CN114345392B - Preparation method of low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect - Google Patents
Preparation method of low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect Download PDFInfo
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Abstract
A preparation method of a low-temperature SCR active coke catalyst based on a nitrogen-oxygen co-doping synergistic effect belongs to the technical field of preparation of denitration catalysts. The activated coke is used as a low-cost carbon-based catalyst and is low-temperature NH of nitrogen oxides (NOx) 3 Selective reduction (NH) 3 SCR) technology; however, the density and activity of catalytic active sites on the surface of the active coke are low, so that the improvement of the catalytic removal activity and efficiency of NOx is limited. The nitrogen-oxygen co-doped active coke takes low-order weakly sticky/non-sticky coal as a precursor, and realizes the deep synergistic grafting of nitrogen-containing active sites and oxygen-containing active sites on the surface of the active coke by the step directional doping of nitrogen-containing and oxygen-containing functional groups on the surface, thereby obtaining a developed pore structure while realizing high doping amount. The nitrogen-oxygen co-doping synergistic effect-based active coke denitration catalyst and the preparation method thereof have the advantages of wide raw material source, low process cost, good application prospect and good industrialization potential.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to Nitrogen Oxide (NO) x ) Low temperature NH 3 Selective reduction (NH) 3 -SCR) catalyst, in particular to a preparation method of a low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect。
Background
Nitrogen Oxides (NO) emitted from coal-fired power plants or mobile sources x ) Can cause acid rain, photochemical smog and stratospheric ozone loss, and is a main atmospheric pollutant causing serious environmental damage. Currently, ammonia selective catalytic reduction (NH) 3 -SCR) is NO x The main stream technology for treatment, however, the existing catalyst has high reaction temperature (300-400 ℃), and the problems of catalyst abrasion, equipment corrosion, heat exchange surface blockage and the like are caused due to high ash distribution, so that the normal operation of a unit is influenced. In addition, in non-electric fields such as industrial boilers (kilns), steel industry, coking industry and the like, the exhaust gas temperature cannot meet the requirement of the temperature window of the existing catalyst. Therefore, the development of the low-temperature catalyst has important application prospect. However, the existing low-temperature catalyst still mainly takes a titanium-based catalyst, the operating temperature is higher than 180 ℃, and the cost of the catalyst is 5-7 ten thousand yuan/m 3 The poisoning resistance is poor and the operation is unstable. The active coke catalyst using coal as precursor has low cost<1 ten thousand yuan/ton), wide adaptability to target adsorption/catalytic removal of pollutant molecules, denitration temperature as low as 80-150 ℃, and important development potential.
Although the prior art of activated coke low-temperature denitration technology is applied to a combined desulfurization and denitration process, for example, patent CN208145768U discloses a powdered activated coke combined desulfurization and denitration system, wherein an activated coke storage bin is connected with a fluidized bed denitration tower, and an ammonia spraying device is connected with the fluidized bed denitration tower; the nitrogen oxides of the ammonia gas are reduced into nitrogen gas under the catalytic action of the powder active coke. However, the original activated coke which is not modified has low internal reaction activity, which causes low denitration efficiency. As shown in the literature (z.zhu et al. Fuel.2000,79, 651-658) the denitrification efficiency of the original activated coke decreases with increasing temperature, with only 50% and 20% denitrification rates at 90 ℃ and 120 ℃. Therefore, improving the low-temperature denitration efficiency of the activated coke is the key for promoting the commercial application of the activated coke. In addition, activated coke (char) can be used as a denitration catalyst support due to its large specific surface area, but its catalyst activity is mainly derived from active metals dispersed in the activated coke (char). For example, patent CN109529808A discloses a method for increasing V by microwave irradiation 2 O 5 SCR low of/AC catalystThe denitration efficiency of the catalyst at 250 ℃ is close to 100 percent by a method of warm reaction activity. Patent CN105597777A discloses a method for preparing a porous carbon-supported CuO catalyst x And MnO x The highest activity of the low-temperature denitration catalyst which is an active component can reach 73 percent at the temperature of between 150 and 250 ℃. Patent CN104941630A discloses a catalyst using carbon-based material as carrier, loading metal active component and rare earth active component, and denitration rate in 90-120 deg.c range is greater than 90%. The above supported catalyst, although exhibiting a high denitration activity, is relatively expensive to prepare. The active coke is used as low-cost carbon-based catalyst and is low-temperature NH of nitrogen oxide (NOx) 3 Selective reduction (NH) 3 SCR) technology; however, the density and activity of the catalytic active sites on the surface of the active coke are low, so that the improvement of the NOx catalytic removal activity and efficiency is limited.
Research shows that nitrogen, oxygen and other heteroatom doping is one of the means for activating the active coke denitration activity. For example, the literature (Q. Guo et al. Chemical Engineering journal.2015,270: 41-49) utilizes an oxygen functionality for NH 3 The adsorption promotion effect of the molecules enables the high-oxygen-doped active coke to show higher denitration efficiency in a higher temperature section (above 150 ℃). The literature (Q.Li et al.science, total environmental, 2020,740, 140158) analyzes the electron-rich character of nitrogen-containing functional groups versus O 2 And NH 3 The activation promotion effect of the molecules shows that the nitrogen doping can promote the denitration rate of the activated coke from 25% to 60%, and the efficiency of the lower temperature section (80 ℃) is highest. Patent CN105170174A discloses a nitriding carbon-based catalyst for low-temperature SCR denitration, which adopts a preparation idea of oxidizing first and then nitriding to obtain nitrogen-doped columnar active coke, wherein the NO conversion rate is 80%. The above analysis is combined to show that: the existing doped active coke denitration catalyst is only doped aiming at a single kind of functional group, and the denitration efficiency is low.
Disclosure of Invention
The invention aims to improve the active coke NH 3 SCR denitration activity, and provides a preparation method of a low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect, wherein the catalyst utilizes a nitrogen-containing functional group to react with a reactant O 2 And the activation oxidation effect and benefit of NOBy coupling of reactive intermediates NH with oxygen-containing functional groups 2 NO to end product N 2 And H 2 And the catalytic effect of O conversion realizes the coupling strengthening of two types of functional groups to the low-temperature denitration process, and the denitration efficiency is close to 90 percent and is improved by more than 40 percent compared with that of commercial active coke. The invention has wide raw material source, low process cost, good application prospect and industrialization potential.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect comprises the following preparation steps:
the method comprises the following steps: taking low-rank weakly caking coal/non-caking coal as a raw material, crushing, screening, washing with acid to remove ash in the coal, and drying to obtain deashed coal powder or indefinite coal powder;
step two: uniformly mixing deashed coal powder or indefinite coal powder with a nitrogen-containing precursor, and performing hydrothermal reaction to obtain a primary nitrogen-doped hydrothermal product;
step three: activating the primary nitrogen-doped hydrothermal product or directly activating the deashed coal powder or the amorphous coal powder obtained in the first step by using a nitrogen-containing activating agent to realize further deep doping of nitrogen elements and development of a pore structure;
step four: and (3) oxidizing the activated product by using a liquid-phase oxidant to realize the directional deep doping of the oxygen-containing carboxyl or hydroxyl functional group in the activated coke.
The active coke contains nitrogen functional groups capable of promoting reactant molecule O 2 Adsorption activation and catalytic oxidation of NO; the oxygen-containing functional group can promote key intermediate NH of reaction 2 NO to end product N 2 And H 2 And (4) converting O. The two functional groups have synergistic effect to improve the NH of the active coke 3 SCR activity, achieving an increase in denitration efficiency.
Further, in the first step, the low-rank weakly caking/non-caking coal comprises one or a mixture of lignite, eastern subbituminous coal, nindon weakly caking or non-caking coal. The reaction activity is higher.
Further, in the step one, the size of the crushed coal powder is 1-10 mm; the washing agent for acid washing is hydrochloric acid and/or hydrofluoric acid, the washing temperature is 20-80 ℃, and the washing time is 10-24 hours; the drying temperature is 60-150 ℃, and the drying time is 6-24 h.
Further, in the second step, the nitrogen-containing precursor is one or a mixture of urea, melamine or ethylenediamine.
Further, in the second step, the hydrothermal temperature is 160-220 ℃, the hydrothermal time is 6-12 h, and the mass ratio of the deashed coal powder or the unshaped coal particles to the nitrogen-containing precursor is 1:0.5 to 2.
Further, in the third step, the activating agent is NH 3 And/or NH 3 ·H 2 And nitrogen-containing activators such as O.
Further, the activator may also include CO 2 And/or H 2 O。
Further, the carrier gas of the activator is one or a mixture of nitrogen, argon and helium, and the volume flow ratio of the activator to the carrier gas is 1:0.1 to 10.
Further, in the third step, the activation temperature is 700-1000 ℃, the time is 0.5-4 h, and the heating rate is 5-20 ℃/min.
Further, in the fourth step, the liquid-phase oxidant is one or more of nitric acid, hydrogen peroxide and piranha solution (piranha solution: a mixture (7) of concentrated sulfuric acid and 30% hydrogen peroxide), the concentration of the oxidant is 5-10 mol/L, the oxidation temperature is 60-80 ℃, the oxidation time is 8-14 h, and the mass ratio of the activated product to the liquid-phase oxidant is 1:1 to 10. The liquid-phase oxidant can realize high-content directional grafting of high-activity oxygen-containing functional groups (carboxyl and hydroxyl) in the active coke, and simultaneously maintain the pore structure of the active coke.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention innovatively provides that the NH of the active coke is improved through the synergistic effect of the nitrogen-containing functional group and the oxygen-containing functional group 3 -SCR catalytic activity. Wherein the nitrogen-containing functional group promotes the reactant molecule O 2 Adsorption activation and NO ofOxidation of (2); oxygen-containing functional group promoting reaction key intermediate NH 2 NO to end product N 2 And H 2 And (4) converting O.
(2) The invention provides a strategy for step directional construction of functional groups containing nitrogen and oxygen, realizes deep directional doping of nitrogen-containing active sites and oxygen-containing active sites in the active coke, and obtains a developed pore structure. Compared with the supported catalyst added with active metal, the active coke prepared by the invention takes low-cost weakly-sticky/non-sticky coal as a raw material, and the cost is low; the preparation process can rely on the existing mature physical activation process and has good application prospect and industrialization potential.
(3) The nitrogen-oxygen co-doped active coke prepared by the method can realize high denitration rate in a wide temperature range (80-240 ℃). The prepared nitrogen doping amount is 3.86at-%, the oxygen doping amount is 9.72at-%, and the specific surface area is 1363m 2 The denitration efficiency of the activated coke per gram is maintained above 70 percent at the low temperature range of 80-240 ℃ and is close to 90 percent at most. Compare in traditional commercial active burnt, denitration efficiency promotes more than 40%.
Drawings
FIG. 1 is a flow chart of the process for preparing nitrogen and oxygen co-doped active coke.
FIG. 2 is a graph showing the nitrogen adsorption isotherms of the activated cokes obtained in the examples of the present invention and the comparative examples.
FIG. 3 is a graph showing the pore size distribution of activated coke obtained in the examples and comparative examples of the present invention.
FIG. 4 is an X-ray photoelectron spectrum of an active coke obtained in examples and comparative examples of the present invention.
FIG. 5 is a diagram showing the C1s peak separation of the activated coke obtained in example 1 of the present invention.
FIG. 6 is a diagram showing the O1s peak separation of the activated coke obtained in example 1 of the present invention.
FIG. 7 is a diagram showing the N1s peak separation of the activated coke obtained in example 1 of the present invention.
FIG. 8 is a graph showing denitration activity at a temperature ranging from 80 ℃ to 240 ℃ in example 1 and comparative example of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, comparative examples, and the accompanying drawings, which will assist those skilled in the art in further understanding the present invention, but do not limit the present invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The group of the invention discovers carbon-based fast NH by quantum chemical computation 3 The specific reaction mechanism of SCR is as follows: o is 2(g) →O 2(ad) ，O 2(ad) +2NO→2NO 2 ，NO 2 +2NH 3 +NO→2NH 2 NO+H 2 O→2N 2 +3H 2 O。
The key for improving the denitration efficiency of the carbon-based catalyst lies in that a reactant O 2 And activation oxidation of NO and intermediate product NH 2 The conversion of NO to the end product is a synergy of these two steps. Therefore, the invention provides a preparation method of the active coke catalyst based on the synergistic effect of the nitrogen-containing functional group and the oxygen-containing functional group, and the catalytic denitration performance of the active coke can be improved through the coupling reinforcement of the two steps.
Comparative example 1:
the method comprises the following steps: crushing Dongdong coal into 100-200 meshes of coal powder, and performing mixed acid pickling on the coal powder for 12 hours at 80 ℃ by using hydrochloric acid and hydrofluoric acid to obtain deashed coal powder;
step two: 2g of deashed coal powder is put into a horizontal tube furnace and treated by 80mLmin -1 The temperature is increased from room temperature to the activation temperature of 900 ℃ at the temperature increase rate of 10 ℃/min by taking the nitrogen as a carrier gas, and then NH with the same flow rate as the nitrogen is injected into the tube furnace 3 ·H 2 And activating the O for 1 hour, and naturally cooling to room temperature to obtain nitrogen-doped active coke which is marked as NAC.
Comparative example 2:
the method comprises the following steps: crushing commercial active coke (marked as AC) from inner Mongolia Xingtai coal chemical company into active coke powder of 100-200 meshes;
step two: mixing activated coke powder with 5mol/L nitric acid solution 1:5, magnetically stirring at 80 ℃ for 10 hours, then centrifugally washing the obtained mixture with distilled water for multiple times until the pH value of the mixture is 7, and finally drying at 80 ℃ for 12 hours to obtain oxygen-doped activated coke, which is recorded as OAC.
Example 1:
the method comprises the following steps: crushing Dongdong coal into 100-200 meshes of coal powder, and performing mixed acid pickling on the coal powder for 12 hours at 80 ℃ by using hydrochloric acid and hydrofluoric acid to obtain deashed coal powder;
step two: 2g of deashed coal powder is put into a horizontal tube furnace and treated by 80mLmin -1 The temperature is increased from room temperature to the activation temperature of 900 ℃ at the temperature increase rate of 10 ℃/min by using nitrogen as carrier gas, and then NH with the same flow as the nitrogen is injected into the tube furnace 3 ·H 2 Activating O for 1 hour;
step three: and (3) mixing the activated product with 5mol/L nitric acid solution according to the ratio of 1:5, magnetically stirring the mixture at 80 ℃ for 10 hours, then centrifugally washing the obtained mixture for multiple times by using distilled water until the pH value of the mixture is 7, and finally drying the mixture at 80 ℃ for 12 hours to obtain nitrogen and oxygen co-doped active coke, wherein the nitrogen and oxygen co-doped active coke is marked as NOAC-1.
Example 2:
the method comprises the following steps: crushing the east China coal into 100-200 meshes of coal powder, and carrying out mixed acid washing for 12 hours at 80 ℃ by using hydrochloric acid and hydrofluoric acid to obtain deashed coal powder;
step two: taking 4g of deashed coal powder according to the mass ratio of 2:1, mixing with urea, adding into 60ml of aqueous solution, fully and uniformly stirring, then moving into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6 hours at 200 ℃;
step three: 2g of the hydrothermal product are placed in a horizontal tube furnace at 80mLmin -1 The temperature is increased from room temperature to the activation temperature of 900 ℃ at the temperature increase rate of 10 ℃/min by taking the nitrogen as a carrier gas, and then NH with the same flow rate as the nitrogen is injected into the tube furnace 3 ·H 2 Activating O for 1 hour;
step four: and (3) mixing the activated product with 5mol/L nitric acid solution according to the ratio of 1:5, magnetically stirring for 10 hours at 80 ℃, then centrifugally washing the obtained mixture for multiple times by using distilled water until the pH value of the mixture is 7, and finally drying for 12 hours at 80 ℃ to obtain the deep nitrogen-oxygen co-doped active coke, which is recorded as NOAC-2.
The activated cokes prepared in the above comparative examples and examples were subjected to nitrogenThe adsorption test shows that the adsorption-desorption isotherms and pore size distribution results are shown in fig. 2 and 3, respectively. FIG. 2 shows that the specific surface area of commercially Active Coke (AC) is 1231m 2 Per g, pore volume of 0.77cm 3 (iv) g; the specific surface area of the oxygen-doped activated coke (OAC) is 1345m 2 Per g, pore volume of 0.84cm 3 (iv) g; the specific surface area of nitrogen-doped active coke (NAC) is 1269m 2 Per g, pore volume of 0.69cm 3 (iv) g; the specific surface areas of the nitrogen and oxygen co-doped active cokes (NOAC-1 and NOAC-2) are 1269m 2 /g、1073m 2 G, pore volume of 0.75cm respectively 3 /g、0.6cm 3 (iv) g. NAC and NOAC-1, NOAC-2 are expressed as I-type isotherms, which shows that the structure is a typical microporous pore structure; AC. The adsorption desorption profile of an OAC carries a slight hysteresis loop, indicating that it contains only few mesopores but still a pore structure dominated by micropores. Fig. 3 also shows that the pores of the obtained activated coke have a higher distribution in the micropore range.
The active foci prepared in the above comparative examples and examples were subjected to X-ray photoelectron spectroscopy, and the results are shown in fig. 4. The oxygen content of AC is 7.87at-%; the oxygen content of the OAC was 11.26at-%; NAC has a nitrogen content of 3.38at-% and an oxygen content of 3.88at-%; the NOAC-1 has a nitrogen content of 3.86at-% and an oxygen content of 9.72at-%; the NOAC-2 had a nitrogen content of 4.68at-% and an oxygen content of 9.79at-%.
The C1s, O1s and N1s of the X-ray photoelectron spectrum of the active coke prepared in the above example 1 were subjected to peak separation to obtain the type and distribution of the atoms doped in the nitrogen and oxygen co-doped active coke (NOAC-1). As shown in FIG. 5, C1s represents a type of oxygen atom, i.e., graphitized carbon C-C sp 2 (284.7 eV), edge defect C-C sp 3 (285.4 eV), carbon-oxygen single bond C-O (286.2 eV), carbon-oxygen double bond C = O (287.3 eV), O-C = O (288.9 eV), and pi-transition (291.2 eV). As shown in fig. 6, O1s can be specifically divided into three peaks representing carbon-oxygen double bond C = O (531.6 eV), carbon-oxygen single bond C — O (533.2 eV), and adsorbed water (535 eV), respectively. As shown in FIG. 7, the N1s peak gives the species and distribution of nitrogen atoms, mainly pyridine nitrogen N-6 (398.5 eV), pyrrole nitrogen N-5 (40.1 eV), graphite nitrogen N-Q (401.3 eV), and nitrogen oxide N-O (404.5 eV). The activated cokes prepared in the other examples have similar doping sourcesSubtype and distribution.
The activated coke prepared in the above comparative example and example 1 was subjected to NH 3 SCR catalytic Activity test with test conditions of 500ppmNO,500ppmNH 3 ，5％O 2 ，N 2 As carrier gas, the space velocity is 3500h -1 The reaction temperature was 80 to 240 ℃ and the resulting NOx removal rate as a function of time was shown in fig. 8. The nitrogen doping amount is 3.86at-%, the oxygen doping amount is 9.72at-%, and the specific surface area is 1363m 2 The denitration efficiency of the/g nitrogen-oxygen co-doped active coke (NOAC-1) in a low temperature range (80-240 ℃) is maintained to be more than 70 percent, and is close to 90 percent at most, and is improved by more than 40 percent compared with the commercial active coke. As shown in fig. 8, the denitration efficiency of commercial Activated Coke (AC) decreased with increasing temperature, up to 50%. After oxygen doping, the denitration efficiency of activated coke (OAC) is improved, and the denitration efficiency is increased along with the increase of temperature, and is up to 68%. The denitration activity of the nitrogen-doped active coke (NAC) is further higher than that of the oxygen-doped active coke, and the denitration activity is maintained to be about 75% in a wide temperature range. Nitrogen and oxygen co-doped active coke (NOAC-1) shows the highest denitration activity, makes up the poor low-temperature section activity of the oxygen-doped active coke, and simultaneously promotes the high-temperature section activity of the nitrogen-doped activity. At 200 ℃, the denitration efficiency is close to 90 percent, is improved by 40 percent compared with commercial active coke, and embodies the nitrogen-containing functional group and the oxygen-containing functional group to NH 3 -coupling enhancement effect of SCR reaction.
Claims (9)
1. A preparation method of a low-temperature SCR active coke catalyst based on a nitrogen-oxygen co-doping synergistic effect is characterized by comprising the following steps: the preparation method comprises the following steps:
the method comprises the following steps: taking low-order weakly caking coal/non-caking coal as a raw material, crushing, screening, washing with acid to remove ash in the coal, and drying to obtain deashed coal powder or indefinite coal powder;
step two: uniformly mixing deashed coal powder or indefinite coal powder with a nitrogen-containing precursor, and performing hydrothermal reaction to obtain a primary nitrogen-doped hydrothermal product;
step three: activating the primary nitrogen-doped hydrothermal product by using a nitrogen-containing activating agent or directly activating the deashed coal powder or the unshaped coal powder obtained in the step I(ii) a The nitrogen-containing activator is NH 3 And/or NH 3 ·H 2 O；
Step four: and (3) carrying out oxidation treatment on the activated product by adopting a liquid-phase oxidant.
2. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized in that: in the first step, the low-rank weakly caking/non-caking coal comprises one or a mixture of several of lignite, eastern Junggar subbituminous coal and Nindon weakly caking or non-caking coal.
3. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized by comprising the following steps: in the first step, the size of the crushed coal powder is 1 mu m-10 mm; the pickling detergent is hydrochloric acid and/or hydrofluoric acid, the washing temperature is 20-80 ℃, and the washing time is 10-24 hours; the drying temperature is 60-150 ℃, and the drying time is 6-24 h.
4. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized by comprising the following steps: in the second step, the nitrogen-containing precursor is one or a mixture of urea, melamine or ethylenediamine.
5. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized by comprising the following steps: in the second step, the hydrothermal temperature is 160-220 ℃, the hydrothermal time is 6-12 h, and the mass ratio of the deashing coal powder or the unshaped coal powder to the nitrogen-containing precursor is 1:0.5 to 2.
6. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized in that: the nitrogen-containing activator further comprises CO 2 And/or H 2 O。
7. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1 or 6, characterized in that: the carrier gas of the nitrogen-containing activating agent is one or a mixture of nitrogen, argon and helium, and the volume flow ratio of the nitrogen-containing activating agent to the carrier gas is 1:0.1 to 10.
8. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized in that: in the third step, the activating temperature is 700-1000 ℃, the time is 0.5-4 h, and the heating rate is 5-20 ℃/min.
9. The preparation method of the low-temperature SCR active coke catalyst based on nitrogen and oxygen co-doping synergistic effect according to claim 1, characterized by comprising the following steps: in the fourth step, the liquid-phase oxidant is one or more of nitric acid, hydrogen peroxide and piranha solution, the concentration of the liquid-phase oxidant is 5-10 mol/L, the oxidation temperature is 60-80 ℃, the oxidation time is 8-14 h, and the mass ratio of the activated product to the liquid-phase oxidant is 1:1 to 10.
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