CN116078349A - SO (SO) device 2 Columnar activated carbon with high removal efficiency and preparation method thereof - Google Patents
SO (SO) device 2 Columnar activated carbon with high removal efficiency and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of activated carbon, in particular to an SO 2 The column-shaped active carbon with high removal efficiency and the preparation method thereof comprise the following steps: primary modification treatment of S1 active carbon, secondary modification treatment of S2 active carbon, preparation of S3 composite active carbon and preparation of S4 columnar active carbon. In the invention, the adhesive formed by starch, carboxymethyl cellulose and xanthan gum is used as a connecting medium, the secondary modified active carbon and the composite active carbon are bonded into a whole and then dried at room temperature, thus avoiding the influence of high-temperature drying on the activity of the thiobacillus ferrooxidans and obtainingThe columnar activated carbon has an excellent removal effect on sulfur dioxide, and can efficiently remove sulfur dioxide, so that pollution of sulfur dioxide in the atmosphere is reduced.
Description
Technical Field
The invention relates to the technical field of activated carbon, in particular to an SO (sulfur dioxide) 2 Column-shaped active carbon with high removal efficiency and a preparation method thereof.
Background
SO 2 Is an atmospheric pollution, the main artificial source is related to energy consumption, the economic development is not separated from the support of energy, and China is a large country for energy production and consumption. SO (SO) 2 Is a colorless medium-stimulative gas, and mainly affects respiratory tract. SO in air 2 The great part comes from thermal power generation process and industrial production, and SO is sucked in 2 Can cause impaired respiratory system function and aggravate existing respiratory system diseases, and can be accompanied by obvious symptoms such as wheezing, shortness of breath, cough, etc. besides pulmonary function change for people with easy influence.
At present, activated carbon is mainly adopted for adsorption removal for the treatment of polluted gas. The active carbon is a very good adsorbent, and is manufactured by using coconut shells, bamboo charcoal, various shells, high-quality coal and the like as raw materials and performing a series of processes of crushing, sieving, catalyst activation, rinsing, drying, screening and the like on the raw materials by a physical and chemical method. It has the dual characteristics of physical adsorption and chemical adsorption, and can selectively adsorb various substances in gas phase and liquid phase so as to attain the goal of decoloring refining, disinfecting and deodorizing, decontaminating and purifying, etc.. For example, the invention patent with publication number CN110559988A discloses a preparation method of active carbon with strong adsorption, carbonized coconut shells are used as raw materials of the active carbon, and the active carbon with strong adsorption performance and recycling performance is prepared through homogenization, so that the active carbon has potential application value in the field of environmental protection; according to the technical scheme, the adsorption efficiency of the activated carbon is improved by improving the specific surface area of the activated carbon, although the activated carbon has strong adsorptivity, the activated carbon does not have pertinence to gas, so that the activated carbon has strong adsorption effect on all toxic and harmful gases, and when the activated carbon is required to have strong adsorption effect only on sulfur dioxide, the inner space of the activated carbon is occupied by a large amount of other types of gas, and sufficient accommodating space cannot be provided for sulfur dioxide, so that the requirements of the special field cannot be met. Therefore, in order to better meet the industrial demand, an activated carbon having a strong adsorption effect on sulfur dioxide is urgently needed.
Disclosure of Invention
The invention aims to provide an SO 2 Column-shaped active carbon with high removal efficiency and a preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
SO (SO) device 2 The preparation method of the columnar activated carbon with high removal efficiency comprises the following steps:
s1 primary modification treatment of activated carbon
1) Respectively ultrasonically washing the activated carbon with absolute ethyl alcohol and deionized water, and then drying to obtain pretreated activated carbon;
2) Immersing pretreated activated carbon into a prepared sufficient amount of treatment liquid A and treatment liquid B respectively, immersing in a constant-temperature water bath for 4-6 hours, oscillating for 20-30 hours by a shaking table, filtering, repeatedly washing with deionized water to neutrality, and drying to obtain modified activated carbon;
s2 secondary modification treatment of activated carbon
1) Adding diethyl sulfate into ethyl acetate, fully stirring, transferring into ice water bath, slowly dripping tetramethyl ethylenediamine, continuously reacting for 12-16h, taking out supernatant after the reaction is finished, repeatedly washing the rest liquid with ethyl acetate, transferring into a vacuum drying oven, and drying to obtain the treating agent;
2) Ultrasonically dispersing modified active carbon in absolute ethyl alcohol to obtain suspension, adding a treating agent into the suspension, stirring for 10-15h at room temperature, then rotationally evaporating the formed mixed solution to remove the absolute ethyl alcohol, transferring to a vacuum drying oven and drying to obtain secondary modified active carbon;
preparation of S3 composite active carbon
1) Inoculating thiobacillus ferrooxidans with 10-20% of inoculum size into a culture medium, placing the culture medium into an incubator, performing shake culture for 5-10h at 100-150r/min, collecting culture solution, centrifuging, washing, and re-suspending in Tris-HCl buffer solution to obtain suspension;
2) Adding sodium alginate and polyvinyl alcohol into deionized water, stirring in a constant-temperature water bath at 90-95 ℃ until the sodium alginate and the polyvinyl alcohol are completely dissolved, cooling to normal temperature, adding modified activated carbon, uniformly dispersing to obtain a dispersion liquid, uniformly mixing the dispersion liquid and the suspension liquid with equal volume, slowly dripping the mixture into a saturated calcium salt solution, standing at constant temperature for 8-10 hours, taking out a product, and repeatedly washing with normal saline to obtain the composite activated carbon;
s4 columnar activated carbon preparation
Uniformly mixing starch, carboxymethyl cellulose and deionized water, heating to 40-45 ℃, adding xanthan gum under stirring, continuously stirring for 20-30min to obtain a binder, fully mixing secondary modified activated carbon, composite activated carbon and the binder, kneading into a column, and drying at room temperature to obtain the required column-shaped activated carbon.
As a further preferable aspect of the present invention, the treating fluid a comprises the following components in a volume ratio of 1: (1-2): the composition of (1-2) 5-10mol/L nitric acid solution, 3-6mol/L sulfuric acid solution and 5-8mol/L phosphoric acid solution;
the volume ratio of the treatment fluid B is 1: 3-7mol/L sodium hydroxide solution of (2-3) and 10-15wt% ammonia water.
As a further preferable scheme of the invention, the water bath temperature is 70-80 ℃;
the shaking table is carried out at 35-40 ℃ and 300-500r/min.
As a further preferable scheme of the invention, the dosage proportion of the diethyl sulfate, the ethyl acetate and the tetramethyl ethylenediamine is (1.5-2.5) g: (200-300) mL: (1.2-1.8) g;
as a further preferable mode of the invention, the dosage proportion of the modified activated carbon, the absolute ethyl alcohol and the treating agent is (1-3) g: (20-50) mL: (1.5-3.0) g;
the stirring speed is 300-500r/min.
As a further preferable scheme of the invention, the culture medium consists of a liquid A and a liquid B which are subjected to sterilization treatment, and the volume ratio of the liquid A to the liquid B is (7-8): (2-3), wherein the liquid A consists of the following components in percentage by mass: (0.1-0.5): (0.5-1.2): (0.01-0.06): (700-800) ammonium sulfate, potassium chloride, magnesium sulfate, calcium nitrate and distilled water;
the mass ratio of the solution B is (42-50): and (200-300) ferrous sulfate and distilled water.
As a further preferable scheme of the invention, the temperature of the incubator is 30-35 ℃;
the concentration of the Tris-HCl buffer solution is 0.2-0.5mol/L;
the concentration of the suspension is 30-50mg/L.
As a further preferable scheme of the invention, the dosage proportion of the sodium alginate, the polyvinyl alcohol, the deionized water and the modified activated carbon is (5-10) g: (8-13) g: (80-100) mL: (3-7) g;
the constant temperature standing temperature is 40-45 ℃.
As a further preferable scheme of the invention, the using amount ratio of the starch, the carboxymethyl cellulose, the deionized water and the xanthan gum in the binder is (5-10) g: (5-10) g: (30-50) mL: (3-7) g;
the mass ratio of the secondary modified activated carbon to the composite activated carbon to the binder is (15-20): (5-10): (8-12).
SO (SO) device 2 The columnar active carbon with high removal efficiency is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, the activated carbon is modified by acid and alkali liquor, the acid and alkali liquor can etch the activated carbon to a certain extent, so that the carbon skeleton structure is changed, and the inner pore canal of the activated carbon is opened to form micropores, so that the micropore surface area and micropore volume of the activated carbon are increased, and sufficient space is provided for the infiltration of a subsequent treating agent and suspension; in order to realize qualitative adsorption of sulfur dioxide, a treating agent formed by diethyl sulfate, ethyl acetate and tetramethyl ethylenediamine is immersed into modified active carbon through a simple immersing method, so that secondary modified active carbon with a coating layer is formed, holes on the surface of the secondary modified active carbon are filled with the formed coating layer, the surface of the secondary modified active carbon is almost in a non-porous state, and the occupied treating agent in the secondary modified active carbon has a good trapping effect on sulfur dioxide, the trapped sulfur dioxide passes through the treating agent and then enters the secondary modified active carbon and fills the internal holes, other types of gases are blocked by the treating agent and cannot enter the secondary modified active carbon, so that the secondary modified active carbon can directionally adsorb sulfur dioxide, and the treating agent cannot permeate deep inside the modified active carbon due to conventional immersing treatment, and is mainly present on the surface of the modified active carbon, so that the formed secondary modified active carbon cannot directionally adsorb sulfur dioxide, and has a good removal effect.
In order to further improve the sulfur dioxide removal effect, the polyvinyl alcohol, sodium alginate and modified activated carbon are used as composite carriers, the thiobacillus ferrooxidans is limited and fixed in a developed microporous structure of the composite carriers, so that the composite activated carbon is obtained, the effect of removing sulfur dioxide can be well achieved by utilizing the removal effect of the thiobacillus ferrooxidans on sulfur dioxide, in addition, in order to prevent the release of the thiobacillus ferrooxidans in the composite carriers, the polyvinyl alcohol and sodium alginate are mixed and then crosslinked in a calcium salt solution to form a reticular structure, the activity space of the thiobacillus ferrooxidans can be well limited, the loss of the thiobacillus ferrooxidans can be well restrained, the limiting effect on the thiobacillus ferrooxidans can be well achieved, the retention rate of the thiobacillus ferrooxidans in the composite carriers can be greatly improved, and the composite activated carbon has long-term use effect.
In the invention, the adhesive formed by starch, carboxymethyl cellulose and xanthan gum is used as a connecting medium, the secondary modified activated carbon and the composite activated carbon are bonded into a whole and then dried at room temperature, so that the influence of high-temperature drying on the activity of thiobacillus ferrooxidans is avoided, and the columnar activated carbon is obtained, has an excellent removal effect on sulfur dioxide, and can efficiently remove the sulfur dioxide, thereby reducing the pollution of sulfur dioxide in the atmosphere.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the embodiment of the invention, the volume ratio of the treatment liquid A is 1:1.5:1.5 of 8mol/L nitric acid solution, 4mol/L sulfuric acid solution and 6mol/L phosphoric acid solution;
the treatment liquid B consists of 5mol/L sodium hydroxide solution and 12wt% ammonia water in a volume ratio of 1:2.5.
The culture medium consists of a solution A and a solution B which are subjected to sterilization treatment, wherein the volume ratio of the solution A to the solution B is 7:3, a step of;
wherein, the A liquid is prepared from the following components in percentage by mass: 0.1:1.2:0.06:700 of ammonium sulfate, potassium chloride, magnesium sulfate, calcium nitrate and distilled water;
the mass ratio of the solution B is 50:300 and distilled water.
Example 1
SO (SO) device 2 The preparation method of the columnar activated carbon with high removal efficiency comprises the following steps:
s1 primary modification treatment of activated carbon
1) Placing activated carbon into absolute ethyl alcohol, ultrasonically washing for 10min, soaking for 20min, ultrasonically washing with deionized water for 20min, repeatedly washing, placing into a baking oven, and drying at 110 ℃ until the weight is constant to obtain pretreated activated carbon;
2) Preparing a treatment solution A and a treatment solution B, respectively immersing the pretreated activated carbon into a sufficient amount of the treatment solution A and the treatment solution B, immersing the pretreated activated carbon in a water bath at a constant temperature of 70 ℃ for 4 hours, oscillating the pretreated activated carbon for 20 hours by a shaking table at 35 ℃ and 300r/min, filtering, repeatedly washing the pretreated activated carbon to be neutral by deionized water, and drying the pretreated activated carbon to obtain the modified activated carbon;
s2 secondary modification treatment of activated carbon
1) Adding 1.5g of diethyl sulfate into 200mL of ethyl acetate, fully stirring, transferring to an ice water bath, slowly dropwise adding 1.2g of tetramethyl ethylenediamine, continuously reacting for 12 hours, taking out supernatant after the reaction is finished, repeatedly washing the rest liquid with ethyl acetate, transferring to a vacuum drying oven, and drying at 80 ℃ for 10 hours to obtain a treating agent;
2) Dispersing 1g of modified activated carbon in 20mL of absolute ethyl alcohol by ultrasonic to obtain a suspension, adding 1.5g of treating agent into the suspension, stirring at room temperature for 10 hours at 300r/min, then rotationally evaporating the formed mixed solution to remove the absolute ethyl alcohol, transferring the mixed solution into a vacuum drying oven, and drying at 80 ℃ for 10 hours to obtain secondary modified activated carbon;
preparation of S3 composite active carbon
1) Inoculating thiobacillus ferrooxidans with 10% inoculum size into a culture medium, regulating the temperature of an incubator to 30 ℃, performing shake culture at 100r/min for 5 hours, collecting culture solution, centrifuging at 10000r/min for 5 minutes, washing and re-suspending in Tris-HCl buffer solution with the concentration of 0.2mol/L to obtain suspension with the concentration of 30 mg/L;
2) Adding 5g of sodium alginate and 8g of polyvinyl alcohol into 80mL of deionized water, stirring in a constant-temperature water bath at 90 ℃ until the sodium alginate and the 8g of polyvinyl alcohol are completely dissolved, cooling to normal temperature, adding 3g of modified activated carbon, uniformly dispersing to obtain a dispersion liquid, uniformly mixing the dispersion liquid and the suspension liquid with equal volume, slowly dripping the mixture into a saturated calcium chloride solution, standing at a constant temperature of 40 ℃ for 8 hours, taking out a product, and repeatedly washing with normal saline to obtain the composite activated carbon;
s4 columnar activated carbon preparation
Uniformly mixing 5g of starch, 5g of carboxymethyl cellulose and 30mL of deionized water, heating to 40 ℃, adding 3g of xanthan gum under stirring, continuously stirring for 20min to obtain a binder, fully mixing 15g of secondary modified activated carbon, 5g of composite activated carbon and 8g of binder, kneading into a column shape, and drying at room temperature to obtain the required column-shaped activated carbon.
Example 2
SO (SO) device 2 The preparation method of the columnar activated carbon with high removal efficiency comprises the following steps:
s1 primary modification treatment of activated carbon
1) Placing activated carbon in absolute ethyl alcohol, ultrasonically washing for 15min, soaking for 25min, ultrasonically washing with deionized water for 25min, repeatedly washing, placing in an oven, and drying at 130 ℃ until the weight is constant to obtain pretreated activated carbon;
2) Preparing a treatment solution A and a treatment solution B, respectively immersing the pretreated activated carbon into a sufficient amount of the treatment solution A and the treatment solution B, immersing the pretreated activated carbon in a water bath at the temperature of 75 ℃ for 5 hours at constant temperature, oscillating the pretreated activated carbon for 25 hours by a shaking table at the temperature of 37 ℃ and the speed of 400r/min, filtering, repeatedly washing the pretreated activated carbon to be neutral by deionized water, and drying the pretreated activated carbon to obtain the modified activated carbon;
s2 secondary modification treatment of activated carbon
1) Adding 2g of diethyl sulfate into 250mL of ethyl acetate, fully stirring, transferring to an ice water bath, slowly dropwise adding 1.5g of tetramethyl ethylenediamine, continuously reacting for 14h, taking out supernatant after the reaction is finished, repeatedly washing the rest liquid with ethyl acetate, transferring to a vacuum drying oven, and drying at 83 ℃ for 12h to obtain a treating agent;
2) Dispersing 2g of modified activated carbon in 40mL of absolute ethyl alcohol by ultrasonic to obtain a suspension, adding 2.6g of treating agent into the suspension, stirring at room temperature for 13h at 400r/min, then rotationally evaporating the formed mixed solution to remove the absolute ethyl alcohol, transferring the mixed solution into a vacuum drying oven, and drying at 82 ℃ for 13h to obtain secondary modified activated carbon;
preparation of S3 composite active carbon
1) Inoculating thiobacillus ferrooxidans with 15% inoculum size into a culture medium, regulating the temperature of an incubator to 32 ℃, performing shake culture at 130r/min for 8 hours, collecting culture solution, centrifuging at 15000r/min for 7 minutes, washing and re-suspending in Tris-HCl buffer solution with the concentration of 0.4mol/L to obtain suspension with the concentration of 40 mg/L;
2) Adding 7g of sodium alginate and 10g of polyvinyl alcohol into 90mL of deionized water, stirring in a constant-temperature water bath at 92 ℃ until the sodium alginate and the 10g of polyvinyl alcohol are completely dissolved, cooling to normal temperature, adding 5g of modified activated carbon, uniformly dispersing to obtain a dispersion liquid, uniformly mixing the dispersion liquid and the suspension liquid with equal volume, slowly dripping the mixture into a saturated calcium nitrate solution, standing at the constant temperature of 42 ℃ for 9 hours, taking out a product, and repeatedly washing with normal saline to obtain the composite activated carbon;
s4 columnar activated carbon preparation
Uniformly mixing 7g of starch, 8g of carboxymethyl cellulose and 40mL of deionized water, heating to 42 ℃, adding 5g of xanthan gum under stirring, continuously stirring for 25min to obtain a binder, fully mixing 18g of secondary modified activated carbon, 6g of composite activated carbon and 10g of binder, kneading into a column shape, and drying at room temperature to obtain the required column-shaped activated carbon.
Example 3
SO (SO) device 2 The preparation method of the columnar activated carbon with high removal efficiency comprises the following steps:
s1 primary modification treatment of activated carbon
1) Placing activated carbon into absolute ethyl alcohol, ultrasonically washing for 20min, soaking for 30min, ultrasonically washing with deionized water for 30min, repeatedly washing, placing into an oven, and drying at 150 ℃ until the weight is constant to obtain pretreated activated carbon;
2) Preparing a treatment solution A and a treatment solution B, respectively immersing the pretreated activated carbon into a sufficient amount of the treatment solution A and the treatment solution B, immersing the pretreated activated carbon in a water bath at the temperature of 80 ℃ for 6 hours at constant temperature, oscillating the pretreated activated carbon for 30 hours by a shaking table at the temperature of 40 ℃ and the speed of 500r/min, filtering, repeatedly washing the pretreated activated carbon to be neutral by deionized water, and drying the pretreated activated carbon to obtain modified activated carbon;
s2 secondary modification treatment of activated carbon
1) Adding 2.5g of diethyl sulfate into 300mL of ethyl acetate, fully stirring, transferring to an ice water bath, slowly dropwise adding 1.8g of tetramethyl ethylenediamine, continuously reacting for 16 hours, taking out supernatant after the reaction is finished, repeatedly washing the rest liquid with ethyl acetate, transferring to a vacuum drying oven, and drying at 85 ℃ for 15 hours to obtain a treating agent;
2) Dispersing 3g of modified activated carbon in 50mL of absolute ethyl alcohol by ultrasonic to obtain a suspension, adding 3.0g of treating agent into the suspension, stirring at room temperature for 15h at 500r/min, then rotationally evaporating the formed mixed solution to remove the absolute ethyl alcohol, transferring the mixed solution into a vacuum drying oven, and drying at 85 ℃ for 15h to obtain secondary modified activated carbon;
preparation of S3 composite active carbon
1) Inoculating thiobacillus ferrooxidans with 20% inoculum size into a culture medium, regulating the temperature of an incubator to 35 ℃, performing shake culture for 10 hours at 150r/min, collecting culture solution, centrifuging for 10 minutes at 20000r/min, washing and re-suspending in Tris-HCl buffer with the concentration of 0.5mol/L to obtain suspension with the concentration of 50 mg/L;
2) Adding 10g of sodium alginate and 13g of polyvinyl alcohol into 100mL of deionized water, stirring in a constant-temperature water bath at 95 ℃ until the sodium alginate and the 13g of polyvinyl alcohol are completely dissolved, cooling to normal temperature, adding 7g of modified activated carbon, uniformly dispersing to obtain a dispersion liquid, uniformly mixing the dispersion liquid and the suspension liquid with equal volume, slowly dripping the mixture into a saturated calcium nitrate solution, standing at a constant temperature of 45 ℃ for 10 hours, taking out a product, and repeatedly washing with normal saline to obtain the composite activated carbon;
s4 columnar activated carbon preparation
Uniformly mixing 10g of starch, 10g of carboxymethyl cellulose and 50mL of deionized water, heating to 45 ℃, adding 7g of xanthan gum under stirring, continuously stirring for 30min to obtain a binder, fully mixing 20g of secondary modified activated carbon, 10g of composite activated carbon and 12g of binder, kneading into a column shape, and drying at room temperature to obtain the required column-shaped activated carbon.
Comparative example 1: this comparative example is substantially the same as example 1, except that the activated carbon was not pretreated.
Comparative example 2: this comparative example is substantially the same as example 1 except that a pretreated activated carbon was used instead of the modified activated carbon in the secondary modification treatment of the activated carbon.
Comparative example 3: this comparative example is substantially the same as example 1, except that a pretreated activated carbon was used instead of a modified activated carbon in the preparation of the composite activated carbon.
Comparative example 4: this comparative example is substantially the same as example 1 except that the columnar activated carbon was prepared without containing the secondary modified activated carbon.
Comparative example 5: this comparative example is substantially the same as example 1 except that the columnar activated carbon was prepared without containing the composite activated carbon.
Control group: modified activated carbon was used directly.
Test experiment:
the columnar activated carbon provided in examples 1 to 3, comparative examples 1 to 5 and the control group was subjected to an adsorption removal test for sulfur dioxide as follows: taking columnar activated carbon provided by examples 1-3, comparative examples 1-5 and control group, placing into a closed reaction chamber, wherein the polluted gas of the reaction chamber is mixed gas of sulfur dioxide and carbon dioxide, and the concentration is 1.0mg/m 3 After exposing and standing the columnar activated carbon for 8 hours, balancing the indoor gas again, measuring the concentration of sulfur dioxide in the reaction chamber by using a gas chromatography, and calculating the removal rate of the sulfur dioxide in 8 hours; the recording results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the columnar activated carbon of the invention has high removal efficiency for sulfur dioxide, and can rapidly and efficiently remove sulfur dioxide in the atmosphere, thereby reducing pollution.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. SO (SO) device 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized by comprising the following steps of:
s1 primary modification treatment of activated carbon
1) Respectively ultrasonically washing the activated carbon with absolute ethyl alcohol and deionized water, and then drying to obtain pretreated activated carbon;
2) Immersing pretreated activated carbon into a prepared sufficient amount of treatment liquid A and treatment liquid B respectively, immersing in a constant-temperature water bath for 4-6 hours, oscillating for 20-30 hours by a shaking table, filtering, repeatedly washing with deionized water to neutrality, and drying to obtain modified activated carbon;
s2 secondary modification treatment of activated carbon
1) Adding diethyl sulfate into ethyl acetate, fully stirring, transferring into ice water bath, slowly dripping tetramethyl ethylenediamine, continuously reacting for 12-16h, taking out supernatant after the reaction is finished, repeatedly washing the rest liquid with ethyl acetate, transferring into a vacuum drying oven, and drying to obtain the treating agent;
2) Ultrasonically dispersing modified active carbon in absolute ethyl alcohol to obtain suspension, adding a treating agent into the suspension, stirring for 10-15h at room temperature, then rotationally evaporating the formed mixed solution to remove the absolute ethyl alcohol, transferring to a vacuum drying oven and drying to obtain secondary modified active carbon;
preparation of S3 composite active carbon
1) Inoculating thiobacillus ferrooxidans with 10-20% of inoculum size into a culture medium, placing the culture medium into an incubator, performing shake culture for 5-10h at 100-150r/min, collecting culture solution, centrifuging, washing, and re-suspending in Tris-HCl buffer solution to obtain suspension;
2) Adding sodium alginate and polyvinyl alcohol into deionized water, stirring in a constant-temperature water bath at 90-95 ℃ until the sodium alginate and the polyvinyl alcohol are completely dissolved, cooling to normal temperature, adding modified activated carbon, uniformly dispersing to obtain a dispersion liquid, uniformly mixing the dispersion liquid and the suspension liquid with equal volume, slowly dripping the mixture into a saturated calcium salt solution, standing at constant temperature for 8-10 hours, taking out a product, and repeatedly washing with normal saline to obtain the composite activated carbon;
s4 columnar activated carbon preparation
Uniformly mixing starch, carboxymethyl cellulose and deionized water, heating to 40-45 ℃, adding xanthan gum under stirring, continuously stirring for 20-30min to obtain a binder, fully mixing secondary modified activated carbon, composite activated carbon and the binder, kneading into a column, and drying at room temperature to obtain the required column-shaped activated carbon.
2. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the volume ratio of the treatment liquid A is 1: (1-2): the composition of (1-2) 5-10mol/L nitric acid solution, 3-6mol/L sulfuric acid solution and 5-8mol/L phosphoric acid solution;
the volume ratio of the treatment fluid B is 1: 3-7mol/L sodium hydroxide solution of (2-3) and 10-15wt% ammonia water.
3. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the water bath temperature is 70-80 ℃;
the shaking table is carried out at 35-40 ℃ and 300-500r/min.
4. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the dosage proportion of diethyl sulfate, ethyl acetate and tetramethyl ethylenediamine is (1.5-2.5) g: (200-300) mL: (1.2-1.8) g.
5. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the dosage proportion of the modified activated carbon, the absolute ethyl alcohol and the treating agent is (1-3) g: (20-50) mL: (1.5-3.0) g;
the stirring speed is 300-500r/min.
6. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the culture medium consists of liquid A and liquid B which are subjected to sterilization treatment, and the volume ratio of the liquid A to the liquid B is (7-8): (2-3), wherein the liquid A consists of the following components in percentage by mass: (0.1-0.5): (0.5-1.2): (0.01-0.06): (700-800) ammonium sulfate, potassium chloride, magnesium sulfate, calcium nitrate and distilled water;
the mass ratio of the solution B is (42-50): and (200-300) ferrous sulfate and distilled water.
7. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the temperature of the incubator is 30-35 ℃;
the concentration of the Tris-HCl buffer solution is 0.2-0.5mol/L;
the concentration of the suspension is 30-50mg/L.
8. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the dosage proportion of the sodium alginate, the polyvinyl alcohol, the deionized water and the modified activated carbon is (5-10) g: (8-13) g: (80-100) mL: (3-7) g;
the constant temperature standing temperature is 40-45 ℃.
9. An SO according to claim 1 2 The preparation method of the columnar activated carbon with high removal efficiency is characterized in that the dosage ratio of starch, carboxymethyl cellulose, deionized water and xanthan gum in the binder is (5-10) g: (5-10) g: (30-50) mL: (3-7) g;
the mass ratio of the secondary modified activated carbon to the composite activated carbon to the binder is (15-20): (5-10): (8-12).
10. SO (SO) device 2 A columnar activated carbon with high removal efficiency, characterized by being produced by the production method according to any one of claims 1 to 9.
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