CN112624291A - Wastewater treatment flocculant and wastewater treatment method - Google Patents
Wastewater treatment flocculant and wastewater treatment method Download PDFInfo
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- CN112624291A CN112624291A CN202011640714.0A CN202011640714A CN112624291A CN 112624291 A CN112624291 A CN 112624291A CN 202011640714 A CN202011640714 A CN 202011640714A CN 112624291 A CN112624291 A CN 112624291A
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- chitosan
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- acrylamide
- methacrylamide
- ammonium chloride
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a wastewater treatment flocculant, which is synthesized by taking chitosan, acrylamide or methacrylamide and methacryloyloxyethyl trimethyl ammonium chloride as raw materials to obtain a chitosan modified cationic polyacrylamide flocculant; wherein the weight ratio of chitosan, acrylamide or methacrylamide to methacryloyloxyethyl trimethyl ammonium chloride is 1: 20-30: 5-10. The flocculating agent has high flocculation precipitation treatment efficiency, the removal rate of heavy metals in the electroplating wastewater with high CODcr can reach more than 80%, and meanwhile, the invention also discloses a sewage treatment method, which belongs to the field of sewage treatment.
Description
Technical Field
The invention belongs to the technical field of waste environment-friendly treatment, and particularly relates to a wastewater treatment flocculant and a wastewater treatment method.
Background
The sources of the electroplating wastewater are generally: (1) cleaning water for the plated part; (2) a waste plating solution; (3) other waste waters including flushing the floor of the shop, scrubbing the polar plates, aeration equipment condensation, and various bath liquids and drains that "run, spill, drip, leak" due to bath leakage or improper operation and management; (4) the equipment cools the water, and the cooling water is not polluted except for temperature rise in the using process. The quality and quantity of the electroplating wastewater are related to the process conditions, production load, operation management, water using mode and other factors of electroplating production. The electroplating wastewater has complex water quality and difficult control of components, contains heavy metal ions such as chromium, cadmium, nickel, copper, zinc, gold, silver and the like, cyanide and the like, and some of the heavy metal ions belong to highly toxic substances with carcinogenic, teratogenic and mutagenic properties.
The prior treatment method of electroplating wastewater is roughly as follows: air floatation, flocculation, electro-reduction, etc.
For large-scale electroplating wastewater treatment, wastewater and waste residues exist, and a flocculation method is generally adopted for treatment.
The efficiency of the flocculating agent has obvious influence on the wastewater treatment cost, so the technical problem to be solved by the scheme is as follows: how to improve the flocculation precipitation effect on the electroplating wastewater.
Disclosure of Invention
The invention mainly aims to provide a wastewater treatment flocculant which has high flocculation precipitation treatment efficiency and can reach a removal rate of more than 80 percent for heavy metals in electroplating wastewater with high CODcr.
According to the first aspect of the invention, a wastewater treatment flocculant is provided, wherein chitosan, acrylamide or methacrylamide and methacryloyloxyethyl trimethyl ammonium chloride are used as raw materials to synthesize a chitosan modified cationic polyacrylamide flocculant;
wherein the weight ratio of chitosan, acrylamide or methacrylamide to methacryloyloxyethyl trimethyl ammonium chloride is 1: 20-30: 5-10.
In the above wastewater treatment flocculant, it is prepared by the following method:
dissolving chitosan in deionized water, adding a reaction system in which acrylamide or methacrylamide is uniformly mixed, independently dissolving an initiator and methacryloxyethyl trimethyl ammonium chloride in the deionized water, adjusting the temperature of the reaction system to 45-65 ℃, respectively and simultaneously dropwise adding an initiator solution and a methacryloxyethyl trimethyl ammonium chloride solution into the reaction system for 1-2 hours, and then carrying out a constant temperature reaction for 3-5 hours; adjusting the pH value of the system to 4-5 to obtain the chitosan modified cationic polyacrylamide flocculant.
In the above wastewater treatment flocculant, the raw material further comprises N-hydroxyethyl acrylamide, and the weight ratio of the chitosan, the acrylamide or the methacrylamide, the methacryloyloxyethyl trimethyl ammonium chloride and the N-hydroxyethyl acrylamide is 1: 20-30: 5-10: 1-2;
the N-hydroxyethyl acrylamide and chitosan, acrylamide or methacrylamide are mixed to form a reaction system.
In the above-mentioned wastewater treatment flocculant, the amount of the deionized water is 2 to 3 times the total weight of the raw materials.
In the above wastewater treatment flocculant, the initiator is a redox initiator, and the initiator is 0.5-1% of the total weight of the raw materials.
In the above flocculant for wastewater treatment, a surfactant in an amount of 1-2% by weight based on the total weight of the raw materials is further added to the reaction system, and the surfactant is tween-80, tween 60 or tween 65.
Meanwhile, the invention also discloses a wastewater treatment method, wherein the wastewater treatment flocculating agent is added into wastewater, and impurities form flocculation precipitation under the stirring action;
preferably, the concentration of the wastewater is preferably 5-50 mg/L;
preferably, the wastewater is electroplating wastewater, and the CODcr concentration of the wastewater is more than 500 mg/L.
One of the above technical solutions of the present invention has at least one of the following advantages or beneficial effects:
according to the invention, methacryloyloxyethyl trimethyl ammonium chloride is used as a cationic monomer, chitosan is used for modification, and the chitosan modified cationic polyacrylamide flocculant is obtained, has high adsorption efficiency on heavy metal ions in electroplating wastewater of more than 500mg/LCODcr, and can remarkably reduce the CODcr value of the wastewater.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described below are exemplary only, are intended to illustrate the present invention, and should not be construed as limiting the present invention.
Example 1
A method for treating electroplating sewage is characterized in that: heavy metal content is high, the organic matter is contained, the CODcr content of the organic matter reaches more than 500mg/L and far exceeds the discharge standard allowed by the national standard.
The method comprises the following steps:
step 1: adding electroplating sewage into a sedimentation tank for sedimentation, and separating out a first sediment;
step 2: introducing the liquid in the step 1 into a flocculation sedimentation tank, adding a flocculating agent, stirring, and collecting flocs on the surface and a second precipitate at the bottom;
the flocculant is an organic flocculant, preferably a chitosan modified cationic polyacrylamide flocculant;
the chitosan modified cationic polyacrylamide flocculant is a water-soluble high-molecular polymer. Because of the polar groups in the molecular chain, the polymer can absorb solid particles suspended in water, bridge the particles or coagulate the particles to form large flocculate through charge neutralization. Therefore, it can accelerate the sedimentation of particles in suspension, and has very obvious effects of accelerating the clarification of solution, promoting filtration and the like.
The amount of flocculant added per cubic meter of wastewater (neutral or weakly alkaline) is preferably 5-15 g.
And step 3: introducing the liquid in the step 2 into a first-stage adsorption tank; the primary adsorption tank is filled with the porous block-shaped bodies;
and 4, step 4: introducing the liquid treated in the step (3) into a secondary adsorption tank; and the secondary adsorption tank is internally filled with an activated carbon layer.
And 5: mixing the first precipitate obtained in the step 1, the flocculate obtained in the step 2 and the second precipitate to prepare electroplating sludge; preparing electroplating sludge, activated carbon and an inorganic adhesive into a porous block-shaped body, and smelting the porous block-shaped body after adsorption saturation to obtain a melt and furnace slag; the slag is used as an inorganic binder after grinding.
The preparation method of the porous block body comprises the following steps:
step 51: controlling the water content of the electroplating sludge to be 25-30% in an extrusion mode;
step 52: mixing and extruding the electroplating sludge, the activated carbon and the inorganic adhesive in the step 51 into blocks; after the block sludge is extruded into blocks, the block sludge is cured for 5 to 10 hours at normal temperature; in the step 3, the central temperature of the blocky sludge subjected to liquid nitrogen quick-freezing treatment is lower than-60 ℃, in the step 54, the vacuum environment refers to that the absolute pressure is lower than 50Pa, and the treatment time of the step 54 is 4-6 h.
Step 53: quickly freezing the blocky sludge in the step 52 by adopting liquid nitrogen; the central temperature of the blocky sludge subjected to liquid nitrogen quick-freezing treatment is lower than-70 ℃, and is preferably-80 ℃;
step 54: and gasifying the water in the quick-frozen blocky sludge under a vacuum environment to obtain a porous blocky body. The vacuum environment is that the absolute pressure is 20Pa, the processing time of the step 54 is 5h, and the water content of the porous block body is controlled to be about 5 percent.
The weight ratio of the electroplating sludge, the activated carbon and the inorganic adhesive in the step 52 is 50-60:5-10:30-45, and in the embodiment, is 55:10: 35.
The smelting process of the porous block body comprises the following steps: ball-milling and crushing the porous block body after saturation adsorption to obtain a granular material, wherein the particle size of the granular material is 100-200 meshes; and then, smelting the granular material and a little of borax as a solvent in an environment of 1300 +/-100 ℃, wherein the adding amount of the borax is 0.05-0.1% of the weight of the block-shaped body in the step 54, and obtaining a melt and slag. The powder of slag ground to 200 mesh or finer can be recycled as an inorganic binder.
The beneficial effects of the invention are as follows:
1. the first precipitate, the second precipitate and flocculate in the electroplating wastewater are treated as electroplating sludge, so that solid hazardous wastewater is prevented from being discharged;
2. the electroplating wastewater reaches the discharge requirement of the discharge standard of electroplating pollutants (GB21900-2008) through flocculation, primary adsorption and secondary adsorption, and the discharge of overproof liquid hazardous waste is avoided;
3. after the preliminarily dehydrated electroplating sludge, the activated carbon and the adhesive are mixed, the activated carbon still has high activity, can adsorb heavy metal ions and organic matters in the sewage and plays a role in primary adsorption and filtration;
4. the active carbon and the adhesive can be used as a reducing agent and a slagging agent in the smelting process without additional supplement.
5. Compare in traditional sewage treatment in the sand bed filter, its filtration adsorption effect is better, reduces the adsorption pressure of follow-up active carbon, prolongs the adsorption life of active carbon.
The chitosan modified cationic polyacrylamide flocculant in example 1 was prepared by the following method:
dissolving chitosan in deionized water, adding acrylamide or methacrylamide, optional N-hydroxyethyl acrylamide and tween-80 which is 1-2% of the total weight of the raw materials into the deionized water, uniformly mixing, independently dissolving an initiator (a hydrogen peroxide-sodium bisulfite reaction system, wherein the initiator is 0.5% of the total weight of the raw materials) and methacryloyloxyethyl trimethyl ammonium chloride into the deionized water, adjusting the temperature of the reaction system to 45-65 ℃, respectively and simultaneously dropwise adding the initiator solution and the methacryloyloxyethyl trimethyl ammonium chloride solution into the reaction system for 1.5h, and then reacting at constant temperature for 4 h; adjusting the pH value of the system to 5 to obtain the chitosan modified cationic polyacrylamide flocculant.
Referring to table 1 below, samples 1-4 were obtained, and samples 1-4 were used as the chitosan-modified cationic polyacrylamide flocculant of example 1.
TABLE 1
Control sample
Dissolving chitosan in deionized water, adding a reaction system in which acrylamide or methacrylamide and tween-80 which is 1-2% of the total weight of the raw materials are uniformly mixed, independently dissolving an initiator (a hydrogen peroxide-sodium bisulfite reaction system, wherein the initiator is 0.5% of the total weight of the raw materials) and dimethyldiallylammonium chloride in the deionized water, adjusting the temperature of the reaction system to 45-65 ℃, respectively and simultaneously dropwise adding an initiator solution and a dimethyldiallylammonium chloride solution into the reaction system for 1.5h, and then carrying out constant temperature reaction for 4 h; adjusting the pH value of the system to 5 to obtain the chitosan modified cationic polyacrylamide flocculant.
The above control sample and samples 1 to 4 were added to step 2 of example 1, and the influent and effluent CODcr of step 2 was collected, and 10g of chitosan-modified cationic polyacrylamide flocculant was added per cubic meter of wastewater.
The test results are shown in Table 2 below
TABLE 2
| COD of inlet water | COD of effluent | Removal rate | |
| Sample 1 | 550 | 112 | 0.796363636 |
| Sample 2 | 535 | 105 | 0.803738318 |
| Sample 3 | 533 | 107 | 0.799249531 |
| Sample No. 4 | 572 | 86 | 0.84965035 |
| Control sample | 558 | 253 | 0.546594982 |
The invention adopts the polymerization of methacryloyloxyethyl trimethyl ammonium chloride, chitosan and acrylamide to prepare the flocculant with high adsorption rate. When the monomer of the N-hydroxyethyl acrylamide with the hydroxyl modified group is added, the adsorption rate can be improved by about 5 percent.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (7)
1. A wastewater treatment flocculant is characterized in that chitosan, acrylamide or methacrylamide and methacryloyloxyethyl trimethyl ammonium chloride are used as raw materials to synthesize a chitosan modified cationic polyacrylamide flocculant;
wherein the weight ratio of chitosan, acrylamide or methacrylamide to methacryloyloxyethyl trimethyl ammonium chloride is 1: 20-30: 5-10.
2. The wastewater treatment flocculant according to claim 1, which is produced by a method comprising:
dissolving chitosan in deionized water, adding a reaction system in which acrylamide or methacrylamide is uniformly mixed, independently dissolving an initiator and methacryloxyethyl trimethyl ammonium chloride in the deionized water, adjusting the temperature of the reaction system to 45-65 ℃, respectively and simultaneously dropwise adding an initiator solution and a methacryloxyethyl trimethyl ammonium chloride solution into the reaction system for 1-2 hours, and then carrying out a constant temperature reaction for 3-5 hours; adjusting the pH value of the system to 4-5 to obtain the chitosan modified cationic polyacrylamide flocculant.
3. The wastewater treatment flocculant according to claim 2, wherein the raw material further comprises N-hydroxyethyl acrylamide, and the weight ratio of the chitosan, the acrylamide or the methacrylamide, the methacryloyloxyethyl trimethyl ammonium chloride and the N-hydroxyethyl acrylamide is 1: 20-30: 5-10: 1-2;
the N-hydroxyethyl acrylamide and chitosan, acrylamide or methacrylamide are mixed to form a reaction system.
4. The wastewater treatment flocculant according to claim 2, wherein the amount of the deionized water is 2 to 3 times the total weight of the raw materials.
5. The wastewater treatment flocculant according to claim 2, wherein the initiator is a redox initiator, and the initiator is 0.5 to 1% by weight based on the total weight of the raw materials.
6. The wastewater treatment flocculant according to claim 2, wherein 1-2% of a surfactant is further added into the reaction system, and the surfactant is tween-80, tween 60 or tween 65.
7. A method for treating wastewater, characterized in that the wastewater treatment flocculant according to any one of claims 1 to 6 is added to wastewater to cause the impurities to form a flocculated precipitate under the action of agitation.
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| CN202011640714.0A CN112624291A (en) | 2020-12-31 | 2020-12-31 | Wastewater treatment flocculant and wastewater treatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028343A (en) * | 2022-07-12 | 2022-09-09 | 南京江北新区公用控股集团有限公司 | Compound sludge conditioner, preparation method and application thereof |
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| CN1654497A (en) * | 2005-01-14 | 2005-08-17 | 华南理工大学 | Chitosan graft ternary polymerization polymeric flocculant and its preparation method and use |
| CN101935097A (en) * | 2010-07-23 | 2011-01-05 | 北京化工大学 | Solid-liquid separation flocculating agent for waste drilling fluid and preparation method thereof |
| CN103121742A (en) * | 2012-11-12 | 2013-05-29 | 武汉斯隆电气有限公司 | Inorganic-modified chitosan composite type polymeric flocculant |
| CN106008822A (en) * | 2016-06-21 | 2016-10-12 | 上海东升新材料有限公司 | Polyacrylamide flocculant modified by chitosan and preparing method thereof |
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2020
- 2020-12-31 CN CN202011640714.0A patent/CN112624291A/en active Pending
Patent Citations (5)
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| EP1236748A1 (en) * | 2001-02-22 | 2002-09-04 | Ecole Polytechnique Federale De Lausanne | Polymer flocculents and preparation thereof |
| CN1654497A (en) * | 2005-01-14 | 2005-08-17 | 华南理工大学 | Chitosan graft ternary polymerization polymeric flocculant and its preparation method and use |
| CN101935097A (en) * | 2010-07-23 | 2011-01-05 | 北京化工大学 | Solid-liquid separation flocculating agent for waste drilling fluid and preparation method thereof |
| CN103121742A (en) * | 2012-11-12 | 2013-05-29 | 武汉斯隆电气有限公司 | Inorganic-modified chitosan composite type polymeric flocculant |
| CN106008822A (en) * | 2016-06-21 | 2016-10-12 | 上海东升新材料有限公司 | Polyacrylamide flocculant modified by chitosan and preparing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028343A (en) * | 2022-07-12 | 2022-09-09 | 南京江北新区公用控股集团有限公司 | Compound sludge conditioner, preparation method and application thereof |
| CN115028343B (en) * | 2022-07-12 | 2024-04-12 | 南京江北新区公用控股集团有限公司 | Compound sludge conditioner, preparation method and application thereof |
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