CN110201672B - ZnO/Fe-Cu-M composite catalyst for degrading VOCs (volatile organic compounds), and preparation method and application thereof - Google Patents
ZnO/Fe-Cu-M composite catalyst for degrading VOCs (volatile organic compounds), and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 230000000593 degrading effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012855 volatile organic compound Substances 0.000 title abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 67
- 239000011787 zinc oxide Substances 0.000 claims description 30
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005119 centrifugation Methods 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
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- 230000003197 catalytic effect Effects 0.000 abstract description 16
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- 238000010521 absorption reaction Methods 0.000 description 2
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- 239000002250 absorbent Substances 0.000 description 1
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- 239000002649 leather substitute Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229920001220 nitrocellulos Polymers 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention discloses a composite catalyst ZnO/Fe-Cu-M composite catalyst for degrading VOCs, which is prepared by taking nano ZnO as a carrier and loading an active component Fe-Cu-M through an alcohol heating method, wherein M is Zr or Ce, and the molar ratio of Fe to Cu to M is 0.5-2: 0.5-2. The composite catalyst shows very low-temperature and high-efficiency catalytic efficiency, and can better catalyze and degrade VOCs waste gas. The invention also discloses a preparation method of the composite catalyst, the preparation process is simple and easy to operate, the yield of the catalyst is high, the price of the used raw materials is low, and the mineral deposits exist in large quantity in China, so that the composite catalyst has a good industrial application prospect. The invention also discloses application of the ZnO/Fe-Cu-M composite catalyst in catalytic degradation of butyl acetate waste gas, has a very high-efficiency removal effect on butyl acetate waste gas, and shows very low-temperature high-efficiency catalytic efficiency.
Description
Technical Field
The invention relates to the field of catalysts for VOCs waste gas treatment, in particular to a ZnO/Fe-Cu-M composite catalyst for degrading VOCs waste gas and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) with low boiling point and Volatile at normal temperature and low temperature, wherein the types of the Volatile Organic Compounds comprise hundreds of types, and the Volatile Organic Compounds are important pollution components forming atmospheric composite pollution. Even low concentrations of organic waste gases can cause varying degrees of harm to human health if exposed to prolonged periods of time. The ecological environment is also negatively influenced. With the improvement of requirements of people on ecological environment and living quality, people pay more and more attention to the quality of the atmospheric environment. The degradation and treatment of organic waste gases is becoming more and more urgent.
Butyl acetate, a type of VOCs, is an excellent organic solvent and is widely used in nitrocellulose varnishes and as a solvent in artificial leather, textile and plastic processing. It is a great hazard to the respiratory system and eyes, and can irritate these parts. Inadvertent inhalation of high concentrations can lead to tearing, sore throat, cough, chest distress, shortness of breath, and the like, as well as skin irritation.
Since most VOCs are harmful to the environment and human health, many techniques are available for controlling VOC emissions, traditional methods such as adsorption, absorption, incineration, photocatalytic oxidation, and catalytic combustion. However, these methods have some disadvantages, such as the condensing method has poor effect on treating the exhaust gas with high volatility; the absorption method has low treatment cost and good effect, but the post-treatment cost of the absorbent is high, and secondary pollution is easily caused; biological methods are not well suited for treating biologically toxic organic waste gases. Low temperature catalytic oxidation is considered one of the most promising routes to reduce VOCs due to its high efficiency and low cost, with the key issue being the availability of high performance catalysts. Therefore, it is desirable to make low temperature, high activity catalysts to reduce the high energy consumption for removing low concentrations of VOCs.
In catalytic combustion technology, the core of catalytic combustion is the activity and stability of the catalyst. The quality of the catalyst performance has a decisive influence on the catalytic efficiency and on the reduction of the operating costs. The active component plays a decisive role in the properties of the catalyst, and the catalyst can be divided into a noble metal catalyst and a non-noble metal catalyst according to the difference of the active components of the catalyst. At present, precious metals are used in low-temperature catalysts more, the cost is higher, the resources are limited, and great limitation is generated in industrial application. Non-noble metal research has become one of the hotspots in recent years; there have been many studies on noble metal-non-noble metal combined catalysts, and also on non-noble metal multi-component composite catalysts. The noble metal is mainly Au, Pt, Pd, etc., and the non-noble metal is mainly non-noble metal oxide of Cu, Mn, Cr, Co, Ce, Fe, etc. The catalyst prepared by two or more than two non-noble metal oxides has better low-temperature catalytic activity and is an important development direction of the VOCs catalytic combustion catalyst.
Disclosure of Invention
The invention aims to provide a ZnO/Fe-Cu-M composite catalyst for degrading VOCs, which shows very low-temperature high-efficiency catalytic efficiency and can better catalyze and degrade VOCs waste gas.
The invention also aims to provide a preparation method of the ZnO/Fe-Cu-M composite catalyst, which is simple, efficient, easy to control and has strong industrial production application prospect.
The invention also aims to provide the application of the ZnO/Fe-Cu-M composite catalyst in catalytic degradation of butyl acetate waste gas, and the ZnO/Fe-Cu-M composite catalyst can show extremely strong catalytic activity in the application process and improve the catalytic degradation efficiency.
A ZnO/Fe-Cu-M composite catalyst for degrading VOCs is prepared by taking nano ZnO as a carrier and loading an active component Fe-Cu-M by an alcohol-thermal method; wherein M is Zr or Ce, and the molar ratio of Fe to Cu is 0.5-2: 0.5-2.
The invention takes nano ZnO with larger specific surface area and larger specific surface energy as a carrier, and the composite catalyst prepared by loading specific active components is loaded by an alcohol heating method, so that the crystal grains of the obtained powder are completely developed by the alcohol heating method, and the obtained catalyst is ensured to have small granularity and uniform distribution; the loaded oxide with specific active components has good degradation capability on VOCs, and Fe on the surface of ZnO3+、Cu2+、Zr3+And surface oxygen has good catalytic activity on VOCs.
Preferably, the ZnO/Fe-Cu-M composite catalyst for degrading VOCs has Fe, Cu and M in an atomic molar ratio of 0.5-2, 0.5-1.
The invention also discloses a preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading VOCs, which comprises the following steps:
(1) dissolving ferric nitrate, cupric nitrate and zirconium nitrate/cerous nitrate in ethanol, heating and stirring, then adding nano zinc oxide powder, and continuously stirring to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 150-170 ℃, carrying out alcohol-thermal reaction for 1-3 h, centrifuging to obtain a precipitate, filtering, drying, heating, calcining, and grinding to obtain the composite catalyst.
In the step (1), the temperature of heating and stirring is 30-80 ℃, the stirring time is 10-30 min, and the stirring is continued for 5-10 min after the nano zinc oxide powder is added. Under the stirring temperature and the stirring time, the solution can be uniformly mixed, and the next reaction is facilitated.
In the step (1), the adding amount of the nano zinc oxide powder is 10-14 g/mol based on the molar weight of Fe atoms. The catalyst obtained by structure modification can be directly used for degrading VOCs by selecting proper dosage and has better degradation effect.
In the step (2), preferably, the temperature rise process of the alcohol thermal reaction is as follows: keeping the temperature at 150 ℃ for 1h, keeping the temperature at 160 ℃ for 1h, and keeping the temperature at 170 ℃ for 1 h. The alcohol thermal reaction utilizes specific programmed gradient temperature rise, so that the crystal grain of the catalyst powder obtained by the reaction is more completely developed, the granularity is smaller, and the distribution is more uniform, thereby leading the catalyst to have ordered structure and stable character.
In the step (2), the rotating speed of the centrifugation is 5000-20000 r/min, and the solid-liquid separation in the reaction liquid can be ensured within the rotating speed range.
And (2) washing by using ethanol or ethylene glycol to remove impurities, and then heating to 80-170 ℃ for drying.
In the step (2), the calcining temperature is 300-600 ℃, and the calcining time is 2-4 h.
Preferably, the calcination temperature is 450 ℃, and the catalyst for low-temperature catalytic combustion prepared at the preferred calcination temperature has the highest catalytic efficiency, so that the degradation rate of the catalyst on butyl acetate waste gas is improved.
The invention also provides a method for degrading butyl acetate waste gas, the ZnO/Fe-Cu-M composite catalyst is placed in a quartz tube in a tubular resistance furnace to catalyze butyl acetate waste gas to carry out degradation reaction, the reaction temperature is 25-280 ℃, and the space velocity is 9000-72000 h-1。
In the application process, when the concentration of the butyl acetate waste gas is 200-1500 ppm, the dosage of the ZnO/Fe-Cu-M composite catalyst is 200-800 mg.
Compared with the prior art, the invention has the following beneficial effects:
1) the ZnO/Fe-Cu-M composite catalyst has small grain diameter, high specific surface area and low-temperature high-efficiency catalytic efficiency, wherein the Fe-based metal has low price, rich mineral reserves and high cost performance, and is beneficial to popularization.
2) The preparation method has the advantages of simple preparation process, large catalyst output and very high-efficiency removal effect on organic waste gas (butyl acetate), wherein ZnO/Fe-Cu-Zr is used for butyl acetate and is at 1500ppExhibits very low-temperature and high-efficiency catalytic efficiency under the condition of butyl acetate concentration of less than m, wherein T90＝200℃。
Detailed Description
The following examples are provided only for illustrating the present invention in detail, and the reagents used in the following examples are all analytical grade.
Example 1
(1) Uniformly mixing 0.07mol/L ferric nitrate/ethanol solution, 0.07mol/L cupric nitrate/ethanol solution and 0.07mol/L zirconium nitrate/ethanol solution to obtain 100ml reaction solution, keeping water bath stirring at the temperature of 80 ℃ in the mixing process, and continuously adding ethanol to keep the total amount of the mixed solution unchanged; and then putting the reaction solution into a magnetic stirrer, slowly adding 1g of nano ZnO powder, slowly increasing the stirring speed, and stirring for 8min to obtain a mixed solution.
(2) And (2) transferring the mixed solution obtained in the step (1) to a 150ml hydrothermal kettle, placing the hydrothermal kettle in an oven for alcohol thermal reaction, heating to 150 ℃, preserving heat for 1h, heating to 160 ℃, preserving heat for 1h, and continuing heating to 170 ℃ and preserving heat for 1 h.
(3) Putting the product obtained in the step (2) into a centrifuge 9500r/min, centrifuging, pouring out supernatant, washing the residual solid part with absolute ethyl alcohol for three times, performing suction filtration, and drying in an oven at 120 ℃; grinding the dried product, placing the ground product in a muffle furnace, heating to 450 ℃, calcining for 3h, and further grinding to obtain nano-modified ZnO powder, namely the ZnO/Fe-Cu-Zr composite catalyst.
Example 2
The same method as that described in example 1, except that the calcination at a temperature of 450 ℃ in step (3) was replaced by calcination at a temperature of 500 ℃, and the obtained nano-modified ZnO powder was the ZnO/Fe-Cu-Zr composite catalyst.
Performance testing
The test method comprises the following steps: the method comprises the steps of taking 800mg of each of the catalysts obtained in the example 1 and the example 2, putting the catalysts into a reactor for fixation, respectively introducing butyl acetate waste gas with certain concentration and the same concentration and space velocity, passing the waste gas through a fixed reaction bed containing the catalyst, and introducing gas chromatography to detect the removal rate of butyl acetate.
Wherein the reaction gas comprises the following components:
200-1500 ppm of butyl acetate mixed gas, wherein the carrier gas is 79% of nitrogen and 21% of oxygen, the relative humidity of the mixed gas is 70%, the flow rate of the reaction mixed gas is 70mL/min, and the space velocity is 9000h-1. The activity evaluation temperature is 25-280 ℃, different temperature intervals are set, and the conversion efficiency of the catalyst for reducing butyl acetate is analyzed, and the results are shown in table 1.
TABLE 1 degradation rate of ZnO/Fe-Cu-Zr composite catalyst on butyl acetate
As can be seen from Table 1, the composite catalyst has good catalytic effects on butyl acetate at normal temperature and low temperature. Catalytic effect at ambient temperature and T50Compared with organic waste gas with the same molecular weight, the organic waste gas has great improvement.
Claims (8)
1. A preparation method of a ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate is characterized in that the catalyst is prepared by taking nano ZnO as a carrier and loading an active component Fe-Cu-M by an alcohol-thermal method; wherein M is Zr or Ce, and the molar ratio of Fe to Cu is 0.5-2: 0.5-2;
(1) dissolving ferric nitrate, cupric nitrate and zirconium nitrate/cerous nitrate in ethanol, heating and stirring, then adding nano zinc oxide powder, and continuously stirring to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 150-170 ℃, carrying out alcohol-thermal reaction for 1-3 h, centrifuging to obtain a precipitate, washing, drying, heating, calcining, and grinding to obtain the composite catalyst.
2. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein the molar ratio of Fe to Cu to M is 0.5-2: 0.5-1.
3. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein in the step (1), the temperature is increased and the stirring is carried out at 30-80 ℃ for 10-30 min, and the stirring is continued for 5-10 min after the nano zinc oxide powder is added.
4. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein in the step (1), the adding amount of the nano zinc oxide powder is 10-14 g/mol based on the molar amount of Fe atoms.
5. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein in the step (2), the temperature rise process of the alcohol thermal reaction is as follows: keeping the temperature at 150 ℃ for 1h, keeping the temperature at 160 ℃ for 1h, and keeping the temperature at 170 ℃ for 1 h.
6. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein in the step (2), the rotation speed of the centrifugation is 5000-20000 r/min.
7. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein in the step (2), the ZnO/Fe-Cu-M composite catalyst is washed by ethanol or ethylene glycol, and then is heated to 80-170 ℃ for drying.
8. The preparation method of the ZnO/Fe-Cu-M composite catalyst for degrading butyl acetate according to claim 1, wherein in the step (2), the calcination temperature is 300-600 ℃, and the calcination time is 2-4 h.
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