CN107138519B - Ectopic chemical oxidation remediation method for soil polluted by cyanide - Google Patents
Ectopic chemical oxidation remediation method for soil polluted by cyanide Download PDFInfo
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Abstract
The invention discloses a method for ex-situ chemical oxidation remediation of cyanide-contaminated soil, and belongs to the field of contaminated site remediation. The method comprises the steps of removing impurities from the cyanide-contaminated soil, crushing, screening and other pretreatment, humidifying, uniformly stirring, adding a double oxidant of activated persulfate and hydrogen peroxide, and completely mineralizing and converting the cyanides in the soil into non-toxic substances so as to reduce the concentration of the cyanides in the soil. The double oxidant formed by the activated persulfate and the hydrogen peroxide is used, the concentration of cyanide in the soil can be effectively removed, the secondary pollution risk of the soil polluted by the cyanide is eliminated, the soil can be backfilled after the remediation is finished, the use function of the soil is not affected, and the soil can be normally developed and utilized.
Description
Technical Field
The invention belongs to the field of polluted site remediation, and particularly relates to a method for ex-situ chemical oxidation of cyanide-polluted soil.
Background
During the production activities of the industries such as pesticide production, metal mining, mineral separation, smelting, chemical engineering and the like, cyanide enters soil in the forms of pollution irrigation, waste residue, equipment leakage, leakage and the like, so that soil pollution is caused. The existence of cyanide in soil can affect the growth of plants, and meanwhile, the soil cyanide can cause a series of secondary pollution, such as cyanide diffusion caused by leaching of the cyanide by rainwater, pollution of underground water and surface water and damage to the ecological environment of a water body, so that the remediation of the soil polluted by the cyanide is necessary.
The method for restoring the cyanide-polluted soil mainly comprises an incineration method, cement kiln cooperative treatment, an electric restoration method, a stabilization/solidification method, a chemical oxidation method and the like. The incineration method is characterized in that the polluted soil and combustible substances are mixed and incinerated, cyanide is decomposed and converted into non-toxic substances at high temperature, the method can thoroughly remove the cyanide in the soil, but the soil is non-combustible substances and combustible substances need to be added, so the incineration disposal method has higher cost; the cement kiln cooperative treatment is to make cyanide-contaminated soil and cement production raw materials enter a cement kiln together, and the cyanide is decomposed and removed in the cement kiln at high temperature, the method can also completely remove the cyanide in the soil, but the soil amount of a general contaminated site is large, and the cement is in a period of excess capacity at the present stage, and the cement kiln cooperative treatment cannot consume a large amount of contaminated soil; the electric repairing method is that an electrode is arranged in cyanide soil, and cyanide is removed by oxidizing the cyanide through free radicals generated around the electrode, so that the method is suitable for small-area polluted soil and has higher cost; the stabilization/solidification method is to reduce the leaching concentration of cyanide by adding a precipitator into the cyanide-polluted soil to convert the cyanide into a difficultly soluble substance, and the method does not completely remove the cyanide, and the cyanide can be released again in a complex soil environment; the chemical oxidation method is to add an oxidizing agent into the soil polluted by cyanide to oxidize the cyanide into a non-toxic substance, and the technology has low cost and can be carried out in situ. Chemical oxidation technology for contaminated soil has a great number of successful application cases at home and abroad, accumulates mature technology and engineering parameters, and is one of the repair technologies recommended by "contaminated site repair technology catalog (first lot)" of the ministry of environmental protection. The chemical oxidation technology is relatively mature in the aspect of treating waste water containing cyanide pollution, but the technology is not widely applied to the restoration of cyanide-polluted soil in China.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention discloses a method for ex-situ chemical oxidation remediation of cyanide-contaminated soil, which has the advantages of simple process, low treatment cost and stable remediation effect, and can be applied to the remediation of cyanide-contaminated sites on a large scale.
Based on the method, the ex-situ chemical oxidation remediation method for the cyanide-contaminated soil is provided, and activated double oxidants and chelating resins are used in the oxidation process.
The ex-situ chemical oxidation remediation method for the soil polluted by the cyanide specifically comprises the following steps:
firstly, preprocessing polluted soil;
secondly, humidifying and stirring the polluted soil;
thirdly, activating a double oxidant;
the fourth step, oxidation of cyanide.
The double oxidant used in the third step is Fe2+Hydrogen peroxide/persulfate double oxidant is activated by salt catalysis.
Said Fe2+The salt is ferrous phosphate.
The third step is further specifically that persulfate is dissolved in water to prepare a solution with a certain concentration, the solution is mixed with hydrogen peroxide, then the pH value of the mixed solution is adjusted, an activating agent ferrous phosphate is added, and stirring is carried out to obtain a double oxidant
The concentration of the persulfate dissolved in water is 0.3-0.5 mol/L.
The volume ratio of the persulfate solution to the hydrogen peroxide is 2-3: 1.
The pH value of a mixed solution formed by mixing the hydrogen peroxide and the persulfate aqueous solution is 7.5-9.5.
And the fourth step is to add a double oxidant accounting for 3-4% of the soil mass and chelating resin accounting for 1% of the soil mass into the polluted soil, fully stir and mix the materials uniformly, fully react and maintain the materials for a certain time, and then the materials can be checked and accepted.
The chelating resin is specifically a modified polystyrene resin.
Compared with the prior art, the invention has the following advantages and effects:
(1) the method takes the activated persulfate and the hydrogen peroxide as the oxidants, the activated persulfate and the hydrogen peroxide are two strong oxidants, and the cyanide in the soil can be effectively removed by a series of complex reactions to reach the target repairing value;
(2) the oxidant does not cause secondary pollution, simultaneously removes cyanide, and eliminates the risk of secondary pollution of cyanide;
(3) the invention eliminates the pollutants by restoring the polluted soil, can backfill after acceptance inspection is qualified, does not influence the land use function, and can be normally developed and utilized after restoration is finished.
Detailed Description
Fe was found as early as 18942+/H2O2Oxide of the system, Fenton's reagent, in Fe2+The hydrogen peroxide is changed into hydroxyl free radical with high reaction activity under the catalytic action of the salt, and the salt has strong oxidizing capability, high reaction speed and no secondary pollution, and can realize good oxidation of cyanide. However, since hydrogen peroxide is unstable, the generated hydroxyl radical has a short life and cannot sufficiently contact cyanide, which affects the use thereof.
Persulfate is a high-grade oxidant, the oxidation-reduction potential of which is close to that of ozone, and is a strong oxidant, but because persulfate has high stability, the reaction rate is slow at normal temperature, and the oxidation effect is slow. Under the conditions of light, heat and transition metal ions, the persulfate ions are activated and decomposed into sulfate ions, the standard oxidation-reduction potential is very high, the oxidizing capability is higher than that of persulfate, the effect of the persulfate ions serving as an oxidizing agent is more remarkable, and the persulfate ions have a good effect on oxidizing cyanide through research.
The persulfate activated by the transition metal ions is a very effective persulfate activation mode, and the transition metal ions can decompose the persulfate to generate SO at normal temperature4 -The common transition metal ion for persulfate activation is Ag+、Cu2 +、Fe2+、Co2+Etc. of Fe2+Is the most effective transition ion for activating persulfate, but Fe is adopted2+Too much of (C) and easy consumption of activated SO4 -The activating effect of persulfate is limited.
According to the invention, the Fe2+ salt is adopted to catalyze and activate the hydrogen peroxide/persulfate double oxidant, and the chemical oxidation repair of the cyanide in the soil is better realized by utilizing the respective effects of the double oxidant.
Due to, Fe2+Easily consume SO4 -Therefore, it is considered to use Fe2+Reduction of Fe by phosphate radical ions with good complexing effect2+With SO4 -The reaction of (1). The invention contemplates the use of ferrous phosphate/H2O2Persulfate forming double oxidants treat cyanide in soil.
The invention considers that the chelating resin is used together with persulfate, the chelating resin can absorb a large amount of gold, silver, iron and copper ions from the metal cyanide in the soil, and the gold, silver, iron and copper ions can be used as transition metal ions to activate persulfate SO as to convert the persulfate into SO4 -Improving the oxidation activity, reducing the use amount of transition metal and avoiding Fe2+Over-consumption of SO4 -。
The invention provides a method for ex-situ chemical oxidation remediation of soil polluted by cyanide, which specifically comprises the following steps:
firstly, polluted soil pretreatment: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
step two, humidifying and stirring the polluted soil: adding water into the pretreated polluted soil, humidifying and uniformly stirring the polluted soil, wherein the water content is close to saturation;
step three, activating a double oxidant: dissolving persulfate in water to prepare a solution with the concentration of 0.3-0.5 mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 2-3: 1, then adjusting the pH value of the mixed solution to 7.5-9.5, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.1-0.2 mol, and stirring for 5min to obtain a double oxidant;
step four, oxidation of cyanide: adding a double oxidant accounting for 3-4% of the mass of the soil and chelating resin accounting for 1% of the mass of the soil into the polluted soil, fully stirring and uniformly mixing, fully reacting, and maintaining for a certain time to perform acceptance inspection.
The contaminated soil can be stirred by adopting an excavator bucket or a powerful stirring head or other stirrers.
The contaminated soil humidifying and stirring method is characterized in that contaminated soil and water are uniformly stirred according to the mass ratio of 1: 0.3-0.4.
The persulfate can be one or a mixture of more than one soluble persulfate such as sodium persulfate, ammonium persulfate, calcium persulfate and the like.
In the range of pH 7.5 to 9.5, it was found that the activating performance of the double oxidant is the best, and that both hydrogen peroxide and persulfate can exert the best oxidizing effect.
The curing time is about 5-12 days.
The chelating resin provided by the invention is modified polystyrene resin, and the preparation method specifically comprises the following steps:
adding 10g of chloromethylated styrene, 0.8 g-1.2 g of pyridine, 0.01 g-0.02 g of cuprous bromide and 3g of acrylonitrile into 100mL of dimethylformamide, vacuumizing the reaction vessel, introducing nitrogen for 3 times of circulation, stirring and reacting at the temperature of 70 ℃ for 3 hours to obtain modified polystyrene, mixing an EDTA solution with the mass percentage of 5% and methanol according to the volume ratio of 1:1 to obtain a mixed solution, putting the modified polystyrene into the mixed solution, stirring for 24 hours, washing with water, and finally vacuum-drying at the temperature of 25 ℃.
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
EXAMPLE 1 preparation of chelate resin
Adding 10g of chloromethylated styrene, 0.8 g-1.2 g of pyridine, 0.01 g-0.02 g of cuprous bromide and 3g of acrylonitrile into 100mL of dimethylformamide, vacuumizing the reaction vessel, introducing nitrogen for 3 times of circulation, stirring and reacting at the temperature of 70 ℃ for 3 hours to obtain modified polystyrene, mixing an EDTA solution with the mass percentage of 5% and methanol according to the volume ratio of 1:1 to obtain a mixed solution, putting the modified polystyrene into the mixed solution, stirring for 24 hours, washing with water, and finally vacuum-drying at the temperature of 25 ℃.
The infrared spectrum of chloromethylated styrene is 2935cm-1And 1450cm-1Has an absorption peak at 760cm-1And 690cm-1Absorption peak, grafting polyacrylonitrile in infrared spectrum of chloromethylated styrene at 2240cm-1The characteristic absorption peak of the nitrile group appears, indicating that acrylonitrile has been grafted to the chloromethylated styrene surface.
Experimental study on ectopic chemical oxidation removal of soil cyanide
And (3) the soil sampling depth is 0-30 cm, the collected soil sample is uniformly mixed, and the soil sample is air-dried in a dark place, subjected to impurity removal and crushed. The cyanide content is measured by using a collected fresh soil sample, and the measuring method refers to the soil environment quality evaluation standard (provisional) of exhibition sites (national environmental protection Bureau, 2007).
Experiment 1
According to investigation results, the site soil is mainly polluted by cyanide-containing waste water and waste residues, the total cyanide content is 1983mg/kg, and the content of easily released cyanides is 32.2 mg/kg.
The method for repairing the soil polluted by the cyanide is specifically implemented as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.3, wherein the water content of the soil is close to saturation;
(3) activating the double oxidant: dissolving ammonium persulfate in water to prepare a solution with the concentration of 0.3mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 2: 1, then adjusting the pH value of the mixed solution to 7.5, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.2mol, and stirring for 5min to obtain a double oxidant;
(4) oxidation of cyanide: the double oxidant accounting for 3 percent of the soil mass and the chelating resin accounting for 1 percent of the soil mass prepared in the embodiment 1 are added into the polluted soil, fully stirred and mixed evenly, fully reacted and maintained for 10 days, and then the acceptance is carried out.
After remediation, the total cyanide concentration in the soil was 2.11mg/kg, and no readily releasable cyanide was detected.
Experiment 2
In the embodiment, cyanide-contaminated soil of a certain chemical plant is taken as a treatment object, the total cyanide content of the original contaminated soil is 986mg/kg, and the content of easily released cyanide is 23.4 mg/kg.
The method for repairing the soil polluted by the cyanide is specifically implemented as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.4, wherein the water content of the soil is close to saturation;
(3) activating the double oxidant: dissolving sodium persulfate in water to prepare a solution with the concentration of 0.5mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 3:1, then adjusting the pH value of the mixed solution to 9.5, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.2mol, and stirring for 5min to obtain a double oxidant;
(4) oxidation of cyanide: adding a double oxidant accounting for 4% of the soil mass and chelating resin accounting for 1% of the soil mass into the contaminated soil, fully stirring and uniformly mixing, fully reacting, and maintaining for 15 days to perform acceptance inspection.
After remediation, the cyanide concentration in the soil was 4.32mg/kg, and no readily releasable cyanide was detected.
Comparative experiment 1
According to investigation results, the site soil is mainly polluted by cyanide-containing waste water and waste residues, the total cyanide content is 1983mg/kg, and the content of easily released cyanides is 32.2 mg/kg.
The concrete implementation method for repairing the soil polluted by the cyanide is as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.3, wherein the water content of the soil is close to saturation;
(3) activating the double oxidant: dissolving ammonium persulfate in water to prepare a solution with the concentration of 0.3mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 2: 1, then adjusting the pH value of the mixed solution to 7.5, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.2mol, and stirring for 5min to obtain a double oxidant;
(4) oxidation of cyanide: adding a double oxidant accounting for 3% of the soil mass into the contaminated soil, fully stirring and uniformly mixing, fully reacting, and maintaining for 10 days to perform acceptance inspection.
The total cyanide concentration in the soil after remediation is 395mg/kg, and the concentration of the cyanide in an easily released state is 4.9 mg/kg.
As can be seen from comparative experiment 1, the same amount of ferrous phosphate, without the addition of chelating resin, will react to SO4 -Too much consumption of (c) affects the oxidizing effect of the final oxidizing agent, and the cyanide treatment effect is inferior to that of test 1.
Comparative experiment 2
According to investigation results, the site soil is mainly polluted by cyanide-containing waste water and waste residues, the total cyanide content is 1983mg/kg, and the content of easily released cyanides is 32.2 mg/kg.
The concrete implementation method for repairing the soil polluted by the cyanide is as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.3, wherein the water content of the soil is close to saturation;
(3) activating the double oxidant: dissolving ammonium persulfate in water to prepare a solution with the concentration of 0.3mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 2: 1, then adjusting the pH value of the mixed solution to 7.5, adding an activating agent ferrous oxalate with the use amount of 0.2mol, and stirring for 5min to obtain a double-oxidant;
(4) oxidation of cyanide: the double oxidant accounting for 3 percent of the soil mass and the chelating resin accounting for 1 percent of the soil mass prepared in the embodiment 1 are added into the polluted soil, fully stirred and mixed evenly, fully reacted and maintained for 10 days, and then the acceptance is carried out.
The total cyanide concentration in the repaired soil is 192mg/kg, and the concentration of the easy-release cyanide is 2.2 mg/kg.
It can be seen from comparative test 2 that the same amount of iron oxalate was used instead of iron phosphate, and phosphate was better bound to ferrous ions than oxalate, therefore, the use of iron oxalate affected the final oxidizing effect of the oxidant, and the cyanide treatment effect was inferior to that of test 1.
Comparative experiment 3
According to investigation results, the site soil is mainly polluted by cyanide-containing waste water and waste residues, the total cyanide content is 1983mg/kg, and the content of easily released cyanides is 32.2 mg/kg.
The method for repairing the soil polluted by the cyanide is specifically implemented as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.3, wherein the water content of the soil is close to saturation;
(3) activation of the oxidizing agent: dissolving ammonium persulfate in water to prepare a solution with the concentration of 0.3mol/L, then adjusting the pH value of the mixed solution to 7.5, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.2mol, and stirring for 5min to obtain an oxidant;
(4) oxidation of cyanide: the chelating resin prepared in example 1, which accounts for 3% of the soil mass, and the oxidant and the chelating resin which accounts for 1% of the soil mass, are added into the contaminated soil, fully stirred and mixed uniformly, fully reacted, and maintained for 10 days, and then the chelating resin can be accepted.
The total cyanide concentration in the repaired soil is 462mg/kg, and the concentration of the cyanide in an easily released state is 5.7 mg/kg.
As can be seen from comparative experiment 3, the cyanide treatment effect was inferior to that of experiment 1 by using only persulfate as the oxidizing agent.
Comparative experiment 4
According to investigation results, the site soil is mainly polluted by cyanide-containing waste water and waste residues, the total cyanide content is 1983mg/kg, and the content of easily released cyanides is 32.2 mg/kg.
The method for repairing the soil polluted by the cyanide is specifically implemented as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.3, wherein the water content of the soil is close to saturation;
(3) activating the double oxidant: dissolving ammonium persulfate in water to prepare a solution with the concentration of 0.3mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 2: 1, then adjusting the pH value of the mixed solution to 5, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.2mol, and stirring for 5min to obtain a double oxidant;
(4) oxidation of cyanide: the double oxidant accounting for 3 percent of the soil mass and the chelating resin accounting for 1 percent of the soil mass prepared in the embodiment 1 are added into the polluted soil, fully stirred and mixed evenly, fully reacted and maintained for 10 days, and then the acceptance is carried out.
The total cyanide concentration in the repaired soil is 793mg/kg, and the concentration of the easy-release cyanide is 8.1 mg/kg.
As can be seen from comparative test 3, the effect of cyanide treatment at a pH value outside the range of 7.5 to 9.5 was inferior to that of test 1.
Pilot test
In this example, a pilot experiment was conducted using cyanide-contaminated soil from a chemical plant as a treatment target. Determining the adding ratio according to the experimental results of the pilot plant, simultaneously considering the influence factors of water, soil physical and chemical properties and the like, selecting the soil for pilot plant use in the range of 10 multiplied by 10m of a specific area, excavating the soil with the depth of 1-2m, and obtaining the total 21 tons of polluted soil through screening pretreatment, wherein the total cyanide content is 1154mg/kg, and the easy-release cyanide content is 21.2 mg/kg. The measurement method refers to evaluation criteria (provisional) for soil environment quality at exhibition sites (national institute of environmental protection, 2007).
The method for repairing the soil polluted by the cyanide is specifically implemented as follows:
(1) pretreatment of contaminated soil: carrying out pretreatment such as impurity removal, crushing, screening and the like on the polluted soil;
(2) humidifying and stirring the polluted soil: uniformly stirring the polluted soil and water according to the mass ratio of 1: 0.4, wherein the water content of the soil is close to saturation;
(3) activating the double oxidant: dissolving persulfate in water to prepare a solution with the concentration of 0.4mol/L, mixing the solution with hydrogen peroxide according to the volume ratio of 2: 1, then adjusting the pH value of the mixed solution to 8, adding an activating agent ferrous phosphate, wherein the usage amount of the ferrous phosphate is 0.2mol, and stirring for 5min to obtain a double oxidant;
(4) oxidation of cyanide: adding a double oxidant accounting for 3 percent of the mass of the soil and chelating resin accounting for 1 percent of the mass of the soil into the polluted soil, fully stirring and uniformly mixing, fully reacting, and maintaining for 15 days to perform acceptance inspection.
After remediation, the cyanide concentration in the soil was 1.79mg/kg, and no readily releasable cyanide was detected.
According to the test results of the pilot test, after the cyanide-contaminated soil is oxidized by the chemical agent, the total cyanide content and the content of the released cyanide are easy to be reduced to the target value range.
The foregoing is only a preferred embodiment of the present invention and is not intended to limit the invention; other modifications, substitutions, simplifications, improvements and the like which do not depart from the spirit and scope of the invention are deemed to be equivalent permutations and equivalents thereof.
Claims (1)
1. A ex-situ chemical oxidation remediation method for soil polluted by cyanide is characterized by comprising the following steps: the method specifically comprises the following steps of,
firstly, preprocessing polluted soil;
secondly, humidifying and stirring the polluted soil;
thirdly, activating a double oxidant;
fourthly, oxidizing cyanide;
dissolving persulfate in water to prepare a solution with a certain concentration, mixing the solution with hydrogen peroxide, then adjusting the pH value of the mixed solution, adding an activating agent ferrous phosphate, and stirring to obtain a double oxidant;
the concentration of the persulfate dissolved in water is 0.3-0.5 mol/L;
the volume ratio of the persulfate solution to the hydrogen peroxide is 2-3: 1;
the pH value of a mixed solution formed by mixing the hydrogen peroxide and the persulfate aqueous solution is 7.5-9.5;
the fourth step is to add a double oxidant accounting for 3% -4% of the soil mass and a chelating resin accounting for 1% of the soil mass into the contaminated soil, fully stir and mix the materials uniformly, fully react and maintain the materials for a certain time, and then the materials can be checked and accepted, wherein the chelating resin is a modified polystyrene resin, and the specific preparation method comprises the following steps:
adding 10g of chloromethylated styrene, 0.8 g-1.2 g of pyridine, 0.01 g-0.02 g of cuprous bromide and 3g of acrylonitrile into 100mL of dimethylformamide, vacuumizing the reaction vessel, introducing nitrogen for 3 times of circulation, stirring and reacting at the temperature of 70 ℃ for 3 hours to obtain modified polystyrene, mixing an EDTA solution with the mass percentage of 5% and methanol according to the volume ratio of 1:1 to obtain a mixed solution, putting the modified polystyrene into the mixed solution, stirring for 24 hours, washing with water, and finally vacuum-drying at the temperature of 25 ℃.
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