CN109110896B - Agent for removing antimony in printing and dyeing wastewater and removing method thereof - Google Patents
Agent for removing antimony in printing and dyeing wastewater and removing method thereof Download PDFInfo
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a medicament for removing antimony in printing and dyeing wastewater and a removing method thereof, wherein the medicament comprises manganese tailing powder and FeSO4The mixture is solid powder, wherein the main component of manganese tailing powder is MnOx/SiO2Particle size of 0.075-0.100mm, MnOx/SiO2/FeSO4The mass ratio of (1): 1: 1-1: 1:8, FeSO4Is FeSO4·7H2O、FeSO4·3H2O or anhydrous ferrous sulfate; the removing method comprises the following steps: step 1, placing antimony-containing printing and dyeing wastewater in a pretreatment tank for impurity removal pretreatment to obtain pretreated antimony-containing printing and dyeing wastewater; step 2, placing the pretreated antimony-containing printing and dyeing wastewater in a reaction contact tank, then adding a certain amount of medicament for contact stirring, and reacting for 30-60min to obtain the antimony-containing printing and dyeing wastewater after reaction; and 3, placing the reacted antimony-containing printing and dyeing wastewater in a coagulating sedimentation tank for standing sedimentation, and then carrying out solid-liquid separation, thereby removing heavy metal antimony in the printing and dyeing wastewater.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a medicament for removing antimony in printing and dyeing wastewater and a removal method thereof.
Background
The printing and dyeing industry is one of the basic industries for national economic development, is rapidly and vigorously developed since the improvement and the development, and is the first of the world in scale. However, the printing and dyeing industry consumes a lot of water, the pollution discharge is serious, and the produced printing and dyeing wastewater contains a large amount of stable and complex chemical substances, such as: dyes, auxiliaries, heavy metals and the like pose great threats to the water environment in China, and become a great problem in industrial wastewater treatment.
Metal Antimony (Antimony, Sb) has become a new challenge in pollution control in the printing and dyeing industry in recent years, and mainly comes from two aspects, one is production of polyester fibers as a textile printing and dyeing raw material, and the other is use of additives in the weaving and printing process, and Antimony compounds (ethylene glycol Antimony, Antimony acetate and the like) are used as catalysts commonly used in the production process of polyester fibers (namely polyester industrial yarns) as a textile industry raw material, and are often remained in woven polyester fabric fabrics and are dissolved and released in a large amount in subsequent printing and dyeing processes (desizing, alkali decrement and dyeing).
Antimony is a fifth main group element, has similar properties to arsenic, and is a typical poisonous and harmful heavy metal element. Antimony exists mainly in pentavalent form (oxidation environment) and trivalent form (reduction environment) in the environment, mainly in inorganic form, and has little organic antimony content. Because pentavalent antimony is more electronegative than trivalent antimony, pentavalent antimony is more soluble in water and more difficult to remove, both of which are present in the form of oxyacids. Antimony and compounds thereof are dangerous substances with chronic toxicity and potential carcinogenicity, and once entering the environment, the antimony and the compounds inevitably produce toxic effects on animals and plants, enter human bodies through food chains, respiratory tracts, direct contact and the like, and cause harm to human health.
The government in China and various places pays high attention to the antimony pollution prevention and control work of the printing and dyeing industry. In 2012, the emission standard of textile dyeing and finishing industry water pollutants (GB 4287-: in the total discharge port of the waste water of the enterprise, the standard limit values of the direct discharge and the indirect discharge of the total antimony are both 100 mu g.L-1. In 2015, emission limit of total antimony was regulated to 50 μ g.L-1 in newly-released emission Standard of pollutants for municipal wastewater treatment plants (GB 18918-20 XX). Meanwhile, antimony and its compounds were also classified as priority pollutants by the United States Environmental Protection Agency (USEPA) and the European Union (EU) in 1979 and 1976, respectively. In terms of drinking standards, the maximum allowable concentration of Sb in drinking water prescribed by the U.S. environmental protection agency (USEPA) and the European Union (EU) is 6. mu.g.L-1And 10. mu.g.L-1The Sb limited concentration in the 'surface water environment quality standard' (GB 3838--1。
The industrial wastewater treatment needs to meet the wastewater discharge standard of the country and relevant departments, and also needs to consider the problems of economic cost, practical value, simple and convenient operation and the like. At present, antimony pollution in wastewater is mainly removed by methods such as chemical precipitation, electrochemistry, adsorption, membrane separation technology, ion exchange and the like.
The chemical precipitation method is mainly classified into a pH adjustment method and a coagulation precipitation method. The pH adjustment method, while theoretically feasible, is difficult to achieve up-to-standard removal of antimony. The coagulating sedimentation method has simple process and convenient operation, has strong adaptability, needs a large amount of precipitator, is easy to generate a large amount of antimony-containing sludge and causes secondary pollution. The adsorption method is used as a common water treatment process, has the advantages of simple operation, high efficiency, strong adaptability, less waste residues and the like, but has less systematic research on antimony treatment in actual industrial wastewater.
Membrane separation technology is widely concerned due to the advantages of cleanness, high efficiency, no pollution and the like, but membrane pollution and high cost become the biggest obstacles restricting practical large-scale application. Although the ion exchange method is very suitable for treating low-concentration antimony-containing wastewater, the ion exchange method is also troubled by the use cost problem, so that the ion exchange methods are still in a laboratory state at present and are difficult to be applied to large-scale actual wastewater treatment.
Aiming at the increasingly strict antimony emission standard at home and abroad, the development of an economical, efficient and stable antimony pollution prevention and control technology is a practical choice on the healthy development road of the printing and dyeing industry. Because the prior monitoring and control of antimony pollution in printing and dyeing wastewater is neglected and the traditional wastewater treatment system does not pay attention to the research on antimony removal technology, the increasingly improved antimony discharge standard of the printing and dyeing industry and the laggard current situation that the traditional wastewater treatment method is difficult to effectively remove antimony form a gradually outstanding contradiction. Therefore, the improvement of the antimony pollution control of the printing and dyeing industrial wastewater is urgent.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a chemical for removing antimony from printing and dyeing wastewater and a method for removing antimony from printing and dyeing wastewater.
The invention provides a medicament for removing antimony in printing and dyeing wastewater, which is characterized by comprising the following components: manganese tailing powder and FeSO4The mixture is solid powder, wherein the main component of the manganese tailing powder is MnOx/SiO2Particle size of 0.075-0.100mm, MnOx/SiO2/FeSO4The mass ratio of (1): 1: 1-1: 1:8, FeSO4Is FeSO4·7H2O、FeSO4·3H2O or anhydrous ferrous sulfate.
The agent for removing antimony from printing and dyeing wastewater provided by the invention can also have the following characteristics: wherein, MnOx/SiO2/FeSO4The mass ratio of (a) to (b) is 1:1: 8.
the invention also provides a method for removing antimony in the printing and dyeing wastewater by using the agent for removing the antimony in the printing and dyeing wastewater, which is characterized by comprising the following steps:
step 1, placing antimony-containing printing and dyeing wastewater in a pretreatment tank for impurity removal pretreatment to obtain pretreated antimony-containing printing and dyeing wastewater;
step 2, placing the pretreated antimony-containing printing and dyeing wastewater in a reaction contact tank, then adding a certain amount of the medicament for contact stirring, and reacting for 30-60min to obtain the antimony-containing printing and dyeing wastewater after reaction;
and 3, placing the antimony-containing printing and dyeing wastewater after reaction in a coagulating sedimentation tank for standing sedimentation, and then carrying out solid-liquid separation, thereby removing heavy metal antimony in the printing and dyeing wastewater.
The method for removing antimony in printing and dyeing wastewater provided by the invention can also have the following characteristics: wherein, the pretreatment in the step 1 comprises the following substeps:
and filtering and precipitating the antimony-containing printing and dyeing wastewater to remove suspended impurities in the antimony-containing printing and dyeing wastewater, thereby obtaining the pretreated antimony-containing printing and dyeing wastewater.
The method for removing antimony in printing and dyeing wastewater provided by the invention can also have the following characteristics: in the step 2, the adding amount of the chemical agent is increased along with the increase of the concentration of the heavy metal antimony in the printing and dyeing wastewater, and is reduced along with the decrease of the pH value of the printing and dyeing wastewater.
The method for removing antimony in printing and dyeing wastewater provided by the invention can also have the following characteristics: wherein, in the step 2, the content of the manganese tailing powder in the medicament is determined according to MnOx/SiO2The ratio of (a) to (b) is calculated.
The method for removing antimony in printing and dyeing wastewater provided by the invention can also have the following characteristics: wherein, the antimony-containing compound in the antimony-containing printing and dyeing wastewater is one or more of ethylene glycol antimony, antimony acetate or antimony trioxide.
The method for removing antimony in printing and dyeing wastewater provided by the invention can also have the following characteristics: wherein, in the step 3, the heavy metal antimony is one or two of trivalent antimony or pentavalent antimony. Action and Effect of the invention
According to the medicament for removing the antimony in the printing and dyeing wastewater and the removing method thereof, the medicament is a mixed material, has small particle size, uniform particle dispersion and large specific surface area, has good oxidation activity, adsorption performance and coprecipitation effect on heavy metal antimony, and greatly improves the removing capacity of the heavy metal antimony through the cooperation of various action mechanisms; and various components in the medicament complement each other, and the optimal proportion combination is adjusted to form advantage complementation, so that the problem that the heavy metal antimony is difficult to efficiently and thoroughly remove can be solved. And the heavy metal antimony contained in the printing and dyeing wastewater after the heavy metal antimony is removed can reach the discharge standard. In addition, the preparation process of the agent is mild in condition, raw materials can be selected from pyrolusite in manganese tailings, the raw materials are low in cost and easy to obtain, and when the agent is applied to removing antimony in printing and dyeing wastewater, the treatment process is simple, and the reaction time is short, so that the application cost is reduced while the high-efficiency removal effect of heavy metal antimony is ensured, and the agent has popularization and application prospects.
In conclusion, the medicament for removing antimony in printing and dyeing wastewater can remove heavy metal antimony in the printing and dyeing wastewater at one time, the removed antimony mainly exists in the manganese ore material or on surface particles, solid-liquid separation is realized through static precipitation, and when the medicament is actually applied to the printing and dyeing industry wastewater treatment, an original hydraulic facility does not need to be newly built or reconstructed, and the medicament can be directly added for use by utilizing an original conventional water treatment structure facility, so that the application and popularization of large-scale wastewater treatment in the printing and dyeing industry at the present stage are very convenient.
Drawings
FIG. 1 is a flow chart of a method for removing antimony in printing and dyeing wastewater by using an agent for removing antimony in printing and dyeing wastewater in an embodiment of the present invention.
Detailed Description
In order to make the technical means and functions of the present invention easy to understand, the present invention is specifically described below with reference to the embodiments and the accompanying drawings.
FIG. 1 is a flow chart of a method for removing antimony in printing and dyeing wastewater by using an agent for removing antimony in printing and dyeing wastewater in an embodiment of the present invention.
The first embodiment is as follows:
the printing and dyeing wastewater comes from the comprehensive wastewater of a certain printing and dyeing mill, and the concentration of T-Sb is 1080 mug.L-1The CODCr concentration is 1091 mg.L-1The pH value of the water is about 10.1. Firstly, the printing and dyeing wastewater is pretreated, and impurity components in the printing and dyeing wastewater are precipitated and filtered, so that interference on subsequent experimental results is prevented.
MnOx/SiO2/FeSO4The preparation of the mixed system matching medicament material: the raw material is selected from ferro-manganese tailings of manganese ore enterprises in Hunan province, and the effective component in the tailings is MnOxGrinding to obtain particles with uniform size as medicinal component, and MnOx/SiO2/FeSO4The mass ratio of (A) to (B) is 1:1: 8.
As shown in figure 1, step 1, firstly, the printing and dyeing wastewater flows into a reaction tank for pretreatment, the concentration of T-Sb is hardly reduced after the pretreatment, the concentration of CODCr is reduced to 467mg/L, and the pH value of water is hardly changed, so that the pretreated printing and dyeing wastewater is obtained.
Step 2, placing the pretreated printing and dyeing wastewater in a reaction contact tank, and then adding the prepared 1 g.L-1And (5) carrying out contact stirring on the medicament, and reacting for 60min to obtain the printing and dyeing wastewater after reaction.
And 3, flowing the printing and dyeing wastewater after reaction into a coagulating sedimentation tank, and naturally precipitating the printing and dyeing wastewater after reaction in the coagulating sedimentation tank through the coagulating sedimentation effect of the iron-based material, so as to remove heavy metal antimony in the printing and dyeing wastewater.
Collecting supernatant, performing ICP test, and determining T-Sb concentration in water to be 5.9 μ g.L-1CODCr concentration of 62 mg.L-1Wherein, the heavy metal antimony reaches the standard limit values of the direct discharge and the indirect discharge of the total antimony specified in the discharge Standard of pollutants for textile dyeing and finishing industry (GB 4287--1The emission standard of (1).
Example two:
the printing and dyeing wastewater comes from the comprehensive wastewater of a certain printing and dyeing mill, and the concentration of T-Sb is 1080 mug.L-1The CODCr concentration is 1091 mg.L-1The pH value of the water is about 10.1. Firstly, the printing and dyeing wastewater is pretreated, precipitated and filteredImpurity components in the printing and dyeing wastewater are removed, and interference on subsequent experimental results is prevented.
MnOx/SiO2/FeSO4The preparation of the mixed system matching medicament material: the raw material is selected from ferro-manganese tailings of manganese ore enterprises in Hunan province, and the effective component in the tailings is MnOxGrinding to obtain particles with uniform size as medicinal component, and MnOx/SiO2/FeSO4The mass ratio of (A) to (B) is 1:1: 8.
As shown in figure 1, step 1, firstly, the printing and dyeing wastewater flows into a reaction tank for pretreatment, the concentration of T-Sb is hardly reduced after the pretreatment, the concentration of CODCr is reduced to 467mg/L, and the pH value of water is hardly changed, so that the pretreated printing and dyeing wastewater is obtained.
Step 2, placing the pretreated printing and dyeing wastewater in a reaction contact tank, and then adding the prepared 0.1 g.L-1And (5) carrying out contact stirring on the medicament, and reacting for 60min to obtain the printing and dyeing wastewater after reaction.
And 3, flowing the printing and dyeing wastewater after reaction into a coagulating sedimentation tank, and naturally precipitating the printing and dyeing wastewater after reaction in the coagulating sedimentation tank through the coagulating sedimentation effect of the iron-based material, so as to remove heavy metal antimony in the printing and dyeing wastewater.
Collecting supernatant, performing ICP test, and determining T-Sb concentration in water to be 31.6 μ g.L-1CODCr concentration 204 mg.L-1Wherein, the heavy metal antimony reaches the emission standard that the standard limit values of direct emission and indirect emission of total antimony specified in the discharge Standard of pollutants for textile dyeing and finishing industry (GB 4287-.
Example three:
the printing and dyeing wastewater comes from the comprehensive wastewater of a certain printing and dyeing mill, and the concentration of T-Sb is 1080 mug.L-1The CODCr concentration is 1091 mg.L-1The pH value of the water is about 10.1. Firstly, the printing and dyeing wastewater is pretreated, and impurity components in the printing and dyeing wastewater are precipitated and filtered, so that interference on subsequent experimental results is prevented.
MnOx/SiO2/FeSO4The preparation of the mixed system matching medicament material: the raw material is selected from iron manganese tail of a manganese ore enterprise in Hunan provinceThe effective component in the ore, tailing ore, is MnOxGrinding to obtain particles with uniform size as medicinal component, and MnOx/SiO2/FeSO4The mass ratio of (A) to (B) is 1:1: 8.
As shown in fig. 1, in step 1, the printing and dyeing wastewater is first fed into a reaction tank for pretreatment, the concentration of T-Sb is hardly reduced after pretreatment, the concentration of CODCr is reduced to 467mg/L, and the pH of the water is adjusted to 4, so that the pretreated printing and dyeing wastewater is obtained.
Step 2, placing the pretreated printing and dyeing wastewater in a reaction contact tank, and then adding the prepared 0.1 g.L-1And (5) carrying out contact stirring on the medicament, and reacting for 60min to obtain the printing and dyeing wastewater after reaction.
And 3, flowing the printing and dyeing wastewater after reaction into a coagulating sedimentation tank, and naturally precipitating the printing and dyeing wastewater after reaction in the coagulating sedimentation tank through the coagulating sedimentation effect of the iron-based material, so as to remove heavy metal antimony in the printing and dyeing wastewater.
Collecting supernatant, performing ICP test, and determining T-Sb concentration in water to be 9.6 μ g.L-CODCr concentration 193 mg.L-1Wherein the heavy metal antimony reaches the standard limit values of direct and indirect total antimony discharge and discharge specified in the discharge Standard of Water pollutants for textile dyeing and finishing industry (GB 4287--1The emission standard of (1).
Example four:
the printing and dyeing wastewater comes from the comprehensive wastewater of a certain printing and dyeing mill, and the concentration of T-Sb is 874 microgram.L-1The CODCr concentration is 1050 mg.L-1The pH value of the water is about 10.1. Firstly, the printing and dyeing wastewater is pretreated, and impurity components in the printing and dyeing wastewater are precipitated and filtered, so that interference on subsequent experimental results is prevented.
MnOxPreparing a mixed system matched medicament material of/SiO 2/FeSO 4: the raw material is selected from iron manganese tailings of manganese ore enterprises in Hunan province, the effective component in tailings is MnOx, and particles with uniform particle size are screened out by grinding to be used as the component of the medicament, wherein MnO is MnOx/SiO2/FeSO4The mass ratio of (A) to (B) is 1:1: 8.
As shown in FIG. 1, in step 1, printing and dyeing wastewater flows into a reaction tank for pretreatment, the concentration of T-Sb is hardly reduced after pretreatment, the concentration of CODCr is reduced to 459mg/L, and the pH of water is hardly changed, so that the pretreated printing and dyeing wastewater is obtained.
Step 2, placing the pretreated printing and dyeing wastewater in a reaction contact tank, and then adding the prepared 1 g.L-1And (5) carrying out contact stirring on the medicament, and reacting for 60min to obtain the printing and dyeing wastewater after reaction.
And 3, flowing the printing and dyeing wastewater after reaction into a coagulating sedimentation tank, and naturally precipitating the printing and dyeing wastewater after reaction in the coagulating sedimentation tank through the coagulating sedimentation effect of the iron-based material, so as to remove heavy metal antimony in the printing and dyeing wastewater.
And (3) taking the supernatant for ICP test, and determining that the concentration of T-Sb in the water is 1.2 mu g.L < -1 > and the concentration of CODCr is 34 mg.L < -1 >, wherein the heavy metal antimony reaches the emission standard of 100 mu g.L < -1 > for direct emission and indirect emission of total antimony specified in the emission standard of pollutants for textile dyeing and finishing industry water (GB 4287-.
Example five:
the printing and dyeing wastewater comes from the comprehensive wastewater of a certain printing and dyeing mill, and the concentration of T-Sb is 874 microgram.L-1The CODCr concentration is 1050 mg.L-1The pH value of the water is about 10.1. Firstly, the printing and dyeing wastewater is pretreated, and impurity components in the printing and dyeing wastewater are precipitated and filtered, so that interference on subsequent experimental results is prevented.
MnOx/SiO2/FeSO4The preparation of the mixed system matching medicament material: the raw material is selected from ferro-manganese tailings of manganese ore enterprises in Hunan province, and the effective component in the tailings is MnOxGrinding to obtain particles with uniform size as medicinal component, and MnOx/SiO2/FeSO4The mass ratio of (A) to (B) is 1:1: 8.
As shown in FIG. 1, in step 1, printing and dyeing wastewater flows into a reaction tank for pretreatment, the concentration of T-Sb is hardly reduced after pretreatment, the concentration of CODCr is reduced to 459mg/L, and the pH of water is hardly changed, so that the pretreated printing and dyeing wastewater is obtained.
Step 2, placing the pretreated printing and dyeing wastewater in a reaction contact tank, and thenAdding 0.1 g.L prepared above-1And (5) carrying out contact stirring on the medicament, and reacting for 60min to obtain the printing and dyeing wastewater after reaction.
And 3, flowing the printing and dyeing wastewater after reaction into a coagulating sedimentation tank, and naturally precipitating the printing and dyeing wastewater after reaction in the coagulating sedimentation tank through the coagulating sedimentation effect of the iron-based material, so as to remove heavy metal antimony in the printing and dyeing wastewater.
Collecting supernatant, performing ICP test, and determining T-Sb concentration in water to be 30.5 μ g.L-1CODCr concentration 181 mg.L-1Wherein the heavy metal antimony reaches the standard limit values of direct and indirect total antimony discharge and discharge specified in the discharge Standard of Water pollutants for textile dyeing and finishing industry (GB 4287--1The emission standard of (1).
Example six:
the printing and dyeing wastewater comes from the comprehensive wastewater of a certain printing and dyeing mill, and the concentration of T-Sb is 874 microgram.L-1The CODCr concentration is 1050 mg.L-1The pH value of the water is about 10.1. Firstly, the printing and dyeing wastewater is pretreated, and impurity components in the printing and dyeing wastewater are precipitated and filtered, so that interference on subsequent experimental results is prevented.
MnOx/SiO2/FeSO4The preparation of the mixed system matching medicament material: the raw material is selected from ferro-manganese tailings of manganese ore enterprises in Hunan province, and the effective component in the tailings is MnOxGrinding to obtain particles with uniform size as medicinal component, and MnOx/SiO2/FeSO4The mass ratio of (A) to (B) is 1:1: 8.
As shown in fig. 1, in step 1, the printing and dyeing wastewater is first introduced into a reaction tank for pretreatment, the concentration of T-Sb is hardly reduced after pretreatment, the concentration of CODCr is reduced to 459mg/L, and the pH of the water is adjusted to 4, thereby obtaining the pretreated printing and dyeing wastewater.
Step 2, placing the pretreated printing and dyeing wastewater in a reaction contact tank, and then adding the prepared 0.1 g.L-1And (5) carrying out contact stirring on the medicament, and reacting for 60min to obtain the printing and dyeing wastewater after reaction.
And 3, flowing the printing and dyeing wastewater after reaction into a coagulating sedimentation tank, and naturally precipitating the printing and dyeing wastewater after reaction in the coagulating sedimentation tank through the coagulating sedimentation effect of the iron-based material, so as to remove heavy metal antimony in the printing and dyeing wastewater.
Collecting supernatant, performing ICP test, and determining T-Sb concentration in water to be 9.3 μ g.L-1CODCr concentration 180 mg.L-1Wherein the heavy metal antimony reaches the standard limit values of direct and indirect total antimony discharge and discharge specified in the discharge Standard of Water pollutants for textile dyeing and finishing industry (GB 4287--1The emission standard of (1).
Effects and effects of the embodiments
According to the first to sixth embodiments, MnOx/FeOx/FeSO4The formed system has excellent performance of removing antimony and reducing COD under a wider pH condition, namely the pH value is 2-12, and simultaneously has stronger adsorption, oxidation and coprecipitation capabilities under the condition that the pH value is less than or equal to 4, and MnO in the system is MnOxThe adsorption sites are activated greatly, the adsorption capacity is improved by more than 10 times, and MnO is simultaneouslyxSurface quilt H+The activated hydroxyl free radical also has the effect of in-situ oxidation, promotes the degradation of organic matters, and FeSO4The existence of the manganese tailings also plays the roles of accelerating the manganese tailings to precipitate and shortening the static precipitation time.
In the first to sixth embodiments, the reagent is a mixed material, has a small particle size, uniform particle dispersion and a large specific surface area, has good oxidation activity, adsorption performance and coprecipitation effect on heavy metal antimony, and greatly improves the removal capability of the heavy metal antimony through the synergy of multiple action mechanisms; and various components in the medicament complement each other, and the optimal proportion combination is adjusted to form advantage complementation, so that the problem that heavy metal antimony is difficult to efficiently and thoroughly remove can be solved, and the heavy metal antimony contained in the printing and dyeing wastewater after the heavy metal antimony is removed can reach the standard limit values of direct discharge and indirect discharge of total antimony specified in the discharge Standard of pollutants for textile dyeing and finishing Industrial Water (GB 4287--1The emission standard of (1).
In addition, the preparation process of the agent is mild in condition, raw materials can be selected from pyrolusite in manganese tailings, the raw materials are low in cost and easy to obtain, and when the agent is applied to removing antimony in printing and dyeing wastewater, the treatment process is simple, and the reaction time is short, so that the application cost is reduced while the high-efficiency removal effect of heavy metal antimony is ensured, and the agent has popularization and application prospects.
In summary, the agent for removing antimony from printing and dyeing wastewater according to the first embodiment to the sixth embodiment can remove heavy metal antimony from printing and dyeing wastewater at one time, the removed antimony mainly exists inside manganese ore materials or on surface particles, solid-liquid separation is realized through static precipitation, and when the agent is actually applied to printing and dyeing industry wastewater treatment, an original hydraulic facility does not need to be newly built or reconstructed, and the agent can be directly added for use by using an original conventional water treatment structure facility, so that the application and popularization of large-scale wastewater treatment in the printing and dyeing industry at the present stage are very convenient.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (5)
1. A method for removing antimony in printing and dyeing wastewater by adopting a medicament for removing antimony in the printing and dyeing wastewater is characterized in that,
the medicament for removing antimony in the printing and dyeing wastewater comprises:
manganese tailing powder and FeSO4A mixture of components, the mixture being a solid powder,
wherein the main component of the manganese tailing powder is MnOx/SiO2The grain diameter is 0.075-0.100mm,
FeSO4is FeSO4·7H2O、FeSO4·3H2O or anhydrous ferrous sulfate, and the like,
wherein, MnOx/SiO2/FeSO4The mass ratio of (1): 1: 8;
the method for removing the antimony in the printing and dyeing wastewater by adopting the agent for removing the antimony in the printing and dyeing wastewater comprises the following steps:
step 1, placing antimony-containing printing and dyeing wastewater in a pretreatment tank for impurity removal pretreatment to obtain pretreated antimony-containing printing and dyeing wastewater;
step 2, placing the pretreated antimony-containing printing and dyeing wastewater in a reaction contact tank, then adding a certain amount of the medicament for contact stirring, and reacting for 30-60min to obtain the antimony-containing printing and dyeing wastewater after reaction;
step 3, placing the antimony-containing printing and dyeing wastewater after reaction in a coagulating sedimentation tank for standing sedimentation and then carrying out solid-liquid separation so as to remove heavy metal antimony in the printing and dyeing wastewater,
in the step 2, the adding amount of the chemical agent is increased along with the increase of the concentration of the heavy metal antimony in the printing and dyeing wastewater, and is reduced along with the decrease of the pH value of the printing and dyeing wastewater.
2. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that:
wherein, the pretreatment in the step 1 comprises the following substeps:
and filtering and precipitating the antimony-containing printing and dyeing wastewater to remove suspended impurities in the antimony-containing printing and dyeing wastewater, thereby obtaining the pretreated antimony-containing printing and dyeing wastewater.
3. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that:
wherein, in the step 2, the content of the manganese tailing powder in the medicament is determined according to MnOx/SiO2The ratio of (a) to (b) is calculated.
4. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that:
wherein, the antimony-containing compound in the antimony-containing printing and dyeing wastewater is one or more of ethylene glycol antimony, antimony acetate or antimony trioxide.
5. The method for removing antimony from printing and dyeing wastewater according to claim 1, characterized in that:
in the step 3, the heavy metal antimony is one or two of trivalent antimony or pentavalent antimony.
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