as VPO-P (0.2) 。
Step two: preparation of the catalyst
First, the VPO-P prepared in the first step (0.2) Dissolving the powder in distilled water, adding carrier TiO according to the mass ratio of the active component to the catalyst of 10% 2 (ii) a Secondly, stirring the solution obtained in the first step at room temperature for 1h, continuously stirring in a water bath at the temperature of 85 ℃ for 3h, drying at the temperature of 105 ℃ for 3h, finally calcining at the temperature of 350 ℃ for 3h, cooling and grinding into catalyst powder, which is recorded as 10VPO (0.3) -P (0.2) /TiO 2-350 。
Example 2
The method of this example is substantially the same as example 1 except that:
the method comprises the following steps: preparation of the active ingredient
In the first step, 0.445g of fructose and 1.5gV were weighed 2 O 5 (C 6 H 12 O 6 /V 2 O 5 = 0.3) dissolving in 50mL of distilled water, stirring at room temperature for 2h to obtain a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, heating at 180 ℃ for reaction for 12h, cooling the autoclave to room temperature, and centrifuging and filtering to separate a black solid (V) 2 O 4 ) Then dried overnight at 80 ℃ and ground to a powder; and step two, according to the molar ratio of phosphorus to vanadium of 0.8:1 ratio of V to 2 O 4 Adding the mixture into a phosphoric acid solution, stirring for 2 hours at normal temperature to obtain a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, heating and reacting for 24 hours at 160 ℃, cooling the high-pressure sterilized bacteria to the room temperature, performing centrifugal filtration separation to obtain a blue solid, drying at 80 ℃ overnight, and grinding into powder; a third step of converting the powder obtained in the second step into N which flows at a temperature of 400 DEG C 2 (100mLmin -1 ) After the intermediate calcination is carried out for 12 hours, an active component VPO is obtained and is marked as VPO-P (0.2) 。
Step two: preparation of the support
First step, with CO (NH) 2 ) 2 As nitrogen source, according to TiO 2 And N in a molar ratio of 98:2 ratio of anatase TiO 2 Dissolving urea in distilled water, stirring for 2h, evaporating to dryness in water bath at 85 deg.C, calcining in muffle furnace at 400 deg.C for 3h, and grinding into powder; in the second step, the first step is to remove the waste water,washing the powder in the first step with dilute sulfuric acid and distilled water, and drying in a drying oven at 105 ℃ for 4h to obtain the nitrogen modified titanium dioxide carrier which is marked as N-TiO 2 。
Step three: preparation of the catalyst
First, the VPO-P prepared in the first step (0.2) Dissolving the powder in distilled water, adding carrier N-TiO according to the ratio of the mass of the active component to the mass of the catalyst of 10 percent 2 (ii) a Secondly, stirring the solution obtained in the first step at room temperature for 1h, continuously stirring in a water bath at the temperature of 85 ℃ for 3h, drying at the temperature of 105 ℃ for 3h, calcining at the temperature of 350 ℃ for 3h, cooling, and grinding into catalyst powder, wherein the catalyst powder is marked as 10VPO (0.3) -P (0.8) /N-TiO 2-350 。
Example 3
The preparation method of the supported vanadium phosphoheteropolyacid catalyst of the present embodiment is basically the same as that of the example 1, and mainly differs from the method in that the molar ratio of phosphorus to vanadium of the catalyst is 1.2:1, as 10VPO (0.3) -P (1.2) /N-TiO 2-350 。
Example 4
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment is basically the same as that of the embodiment 1, and mainly comprises the following steps of: 1, as 10VPO (0.3) -P (1.6) /N-TiO 2-350 。
Example 5
The preparation method of the supported vanadium phosphoheteropolyacid catalyst of the present embodiment is basically the same as that of the example 1, and mainly differs from the method in that the molar ratio of phosphorus to vanadium of the catalyst is 2:1, as 10VPO (0.3) -P (2) /N-TiO 2-350 。
Example 6
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment basically has the same steps as the embodiment 1, and mainly has the difference that the loading amount of the active component of the catalyst is 7%, which is marked as 7VPO (0.3) -P (0.2) /N-TiO 2-350 。
Example 7
The preparation method of the supported catalyst for catalytic oxidation of VOCs by vanadium phosphorus oxygen in this example is substantially the same as that of example 1, and mainly differs from example 1 in that the loading amount of the active component of the catalyst is 13%, which is recorded as 13VPO (0.3) -P (0.2) /N-TiO 2-350 。
Example 8
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment basically has the same steps as the embodiment 1, and mainly has the difference that the loading amount of the active component of the catalyst is 15 percent, which is recorded as 15VPO (0.3) -P (0.2) /N-TiO 2-350 。
Example 9
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment basically has the same steps as the embodiment 1, and mainly has the difference that the calcination temperature of the catalyst is 300 ℃, which is recorded as 10VPO (0.3) -P (0.2) /N-TiO 2-300 。
Example 10
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment basically has the same steps as the embodiment 1, and mainly has the difference that the calcination temperature of the catalyst is 400 ℃, and is marked as 10VPO (0.3) -P (0.2) /N-TiO 2-400 。
Example 11
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment basically has the same steps as the embodiment 1, and mainly has the difference that the calcination temperature of the catalyst is 450 ℃, which is marked as 10VPO (0.3) -P (0.2) /N-TiO 2-450 。
Example 12
The preparation method of the supported vanadium phosphorus oxapolyacid catalyst of the embodiment is as follows:
the method comprises the following steps: preparation of the active ingredient
In the first step, 0.297g of fructose and 1.5g of V are weighed 2 O 5 (C 6 H 12 O 6 /V 2 O 5 = 0.2) is dissolved in 50mL of distilled water and stirred for 2h at normal temperature to obtain mixed liquid, the mixed liquid is poured into a high-pressure reaction kettle and is heated and reacted for 12h at 180 ℃,after the autoclaving bacteria had cooled to room temperature, the black solid (V) was separated by centrifugal filtration 2 O 4 ) Then dried overnight at 80 ℃ and ground into a powder; and step two, according to the molar ratio of phosphorus to vanadium of 0.2:1 ratio will be a certain amount of V 2 O 4 Adding the mixture into a phosphoric acid solution, stirring for 2 hours at normal temperature to obtain a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, heating and reacting for 24 hours at 160 ℃, cooling the high-pressure sterilized bacteria to the room temperature, performing centrifugal filtration separation to obtain a blue solid, drying at 80 ℃ overnight, and grinding into powder; a third step of converting the powder obtained in the second step into N which flows at a temperature of 400 DEG C 2 (100mLmin -1 ) Calcining for 12h to obtain active component VPO, and marking as VPO-P (0.2) 。
Step two: preparation of the support
First, with CO (NH) 2 ) 2 As nitrogen source, according to TiO 2 And a N molar ratio of 98:2 ratio of anatase TiO 2 Dissolving urea in distilled water, stirring for 2h, evaporating to dryness in water bath at 85 deg.C, calcining in muffle furnace at 400 deg.C for 3h, and grinding into powder; secondly, cleaning the powder obtained in the first step by using dilute sulfuric acid and distilled water, and then drying the powder for 4 hours in a drying oven at the temperature of 105 ℃ to obtain a nitrogen modified titanium dioxide carrier which is marked as N-TiO 2 。
Step three: preparation of the catalyst
The first step is to subject the VPO-P obtained in the first step to (0.2) Dissolving the powder in distilled water, adding carrier N-TiO according to the ratio of the mass of the active component to the mass of the catalyst of 10 percent 2 (ii) a Secondly, stirring the solution obtained in the first step at room temperature for 1h, continuously stirring in a water bath at the temperature of 85 ℃ for 3h, drying at the temperature of 105 ℃ for 3h, calcining at the temperature of 350 ℃ for 3h, cooling, and grinding into catalyst powder, wherein the catalyst powder is marked as 10VPO (0.2) -P (0.2) /N-TiO 2-350 。
Example 13
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment is basically the same as that of the embodiment 12, and mainly differs from the catalyst C 6 H 12 O 6 /V 2 O 5 =0.4, noted as 10VPO (0.4) -P (0.2) /N-TiO 2-350 。
Example 14
The preparation method of the supported vanadium phosphorus oxo heteropoly acid catalyst of the embodiment is basically the same as that of the embodiment 12, and mainly differs from the catalyst C 6 H 12 O 6 /V 2 O 5 =0.5, noted as 10VPO (0.5) -P (0.2) /N-TiO 2-350 。
Performance testing of catalysts
A fixed bed reactor having a diameter of 8mm was charged with 0.4g of the catalyst of preparation examples 1 to 14 made of the catalyst, and N 2 As carrier gas, the space velocity is controlled to be 15000h -1 Controlling the concentration of toluene at inlet to 110ppm 2 The toluene conversion was measured at a concentration of 10% by volume at a temperature in the range of 150 ℃ to 350 ℃ and the results are shown in Table 1.
The activity tests at different temperatures of the catalysts of the examples in Table 1 show that in the absence of SO 2 And H 2 In the presence of O steam, the conversion rate of toluene in examples 1-11 is kept between 50% and 100% in the temperature range of 200-300 ℃, the toluene removal efficiency is better, and the catalyst activity of example 1 is optimal by examining the influence of the phosphorus-vanadium molar ratio on the catalyst activity and the influence of other process parameters (heating temperature, heating time, active component loading amount, calcination temperature and the like). It should be noted that the other examples are inferior to example 1 in effect, but are still superior to the conventional catalysts in effect. In addition, by combining the comparative example 1 and the example 1, the low-temperature activity of the obtained catalyst can be improved by adding the urea modified carrier, the temperature window of the catalyst can be widened, the stability of the catalytic activity of the catalyst at different temperatures can be improved, and the catalytic effect of the catalyst can be further ensured.
Example 15
A fixed-bed reactor having a diameter of 8mm was charged with 0.4g of the catalyst prepared in example 1, as N 2 As carrier gas, the space velocity is controlled to be 15000h -1 Controlling the concentration of toluene at inlet to 110ppm 2 Volume concentration of 10%, reaction temperatureAt 220 ℃ SO was investigated 2 Influence on toluene conversion.
When 200ppm of SO is introduced 2 There was a certain reduction in catalyst activity and the analytical reason may be a little SO 2 Competitive adsorption with toluene molecules occurs, but the efficiency can still be kept at about 90%, which shows that the catalyst still keeps good toluene purification activity, therefore, the catalyst has stronger SO resistance 2 Ability of catalyst to resist SO 2 The activity diagram of (A) is shown in FIG. 1, and the SO resistance of the catalysts obtained in other examples 2 The poisoning ability is similar to that of the present embodiment, and is slightly inferior to that of the present embodiment.
Table 1 comparison of the activity of the product catalysts of the examples of the invention at different temperatures
Claims (9)
1. A supported vanadium phosphorus oxapolyacid catalyst is characterized in that: the catalyst takes vanadium-phosphorus-oxygen as an active component and adopts N-doped modified TiO 2 Is used as a carrier, and the mass of the active component is 7-15% of the total mass of the catalyst.
2. The method for preparing a supported vanadium phosphoheteropolyacid catalyst according to claim 1, characterized by comprising the steps of:
the method comprises the following steps: preparation of the active ingredient
(1) Will C 6 H 12 O 6 And V 2 O 5 According to the molar ratio of 0.2-0.5: 1, dissolving in water, stirring uniformly, heating at the high temperature of 180 ℃ for 12 hours to obtain a mixed solution, centrifuging the mixed solution to obtain a solid, drying the solid, and grinding to obtain powder;
(2) Dissolving the powder obtained in the step (1) in phosphorusHeating the acid solution at 160 deg.C for 24 hr to obtain a mixed solution, centrifuging, drying, and grinding to obtain active component precursor, wherein H is 3 PO 4 Phosphorus and V 2 O 5 The molar ratio of vanadium in the vanadium is 0.2-2.0;
(3) Roasting the active component precursor obtained in the step (2) in a nitrogen atmosphere to obtain active component powder;
step two: preparation of the catalyst
(1) Dissolving the active component obtained in the step one in distilled water, and then adding TiO 2 The carrier enables the mass percentage of the active component in the catalyst to be 7-15%;
(2) And (2) stirring the mixed solution in the step (1), then sequentially carrying out constant-temperature water bath, drying and roasting, and then grinding to obtain a target product, namely supported vanadium-phosphorus oxapolyacid catalyst powder.
3. The method for preparing a supported vanadium phosphorus oxo heteropoly acid catalyst according to claim 2, wherein: the TiO is 2 The carrier is nitrogen-doped modified anatase TiO 2 And (3) a carrier.
4. The method for preparing a supported vanadium phosphoheteropolyacid catalyst according to claim 2, wherein: the stirring in the first step and the second step refers to: stirring for 1-3 h at room temperature, raising the temperature to 70-85 ℃, and then stirring in a thermostatic water bath until the mixture is evaporated to dryness.
5. The method for preparing a supported vanadium phosphoheteropolyacid catalyst according to claim 2, wherein: the drying temperature in the first step is 80 ℃, the drying time is 10-12 h, the drying temperature in the second step is 100-110 ℃, and the drying time is 3-6 h.
6. The method for preparing a supported vanadium phosphoheteropolyacid catalyst according to claim 2, wherein: the roasting temperature in the first step and the roasting temperature in the second step are both 300-450 ℃, and the roasting time is 3-5 h.
7. The method for preparing a supported vanadium phosphoheteropolyacid catalyst according to claim 2, wherein: the mol ratio of phosphorus to vanadium in the first step is 0.2.
8. Use of the supported vanadium phosphorus oxapolyacid catalyst of claim 1 in the catalytic oxidation of VOCs.
9. The use of a supported vanadium phosphorus oxapolyacid catalyst as claimed in claim 8, wherein said VOCs are toluene.
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