CN115180752B - Desalination method for SRG washing wastewater by catalyzing sulfur-containing activated carbon - Google Patents

Desalination method for SRG washing wastewater by catalyzing sulfur-containing activated carbon Download PDF

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CN115180752B
CN115180752B CN202110359144.6A CN202110359144A CN115180752B CN 115180752 B CN115180752 B CN 115180752B CN 202110359144 A CN202110359144 A CN 202110359144A CN 115180752 B CN115180752 B CN 115180752B
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sulfur
active carbon
activated carbon
heating
carbon
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CN115180752A (en
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杨本涛
李佳
李俊杰
李小龙
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Zhongye Changtian International Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/12—Insoluble sulfur (mu-sulfur)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

Abstract

The invention discloses a desalination method for SRG washing wastewater by sulfur-containing activated carbon catalysis. The sulfur-containing active carbon is used as a catalyst, and the disproportionation reaction recovery of high-concentration bisulfide ions can be realized at about 50 ℃ to obtain sulfur resources. On one hand, the salt content in the SRG washing wastewater is reduced, and on the other hand, the purpose of recycling sulfur is realized, so that the liquid alkali consumption of the wastewater after-treatment is greatly reduced. The sulfur-containing activated carbon used in the invention has the advantages of simple preparation process, easily available raw materials, low price and large-scale application prospect, and the prepared sulfur-containing activated carbon can be recycled. In addition, the invention can recycle sulfur while treating the wastewater, realize the recycling treatment of the wastewater and avoid secondary pollution. Has wide market prospect and economic benefit.

Description

Desalination method for SRG washing wastewater by catalyzing sulfur-containing activated carbon
Technical Field
The invention relates to an SRG washing wastewater treatment technology, in particular to a desalination method for catalyzing SRG washing wastewater by sulfur-containing activated carbon, belonging to the technical fields of SRG flue gas washing wastewater treatment and sulfur resource recovery.
Background
The sintering flue gas in the steel industry adopts an active carbon method to carry out desulfurization and denitrification to carry out a flue gas purification process, and sulfur dioxide gas collected by active carbon is concentrated and released and then is sent to a sulfur resource workshop to produce sulfur resources. The flue gas enriched with sulfur dioxide gas is called sulfur-rich gas (SRG flue gas) for short, and the gas can be prepared into sulfur resources meeting the national standard through the procedures of purification, drying, conversion, absorption and the like, and the resource recovery value is high. However, impurities and harmful elements in the flue gas can be simultaneously washed and enter acid washing wastewater in a purification process in the sulfur resource production process, and part of sulfur dioxide gas in the flue gas can be absorbed by water vapor and brought into the wastewater.
Generally, the SRG flue gas scrubbing wastewater tends to be acidic because the acidic species in the SRG gas are greater than the basic species. When cyanide and derivatives thereof exist in the front-end flue gas, the cyanide and derivatives thereof enter SRG gas and are finally dissolved in the acidic washing wastewater, so that the alkalinity of the wastewater (such as hydrolysis of cyanic acid to generate ammonia nitrogen) is increased, and the acidic washing wastewater is neutral. Since the acidic washing wastewater is neutral, a large amount of SO in SRG gas can be caused 2 The acid gas dissolves, causing a dramatic increase in bisulphite in the wastewater. The detection result shows that the concentration of the hydrogen sulfite in the acid washing wastewater generated by the cyanide-free SRG gas washing is 2-5 g/L, and the concentration of the hydrogen sulfite in the acid washing wastewater generated by the cyanide-containing SRG gas washing is 240-300 g/L. The acidic washing wastewater containing the bisulfide with high concentration has huge treatment difficulty if entering a subsequent wastewater treatment system. On one hand, the alkali consumption is increased sharply, so that the waste of liquid alkali is caused, and the wastewater discharge amount is increased; in addition, sodium sulfite is formed to crystallize and separate out during the alkali adding process, which results in system blocking and paralysis.
Sulfur is an oxygen group simple substance nonmetallic solid, is an important chemical raw material, and is widely used for producing various chemical products, gunpowder, matches, pigments and medicinal products. Powdered sulfur is agriculturally useful as an insecticide and bactericide. Sulfur is mainly derived from natural sulfur deposit extraction and recovery of sulfur from natural gas, coal gas and industrial waste gas. With the expansion of sulfur demand, the recovery of sulfur from waste gas or wastewater is becoming an important source of sulfur.
The liquid phase disproportionation sulfur production method is to utilize the characteristic that sulfur element in bisulphite is in an intermediate valence state, and disproportionation is carried out under the conditions of high temperature and catalyst, so that the recovery of elemental sulfur is realized. Aiming at the defects that the concentration of hydrogen sulfite in wastewater is high, direct alkali addition can cause crystallization of a wastewater system and cause blockage. The use of "acid stripping" and "precipitation" has been reported earlier, but these methods have been somewhat inadequate. The main steps are as follows:
acidification and blowing off method: the hydrogen sulfite can be changed into sulfur dioxide to escape under the acidic condition, so that the concentration of the hydrogen sulfite is reduced. The reactions involved are: HSO (high speed oxygen) 3 - +H + →H 2 SO 3 ；H 2 SO 3 +air→H 2 O+SO 2 And ≡. However, the method needs to add an acid solution, the total water amount is increased, and the addition amount of the acid solution is larger. In addition, the method utilizes strong acid to prepare weak acid, and the total salt content can be reduced by 50% at most.
Precipitation method: the sulfate is removed by utilizing the property that the bisulfate and the metal cations form sulfate, such as adding calcium oxide, magnesium oxide, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate and ferrous nitrate. The reactions involved are: SO (SO) 3 2- +precipitant M.fwdarw.MSO 3 And ∈. This process produces a large amount of solid slag and metal salts are generally expensive.
Disproportionation method: such as chinese patent documents 201210391355.9, 201210392392.1, 201711078170.1. Based on the property that the bisulfide can be disproportionated into elemental sulfur and sulfate radical, the 1/3 reduction of the bisulfide is realized under the condition of not consuming additional substances. The reactions involved are: 3HSO 3 - →S+2SO 4 2- +H + +H 2 O. The temperature of the direct reaction was > 160 ℃. The addition of the catalyst can reduce the reaction temperature: if selenium is added, the reaction temperature can be reduced to 80-100 ℃; adding iodine and exposing to lightThe catalyst can be carried out at normal temperature. But because selenium and iodine are expensive, the possibility of industrial application is not provided. In the method, the disproportionation method has the advantages of no additional consumption of substances, no increase of water quantity and the like. Disproportionation of bisulphite by catalytic means to recover sulphur is a low cost operation. However, the process has not been widely popularized due to the high price of the catalyst. Therefore, the finding of a low-cost and high-efficiency bisulphite disproportionation catalyst for recycling the SRG washing wastewater has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a desulfurization method for catalyzing cyanide-containing SRG washing wastewater by using sulfur-containing activated carbon. The sulfur-containing active carbon is used as a catalyst, and the disproportionation reaction recovery of high-concentration bisulfide ions can be realized at about 50 ℃ to obtain sulfur resources. On one hand, the salt content in the SRG washing wastewater is reduced, and on the other hand, the purpose of recycling sulfur is realized; the consumption of liquid alkali is greatly reduced, and the consumption of liquid alkali can be reduced by about 60 percent through a comparison test. The sulfur-containing activated carbon used in the invention has the advantages of simple preparation process, easily available raw materials, low price and large-scale application prospect, and the prepared sulfur-containing activated carbon can be recycled. In addition, the invention can recycle sulfur while treating the wastewater, realize the recycling treatment of the wastewater and avoid secondary pollution. Therefore, the catalyst for the disproportionation and desulfurization of the bisulfide ions in the SRG washing wastewater by using the sulfur-containing activated carbon has wide market prospect and economic benefit.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a process for desalinating SRG wash wastewater catalyzed by sulfur-containing activated carbon, the process comprising the steps of:
1) The sulfur-containing active carbon is prepared by taking elemental sulfur or sulfur-containing compounds as a sulfur source and active carbon as a carrier.
2) And adding sulfur-containing activated carbon into the SRG washing wastewater to perform catalytic disproportionation reaction.
3) Continuously monitoring the pH value of the reaction system in the step 2) until the pH value changes to the pH set value. Then solid-liquid separation is carried out to obtain filtrate.
4) And (3) continuously heating the filtrate obtained in the step (3) to react until precipitation is generated and clear supernatant appears, and recovering the precipitation to obtain elemental sulfur.
Preferably, the step 1) specifically comprises: 1a) Adding active carbon into sodium thiosulfate solution, uniformly mixing, adding acid for acidizing treatment, and finally carrying out load reaction to obtain the sulfur-containing active carbon.
Alternatively, preferably, step 1) specifically includes: 1b) And respectively placing elemental sulfur and active carbon into different heating sections, and introducing protective gas. Then the heating section with elemental sulfur and the heating section with active carbon are heated respectively. And finally, introducing sulfur vapor generated by the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction, and obtaining the sulfur-containing active carbon after the reaction is completed.
Alternatively, preferably, step 1) specifically includes: 1c) Uniformly mixing elemental sulfur, active carbon, a binder and water to obtain a mixture, then carrying out molding treatment on the mixture, and finally drying to obtain the sulfur-containing active carbon.
Preferably, in step 1), the activated carbon is one or more of coal activated carbon, wood activated carbon, coconut activated carbon, and fruit shell activated carbon, preferably coal activated carbon.
Preferably, the particle size of the activated carbon is granular activated carbon or powdered activated carbon;
preferably, the sulfur-bearing active carbon has a sulfur-bearing amount of 1.6 to 16g, preferably 3.2 to 9.6g, more preferably 4.8 to 8g, per gram of active carbon.
Preferably, in step 2), the SRG wash wastewater is a cyanide-containing SRG wash wastewater. The temperature of the disproportionation reaction is 40-80 ℃, preferably 45-70 ℃, more preferably 50-60 ℃. The disproportionation reaction time is 0.3 to 10 hours, preferably 0.5 to 8 hours, more preferably 0.8 to 5 hours.
Preferably, in step 3), the pH set point is < 3, preferably the pH set point is < 2.5, more preferably the pH set point is < 2.
Preferably, in step 4), the reaction temperature of the heating reaction is 50 to 120 ℃, preferably 60 to 110 ℃, more preferably 70 to 100 ℃.
Preferably, in step 1 a), the numerical ratio of the molar amount (moL) of sodium thiosulfate to the weight (g) of activated carbon is from 0.05 to 0.5:1, preferably from 0.1 to 0.3:1, more preferably from 0.15 to 0.25:1.
Preferably, in step 1 a), the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid. Preferably sulfuric acid.
Preferably, in step 1 b), the mass ratio of elemental sulfur to activated carbon is 1.5-18:1, preferably 3-15:1, more preferably 4.5-12:1.
Preferably, in step 1 b), the protective gas is one or more of nitrogen, argon and helium, preferably nitrogen.
Preferably, in step 1 b), the temperature after heating in the heating section with elemental sulphur is between 400 and 600 ℃, preferably between 450 and 550 ℃. The temperature of the heating section with the activated carbon is 60-180 ℃, preferably 80-150 ℃.
Preferably, in step 1 c), the binder is one or more of coal tar, sodium carboxymethyl cellulose, polyvinyl alcohol, sesbania powder, soluble starch, polyethylene glycol, ethanol, glycerol, silica sol, alumina sol, bentonite, water glass, and waste syrup, preferably sodium carboxymethyl cellulose.
Preferably, in step 1 c), the mass ratio of the mixture to the total amount of binder and water added is 1.5-15:1, preferably 2-10:1, more preferably 3-6:1. Wherein the mass ratio of the binder to the water is 0.15-1:1, preferably 0.2-0.8:1, more preferably 0.3-0.7:1.
Preferably, step 1 a) is specifically: firstly, dissolving sodium thiosulfate to obtain a sodium thiosulfate solution, then adding active carbon particles according to a proportion, and stirring and uniformly mixing (for example, stirring and mixing for 3-30min, preferably stirring and mixing for 5-20 min) to obtain a mixed solution. Stirring is then continued while adding the acid (e.g., sulfuric acid) dropwise or in portions to the mixed solution, and the mixed solution is adjusted to be acidic (e.g., pH < 6.5, preferably pH < 5, more preferably pH < 3) to obtain an acidic mixed solution. The acidic mixed solution is stirred again to carry out the supporting reaction (for example, the stirring supporting reaction is carried out for 0.3 to 5 hours, preferably 0.5 to 3 hours). After the reaction was completed, filtration and drying were performed.
Preferably, step 1 b) is specifically: according to the flow direction of the gas, elemental sulfur and activated carbon are sequentially placed in different heating sections of a heater (e.g., a staged heating reactor), and then a protective gas (e.g., nitrogen) is introduced at a rate of 0.05 to 1.0L/min (preferably 0.1 to 0.5L/min). After a period of time (e.g., after the nitrogen has exhausted the air in the heater) the protective gas is introduced. The heating section with elemental sulfur is heated (e.g., the heating section with elemental sulfur is heated to 400-600 c) while the heating section with activated carbon is heated (e.g., the heating section with activated carbon is heated to 60-180 c). And then introducing sulfur vapor generated in the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction for 1-5h (preferably 2-3 h) to obtain the sulfur-containing active carbon.
Preferably, step 1 c) is specifically: the elemental sulfur powder and the activated carbon powder are mixed to obtain a sulfur-carbon mixed powder (the average particle diameter of the sulfur-carbon mixed powder is 10 to 100 mesh, preferably 15 to 80 mesh, more preferably 20 to 50 mesh). And then adding the binder and water into the sulfur-carbon mixed powder in batches (for example, 1-10 times, preferably 2-8 times) according to a proportion in the stirring process, and continuously stirring and uniformly mixing (for example, stirring and mixing for 5-60min, preferably stirring and mixing for 10-30 min) to obtain the mixture. Finally, the mixture is added into a forming machine (such as one or more of an extrusion forming machine, an extrusion granulator and a disc granulator) for forming treatment to obtain a formed material, and the formed material is dried (such as dried under the condition of hot air or humid hot air at 80-100 ℃ for 1-3h, preferably dried under the condition of hot air at 80-90 ℃ for 1-3 h) to obtain the sulfur-containing activated carbon.
Preferably, the step 2) specifically comprises: the bisulphite content of the SRG washing wastewater is detected. Then adding sulfur-containing active carbon, heating to 40-80 ℃ (preferably 50-60 ℃) to perform disproportionation reaction for 0.3-10h (preferably 0.5-8 h), and performing step 3 after obtaining a disproportionation reaction system.
Preferably, the step 3) specifically comprises: continuously monitoring the pH value of the reaction system in the step 2), filtering after the pH value of the reaction system is lower than 3 (preferably, the pH value is lower than 2), separating sulfur-containing active carbon and obtaining filtrate. The sulfur-containing activated carbon is returned to the step 2) and is continuously used as a catalyst, and the filtrate is subjected to the step 4).
Preferably, the step 4) specifically comprises: the filtrate obtained in step 3) is further heated to 50-120 c (preferably 70-100 c) for reaction until sulphur precipitation occurs and a relatively clear supernatant is obtained. And separating out sulfur precipitate, and drying to obtain elemental sulfur.
In the prior art, because the acidic substances in the SRG gas are larger than the alkaline substances, the SRG flue gas washing wastewater tends to be acidic. When cyanide and derivatives thereof exist in the front-end flue gas, the cyanide and derivatives thereof enter SRG gas and are finally dissolved in the acidic washing wastewater, so that the alkalinity of the wastewater (such as hydrolysis of cyanic acid to generate ammonia nitrogen) is increased, and the acidic washing wastewater is neutral. Since the acidic washing wastewater is neutral, a large amount of SO in SRG gas can be caused 2 The acid gas dissolves, causing a dramatic increase in bisulphite in the wastewater. The detection result shows that the concentration of the hydrogen sulfite in the acid washing wastewater generated by the cyanide-free SRG gas washing is 2-5 g/L, and the concentration of the hydrogen sulfite in the acid washing wastewater generated by the cyanide-containing SRG gas washing is 240-300 g/L. The acidic washing wastewater containing the bisulfide with high concentration has huge treatment difficulty if entering a subsequent wastewater treatment system. On one hand, the alkali consumption is increased sharply, so that the waste of liquid alkali is caused, and the wastewater discharge amount is increased; in addition, sodium sulfite is formed to crystallize and separate out during the alkali adding process, which results in system blocking and paralysis. The existing acidification stripping method, precipitation method and disproportionation method have the problems of low treatment efficiency and high input cost, and are not beneficial to large-scale industrialized popularization and application.
At present, sulfur mainly comes from ore deposit extraction of natural sulfur and recovery of sulfur from natural gas, coal gas and industrial waste gas. With the expansion of sulfur demand, the recovery of sulfur from waste gas or wastewater is becoming an important source of sulfur. The liquid phase disproportionation sulfur production method is characterized in that the characteristic that the sulfur element in the bisulphite is in an intermediate valence state is utilized, and the disproportionation is carried out under the conditions of high temperature (for example, the temperature at which the bisulphite directly carries out disproportionation reaction is more than 160 ℃) and a catalyst, so that the recovery of elemental sulfur is realized. However, the existing catalysts such as selenium and iodine are expensive, and are not suitable for industrial mass production and application at present.
In the present invention, the inventors of the present application have found through studies that, with respect to the high bisulfite-containing property of cyanide-containing SRG wastewater, disproportionation of high concentration of bisulfite can be achieved under low temperature (around 50 ℃) conditions when elemental sulfur and activated carbon coexist. The sulfur resource is obtained by disproportionation reaction recovery of high-concentration bisulfide ions by adopting sulfur-containing active carbon as a catalyst. On one hand, the salt content in the SRG washing wastewater is reduced, and on the other hand, the purpose of recycling sulfur is realized; greatly reduces the liquid alkali consumption in the subsequent wastewater treatment process, and the liquid alkali consumption can be reduced by about 60 percent through a comparison test. The sulfur-containing activated carbon used in the invention has the advantages of simple preparation process, easily available raw materials, low price and large-scale application prospect, and the prepared sulfur-containing activated carbon can be recycled.
In the invention, under the catalysis of sulfur-containing activated carbon, hydrogen ions and sulfite ions in SRG washing wastewater undergo catalytic disproportionation reaction. Namely, the bisulphite can undergo disproportionation reaction under the catalysis of sulfur-containing activated carbon at the temperature of 40-80 ℃ (preferably 50-60 ℃), and the S (IV) is disproportionated into S (0) and S (VI). The pH of the solution will always decrease during this reaction. When the pH of the solution is reduced to below 3 (preferably to below 2), the catalyst is filtered and separated (the separated sulfur-containing catalyst can be recycled after being dried), so that the investment cost of the catalyst is greatly reduced. The remaining solution is a sulfur colloid, and the colloid is destabilized by continuing to heat (e.g., to 50-120 ℃, preferably to 70-100 ℃) to finally form sulfur particles. Separating out sulfur particle precipitate and drying to obtain elemental sulfur. The invention can recycle sulfur while reducing the salt content of the washing wastewater, realizes the resource utilization and treatment of the wastewater, and has no secondary pollution. The reaction process for disproportionation of S (IV) into S (0) and S (VI) is shown below: the sulfur-containing activated carbon is used as a catalyst for catalytic disproportionation:
generally, the sulfur-containing activated carbon is prepared by adopting high-quality activated carbon as base carbon and adopting a special process, and is mainly used for mercury removal in mercury-containing gas mercury removal devices such as natural gas/coal gas and the like. In the invention, sulfur-containing activated carbon is prepared and obtained by an adsorption method, which comprises the following specific steps: the method comprises the steps of taking sodium thiosulfate acidolysis as a sulfur source, taking activated carbon as an adsorption carrier, mixing the activated carbon with sodium thiosulfate (the added amount of the sodium thiosulfate is larger than that of the activated carbon), then adding acid (such as sulfuric acid) for acidizing treatment, and releasing colloid sulfur when the sodium thiosulfate meets the acid. Meanwhile, in the acidolysis process, as the active carbon powder or the active carbon particles are mixed in the solution in advance, the colloid sulfur separated out by acidolysis of sodium thiosulfate can be adsorbed into the active carbon powder or the active carbon particles through the adsorption effect of the active carbon powder or the active carbon particles to form sulfur-containing active carbon. The specific reaction formula is as follows: acidolysis of sodium thiosulfate under acidic conditions: s is S 2 O 3 2- +H + →S+HSO 3 - 。
In the present invention, sulfur-containing activated carbon can also be obtained by vapor deposition, specifically: the elemental sulfur and the activated carbon are respectively put into different heating sections of the sectional heater according to the flow direction of the gas, and then protective gas (such as nitrogen) is introduced. After the protective gas has evacuated the air in the heater, the heated section containing elemental sulfur is heated to 400-600℃ (preferably 450-550℃) until sulfur vapor is produced, while the heated section containing activated carbon is heated to 60-180℃ (preferably 80-150℃) for vapor deposition adsorption. In this process, the protective gas continuously transports sulfur vapor generated in the heating section containing elemental sulfur into the heating section containing activated carbon. Through the adsorption of the activated carbon powder or activated carbon particles, the sulfur vapor is subjected to vapor deposition on the surface of the activated carbon at 60-180 ℃. In the vapor deposition process, the active carbon carrier has developed gaps, so that sulfur vapor can be fully and uniformly loaded into the pore channels of the active carbon to form the sulfur-containing active carbon.
In the invention, sulfur-containing activated carbon can also be prepared by a mixing molding method, and the method specifically comprises the following steps: and binding the powder elemental sulfur and the active carbon powder by using a binder, and forming by using a forming machine to obtain the granular sulfur-carbon composite material with certain strength. The method comprises the steps of firstly taking elemental sulfur and active carbon, and respectively drying (for example, drying under the protection of atmosphere) and screening (for example, the pore diameter of a sieve is smaller than 30 meshes) to obtain dry sulfur powder and dry active carbon powder. And then adding the binder and the water (the total amount of the binder and the water is unchanged and the single addition amount is regulated according to the actual working condition) into the sulfur-carbon mixed powder in batches (for example, 1-10 times, preferably 2-8 times) in the stirring process, and continuously stirring and uniformly mixing (for example, stirring and mixing for 5-60min, preferably stirring and mixing for 10-30 min) to obtain the mixed material. The mixture is then added to a molding machine (such as one or more of an extrusion molding machine, an extrusion granulator and a disk granulator) to be molded to obtain a granular molding material, and the molding material is dried (generally dried under hot air or hot air containing moisture at 80-100 ℃ for 1-3 hours, preferably dried under hot air at 80-90 ℃ for 1-3 hours) to obtain granular sulfur-containing activated carbon with certain strength.
In the present invention, the compounding process of the sulfur-containing activated carbon is as follows: S+AC→S@AC. (AC refers to activated carbon). The sulfur-containing activated carbon has the advantages of simple preparation process, low price, wide source, easy separation and recovery and long service life.
In the invention, sulfur-containing active carbon is added into the waste water containing bisulphite to catalyze and disproportionate bisulphite ions, the reaction temperature is controlled to be about 50 ℃, and after a period of reaction, the solution becomes light yellow. Filtering to separate sulfur-containing active carbon, and continuing to react the residual filtrate at 70-100 ℃ until sulfur precipitation is generated and clear supernatant is obtained, namely, the reaction is finished (the residual filtrate is sulfur colloid, and then, heating reaction is continued to destabilize the colloid to form sulfur particles).
In the present invention, the sulfur loading per gram of activated carbon is the sulfur content per unit mass of activated carbon in the sulfur-containing activated carbon after passing through the embodiments provided herein. I.e., the mass ratio of sulfur to activated carbon in the sulfur-containing activated carbon.
Compared with the prior art, the beneficial technical effects of the invention are as follows:
1. the invention adopts cheap and easily available sulfur or sulfur-containing compounds as a sulfur source, activated carbon as an adsorption carrier and utilizes the strong adsorption effect of activated carbon particles. The sulfur-containing activated carbon with excellent catalytic performance can be prepared through simple process conditions.
2. The sulfur-carrying active carbon synthesized by the invention is used as a catalyst for the disproportionation reaction of the bisulfites (or the acidic solution of the sulfites), and has the advantages of low price, wide sources, easy separation and recovery and long service life compared with the existing catalyst. And the sulfur-carrying activated carbon is used as a catalyst, so that elemental sulfur can be prepared and recovered at a lower temperature (about 50 ℃), the engineering application prospect is wide, and the method has great economic benefit.
3. The invention innovatively adopts sulfur-carrying activated carbon for the catalytic disproportionation reaction of bisulphite in cyanide-containing SRG washing wastewater, thereby realizing the low-temperature catalytic disproportionation. The method can recycle sulfur while reducing the salt content of the washing wastewater, realizes the resource utilization and treatment of the wastewater, and has no secondary pollution.
4. Based on the property of producing sulfur by the hydrogen sulfite disproportionation, the invention creatively provides a new technology for desalting and desulfurizing by a disproportionation method, realizes the reduction of the salt content in the wastewater and the recovery of sulfur resources, and greatly reduces the consumption of liquid alkali in the subsequent wastewater treatment process (about 60% can be reduced by a comparison test). Provides a new way for the treatment and resource utilization of SRG washing wastewater.
Drawings
FIG. 1 is a flow chart of a process for desalting SRG wash wastewater by sulfur-containing activated carbon catalysis in accordance with the present invention.
FIG. 2 is a flow chart of the adsorption method for preparing sulfur-containing activated carbon.
FIG. 3 is a flow chart of the method for preparing sulfur-containing activated carbon by vapor deposition.
FIG. 4 is a flow chart of the present invention for preparing sulfur-containing activated carbon using a blend-forming process.
FIG. 5 is a graph comparing the post-alkali consumption of wastewater treated by the method of the present invention with the post-alkali consumption of wastewater of the prior art.
Detailed Description
The following examples illustrate the technical aspects of the invention, and the scope of the invention claimed includes but is not limited to the following examples.
A process for desalinating SRG wash wastewater catalyzed by sulfur-containing activated carbon, the process comprising the steps of:
1) The sulfur-containing active carbon is prepared by taking elemental sulfur or sulfur-containing compounds as a sulfur source and active carbon as a carrier.
2) And adding sulfur-containing activated carbon into the SRG washing wastewater to perform catalytic disproportionation reaction.
3) Continuously monitoring the pH value of the reaction system in the step 2) until the pH value changes to the pH set value. Then solid-liquid separation is carried out to obtain filtrate.
4) And (3) continuously heating the filtrate obtained in the step (3) to react until precipitation is generated and clear supernatant appears, and recovering the precipitation to obtain elemental sulfur.
Preferably, the step 1) specifically comprises: 1a) Adding active carbon into sodium thiosulfate solution, uniformly mixing, adding acid for acidizing treatment, and finally carrying out load reaction to obtain the sulfur-containing active carbon.
Alternatively, preferably, step 1) specifically includes: 1b) And respectively placing elemental sulfur and active carbon into different heating sections, and introducing protective gas. Then the heating section with elemental sulfur and the heating section with active carbon are heated respectively. And finally, introducing sulfur vapor generated by the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction, and obtaining the sulfur-containing active carbon after the reaction is completed.
Alternatively, preferably, step 1) specifically includes: 1c) Uniformly mixing elemental sulfur, active carbon, a binder and water to obtain a mixture, then carrying out molding treatment on the mixture, and finally drying to obtain the sulfur-containing active carbon.
Preferably, in step 1), the activated carbon is one or more of coal activated carbon, wood activated carbon, coconut activated carbon, and fruit shell activated carbon, preferably coal activated carbon. Preferably, the particle size of the activated carbon is granular activated carbon or powdered activated carbon.
Preferably, the sulfur-bearing active carbon has a sulfur-bearing amount of 1.6 to 16g, preferably 3.2 to 9.6g, more preferably 4.8 to 8g, per gram of active carbon.
Preferably, in step 2), the SRG wash wastewater is a cyanide-containing SRG wash wastewater. The temperature of the disproportionation reaction is 40-80 ℃, preferably 45-70 ℃, more preferably 50-60 ℃. The disproportionation reaction time is 0.3 to 10 hours, preferably 0.5 to 8 hours, more preferably 0.8 to 5 hours.
Preferably, in step 3), the pH set point is < 3, preferably the pH set point is < 2.5, more preferably the pH set point is < 2.
Preferably, in step 4), the reaction temperature of the heating reaction is 50 to 120 ℃, preferably 60 to 110 ℃, more preferably 70 to 100 ℃.
Preferably, in step 1 a), the numerical ratio of the molar amount (moL) of sodium thiosulfate to the weight (g) of activated carbon is from 0.05 to 0.5:1, preferably from 0.1 to 0.3:1, more preferably from 0.15 to 0.25:1.
Preferably, in step 1 a), the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid. Preferably sulfuric acid.
Preferably, in step 1 b), the mass ratio of elemental sulfur to activated carbon is 1.5-18:1, preferably 3-15:1, more preferably 4.5-12:1.
Preferably, in step 1 b), the protective gas is one or more of nitrogen, argon and helium, preferably nitrogen.
Preferably, in step 1 b), the temperature after heating in the heating section with elemental sulphur is between 400 and 600 ℃, preferably between 450 and 550 ℃. The temperature of the heating section with the activated carbon is 60-180 ℃, preferably 80-150 ℃.
Preferably, in step 1 c), the binder is one or more of coal tar, sodium carboxymethyl cellulose, polyvinyl alcohol, sesbania powder, soluble starch, polyethylene glycol, ethanol, glycerol, silica sol, alumina sol, bentonite, water glass, and waste syrup, preferably sodium carboxymethyl cellulose.
Preferably, in step 1 c), the mass ratio of the mixture to the total amount of binder and water added is 1.5-15:1, preferably 2-10:1, more preferably 3-6:1. Wherein the mass ratio of the binder to the water is 0.15-1:1, preferably 0.2-0.8:1, more preferably 0.3-0.7:1.
Preferably, step 1 a) is specifically: firstly, dissolving sodium thiosulfate to obtain a sodium thiosulfate solution, then adding active carbon particles according to a proportion, and stirring and uniformly mixing (for example, stirring and mixing for 3-30min, preferably stirring and mixing for 5-20 min) to obtain a mixed solution. Stirring is then continued while adding the acid (e.g., sulfuric acid) dropwise or in portions to the mixed solution, and the mixed solution is adjusted to be acidic (e.g., pH < 6.5, preferably pH < 5, more preferably pH < 3) to obtain an acidic mixed solution. The acidic mixed solution is stirred again to carry out the supporting reaction (for example, the stirring supporting reaction is carried out for 0.3 to 5 hours, preferably 0.5 to 3 hours). After the completion of the reaction, the sulfur-containing activated carbon is obtained by filtration and drying (for example, drying at 50 to 100℃for 0.5 to 2 hours, preferably at 60 to 80℃for 1 to 1.5 hours).
Preferably, step 1 b) is specifically: according to the flow direction of the gas, elemental sulfur and activated carbon are sequentially placed in different heating sections of a heater (e.g., a staged heating reactor), and then a protective gas (e.g., nitrogen) is introduced at a rate of 0.05 to 1.0L/min (preferably 0.1 to 0.5L/min). After a period of time (e.g., after the nitrogen has exhausted the air in the heater) the protective gas is introduced. The heating section with elemental sulfur is heated (e.g., the heating section with elemental sulfur is heated to 400-600 c) while the heating section with activated carbon is heated (e.g., the heating section with activated carbon is heated to 60-180 c). And then introducing sulfur vapor generated in the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction for 1-5h (preferably 2-3 h) to obtain the sulfur-containing active carbon.
Preferably, step 1 c) is specifically: the elemental sulfur powder and the activated carbon powder are mixed to obtain a sulfur-carbon mixed powder (the average particle diameter of the sulfur-carbon mixed powder is 10 to 100 mesh, preferably 15 to 80 mesh, more preferably 20 to 50 mesh). And then adding the binder and water into the sulfur-carbon mixed powder in batches (for example, 1-10 times, preferably 2-8 times) according to a proportion in the stirring process, and continuously stirring and uniformly mixing (for example, stirring and mixing for 5-60min, preferably stirring and mixing for 10-40 min) to obtain the mixture. Finally, the mixture is added into a forming machine (such as one or more of an extrusion forming machine, an extrusion granulator and a disc granulator) for forming treatment to obtain a formed material, and the formed material is dried (such as dried under the condition of hot air or humid hot air at 80-100 ℃ for 1-3h, preferably dried under the condition of hot air at 80-90 ℃ for 1-3 h) to obtain the sulfur-containing activated carbon.
Preferably, the step 2) specifically comprises: the bisulphite content of the SRG washing wastewater is detected. Then adding sulfur-containing active carbon, heating to 40-80 ℃ (preferably 50-60 ℃) to perform disproportionation reaction, and performing step 3) after obtaining a disproportionation reaction system.
Preferably, the step 3) specifically comprises: continuously monitoring the pH value of the reaction system in the step 2), filtering after the pH value of the reaction system is lower than 3 (preferably, the pH value is lower than 2), separating sulfur-containing active carbon and obtaining filtrate. The sulfur-containing activated carbon is returned to the step 2) and is continuously used as a catalyst, and the filtrate is subjected to the step 4).
Preferably, the step 4) specifically comprises: the filtrate obtained in step 3) is further heated to 50-120 c (preferably 70-100 c) for reaction until sulphur precipitation occurs and a relatively clear supernatant is obtained. And separating out sulfur precipitate, and drying to obtain elemental sulfur.
Example 1
158g of sodium thiosulfate was dissolved in 500mL of water, and then 10g of activated carbon particles (average particle diameter: 10 μm) were added, followed by stirring and mixing for 10 minutes to obtain a mixed solution. Then stirring is continued, sulfuric acid is added dropwise into the mixed solution in the stirring process, and the pH value of the mixed solution is regulated to be less than 3; after the dripping is completed, stirring and mixing are continued for 15min, and the reaction is carried out for 2h at normal temperature and normal pressure; finally, the mixture was filtered and dried at 80℃for 2 hours to obtain sulfur-containing activated carbon I (3.11. 3.11g S/g powder AC).
Example 2
40g of elemental sulfur was added to the front section of the segmented heater, and then 10g of activated carbon particles (average particle size 75 μm) were added to the rear section of the segmented heater. Then, nitrogen was passed through at a rate of 0.1L/min for 5-10min. Then heating the front section of the sectional heater containing elemental sulfur to 450 ℃, and simultaneously heating the rear section of the sectional heater containing active carbon to 120 ℃; and (3) connecting the front section and the rear section of the sectional heater, performing vapor deposition reaction on sulfur vapor and active carbon for 2 hours, and drying to obtain sulfur-containing active carbon II (3.78 g S/g of powder AC).
Example 3
And respectively drying and screening the elemental sulfur and the activated carbon to obtain dry sulfur powder and dry activated carbon powder (with the mesh diameter of less than 30 meshes). And stirring and mixing 40g of dried sulfur powder and 10g of dried activated carbon powder uniformly to obtain sulfur-carbon mixed powder. Then 5g of bonding and 5g of water are added into the sulfur-carbon mixed powder for 5 times in the stirring process, and stirring and mixing are continued for 20min after the addition is completed to obtain a mixture; and then adding the mixture into a disc granulator for forming treatment to obtain granular forming materials (the particle size is 8 mm), and finally drying the forming materials for 1h at 80 ℃ by adopting hot air to obtain the sulfur-containing activated carbon III (3.85 g S/g powder AC).
Example 4
100mL of the cyanide-containing SRG washing wastewater was taken, and the bisulfite content of the cyanide-containing SRG washing wastewater was detected to be 260g/L. Then adding 4.0g of sulfur-containing activated carbon I, and then heating to 55 ℃ for disproportionation reaction; and continuously monitoring the pH value of the reaction system, and filtering after the pH value of the reaction system is lower than 2, separating sulfur-containing activated carbon and obtaining filtrate. The reaction was continued by heating the filtrate to 90 c until a sulfur precipitate was formed and a relatively clear supernatant was obtained. The sulphur precipitate was then separated and dried to yield 3.08g elemental sulphur. The content of bisulphite in the wastewater after catalytic desulfurization was detected to be 17.0g/L.
Example 5
100mL of the cyanide-containing SRG washing wastewater was taken, and the bisulfite content of the cyanide-containing SRG washing wastewater was detected to be 260g/L. Then adding 3.0g of sulfur-containing activated carbon II, and then heating to 55 ℃ for disproportionation reaction; and continuously monitoring the pH value of the reaction system, and filtering after the pH value of the reaction system is lower than 2, separating sulfur-containing activated carbon and obtaining filtrate. The reaction was continued by heating the filtrate to 90 c until a sulfur precipitate was formed and a relatively clear supernatant was obtained. The sulfur precipitate was then separated and dried to yield 3.01g elemental sulfur. The content of bisulphite in the wastewater after catalytic desulfurization was detected to be 24.6g/L.
Example 6
100mL of the cyanide-containing SRG washing wastewater was taken, and the bisulfite content of the cyanide-containing SRG washing wastewater was detected to be 260g/L. Then adding 6.0g of sulfur-containing activated carbon III, and then heating to 50 ℃ for disproportionation reaction; and continuously monitoring the pH value of the reaction system, and filtering after the pH value of the reaction system is lower than 3, separating sulfur-containing activated carbon and obtaining filtrate. The reaction was continued by heating the filtrate to 90 c until a sulfur precipitate was formed and a relatively clear supernatant was obtained. The sulphur precipitate was then separated and dried to yield 3.22g elemental sulphur. The content of bisulphite in the wastewater after catalytic desulfurization was detected to be 9.4g/L.

Claims (27)

1. A method for desalting SRG washing wastewater by sulfur-containing activated carbon catalysis, which is characterized by comprising the following steps: the method comprises the following steps:
1) Preparing sulfur-containing active carbon by taking elemental sulfur or sulfur-containing compounds as a sulfur source and active carbon as a carrier; in the sulfur-containing active carbon, the sulfur carrying amount of each gram of active carbon is 1.6-16g;
2) Adding sulfur-containing activated carbon into the SRG washing wastewater to perform catalytic disproportionation reaction; the temperature of the disproportionation reaction is 40-55 ℃;
3) Continuously monitoring the pH value of the reaction system in the step 2) until the pH value changes to a pH set value; then carrying out solid-liquid separation to obtain filtrate;
4) Continuously heating the filtrate obtained in the step 3) to react until precipitation is generated and clear supernatant appears, and recovering the precipitation to obtain elemental sulfur;
the step 1) is specifically as follows: 1a) Adding active carbon into a sodium thiosulfate solution, uniformly mixing, adding acid for acidizing treatment, and finally carrying out load reaction to obtain sulfur-containing active carbon;
alternatively, the step 1) specifically includes: 1b) Respectively placing elemental sulfur and active carbon into different heating sections, and introducing protective gas; then heating the heating section with elemental sulfur and the heating section with active carbon respectively; finally, introducing sulfur vapor generated by the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction, and obtaining sulfur-containing active carbon after the reaction is completed;
Alternatively, the step 1) specifically includes: 1c) Uniformly mixing elemental sulfur, active carbon, a binder and water to obtain a mixture, then carrying out molding treatment on the mixture, and finally drying to obtain the sulfur-containing active carbon.
2. The method according to claim 1, characterized in that: in the step 1), the activated carbon is one or more of coal activated carbon, wood activated carbon, coconut activated carbon and fruit shell activated carbon;
and/or
In step 2), the SRG washing wastewater is cyanide-containing SRG washing wastewater; the disproportionation reaction time is 0.3-10h;
in step 3), the pH set point is < 3;
in step 4), the reaction temperature of the heating reaction is 50-120 ℃.
3. The method according to claim 2, characterized in that: in the step 1), the activated carbon is coal activated carbon;
the sulfur carrying amount of each gram of active carbon is 3.2-9.6g; and/or
In the step 2), the disproportionation reaction time is 0.5-8h;
in step 3), the pH set point is < 2.5;
in step 4), the reaction temperature of the heating reaction is 60-110 ℃.
4. A method according to claim 3, characterized in that: in step 1), the activated carbon is granular activated carbon or powdered activated carbon; the sulfur carrying amount of each gram of active carbon is 4.8-8g; and/or
In the step 2), the disproportionation reaction time is 0.8-5h;
in step 3), the pH set point is < 2;
in step 4), the reaction temperature of the heating reaction is 70-100 ℃.
5. The method according to any one of claims 1-4, wherein: in step 1 a), the numerical ratio of the molar quantity (mol) of sodium thiosulfate to the weight (g) of the activated carbon is 0.05-0.5:1;
the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, nitrous acid and phosphoric acid;
in the step 1 b), the mass ratio of the elemental sulfur to the active carbon is 1.5-18:1;
the protective gas is one or more of nitrogen, argon and helium;
the temperature of the heating section with elemental sulfur is 400-600 ℃; the temperature of the heated section with the active carbon is 60-180 ℃;
in the step 1 c), the binder is one or more of coal tar, sodium carboxymethyl cellulose, polyvinyl alcohol, sesbania powder, soluble starch, polyethylene glycol, ethanol, glycerol, silica sol, alumina sol, bentonite, water glass and waste syrup;
the mass ratio of the mixture to the total addition amount of the binder and the water is 1.5-15:1; wherein the mass ratio of the binder to the water is 0.15-1:1.
6. The method according to claim 5, wherein: in step 1 a), the numerical ratio of the molar quantity (mol) of sodium thiosulfate to the weight (g) of the activated carbon is 0.1-0.3:1; the acid is sulfuric acid; and/or
In the step 1 b), the mass ratio of the addition amount of the elemental sulfur to the addition amount of the active carbon is 3-15:1; the protective gas is nitrogen; the temperature of the heating section with elemental sulfur is 450-550 ℃; the temperature of the heated section with the active carbon is 80-150 ℃;
in step 1 c), the binder is sodium carboxymethyl cellulose; the mass ratio of the mixture to the total addition amount of the binder and the water is 2-10:1; wherein the mass ratio of the binder to the water is 0.2-0.8:1.
7. The method according to claim 6, wherein: in step 1 a), the numerical ratio of the molar quantity (mol) of sodium thiosulfate to the weight (g) of the activated carbon is 0.15-0.25:1;
in the step 1 b), the mass ratio of the addition amount of the elemental sulfur to the addition amount of the active carbon is 4.5-12:1;
in the step 1 c), the mass ratio of the mixture to the total addition amount of the binder and the water is 3-6:1; wherein the mass ratio of the binder to the water is 0.3-0.7:1.
8. The method according to claim 5, wherein: the step 1 a) comprises the following specific steps: firstly dissolving sodium thiosulfate to obtain a sodium thiosulfate solution, then adding active carbon particles according to a proportion, and stirring and mixing for 3-30min to obtain a mixed solution; then continuing stirring, and simultaneously adding acid dropwise or in batches into the mixed solution, and regulating the pH value of the mixed solution to be less than 6.5 to obtain an acidic mixed solution; stirring the acidic mixed solution continuously for carrying out stirring load reaction for 0.3-5h; filtering after the reaction is finished and drying at 50-100 ℃ for 0.5-2h to obtain the sulfur-containing activated carbon.
9. The method according to claim 8, wherein: the step 1 a) comprises the following specific steps: firstly dissolving sodium thiosulfate to obtain a sodium thiosulfate solution, then adding active carbon particles according to a proportion, and stirring and mixing for 5-20min to obtain a mixed solution; then continuing stirring, and simultaneously adding sulfuric acid into the mixed solution dropwise or in batches, and regulating the pH value of the mixed solution to be less than 5 to obtain an acidic mixed solution; stirring the acidic mixed solution continuously for carrying out stirring load reaction for 0.5-3h; filtering after the reaction is finished and drying at 60-80 ℃ for 1-1.5h to obtain the sulfur-containing activated carbon.
10. The method according to claim 9, wherein: the mixed solution was adjusted to a pH < 3.
11. The method according to claim 5, wherein: the step 1 b) is specifically as follows: according to the flow direction of the gas, sequentially placing elemental sulfur and active carbon into different heating sections of a sectional heating reactor, and then introducing protective gas at the speed of 0.05-1.0L/min; introducing protective gas for a period of time; heating the heating section with elemental sulfur and simultaneously heating the heating section with active carbon; and then introducing sulfur vapor generated in the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction of 1-5 h to obtain the sulfur-containing active carbon.
12. The method according to claim 11, wherein: the step 1 b) is specifically as follows: according to the flow direction of the gas, sequentially placing elemental sulfur and active carbon into different heating sections of a sectional heating reactor, and then introducing nitrogen at the speed of 0.1-0.5L/min; after the nitrogen is exhausted from the air in the heater; heating the heating section with elemental sulfur to 400-600 ℃ and simultaneously heating the heating section with active carbon to 60-180 ℃; and then introducing sulfur vapor generated in the heating section with elemental sulfur into the heating section with active carbon for vapor deposition reaction of 2-3 h to obtain the sulfur-containing active carbon.
13. The method according to claim 5, wherein: the step 1 c) is specifically as follows: mixing elemental sulfur powder and active carbon powder to obtain sulfur-carbon mixed powder, wherein the average particle size of the sulfur-carbon mixed powder is 10-100 meshes; then adding the binder and water into the sulfur-carbon mixed powder in proportion for 1-10 times in the stirring process, and continuously stirring and mixing for 5-60min to obtain a mixture; and finally, adding the mixture into a forming machine for forming treatment to obtain a forming material, and drying the forming material for 1-3 hours at the temperature of 80-100 ℃ under the condition of drying hot air or moist hot air to obtain the sulfur-containing activated carbon.
14. The method according to claim 13, wherein: the step 1 c) is specifically as follows: mixing elemental sulfur powder and active carbon powder to obtain sulfur-carbon mixed powder, wherein the average particle size of the sulfur-carbon mixed powder is 15-80 meshes; then adding binder and water into the sulfur-carbon mixed powder in proportion for 2-8 times in the stirring process, and continuously stirring and mixing for 10-30min to obtain a mixture; and finally, adding the mixture into one or more of an extrusion molding machine, an extrusion granulator and a disc granulator for molding treatment to obtain a molding material, and drying the molding material at 80-90 ℃ for 1-3 hours under the condition of hot air to obtain the sulfur-containing activated carbon.
15. The method according to claim 14, wherein: the average grain diameter of the sulfur-carbon mixed powder is 20-50 meshes.
16. The method according to any one of claims 1-4, 6-15, wherein: the step 2) is specifically as follows: firstly, detecting the bisulfite content of SRG washing wastewater; then adding sulfur-containing active carbon, heating to perform disproportionation reaction for 0.3-10h, and performing step 3) after obtaining a disproportionation reaction system.
17. The method according to claim 5, wherein: the step 2) is specifically as follows: firstly, detecting the bisulfite content of SRG washing wastewater; then adding sulfur-containing active carbon, heating to disproportionation reaction for 0.3-10h, and carrying out step 3) after obtaining a disproportionation reaction system.
18. The method according to claim 16, wherein: the step 2) is specifically as follows: firstly, detecting the bisulfite content of SRG washing wastewater; then adding sulfur-containing active carbon, heating to disproportionation reaction for 0.5-8h, and carrying out step 3) after obtaining a disproportionation reaction system.
19. The method according to claim 17, wherein: the step 2) is specifically as follows: firstly, detecting the bisulfite content of SRG washing wastewater; then adding sulfur-containing active carbon, heating to disproportionation reaction for 0.5-8h, and carrying out step 3) after obtaining a disproportionation reaction system.
20. The method according to any one of claims 1-4, 6-15, 17-19, wherein: the step 3) is specifically as follows: continuously monitoring the pH value of the disproportionation reaction system in the step 2), and filtering when the pH value of the disproportionation reaction system is lower than 3, separating sulfur-containing active carbon and obtaining filtrate; the sulfur-containing activated carbon is returned to the step 2) and is continuously used as a catalyst, and the filtrate is subjected to the step 4).
21. The method according to claim 5, wherein: the step 3) is specifically as follows: continuously monitoring the pH value of the disproportionation reaction system in the step 2), and filtering when the pH value of the disproportionation reaction system is lower than 3, separating sulfur-containing active carbon and obtaining filtrate; the sulfur-containing activated carbon is returned to the step 2) and is continuously used as a catalyst, and the filtrate is subjected to the step 4).
22. The method according to claim 20, wherein: the step 3) is specifically as follows: continuously monitoring the pH value of the disproportionation reaction system in the step 2), and filtering when the pH value of the disproportionation reaction system is lower than 2, separating sulfur-containing active carbon and obtaining filtrate; the sulfur-containing activated carbon is returned to the step 2) and is continuously used as a catalyst, and the filtrate is subjected to the step 4).
23. The method according to claim 21, wherein: the step 3) is specifically as follows: continuously monitoring the pH value of the disproportionation reaction system in the step 2), and filtering when the pH value of the disproportionation reaction system is lower than 2, separating sulfur-containing active carbon and obtaining filtrate; the sulfur-containing activated carbon is returned to the step 2) and is continuously used as a catalyst, and the filtrate is subjected to the step 4).
24. The method according to any one of claims 1-4, 6-15, 17-19, 21-23, wherein: the step 4) is specifically as follows: continuously heating the filtrate obtained in the step 3) to 50-120 ℃ for reaction until sulfur precipitation is generated and a clear supernatant is obtained; and separating out sulfur precipitate, and drying to obtain elemental sulfur.
25. The method according to claim 5, wherein: the step 4) is specifically as follows: continuously heating the filtrate obtained in the step 3) to 50-120 ℃ for reaction until sulfur precipitation is generated and a clear supernatant is obtained; and separating out sulfur precipitate, and drying to obtain elemental sulfur.
26. The method according to claim 24, wherein: the step 4) is specifically as follows: continuously heating the filtrate obtained in the step 3) to 70-100 ℃ to react until sulfur precipitation is generated and a clear supernatant is obtained; and separating out sulfur precipitate, and drying to obtain elemental sulfur.
27. The method according to claim 25, wherein: the step 4) is specifically as follows: continuously heating the filtrate obtained in the step 3) to 70-100 ℃ to react until sulfur precipitation is generated and a clear supernatant is obtained; and separating out sulfur precipitate, and drying to obtain elemental sulfur.
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