CN111039466A - High-efficiency industrial wastewater treatment method - Google Patents
High-efficiency industrial wastewater treatment method Download PDFInfo
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- CN111039466A CN111039466A CN201911421571.1A CN201911421571A CN111039466A CN 111039466 A CN111039466 A CN 111039466A CN 201911421571 A CN201911421571 A CN 201911421571A CN 111039466 A CN111039466 A CN 111039466A
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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
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention relates to the technical field of wastewater treatment, in particular to a high-efficiency industrial wastewater treatment method. A high-efficiency industrial wastewater treatment method at least comprises the following steps: (1) pretreatment of industrial wastewater: adding lime milk into the industrial wastewater under the stirring condition, adjusting the pH value to 7.5-9, then adding diatom ooze, continuously stirring for 1-3h, standing for 2-5h, and filtering to obtain industrial wastewater supernatant; (2) primary treatment of industrial wastewater: adding a water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 20-50min, standing for 2-5h, and filtering to obtain supernatant after primary treatment of the industrial wastewater; (3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater obtained in the step (2) to obtain the discharged water meeting the environmental protection standard. The treatment method has the advantages that the removal rate of COD is more than 99 percent, the removal rate of ammonia nitrogen is more than 98 percent, meanwhile, the treatment method hardly has influence on the surrounding environment, and secondary pollution is avoided.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a high-efficiency industrial wastewater treatment method.
Background
The industrial wastewater refers to wastewater, sewage and waste liquid generated in the industrial production process, and contains industrial production materials, intermediate products and products which are lost along with water, and pollutants generated in the production process. Industrial waste water is generally classified into three categories: the first is classified according to the chemical properties of main pollutants contained in industrial wastewater, and inorganic wastewater mainly contains inorganic pollutants and organic wastewater mainly contains organic pollutants. For example electroplating wastewater and wastewater from mineral processing, are inorganic wastewater; the waste water from food or petroleum processing is organic waste water. The second is classified according to the products and processing objects of industrial enterprises, such as metallurgical wastewater, paper-making wastewater, coke-oven gas wastewater, metal pickling wastewater, chemical fertilizer wastewater, textile printing and dyeing wastewater, dye wastewater, tanning wastewater, pesticide wastewater, power station wastewater and the like. The third is classified according to the main components of the pollutants contained in the wastewater, such as acidic wastewater, alkaline wastewater, cyanide-containing wastewater, chromium-containing wastewater, cadmium-containing wastewater, mercury-containing wastewater, phenol-containing wastewater, aldehyde-containing wastewater, oil-containing wastewater, sulfur-containing wastewater, organic phosphorus-containing wastewater, radioactive wastewater, and the like.
With the rapid development of industrialization and urbanization processes in China, the discharge amount of industrial wastewater is increasing, the industrial wastewater contains a large amount of heavy metal ions, inorganic compounds, organic compounds and other harmful substances, such as Cr, Ni, phosphate, ammonia nitrogen compounds, organic acids and the like, if the treatment is not up to standard, the substances entering the environment can generate wide and serious harm to the ecological environment and human beings, even are enriched in the organism through a food chain, respiration or direct contact path, pose a threat to the health of the organism and human body, and even cause gene mutation or induce cancer when the treatment is serious; if the concentration of heavy metal ions, inorganic compounds and organic compounds in the treated wastewater is only close to the discharge standard, the industrial wastewater can be directly discharged and cannot be reused, so that the great waste of water resources is caused, and the requirement of sustainable development is not met
In order to ensure public health, the method reasonably and effectively removes harmful substances such as heavy metals, inorganic compounds, organic compounds and the like in the industrial wastewater, and simultaneously improves the reutilization rate of the treated wastewater, thereby becoming an important problem which is commonly concerned by human beings.
Disclosure of Invention
In order to solve the technical problem, the invention provides a high-efficiency industrial wastewater treatment method, which at least comprises the following steps:
(1) pretreatment of industrial wastewater: adding lime milk into the industrial wastewater under the stirring condition, adjusting the pH value to 7.5-9, then adding diatom ooze, continuously stirring for 1-3h, standing for 2-5h, and filtering to obtain industrial wastewater supernatant;
(2) primary treatment of industrial wastewater: adding a water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 20-50min, standing for 2-5h, and filtering to obtain supernatant after primary treatment of the industrial wastewater;
(3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater obtained in the step (2) to obtain the discharged water meeting the environmental protection standard.
As a preferable technical scheme of the invention, in the step (1), the concentration of the lime milk is 20-50%.
As a preferable technical scheme of the invention, in the step (1), 1-5Kg of diatom ooze is added into every 1000L of industrial wastewater.
As a preferred technical solution of the present invention, in the step (2), the water purifying agent at least comprises the following components in parts by weight: 25-40 parts of load type modified chitosan, 20-35 parts of polymeric ferric aluminum silicate, 12-20 parts of xanthate, 10-15 parts of activated carbon, 6-15 parts of polyacrylamide, 8-15 parts of chlorine dioxide, 8-15 parts of magnesium peroxide, 5-10 parts of potassium ferrate and 3-6 parts of dodecyl dimethyl benzyl ammonium bromide.
As a preferable technical scheme of the invention, the supported modified chitosan is supported ammonium salt modified chitosan.
As a preferable technical scheme of the invention, the carrier of the supported modified chitosan is at least one selected from attapulgite clay, zeolite, diatomite and hydrotalcite.
As a preferable technical scheme of the invention, the preparation method of the purifying agent comprises the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 90-120 ℃ for 3-6h to obtain the product.
As a preferred technical scheme of the invention, in the step (2), 0.8 to 1.7Kg of water purifying agent is added into every 1000L of water.
As a preferred technical solution of the present invention, in the step (3), the following processes are sequentially adopted for filtration treatment: a security filtration process, a microfiltration membrane filtration process, an ultrafiltration membrane filtration process and a reverse osmosis membrane filtration process.
In a second aspect, the invention provides a water purifying agent for industrial wastewater treatment.
Has the advantages that: the high-efficiency industrial wastewater treatment method provided by the invention is mainly used for treating ammonia nitrogen, nickel, chromium, COD and the like in industrial wastewater, when the industrial wastewater is treated by the method, the removal rate of COD is more than 99%, the removal rate of ammonia nitrogen is more than 98%, and meanwhile, the method hardly influences the surrounding environment and avoids secondary pollution.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the technical problem, the invention provides a high-efficiency industrial wastewater treatment method, which at least comprises the following steps:
(1) pretreatment of industrial wastewater: adding lime milk into the industrial wastewater under the stirring condition, adjusting the pH value to 7.5-9, then adding diatom ooze, continuously stirring for 1-3h, standing for 2-5h, and filtering to obtain industrial wastewater supernatant;
(2) primary treatment of industrial wastewater: adding a water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 20-50min, standing for 2-5h, and filtering to obtain supernatant after primary treatment of the industrial wastewater;
(3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater obtained in the step (2) to obtain the discharged water meeting the environmental protection standard.
Pretreatment of industrial waste water
Preferably, in the step (1), the concentration of the lime milk is 20-50%.
More preferably, in the step (1), the concentration of the milk of lime is 35%.
Preferably, the lime milk is added in an amount of adjusting the pH of the industrial wastewater to 7.5-9.
More preferably, the lime milk is added in an amount to adjust the pH of the industrial wastewater to 8.5.
Preferably, in the step (1), 1 to 5Kg of diatom ooze is added per 1000L of industrial wastewater.
More preferably, in the step (1), 2Kg of diatom ooze is added to every 1000L of industrial wastewater.
The inventor believes that a certain amount of lime milk is added into the industrial wastewater, on one hand, calcium ions can be combined with acid radical ions in the industrial wastewater to effectively remove the acid radical ions in the wastewater, so that the treated wastewater reaches the discharge standard, and the environmental pollution is avoided; on the other hand, the pH value of the industrial wastewater can be adjusted, which is more beneficial to the further treatment of the industrial wastewater. Secondly, adding a certain amount of diatom ooze under the alkalescent condition to remove grease, large-particle pollutants and small-particle pollutants in the industrial wastewater.
First-stage treatment of industrial wastewater
In the invention, in the step (2), the water purifying agent at least comprises the following components in parts by weight: 25-40 parts of load type modified chitosan, 20-35 parts of polymeric ferric aluminum silicate, 12-20 parts of xanthate, 10-15 parts of activated carbon, 6-15 parts of polyacrylamide, 8-15 parts of chlorine dioxide, 8-15 parts of magnesium peroxide, 5-10 parts of potassium ferrate and 3-6 parts of dodecyl dimethyl benzyl ammonium bromide.
Preferably, the weight ratio of the supported modified chitosan to the xanthate is (2-3): 1.
preferably, the weight ratio of the polymeric aluminum ferric silicate to the magnesium peroxide to the potassium ferrate is (2.5-4): (1-1.5): 1.
preferably, the water purifying agent comprises the following components in parts by weight: 35 parts of load type modified chitosan, 30 parts of polymeric ferric aluminum silicate, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Preferably, the supported modified chitosan is supported ammonium salt modified chitosan.
Preferably, the carrier of the supported modified chitosan is at least one selected from attapulgite clay, zeolite, diatomite and hydrotalcite.
More preferably, the carrier is attapulgite clay.
In the invention, the preparation method of the supported modified chitosan at least comprises the following steps:
(a) preparation of modifier ammonium salt: under the condition of ice bath, mixing the epoxy compound and acetone, stirring for 20-50min, then dropwise adding the organic amine compound, continuously stirring for 20-50min, removing the ice bath, heating to 20-30 ℃, stirring for 2-3h, filtering while hot, washing a filter cake for a plurality of times by ethyl acetate, and drying to obtain the ammonium salt.
(b) Preparing modified chitosan: swelling chitosan in 5% acetic acid solution, adjusting the pH value to 8-9 by using sodium hydroxide or potassium hydroxide solution, adding isopropanol after chitosan is completely separated out, heating to 50-70 ℃ while stirring, then adding the aqueous solution of ammonium salt prepared in the step (1), adjusting the pH value to 7 by using strong acid, continuously heating to 80-100 ℃, stirring for 12-15h, standing, performing suction filtration, washing a filter cake for several times by using ethanol, and drying to obtain the modified chitosan.
(c) Pretreatment of the carrier attapulgite clay: soaking a certain amount of attapulgite clay in sodium hydroxide or potassium oxide solution for 7-9h, washing with hydrochloric acid to neutrality, drying, pulverizing, calcining and activating in muffle furnace at 350 deg.C for 2.5-3.5h, and sieving with 300 mesh sieve.
(d) Preparing load type modified chitosan: slowly adding the attapulgite clay treated in the step (3) into the aqueous solution of the modified chitosan, stirring at room temperature for 23-26h, centrifugally separating, washing with water and drying to obtain the attapulgite clay modified chitosan.
Preferably, in the step (a), the epoxy compound is at least one selected from the group consisting of epichlorohydrin, propylene oxide, styrene oxide, ethylene oxide chloride, isobutyl 2-ethylene oxide acetate, 2-propyl-ethylene oxide, 2- [ (2-methylphenoxy) methyl ] ethylene oxide, 1, 2-epoxy-5-hexene, and 1- (4- (2-hydroxyethyl) phenoxy) -2, 3-propylene oxide.
Preferably, in the step (a), the organic amine compound is at least one selected from aniline, triethylamine, p-dimethylaminobenzaldehyde, benzylamine, triphenylamine, trimethylamine, and tributylamine.
Preferably, in the step (a), the molar ratio of the epoxy compound to the organic amine compound is 3: 1.
more preferably, the preparation method of the supported modified chitosan at least comprises the following steps:
(a) preparation of modifier ammonium salt: under the ice bath condition, 3mol of epoxy chloropropane and 500mL of acetone are mixed, stirred for 30min, then 1mol of triethylamine is added dropwise, stirring is continued for 30min, the ice bath is removed, the temperature is raised to 25 ℃, stirring is carried out for 2h, hot filtering is carried out, a filter cake is washed by ethyl acetate for 3 times, and drying is carried out at 100 ℃ to obtain the ammonium salt.
(b) Preparing modified chitosan: swelling 10g of chitosan in 200mL of 5% acetic acid solution, adjusting the pH to 8 with sodium hydroxide or potassium hydroxide solution, adding 100mL of isopropanol after chitosan is completely separated out, heating to 60 ℃ while stirring, then adding 150mL of ammonium salt aqueous solution prepared in the step (1), adjusting the pH to 7 with strong acid, continuing heating to 90 ℃, stirring for 14h, standing, performing suction filtration, washing a filter cake with ethanol for 3 times, and drying at 100 ℃ to obtain the modified chitosan.
(c) Pretreatment of the carrier attapulgite clay: soaking 50g of attapulgite clay in 5% sodium hydroxide solution for 8h, washing with hydrochloric acid to neutrality, drying, pulverizing, calcining in a muffle furnace at 300 deg.C for 3h, and sieving with 300 mesh sieve.
(d) Preparing load type modified chitosan: and (3) slowly adding 10g of the attapulgite clay treated in the step (3) into 300mL of a 15% modified chitosan aqueous solution, stirring for 24h at room temperature, performing centrifugal separation, washing a filter cake for 3 times, and drying at 100 ℃ to obtain the attapulgite clay modified chitosan.
In the invention, the preparation method of the purifying agent comprises the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 90-120 ℃ for 3-6h to obtain the product.
Preferably, the preparation method of the purifying agent comprises the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 110 ℃ for 5h to obtain the product.
The water purifying agent provided by the invention overcomes the problem that the existing water purifying agent has poor effect of removing ammonia nitrogen, phosphorus and COD sewage. The inventor conjectures that the pretreated industrial wastewater is rich in calcium ions, and the water purifying agent of the invention contains silicon and magnesium ions, and achieves and realizes the purpose of synchronously removing harmful substances such as ammonia nitrogen, COD and the like in the wastewater by utilizing the remarkable synergistic and complementary action of the silicon, calcium and magnesium ions in the water purifying agent. Meanwhile, polynuclear high-valence complex ions formed by aluminum ions and magnesium ions generate association adsorption on phosphate radicals, hydrogen phosphate radicals and dihydrogen phosphate radicals with negative charges to form ion associations with low water solubility, so that a certain phosphorus removal effect is achieved. In addition, the water purifying agent also fully utilizes the mutual compensation performance of iron ions and aluminum ions, and avoids the limitation of metal ions on the use range of the water purifying agent. Aluminum ions, magnesium ions and the like in the water purifying agent are hydrolyzed in the wastewater to form negative charges, so that a large number of pollutants with positive charges are adsorbed, and more pollutants are adsorbed to generate larger floccules. The modified chitosan loaded by the attapulgite clay has large specific surface area and porosity and strong adsorption capacity, is more favorable for coagulation of the attapulgite clay under a weak alkaline condition, and has the best effect of removing heavy metal ions under the synergistic action of the modified chitosan and xanthate. The polyacrylamide and the ferric aluminum silicate are compounded for use, the coagulation aiding capacity is good, precipitates after coagulation are conveniently removed, heavy metals can be effectively removed, separation is easier, COD in industrial wastewater can be further reduced, dye substances are adsorbed, and the oil removing and decoloring effects are obvious. The invention provides a method which has the advantages of better performance, no residual toxin, convenient use, low cost and good effect and is suitable for treating industrial wastewater with the pH value of 4-10.
Preferably, in the step (2), 0.8 to 1.7Kg of water purifying agent is added to 1000L of water.
More preferably, in the step (2), 1Kg of water purifying agent is added to 1000L of water.
Preferably, in the step (3), the following processes are sequentially adopted for filtration treatment: a security filtration process, a microfiltration membrane filtration process, an ultrafiltration membrane filtration process and a reverse osmosis membrane filtration process.
More preferably, the cartridge filter is adopted in the cartridge filtration process, the microfiltration membrane filter is adopted in the microfiltration membrane filtration process, the ultrafiltration membrane filter is adopted in the ultrafiltration membrane filtration process, and the reverse osmosis membrane filter is adopted in the reverse osmosis membrane filtration process.
In a second aspect, the invention provides a water purifying agent for industrial wastewater treatment.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a high efficiency industrial wastewater treatment method, comprising the steps of:
(1) pretreatment of industrial wastewater: adding 35% lime milk into 1000L of industrial wastewater under stirring, adjusting pH to 8.5, adding 2Kg diatom ooze, stirring for 2h, standing for 5h, and filtering to obtain industrial wastewater supernatant;
(2) primary treatment of industrial wastewater: adding 1Kg of water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 30min, standing for 5h, and filtering to obtain the supernatant after primary treatment of the industrial wastewater;
(3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater in the step (2) by a security filtration process, a microfiltration membrane filtration process, an ultrafiltration membrane filtration process and a reverse osmosis membrane filtration process in sequence to obtain the discharge water meeting the environmental protection standard.
The water purifying agent comprises the following components in parts by weight: 35 parts of load type modified chitosan, 30 parts of polymeric ferric aluminum silicate, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
The preparation method of the supported modified chitosan comprises the following steps:
(a) preparation of modifier ammonium salt: under the ice bath condition, 3mol of epoxy chloropropane and 500mL of acetone are mixed, stirred for 30min, then 1mol of triethylamine is added dropwise, stirring is continued for 30min, the ice bath is removed, the temperature is raised to 25 ℃, stirring is carried out for 2h, hot filtering is carried out, a filter cake is washed by ethyl acetate for 3 times, and drying is carried out at 100 ℃ to obtain the ammonium salt.
(b) Preparing modified chitosan: swelling 10g of chitosan in 200mL of 5% acetic acid solution, adjusting the pH to 8 with sodium hydroxide or potassium hydroxide solution, adding 100mL of isopropanol after chitosan is completely separated out, heating to 60 ℃ while stirring, then adding 150mL of ammonium salt aqueous solution prepared in the step (1), adjusting the pH to 7 with strong acid, continuing heating to 90 ℃, stirring for 14h, standing, performing suction filtration, washing a filter cake with ethanol for 3 times, and drying at 100 ℃ to obtain the modified chitosan.
(c) Pretreatment of the carrier attapulgite clay: soaking 50g of attapulgite clay in 5% sodium hydroxide solution for 8h, washing with hydrochloric acid to neutrality, drying, pulverizing, calcining in a muffle furnace at 300 deg.C for 3h, and sieving with 300 mesh sieve.
(d) Preparing load type modified chitosan: and (3) slowly adding 10g of the attapulgite clay treated in the step (3) into 300mL of a 15% modified chitosan aqueous solution, stirring for 24h at room temperature, performing centrifugal separation, washing a filter cake for 3 times, and drying at 100 ℃ to obtain the attapulgite clay modified chitosan.
The preparation method of the water purifying agent comprises the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 110 ℃ for 5h to obtain the product.
Example 2
Embodiment 2 provides a high efficiency industrial wastewater treatment method, comprising the steps of:
(1) pretreatment of industrial wastewater: adding lime milk with the concentration of 20% into 1000L of industrial wastewater under the stirring condition, adjusting the pH to 7.5, then adding 1Kg of diatom ooze, continuously stirring for 1h, standing for 2h, and filtering to obtain the industrial wastewater supernatant;
(2) primary treatment of industrial wastewater: adding 0.8Kg of water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 20min, standing for 2h, and filtering to obtain the supernatant after primary treatment of the industrial wastewater;
(3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater in the step (2) by a security filtration process, a microfiltration membrane filtration process, an ultrafiltration membrane filtration process and a reverse osmosis membrane filtration process in sequence to obtain the discharge water meeting the environmental protection standard.
The water purifying agent comprises the following components in parts by weight: 20 parts of load type modified chitosan, 20 parts of polymeric ferric aluminum silicate, 12 parts of xanthate, 10 parts of activated carbon, 6 parts of polyacrylamide, 8 parts of chlorine dioxide, 8 parts of magnesium peroxide, 5 parts of potassium ferrate and 3 parts of dodecyl dimethyl benzyl ammonium bromide.
The preparation method of the supported modified chitosan comprises the following steps:
(a) preparation of modifier ammonium salt: under the ice bath condition, 3mol of epoxy chloropropane and 500mL of acetone are mixed, stirred for 30min, then 1mol of triethylamine is added dropwise, stirring is continued for 30min, the ice bath is removed, the temperature is raised to 25 ℃, stirring is carried out for 2h, hot filtering is carried out, a filter cake is washed by ethyl acetate for 3 times, and drying is carried out at 100 ℃ to obtain the ammonium salt.
(b) Preparing modified chitosan: swelling 10g of chitosan in 200mL of 5% acetic acid solution, adjusting the pH to 8 with sodium hydroxide or potassium hydroxide solution, adding 100mL of isopropanol after chitosan is completely separated out, heating to 60 ℃ while stirring, then adding 150mL of ammonium salt aqueous solution prepared in the step (1), adjusting the pH to 7 with strong acid, continuing heating to 90 ℃, stirring for 14h, standing, performing suction filtration, washing a filter cake with ethanol for 3 times, and drying at 100 ℃ to obtain the modified chitosan.
(c) Pretreating the attapulgite clay: soaking 50g of attapulgite clay in 5% sodium hydroxide solution for 8h, washing with hydrochloric acid to neutrality, drying, pulverizing, calcining in a muffle furnace at 300 deg.C for 3h, and sieving with 300 mesh sieve.
(d) The preparation method of the attapulgite clay loaded modified chitosan comprises the following steps: and (3) slowly adding 10g of the attapulgite clay treated in the step (3) into 300mL of a 15% modified chitosan aqueous solution, stirring for 24h at room temperature, performing centrifugal separation, washing a filter cake for 3 times, and drying at 100 ℃ to obtain the attapulgite clay modified chitosan.
The preparation method of the water purifying agent comprises the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 110 ℃ for 5h to obtain the product.
Example 3
Embodiment 3 provides a high efficiency industrial wastewater treatment method, comprising the steps of:
(1) pretreatment of industrial wastewater: adding 50% lime milk into 1000L of industrial wastewater under stirring, adjusting pH to 9, adding 5Kg of diatom ooze, stirring for 3h, standing for 5h, and filtering to obtain industrial wastewater supernatant;
(2) primary treatment of industrial wastewater: adding 1.7Kg of water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 50min, standing for 5h, and filtering to obtain the supernatant after primary treatment of the industrial wastewater;
(3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater in the step (2) by a security filtration process, a microfiltration membrane filtration process, an ultrafiltration membrane filtration process and a reverse osmosis membrane filtration process in sequence to obtain the discharge water meeting the environmental protection standard.
The water purifying agent comprises the following components in parts by weight: 40 parts of load type modified chitosan, 35 parts of polymeric ferric aluminum silicate, 20 parts of xanthate, 15 parts of activated carbon, 15 parts of polyacrylamide, 15 parts of chlorine dioxide, 15 parts of magnesium peroxide, 10 parts of potassium ferrate and 6 parts of dodecyl dimethyl benzyl ammonium bromide.
The preparation method of the supported modified chitosan comprises the following steps:
(a) preparation of modifier ammonium salt: under the ice bath condition, 3mol of epoxy chloropropane and 500mL of acetone are mixed, stirred for 30min, then 1mol of triethylamine is added dropwise, stirring is continued for 30min, the ice bath is removed, the temperature is raised to 25 ℃, stirring is carried out for 2h, hot filtering is carried out, a filter cake is washed by ethyl acetate for 3 times, and drying is carried out at 100 ℃ to obtain the ammonium salt.
(b) Preparing modified chitosan: swelling 10g of chitosan in 200mL of 5% acetic acid solution, adjusting the pH to 8 with sodium hydroxide or potassium hydroxide solution, adding 100mL of isopropanol after chitosan is completely separated out, heating to 60 ℃ while stirring, then adding 150mL of ammonium salt aqueous solution prepared in the step (1), adjusting the pH to 7 with strong acid, continuing heating to 90 ℃, stirring for 14h, standing, performing suction filtration, washing a filter cake with ethanol for 3 times, and drying at 100 ℃ to obtain the modified chitosan.
(c) Pretreating the attapulgite clay: soaking 50g of attapulgite clay in 5% sodium hydroxide solution for 8h, washing with hydrochloric acid to neutrality, drying, pulverizing, calcining in a muffle furnace at 300 deg.C for 3h, and sieving with 300 mesh sieve.
(d) The preparation method of the attapulgite clay loaded modified chitosan comprises the following steps: and (3) slowly adding 10g of the attapulgite clay treated in the step (3) into 300mL of a 15% modified chitosan aqueous solution, stirring for 24h at room temperature, performing centrifugal separation, washing a filter cake for 3 times, and drying at 100 ℃ to obtain the attapulgite clay modified chitosan.
The preparation method of the water purifying agent comprises the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 110 ℃ for 5h to obtain the product.
Example 4
Example 4 differs from example 1 in that the step (1) of pretreatment of the industrial wastewater is: adding 35% lime milk into 1000L of industrial wastewater under stirring, adjusting pH to 7, adding 2Kg of diatom ooze, stirring for 2h, standing for 5h, and filtering to obtain industrial wastewater supernatant.
Example 5
Example 5 differs from example 1 in that the step (1) of pretreatment of the industrial wastewater is: adding 35% lime milk into 1000L of industrial wastewater under stirring, adjusting pH to 12, adding 2Kg of diatom ooze, stirring for 2h, standing for 5h, and filtering to obtain industrial wastewater supernatant.
Example 6
Example 6 differs from example 1 in that the step (1) of pretreatment of the industrial wastewater is: adding 2Kg of diatom ooze into 1000L of industrial wastewater under the stirring condition, stirring for 2h, standing for 5h, and filtering to obtain the industrial wastewater supernatant.
Example 7
Example 7 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of modified chitosan, 35 parts of attapulgite clay, 30 parts of polymeric aluminum ferric silicate, 15 parts of xanthate, 12 parts of active carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Example 8
Example 8 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of modified chitosan, 30 parts of polymeric ferric aluminum silicate, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Example 9
Example 9 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of attapulgite clay, 30 parts of polymeric aluminum ferric silicate, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Example 10
Example 10 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of load type modified chitosan, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Example 11
Example 11 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of load type modified chitosan, 30 parts of polymeric ferric aluminum silicate, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Example 12
Example 12 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of load type modified chitosan, 30 parts of polymeric ferric aluminum silicate, 15 parts of xanthate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Example 13
Example 13 differs from example 1 in that the water purifying agent comprises the following components in parts by weight: 35 parts of load type modified chitosan, 30 parts of polymeric ferric aluminum silicate, 12 parts of activated carbon, 12 parts of polyacrylamide, 10 parts of chlorine dioxide, 10 parts of magnesium peroxide, 8 parts of potassium ferrate and 5 parts of dodecyl dimethyl benzyl ammonium bromide.
Performance testing
The industrial waste water from 5 home chemical plants was collected and mixed uniformly and treated by the methods of examples 1 to 13, and the effects are shown in table 1.
TABLE 1 Effect of the Industrial wastewater treatment Processes provided in examples 1 to 13
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A high-efficiency industrial wastewater treatment method is characterized by at least comprising the following steps:
(1) pretreatment of industrial wastewater: adding lime milk into the industrial wastewater under the stirring condition, adjusting the pH value to 7.5-9, then adding diatom ooze, continuously stirring for 1-3h, standing for 2-5h, and filtering to obtain industrial wastewater supernatant;
(2) primary treatment of industrial wastewater: adding a water purifying agent into the supernatant of the industrial wastewater obtained in the step (1), stirring for 20-50min, standing for 2-5h, and filtering to obtain supernatant after primary treatment of the industrial wastewater;
(3) secondary treatment of industrial wastewater: and (3) filtering the supernatant obtained after the primary treatment of the industrial wastewater obtained in the step (2) to obtain the discharged water meeting the environmental protection standard.
2. A high efficiency industrial wastewater treatment method according to claim 1, characterized in that, in the step (1), the concentration of lime milk is 20-50%.
3. The method for treating industrial wastewater with high efficiency as claimed in claim 1, wherein in the step (1), 1-5Kg of diatom ooze is added per 1000L of industrial wastewater.
4. The method for treating industrial wastewater with high efficiency according to claim 1, wherein in the step (2), the water purifying agent at least comprises the following components in parts by weight: 25-40 parts of load type modified chitosan, 20-35 parts of polymeric ferric aluminum silicate, 12-20 parts of xanthate, 10-15 parts of activated carbon, 6-15 parts of polyacrylamide, 8-15 parts of chlorine dioxide, 8-15 parts of magnesium peroxide, 5-10 parts of potassium ferrate and 3-6 parts of dodecyl dimethyl benzyl ammonium bromide.
5. The method for treating high-efficiency industrial wastewater according to claim 4, wherein the supported modified chitosan is a supported ammonium salt modified chitosan.
6. The method for treating high efficiency industrial wastewater according to claim 4, wherein the carrier of the supported modified chitosan is at least one selected from attapulgite clay, zeolite, diatomite and hydrotalcite.
7. The method for treating high-efficiency industrial wastewater according to claim 4, wherein the purifying agent is prepared by the following steps: mixing the load type modified chitosan, polymeric ferric aluminum silicate, xanthate, activated carbon, polyacrylamide, chlorine dioxide, magnesium peroxide, potassium ferrate and dodecyl dimethyl benzyl ammonium bromide to obtain a mixture; then crushing and stirring the mixture until the mixture is uniformly mixed; and finally drying at 90-120 ℃ for 3-6h to obtain the product.
8. The method for treating industrial wastewater with high efficiency as claimed in claim 1, wherein in the step (2), 0.8-1.7Kg of water purifying agent is added to 1000L of water.
9. The method for treating high-efficiency industrial wastewater according to claim 1, wherein in the step (3), the following processes are sequentially adopted for filtration treatment: a security filtration process, a microfiltration membrane filtration process, an ultrafiltration membrane filtration process and a reverse osmosis membrane filtration process.
10. A water purifying agent for industrial wastewater treatment according to any one of claims 4 to 7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551788A (en) * | 2020-11-27 | 2021-03-26 | 苏州德盛环安科技有限公司 | Industrial wastewater treatment method |
| CN112592915A (en) * | 2021-01-05 | 2021-04-02 | 浙江树人学院（浙江树人大学） | Preparation method of modified environment-friendly carrier for microalgae immobilization in environmental remediation |
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2019
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551788A (en) * | 2020-11-27 | 2021-03-26 | 苏州德盛环安科技有限公司 | Industrial wastewater treatment method |
| CN112592915A (en) * | 2021-01-05 | 2021-04-02 | 浙江树人学院（浙江树人大学） | Preparation method of modified environment-friendly carrier for microalgae immobilization in environmental remediation |
| CN112592915B (en) * | 2021-01-05 | 2022-07-08 | 浙江树人学院（浙江树人大学） | Preparation method of modified environment-friendly carrier for microalgae immobilization in environmental remediation |
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