CN109865535B - Metastable state cerium oxide or cerium-zirconium solid solution nano material - Google Patents
Metastable state cerium oxide or cerium-zirconium solid solution nano material Download PDFInfo
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Abstract
The invention provides a metastable state cerium oxide or cerium-zirconium solid solution nano material, and the key technology for preparing the material is to ensure the formation of oxide particles with high crystallinity and avoid long-time high-temperature roasting. The invention utilizes the high temperature generated by flame combustion to rapidly decompose the precursor into oxide particles, and simultaneously introduces a large amount of air to rapidly move the generated particles out of a high-temperature region and extremely rapidly cool the particles, so that the high-temperature sintering stabilization process is avoided, and the oxide is fixed in a metastable state. The surface of the prepared metastable cerium oxide or cerium-zirconium solid solution nano material has a large amount of active oxygen, no or a small amount of oxygen vacancies, and lattice oxygen is in a metastable state and can be converted into a stable cerium-zirconium solid solution if being roasted at high temperature for a long time.
Description
Technical Field
The invention relates to a metastable cerium oxide or cerium-zirconium solid solution nano material, in particular to a cerium oxide or cerium-zirconium solid solution, which is prepared by extracting oxides which do not reach a stable state in the process from the initial formation to the stabilization of oxide particles. The key technology is to ensure the formation of oxide particles with high crystallinity and avoid long-time high-temperature roasting. The invention utilizes the high temperature generated by flame combustion to rapidly decompose the precursor into oxide particles, and simultaneously introduces a large amount of air to rapidly move the generated particles out of a high-temperature region and extremely rapidly cool the particles, so that the high-temperature sintering stabilization process is avoided, and the oxide is fixed in a metastable state. The surface of the material has a large amount of active oxygen, no or a small amount of oxygen vacancies, lattice oxygen is in a metastable state, and if the material is roasted at high temperature for a long time, atomic rearrangement can occur to convert the material into a stable cerium-zirconium solid solution.
Background
The nano material and the nano catalyst have important functions in many fields related to the national civilization, such as chemical industry, materials, energy, environmental protection and the like. In the redox reaction, the active oxygen in the oxide nano material determines the redox capability of the oxide nano material, so that the activation capability of the oxide nano material on oxygen is influenced, and therefore, the development of a preparation method for preparing the nano material with a large amount of active oxygen has important significance. The traditional preparation methods, such as the traditional impregnation method, the precipitation method, the hydrothermal synthesis method, the ball milling method, the chemical reduction method and the like, can not avoid the subsequent high-temperature heat treatment, and the heat treatment procedure can cause the atoms to be rearranged and lose active oxygen species. But if the high-temperature heat treatment is not carried out, a better oxide crystal form cannot be formed. The flame combustion method adopted by the invention is different from the traditional method, the precursor solution is decomposed in high-temperature flame, the decomposition temperature can reach 1000-2000 ℃, and oxide crystals with high crystallinity are ensured to be formed. Meanwhile, a large amount of protective gas quickly removes the generated oxide particles out of a flame high-temperature area, and the temperature is quickly reduced, so that the particles are prevented from being roasted at high temperature for a long time, the contradiction is just solved, the oxide is fixed in a metastable state, and more active oxygen can be provided.
Disclosure of Invention
The invention provides a metastable state cerium oxide or cerium-zirconium solid solution nano material which is characterized by being prepared by the following steps: 1) preparing a precursor solution: stirring and mixing a cerium precursor and a solvent to form a precursor solution; or according to the composition of the cerium-zirconium solid solution, stirring and mixing the cerium precursor, the zirconium precursor and the solvent; forming a precursor solution; 2) preparation of a sample: igniting the mixed gas of methane and oxygen to form flame, injecting the precursor solution prepared in the step 1) into the flame by using a constant flow pump for combustion, and simultaneously blowing air to the flame area to bring the combustion products out of the flame area. 3) Collecting a sample: the device comprises a flame area, a cylinder body, a vacuum pump, circulating cooling water and a filter paper, wherein two ends of the cylinder body are opened at one side of the flame area, one opening end of the cylinder body is covered with glass fiber filter paper, the side, away from the cylinder body, of the glass fiber filter paper is provided with the vacuum pump, an air inlet of the vacuum pump faces the glass fiber filter paper, the other opening end of the cylinder body faces the flame area, the air flowing direction of the cylinder body is towards the other opening end face of the cylinder body, the vacuum pump is used for assisting combustion products to rapidly leave the flame area to stop on the glass fiber filter paper, the circulating cooling water is arranged around the glass fiber filter paper, and the filter paper is taken down to collect a sample after preparation is finished. The precursor solution is injected into the flame through the pipeline for combustion, and the outlet of the pipeline is positioned in the middle of the flame. In the step 1), the cerium precursor is a compound capable of being dissolved in an organic solvent, preferably one or more of cerium nitrate, ammonium cerium nitrate, cerium sulfate, cerium chloride, cerium carbonate, cerium oxalate, cerium acetate and cerium acetylacetonate; in the step 1), the zirconium precursor is a compound capable of being dissolved in an organic solvent, preferably one or more of zirconium nitrate, zirconyl nitrate, zirconium n-propoxide, zirconium acetate, zirconium acetylacetonate, zirconium oxychloride and n-butyl zirconium; the solvent in the step 1) is a combustible organic solvent, preferably one or more than two of methanol, ethanol, xylene and organic acid. The combustion gas required by flame combustion is a mixed gas of methane and oxygen, the mixed gas is sprayed out from a nozzle with the diameter of 1-10mm, and the flow rates of the methane and the oxygen are both 0.1-5L/min; the speed of pumping the solution into the flame is 0.1-20 ml/min; the flame ignites the organic solution, the precursor compounds of each component are decomposed at the high temperature of the flame to form oxide particles, the formed oxide particles leave a flame area under the drive of air, the air is blown to the whole flame area from one side of the flame by an air distribution plate with uniformly distributed air through holes on the surface, the sum of the radial cross-sectional areas of the air through holes on the air distribution plate is 0.1-10 square centimeters, the air flow is 2-20L/min, circulating cooling water is arranged around the glass fiber filter paper, and the temperature of a particle sample reaching the glass fiber filter paper is 20-70 ℃. The composition of the combustion products is adjustable, wherein the molar percentage of zirconium is 0-99%; the total concentration of the cerium precursor and the zirconium precursor in the precursor solution is 0.1-1 mol/L.
The surface of the metastable state cerium oxide or cerium zirconium solid solution nano material prepared by the invention has a large amount of active oxygen, no or a small amount of oxygen vacancies exist, and lattice oxygen is in a metastable state. If the nano material is roasted under the conditions that the temperature is more than 500 ℃ and the time is more than 1 hour, atomic rearrangement can occur, active oxygen is reduced, and the nano material is converted into a stable cerium oxide or cerium-zirconium solid solution.
The metastable state cerium oxide or cerium zirconium solid solution nano material prepared by the invention can be used as a catalyst or a catalyst carrier and used in reactions containing oxidation-reduction cycles, such as CO oxidation, NO oxidation, NOx reduction and the like. The carrier may carry one or more active metals selected from Au, Pt, Cu, Rh, Pd, Fe, Co, Mn, V, etc. The metastable cerium oxide or cerium-zirconium solid solution can provide a large amount of active oxygen, promote the activation of the oxygen in the oxidation-reduction reaction and show higher activity.
The invention has the advantages that: (1) the flame combustion method combines high-temperature thermal decomposition and instant quenching, can ensure the generation of high-crystallinity oxides, and can avoid subsequent high-temperature roasting to enable the oxides to stay in a metastable state with a large amount of active oxygen. (2) The surface of the metastable cerium-zirconium solid solution material has a large amount of active oxygen and no or a small amount of oxygen vacancies, so that a large amount of active oxygen can be provided in the catalytic oxidation reaction, the activation of oxygen is promoted, and higher activity is shown. (3) The method has universality, can be applied to the preparation of one or more components of metal oxide nanoparticles, and improves the active oxygen supply capacity of the metal oxide.
Drawings
FIG. 1 shows X-ray diffraction patterns and lattice parameter comparisons between cerium oxide and cerium-zirconium solid solutions prepared by flame combustion (examples 1 to 4) and coprecipitation (comparative examples 1 to 4).
FIG. 1 (a) is an X-ray diffraction pattern of a co-precipitation-prepared cerium oxide and a cerium-zirconium solid solution of different composition (comparative examples 1 to 4); (b) x-ray diffraction patterns of cerium oxide prepared for flame combustion and cerium-zirconium solid solutions of different compositions (examples 1-4); (c) comparing the lattice parameters of the nano materials prepared by the two methods; (d) the cerium-zirconium solid solution with the zirconium content of 75 percent prepared by the two methods has X-ray diffraction patterns before and after being roasted for 30 hours at 800 ℃ and the particle size calculated by the equation. As can be seen from FIG. 1, the cerium oxide and the cerium zirconium solid solution prepared by the two methods have higher crystallinity and the same lattice parameters, which shows that the cerium oxide and the cerium zirconium solid solution have the same crystal phase structure, and the nano material prepared by the invention is the cerium oxide and the cerium zirconium solid solution, and the cerium zirconium ratio is adjustable. In addition, fig. 1(d) illustrates that the cerium-zirconium solid solution prepared by the coprecipitation method in the comparative example is aggregated by high-temperature firing, resulting in the growth of particles, whereas the cerium-zirconium solid solution prepared by the present invention has high thermal stability during high-temperature firing because it has been subjected to high temperature.
FIG. 2 is a high-resolution electron micrograph of a cerium-zirconium solid solution prepared by a flame combustion method.
FIG. 2 is an electron micrograph of nanoparticles prepared by flame combustion method and having Zr molar contents of 50% and 75%, from which it can be seen that the particle diameters are all between 6-15nm and the distribution is relatively uniform. The material prepared by the method is a nano cerium zirconium solid solution.
FIG. 3 shows the paramagnetic resonance spectra of cerium-zirconium solid solutions prepared by the coprecipitation method (a) and the flame combustion method (b) in different ratios.
FIG. 3 (a) shows the paramagnetic resonance spectra of co-precipitated cerium oxide and cerium-zirconium solid solutions of different compositions (comparative examples 1, 2 and 4); (b) paramagnetic resonance spectra of cerium oxide prepared for flame combustion and cerium zirconium solid solutions (examples 1, 2 and 4) in different proportions. In FIG. 3, three peaks of g-2.011, g-2.032 and g-2.049 in paramagnetic resonance spectrum represent O2 -Paramagnetic signal adsorbed at oxygen vacancies. It can be seen that the cerium-zirconium solid solution prepared by the coprecipitation method in the comparative example has a large amount of oxygen vacancies, while the cerium-zirconium solid solution material prepared by the invention has no or a small amount of oxygen vacancies, and the oxygen vacancies gradually decrease until disappear as the Zr content increases.
FIG. 4 is a Raman spectrum analysis of the crystal lattice oxygen removal and oxygen vacancy generation of the cerium-zirconium solid solution nano-material.
FIG. 4 shows an in-situ Raman spectrum under an atmosphere of 2% CO/He: wherein (a) FC-Ce0.75Zr0.25O2；(b)FC-Ce0.5Zr0.5O2；(c)FC-Ce0.25Zr0.75O2；(d)CP-Ce0.75Zr0.25O2；(e)CP-Ce0.5Zr0.5O2；(f)CP-Ce0.25Zr0.75O2(ii) a (B) Is FC-Ce1-xZrxO2Examples 2 to 4 and CP-Ce1-xZrxO2(comparative examples 2 to 4) oxygen vacancies (Ov) with Ce in the materials4+(F2g) peak area ratio; (C) is CP-Ce0.25Zr0.75O2Comparative example 4 and FC-Ce0.25Zr0.75O2(example 4) number of oxygen vacancies generated by the material at different temperatures. As can be seen from the in-situ raman characterization result of fig. 4(a), the lattice oxygen in the cerium-zirconium solid solution prepared by the flame combustion method is more active, and can react with CO in the atmosphere at a lower temperature, and more oxygen vacancies can be generated at the same temperature. As can be seen from fig. 4(B), the cerium-zirconium solid solution prepared by coprecipitation in the comparative example generates only a small amount of oxygen vacancies as the temperature rises, while the cerium-zirconium solid solution prepared by flame combustion in the example generates a sharp increase in the amount of oxygen vacancies as the temperature rises, indicating that the lattice oxygen in the material is more active. As can be seen from FIG. 4(C), FC-Ce produced by flame combustion in the examples at 20, 100 and 200 deg.C0.25Zr0.75O2The number of oxygen vacancies generated by the material is respectively CP-Ce in the comparative example0.25Zr0.75O2The number of oxygen vacancies generated was 19, 13 and 11 times, which indicates that the flame combustion method of the examples produces cerium zirconium solid solution having more active oxygen.
FIG. 5 shows the lattice oxygen removal and oxygen vacancy change before and after high temperature roasting treatment of the cerium-zirconium solid solution nano-material prepared by Raman spectroscopy flame combustion method.
FIG. 5 shows a cerium-zirconium solid solution FC-Ce prepared by a flame combustion method0.25Zr0.75O2Example 4 cerium zirconium solid solution FC-Ce after high temperature calcination0.25Zr0.75O2-800 (comparative example 5) and the traditional coprecipitation method to prepare the cerium-zirconium solid solution CP-Ce0.25Zr0.75O2(comparative example 4) Raman Spectrum and oxygen vacancyAnd (4) comparing the quantity. FIG. 5(A) is an in situ Raman spectrum under an atmosphere of 2% CO/He; (B) is oxygen vacancy (Ov) with Ce4+(F2g) peak area ratio; (C) for the number of oxygen vacancies in different samples: (a) FC-Ce0.25Zr0.75O2；(b)FC-Ce0.25Zr0.75O2-800；(c)CP-Ce0.25Zr0.75O2. It can be seen that FC-Ce is the same as that in example 40.25Zr0.75O2In contrast, FC-Ce of comparative example 5 after high temperature calcination0.25Zr0.75O2The number of oxygen vacancies generated in the CO atmosphere was drastically reduced in the-800 cerium-zirconium solid solution, and the amount of active oxygen was comparable to that of the cerium-zirconium solid solution prepared by the CO-precipitation method in comparative example 4. The cerium-zirconium solid solution with more active oxygen prepared by the invention is in a metastable state, and the active oxygen is lost in the high-temperature roasting process to reach a stable state, and at the moment, the performance of the cerium-zirconium solid solution is equivalent to that of the cerium-zirconium solid solution prepared by a coprecipitation method.
Detailed Description
The technical details of the present invention are described in detail by the following examples. The embodiments are described for further illustrating the technical features of the invention, and are not to be construed as limiting the invention.
Example 1
116.3g of cerium acetylacetonate (with a Ce content of 12%) and 82ml of xylene are mixed to prepare a precursor solution, and the concentration of the cerium precursor is 0.5 mol/L. The solution was placed on a magnetic stirrer and stirred until a clear solution was obtained. The prepared solution was pumped into the flame using a syringe at a rate of 5 ml/min. The flame combustion gas is a mixed gas composed of methane (0.6L/min) and oxygen (1.9L/min), and the mixed gas is sprayed out from a nozzle with the diameter of 2 mm. A large amount of air (6L/min) is blown into a flame area by adopting a gas distribution plate, combustion products are quickly separated from the flame area under the drive of high-speed air flow, the sum of the radial cross-sectional areas of gas through holes on the gas distribution plate is 3.5 square centimeters, and the temperature of a sample reaching the glass fiber filter paper is reduced to 40 ℃. The catalyst particles obtained by combustion were collected using glass fiber filter paper. The particle diameter is between 6-15 nm. The catalyst thus obtained was designated as FC-CeO2。
Example 2
65.4g of cerium acetylacetonate (Ce content: 12%), 9.8ml of zirconium acetylacetonate and 74ml of xylene were mixed to prepare a precursor solution. The solution was placed on a magnetic stirrer and stirred until a clear solution was obtained. The prepared solution was pumped into the flame using a syringe at a rate of 5 ml/min. The flame combustion gas is a mixed gas composed of methane (0.6L/min) and oxygen (1.9L/min), and the mixed gas is sprayed out from a nozzle with the diameter of 2 mm. A large amount of air (6L/min) is blown into a flame area by adopting a gas distribution plate, combustion products are quickly separated from the flame area under the drive of high-speed air flow, the sum of the radial cross-sectional areas of gas through holes on the gas distribution plate is 3.5 square centimeters, and the temperature of a sample reaching the glass fiber filter paper is reduced to 40 ℃. The catalyst particles obtained by combustion were collected using glass fiber filter paper. The particle diameter is between 6-15 nm. The catalyst thus obtained was designated FC-Ce0.75Zr0.25O2。
Example 3
43.6g of cerium acetylacetonate (Ce content: 12%), 19.6ml of zirconium acetylacetonate and 86ml of xylene were mixed to prepare a precursor solution. The solution was placed on a magnetic stirrer and stirred until a clear solution was obtained. The prepared solution was pumped into the flame using a syringe at a rate of 5 ml/min. The flame combustion gas is a mixed gas composed of methane (0.6L/min) and oxygen (1.9L/min), and the mixed gas is sprayed out from a nozzle with the diameter of 2 mm. A large amount of air (6L/min) is blown into a flame area by adopting a gas distribution plate, combustion products are quickly separated from the flame area under the drive of high-speed air flow, the sum of the radial cross-sectional areas of gas through holes on the gas distribution plate is 3.5 square centimeters, and the temperature of a sample reaching the glass fiber filter paper is reduced to 40 ℃. The catalyst particles obtained by combustion were collected using glass fiber filter paper. The particle diameter is between 6-15 nm. The catalyst thus obtained was designated FC-Ce0.5Zr0.5O2。
Example 4
21.8g of cerium acetylacetonate (Ce content: 12%), 29.3ml of zirconium acetylacetonate and 98ml of xylene were mixed to prepare a precursor solution. The solution was placed on a magnetic stirrer and stirred until a clear solution was obtained. Use a syringe to 5 ml-The prepared solution was pumped into the flame at min. The flame combustion gas is a mixed gas composed of methane (0.6L/min) and oxygen (1.9L/min), and the mixed gas is sprayed out from a nozzle with the diameter of 2 mm. A large amount of air (6L/min) is blown into a flame area by adopting a gas distribution plate, combustion products are quickly separated from the flame area under the drive of high-speed air flow, the sum of the radial cross-sectional areas of gas through holes on the gas distribution plate is 3.5 square centimeters, and the temperature of a sample reaching the glass fiber filter paper is reduced to 40 ℃. The catalyst particles obtained by combustion were collected using glass fiber filter paper. The particle diameter is between 6-15 nm. The catalyst thus obtained was designated FC-Ce0.25Zr0.75O2。
Comparative example 1
Preparation of a cerium-zirconium solid solution by a coprecipitation method: weigh 15.9g (NH)4)2Ce(NO3)6Dissolved in 100mL of deionized water and added dropwise (NH) in a water bath at 50 ℃4)2CO3The solution is dissolved until precipitation occurs, and the pH value is 8-9. The precipitate was filtered and washed, transferred to a crucible, and placed in an oven to dry at 110 ℃ for 10h, and the dried solid was placed in a muffle oven to bake at 500 ℃ for 4 h. The catalyst thus obtained was designated CP-CeO2。
Comparative example 2
Preparation of a cerium-zirconium solid solution by a coprecipitation method: weigh 12.0g (NH)4)2Ce(NO3)6And 3.1gZr (NO)3)4·5H2O was added dropwise (NH) in 100mL of deionized water in a water bath at 50 ℃4)2CO3The solution is dissolved until precipitation occurs, and the pH value is 8-9. The precipitate was filtered and washed, transferred to a crucible, and placed in an oven to dry at 110 ℃ for 10h, and the dried solid was placed in a muffle oven to bake at 500 ℃ for 4 h. The catalyst thus obtained was designated CP-Ce0.75Zr0.25O2。
Comparative example 3
Preparation of a cerium-zirconium solid solution by a coprecipitation method: weigh 9.3g (NH)4)2Ce(NO3)6And 7.3gZr (NO)3)4·5H2O was added dropwise (NH) in 100mL of deionized water in a water bath at 50 ℃4)2CO3The solution is dissolved until precipitation occurs, and the pH value is 8-9. The precipitate was filtered and washed, transferred to a crucible, and placed in an oven to dry at 110 ℃ for 10h, and the dried solid was placed in a muffle oven to bake at 500 ℃ for 4 h. The catalyst thus obtained was designated CP-Ce0.5Zr0.5O2。
Comparative example 4
Preparation of a cerium-zirconium solid solution by a coprecipitation method: weigh 6.0g (NH)4)2Ce(NO3)6And 14.1gZr (NO)3)4·5H2O was added dropwise (NH) in 100mL of deionized water in a water bath at 50 ℃4)2CO3The solution is dissolved until precipitation occurs, and the pH value is 8-9. The precipitate was filtered and washed, transferred to a crucible, and placed in an oven to dry at 110 ℃ for 10h, and the dried solid was placed in a muffle oven to bake at 500 ℃ for 4 h. The catalyst thus obtained was designated CP-Ce0.25Zr0.75O2。
Comparative example 5
The sample from example 4 was fired in a muffle furnace at 800 ℃ for 30 h. The catalyst thus obtained was designated FC-Ce0.25Zr0.75O2-800。
Comparative example 6
The sample of comparative example 4 was fired in a muffle furnace at 800 ℃ for 30 h. The catalyst thus obtained was designated CP-Ce0.25Zr0.75O2-800。
Claims (3)
1. A metastable state cerium oxide or cerium zirconium solid solution nano material is characterized by being prepared by the following steps:
1) preparing a precursor solution: stirring and mixing a cerium precursor and a solvent to form a precursor solution; or according to the composition of the cerium-zirconium solid solution, stirring and mixing the cerium precursor, the zirconium precursor and the solvent; forming a precursor solution;
2) preparation of a sample: igniting the mixed gas of methane and oxygen to form flame, injecting the precursor solution prepared in the step 1) into the flame by using a constant flow pump for combustion, and simultaneously blowing air to the flame area to bring the combustion products out of the flame area;
3) collecting a sample: a cylinder with two open ends is arranged on one side of the flame area, glass fiber filter paper covers the open end of the cylinder, a vacuum pump is arranged on one side of the glass fiber filter paper, which is far away from the cylinder, the air inlet of the vacuum pump faces the glass fiber filter paper, the other open end of the cylinder faces the flame area, the air flow direction of the cylinder blows to the flame area faces the end face of the other open end of the cylinder, the vacuum pump is used for assisting combustion products to quickly leave the flame area, so that the combustion products stay on the glass fiber filter paper, circulating cooling water is arranged around the glass fiber filter paper, and the filter paper is taken down for collecting samples after preparation; the precursor solution is injected into the flame through a pipeline for combustion, and the outlet of the pipeline is positioned in the middle of the flame;
the combustion gas required by flame combustion is a mixed gas of methane and oxygen, the mixed gas is sprayed out from a nozzle with the diameter of 1-10mm, and the flow rates of the methane and the oxygen are both 0.1-5L/min; the speed of pumping the solution into the flame is 0.1-20 ml/min; igniting the organic solution by flame, decomposing precursor compounds of each component at high temperature of the flame to form oxide particles, wherein the formed oxide particles leave a flame area under the drive of air, the air is blown to the whole flame area from one side of the flame by an air distribution plate with uniformly distributed air through holes on the surface, the sum of the radial cross-sectional areas of the air through holes on the air distribution plate is 0.1-10 square centimeters, the air flow is 2-20L/min, circulating cooling water is arranged around the glass fiber filter paper, and the temperature of a particle sample reaching the glass fiber filter paper is 20-70 ℃;
the composition of the combustion products is adjustable, wherein the molar percentage of zirconium is 0-99%; the total concentration of the cerium precursor and the zirconium precursor in the precursor solution is 0.1-1 mol/L;
the surface of the material has a large amount of active oxygen, no or a small amount of oxygen vacancies, the lattice oxygen is in a metastable state, and the active oxygen is reduced and converted into a stable cerium-zirconium solid solution after long-time high-temperature roasting.
2. The nanomaterial of claim 1, wherein:
in the step 1), the cerium precursor is a compound capable of being dissolved in an organic solvent;
in the step 1), the zirconium precursor is a compound capable of being dissolved in an organic solvent;
the solvent in the step 1) is a combustible organic solvent.
3. The nanomaterial of claim 1, wherein:
in the step 1), the cerium precursor is one or more than two of cerium nitrate, ammonium ceric nitrate, cerium sulfate, cerium chloride, cerium carbonate, cerium oxalate, cerium acetate and cerium acetylacetonate;
in the step 1), the zirconium precursor is one or more than two of zirconium nitrate, zirconyl nitrate, zirconium n-propoxide, zirconium acetate, zirconium acetylacetonate, zirconium oxychloride and zirconium n-butyl alcohol;
the solvent in the step 1) is one or more than two of methanol, ethanol, xylene and organic acid.
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