CN109437459B - Mixed industrial sewage treatment method - Google Patents
Mixed industrial sewage treatment method Download PDFInfo
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- CN109437459B CN109437459B CN201811497584.2A CN201811497584A CN109437459B CN 109437459 B CN109437459 B CN 109437459B CN 201811497584 A CN201811497584 A CN 201811497584A CN 109437459 B CN109437459 B CN 109437459B
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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
- C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Abstract
The invention discloses a mixed industrial sewage treatment method, which belongs to the field of sewage treatment and comprises the following steps: the method comprises the following steps of pretreatment, mixing, adjusting, irradiation, heavy metal adsorption and filtering, wherein heavy metal is removed by adopting an irradiation gel method in the heavy metal adsorption step, gamma rays are adopted in both the irradiation treatment step and the heavy metal adsorption step, the irradiation absorption dose is 4-6kGy in the irradiation treatment step, and the irradiation absorption dose is 2-4kGy in the heavy metal adsorption step. The method has high efficiency, can carry out mixed treatment on various industrial sewage of different types, has good treatment effect, can not bring new pollutants, and can not generate radiation after the irradiation.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a mixed industrial sewage treatment method.
Background
The industrial sewage contains a large amount of metal simple substances and metal ions, such as mercury, chromium, cadmium and the like, and inorganic substances, such as alkali, sulfide, salts and the like, so that the industrial sewage shows unique color and has strong pollution. If the microorganism is directly introduced into an aquatic ecosystem, the microorganism can not only reduce the concentration of heavy metals, but also enrich and amplify the effect. After entering into organisms, heavy metals can be accumulated in certain organs to cause cumulative poisoning, and finally, the life is endangered. The polluted inorganic matters in the sewage deteriorate the water quality, harm aquatic organisms and harm agriculture; some people have chronic poisoning and destroy the normal physiological process of human body, wherein heavy metals have the greatest harm to the human body and even cause cancer. In the current situation of China, the variety of industrial wastewater is more, and if a treatment scheme is specially formulated for each type of wastewater and a sewage treatment plant is built, the investment cost is too high and the efficiency is low.
At present, industrial sewage treatment adopts membrane separation, electrochemistry, biological methods, adsorption methods and other methods for treatment, the adsorption method has low process cost and no secondary pollution, but the efficiency is not high, and other methods are required for treatment. Heavy metal simple substance gets rid of more easily for heavy metal ion, but heavy metal simple substance and heavy metal ion separately get rid of and administer, and the step is loaded down with trivial details, and the cost increases, if reduce heavy metal ion into simple substance, operating condition is comparatively complicated, and the cost is higher, so, can reduce high valence state heavy metal ion into behind the heavy metal ion of low valence state, get rid of with heavy metal simple substance together, to middle-size and small-size enterprise, more be fit for actual conditions.
The gamma irradiation technology belongs to a new advanced oxidation technology, and has the characteristics of wide application range, high reaction speed, no secondary pollution and the like, so the gamma irradiation technology is widely concerned in the field of environment. The gamma irradiation technology utilizes the action of gamma rays and water to generate free radicals such as hydroxyl free radicals, hydrogen free radicals, hydrated electrons, peroxides and the like, and the free radicals have high activity and are easy to react with pollutants in water to decompose, thereby achieving the effect of water treatment.
Therefore, the invention researches a novel efficient adsorption method for industrial sewage treatment, and the method has the advantages of good sterilization effect, no secondary pollution and good treatment effect on sewage containing heavy metal ions.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a mixed industrial sewage treatment method, which adopts a mixed radiation technology to treat sewage, treats various industrial sewage respectively, and then treats, disinfects and purifies the sewage uniformly and removes heavy metal ions. The method has high efficiency, can carry out mixed treatment on various industrial sewage of different types, has good treatment effect, can not bring new pollutants, and can not generate radiation after the irradiation.
The invention solves the technical problems by the following technical means:
a mixed industrial sewage treatment method comprises the following steps:
the method comprises the following steps of pretreatment, mixing, adjusting, irradiation, heavy metal adsorption and filtering, wherein heavy metal is removed by adopting an irradiation gel method in the heavy metal adsorption step, gamma rays are adopted in both the irradiation treatment step and the heavy metal adsorption step, the irradiation absorption dose in the irradiation treatment step is 4-6kGy, and the irradiation absorption dose in the heavy metal adsorption step is 2-4 kGy.
Furthermore, the irradiation gel method is to put the gel into the industrial wastewater after irradiation treatment, and the gel is complexed with the heavy metal under the irradiation action to form a gel complex.
Further, the treatment method comprises the following specific operations:
a pretreatment procedure: respectively screening, filtering, removing impurities, floating and removing oil from various industrial wastewater;
a mixing procedure: mixing the industrial wastewater subjected to the pretreatment process, and pre-aerating for 1-2 days;
an adjusting procedure: adjusting the pH value of the industrial wastewater to 8-11;
an irradiation treatment process: irradiating the industrial wastewater subjected to the adjusting process for 2-3h by gamma-rays at normal temperature;
heavy metal adsorption process: adjusting the pH value of the industrial wastewater subjected to the irradiation treatment process to 6-8, adding a gelling agent, heating to 40-55 ℃, and performing irradiation treatment for 2-4h to form a gel complex;
a filtering process: and (4) filtering the gel complex precipitate, and discharging the filtered filtrate.
Furthermore, the heavy metals in the industrial wastewater mainly comprise cadmium, chromium and lead, and the content of the cadmium, the chromium and the lead is more than or equal to 5 mg/L.
Further, the gel is mainly prepared by the reflux reaction of polyacrylamide, potassium permanganate-citric acid solution and coconut oil fatty acid, and then the graft copolymerization of the polyacrylamide, potassium permanganate-citric acid solution and coconut oil fatty acid solution and amino acid hydrochloride.
Further, the preparation method of the gel comprises the following steps:
preparation of polyacrylamide: dissolving acrylamide and N, N' -methylene bisacrylamide, adding ammonium sulfate and tetramethyl ethylenediamine, then adjusting the pH to 9-11, uniformly stirring, and standing to obtain polyacrylamide;
preparing a gel agent: adding a methanol solution into polyacrylamide, heating and refluxing at 80-90 ℃ for 30-50min, then adding a potassium permanganate-citric acid solution and coconut oil fatty acid, stirring at normal temperature for 1-2h, heating and refluxing at 50-60 ℃ for 5-6h, adjusting the pH to 8-9, adding L-lysine hydrochloride, stirring and reacting at 30-40 ℃ for 3-6h to obtain gel, washing and drying to obtain the gel.
Further, the mass ratio of the acrylamide to the N, N' -methylene bisacrylamide is 10: 1.
Further, the mass concentration of potassium permanganate in the potassium permanganate-citric acid solution is 0.5-1%.
Further, the mass ratio of the polyacrylamide to the L-lysine hydrochloride is 1: (0.5-0.9), wherein the solid-to-liquid ratio of the polyacrylamide to the coconut oil fatty acid is (4-5): 1 g/ml.
The invention has the beneficial effects that:
1. through the pretreatment process, the mixing process and the adjusting process in the early stage, various industrial wastewater is mixed and treated simultaneously, and the wastewater treatment efficiency is improved.
2. Through the irradiation treatment process, the bacteria and the microorganisms in the industrial wastewater are killed, so that the aim of disinfection is fulfilled. Meanwhile, the heavy metal ions with high valence can be reduced to low valence, so that the heavy metal ions are easily absorbed by the gel, and the wastewater treatment effect is improved.
3. The industrial wastewater generates a large amount of high-activity free radicals after being irradiated, the existence of the high-activity free radicals promotes the self-crosslinking reaction of the gel, and the gel adsorbs heavy metal ions while crosslinking, so that the purpose of treating the industrial wastewater is achieved, and the heavy metal adsorption effect is good.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
example 1: preparing a gel agent:
preparation of polyacrylamide: adding 200g of acrylamide and 20g of N, N '-methylene bisacrylamide into deionized water, stirring for dissolving, adding 3g of ammonium sulfate and 1g of tetramethyl ethylene diamine, then adjusting the pH value to 9-10 by using a sodium hydroxide solution, uniformly stirring, standing for 2 hours at normal temperature, generating polyacrylamide by using acrylamide and a crosslinking agent N, N' -methylene bisacrylamide under the conditions of an initiator ammonium sulfate and a speed accelerator tetramethyl ethylene diamine, and cleaning unreacted monomers and solvents by using deionized water to obtain pure polyacrylamide;
preparing a gel agent: adding 50ml of 3 wt% methanol solution into 100g of polyacrylamide, stirring and mixing, heating and refluxing for 30min at 80 ℃ after the polyacrylamide is subjected to hydroxymethylation, adding 50ml of potassium permanganate-citric acid solution, wherein the mass concentration of potassium permanganate is 0.5%, citric acid is oxidized in the potassium permanganate solution, citric acid can remove acid to generate acetone dicarboxylic acid, the acetone dicarboxylic acid is easily decomposed to generate a small amount of acetone, adding 20ml of saturated coconut oil fatty acid under the acidic condition of being mixed with the acetone, uniformly mixing, stirring for 1h at the normal temperature at the speed of 100r/min, the saturated coconut oil fatty acid contains a large amount of carboxyl, heating and refluxing for 6h at 50 ℃ after the carboxyl is subjected to condensation reaction with carboxymethyl contained in polyacrylamide, adjusting the pH to be 8, adding 90g L-lysine hydrochloride, and performing nitrogen atmosphere, stirring and reacting for 6h at 30 ℃, activating end position groups of the intermediate product by using amino acid hydrochloride, grafting lysine to obtain a gelatinous product, washing the gel with active position groups capable of self-crosslinking, and drying the solvent which is not reacted in the gel at 60 ℃ after being washed by deionized water to obtain the gel. Because industrial wastewater is irradiated, a large amount of high-activity free radicals are contained in the water, under the irradiation condition, the free radicals promote the crosslinking reaction of active site groups with self-crosslinking of the gel, and meanwhile, various heavy metal ions can be adsorbed during crosslinking and are well adsorbed, so that the aim of treating the sewage is fulfilled.
Example 2: preparing a second gel agent:
preparation of polyacrylamide: adding 180g of acrylamide and 18g N, N' -methylene bisacrylamide into deionized water, stirring and dissolving, adding 1.5g of ammonium sulfate and 0.5g of tetramethylethylenediamine, then adjusting the pH value to 10-10.5 with a sodium hydroxide solution, uniformly stirring, standing at normal temperature for 2 hours to obtain polyacrylamide, and washing the unreacted monomers and the solvent with deionized water to obtain pure polyacrylamide;
preparing a gel agent: adding 35ml of 3 wt% methanol solution into 70g of polyacrylamide, stirring and mixing, heating and refluxing at 85 ℃ for 35min after the polyacrylamide is subjected to hydroxymethylation, adding 20ml of potassium permanganate-citric acid solution, wherein the mass concentration of potassium permanganate is 0.5%, adding 15ml of saturated coconut oil fatty acid, uniformly mixing, stirring at the speed of 100r/min for 1h at normal temperature, heating and refluxing at 55 ℃ for 5.5h, adjusting the pH to 8.5, adding 40g L-lysine hydrochloride, stirring and reacting at 35 ℃ for 4h under the nitrogen atmosphere to obtain a gelatinous product, washing an unreacted gel solvent with deionized water, and drying at 60 ℃ to obtain the gel.
Example 3: preparing the gel agent III:
preparation of polyacrylamide: adding 160g of acrylamide and 16g N, N' -methylene bisacrylamide into deionized water, stirring and dissolving, adding 1g of ammonium sulfate and 0.5g of tetramethylethylenediamine, then adjusting the pH value to 10.5-11 by using a sodium hydroxide solution, uniformly stirring, standing at normal temperature for 2 hours to obtain polyacrylamide, washing the polyacrylamide with deionized water, and washing the unreacted monomers and the solvent completely to obtain pure polyacrylamide;
preparing a gel agent: adding 25ml of 3 wt% methanol solution into 60g of polyacrylamide, stirring and mixing, heating and refluxing for 30min at 90 ℃ after the polyacrylamide is subjected to hydroxymethylation, adding 10ml of potassium permanganate-citric acid solution, wherein the mass concentration of potassium permanganate is 0.5%, adding 15ml of saturated coconut oil fatty acid, uniformly mixing, stirring for 2h at the speed of 100r/min at normal temperature, heating and refluxing for 5h at 60 ℃, adjusting the pH to 9, adding 30g L-lysine hydrochloride, stirring and reacting for 3h at 40 ℃ in a nitrogen atmosphere to obtain a gelatinous product, washing the solvent which does not react with the gel with deionized water, and drying at 60 ℃ to obtain the gel.
Example 4: treating sewage:
a pretreatment procedure: respectively screening and removing impurities from the cadmium-containing wastewater of 10mg/L, the chromium-containing wastewater of 10mg/L and the lead-containing wastewater of 10mg/L by using a screen, removing suspended matters, then settling sand, removing sediments, and removing oil slick on the surface until no visible impurities exist;
a mixing procedure: mixing the industrial wastewater subjected to the pretreatment process, and pre-aerating for 2 days at normal temperature;
an adjusting procedure: adjusting the pre-aerated industrial wastewater until the pH value is 11;
an irradiation treatment process: discharging the industrial wastewater subjected to the adjusting process into a sealed irradiation zone, and passing the industrial wastewater through 4kGy at normal temperature60Irradiating for 2 hours by Co-gamma rays;
heavy metal adsorption process: adjusting the pH value of the industrial wastewater after the irradiation treatment process8, adding the gel, uniformly stirring, heating to 40 ℃, and irradiating to 2kGy60Irradiating for 4h by Co-gamma rays to obtain a gel complex;
a filtering process: and precipitating and filtering the gel complex obtained in the heavy metal adsorption process, finishing the treatment of industrial wastewater, and measuring that the cadmium content in the water is 0.05mg/L, the chromium content is 0.11mg/L and the lead content is 0.1 mg/L.
Example 5: and (2) sewage treatment II:
a pretreatment procedure: respectively screening 5mg/L cadmium-containing wastewater, 5mg/L chromium-containing wastewater and 5mg/L lead-containing wastewater by using a screen to remove impurities, removing suspended matters, then settling sand, removing sediments, and removing oil slick on the surface until no visible impurities exist;
a mixing procedure: mixing the industrial wastewater subjected to the pretreatment process, and pre-aerating for 1 day at normal temperature;
an adjusting procedure: adjusting the pre-aerated industrial wastewater until the pH value is 8;
an irradiation treatment process: discharging the industrial wastewater subjected to the adjusting process into a sealed irradiation zone, and passing the industrial wastewater through 6kGy at normal temperature60Irradiating for 2 hours by Co-gamma rays;
heavy metal adsorption process: adjusting pH to 6, adding gel, stirring, heating to 55 deg.C, and irradiating to 4kGy60Irradiating for 4h by Co-gamma rays to obtain a gel complex;
a filtering process: precipitating and filtering the gel complex obtained in the heavy metal adsorption process, finishing the treatment of industrial wastewater, and measuring that the cadmium content in the water is 0.03mg/L, the chromium content is 0.09mg/L and the lead content is 0.1 mg/L.
It should be noted that the mixed industrial wastewater treatment method of the present invention is required to be performed in a shielded space, and the treated industrial wastewater can stably exist after being mixed without causing chemical reaction with each other.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (6)
1. A mixed industrial sewage treatment method is characterized by comprising the following steps:
the method comprises the following steps of pretreatment, mixing, adjusting, irradiating, heavy metal adsorbing and filtering, wherein in the heavy metal adsorbing step, heavy metal is removed by adopting an irradiation gel method, gamma rays are adopted in both the irradiating step and the heavy metal adsorbing step, the irradiation absorption dose in the irradiating step is 4-6kGy, the irradiation absorption dose in the heavy metal adsorbing step is 2-4kGy, the irradiation gel method is that a gel agent is put into irradiated industrial wastewater, the gel agent and the heavy metal are complexed to form a gel complex under the irradiation effect, and the gel agent is mainly obtained by the reflux reaction of polyacrylamide, a potassium permanganate-citric acid solution and coconut oil fatty acid and then the graft copolymerization of polyacrylamide, an amino acid hydrochloride;
the preparation method of the gel comprises the following steps:
preparation of polyacrylamide: dissolving acrylamide and N, N' -methylene bisacrylamide, adding ammonium sulfate and tetramethyl ethylenediamine, then adjusting the pH to 9-11, uniformly stirring, and standing to obtain polyacrylamide;
preparing a gel agent: adding a methanol solution into polyacrylamide, heating and refluxing at 80-90 ℃ for 30-50min, then adding a potassium permanganate-citric acid solution and coconut oil fatty acid, stirring at normal temperature for 1-2h, heating and refluxing at 50-60 ℃ for 5-6h, adjusting the pH to 8-9, adding L-lysine hydrochloride, stirring and reacting at 30-40 ℃ for 3-6h to obtain gel, washing and drying to obtain the gel.
2. The mixed industrial sewage treatment method according to claim 1, wherein the treatment method is specifically operated as follows:
a pretreatment procedure: respectively screening, filtering, removing impurities, floating and removing oil from various industrial wastewater;
a mixing procedure: mixing the industrial wastewater subjected to the pretreatment process, and pre-aerating for 1-2 days;
an adjusting procedure: adjusting the pH value of the industrial wastewater to 8-11;
an irradiation treatment process: irradiating the industrial wastewater subjected to the adjusting process for 2-3h by gamma-rays at normal temperature;
heavy metal adsorption process: adjusting the pH value of the industrial wastewater subjected to the irradiation treatment process to 6-8, adding a gelling agent, heating to 40-55 ℃, and performing irradiation treatment for 2-4h to form a gel complex;
a filtering process: and (4) filtering the gel complex precipitate, and discharging the filtered filtrate.
3. The mixed industrial sewage treatment method according to claim 2, wherein the heavy metals in the industrial wastewater mainly comprise cadmium, chromium and lead, and the content of the cadmium, the chromium and the lead is more than or equal to 5 mg/L.
4. The mixed industrial sewage treatment method according to claim 3, wherein the mass ratio of the acrylamide to the N, N' -methylenebisacrylamide is 10: 1.
5. The mixed industrial sewage treatment method according to claim 4, wherein the mass concentration of potassium permanganate in the potassium permanganate-citric acid solution is 0.5-1%.
6. The mixed industrial sewage treatment method according to claim 5, wherein the mass ratio of the polyacrylamide to the L-lysine hydrochloride is 1: (0.5-0.9), wherein the solid-to-liquid ratio of the polyacrylamide to the coconut oil fatty acid is (4-5): 1 g/ml.
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