CN114853925A - Organic polymer heavy metal chelating flocculant and preparation method and application thereof - Google Patents
Organic polymer heavy metal chelating flocculant and preparation method and application thereof Download PDFInfo
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- CN114853925A CN114853925A CN202210598781.3A CN202210598781A CN114853925A CN 114853925 A CN114853925 A CN 114853925A CN 202210598781 A CN202210598781 A CN 202210598781A CN 114853925 A CN114853925 A CN 114853925A
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- heavy metal
- metal chelating
- flocculant
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 62
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920001661 Chitosan Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 25
- 239000004220 glutamic acid Substances 0.000 claims abstract description 25
- 239000010865 sewage Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 235000001014 amino acid Nutrition 0.000 claims abstract description 3
- 150000001413 amino acids Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 21
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008394 flocculating agent Substances 0.000 description 8
- 239000003002 pH adjusting agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 210000005036 nerve Anatomy 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010036872 Prolonged labour Diseases 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the field of sewage treatment, and relates to an organic polymer heavy metal chelating flocculant, and a preparation method and application thereof. The preparation method comprises the following steps: glutamic acid with two carboxyl groups in natural amino acid is introduced into a molecular chain of high molecular polymer Chitosan (CTS) to obtain the organic high molecular heavy metal chelating flocculant GAC. The invention has good flocculation effect, reduces the turbidity of the water body, has simple and convenient treatment process, realizes the recycling of heavy metal and reduces the industrial cost.
Description
Technical Field
The invention belongs to the field of sewage treatment, and relates to an organic polymer heavy metal chelating flocculant, and a preparation method and application thereof.
Background
The waste water discharged in the industries of electroplating, mining, chemical engineering and the like contains a large amount of heavy metals, including cadmium, mercury, lead, arsenic, chromium, copper, zinc, nickel and the like. Most heavy metals once introduced into living organisms cannot be biodegraded and tend to accumulate in the living organisms, causing irreversible damage to the natural environment and human body if discharged without treatment. For example, cadmium is a heavy metal with very high toxicity, most of its compounds are toxic substances, and after a large amount of cadmium is accumulated in the human body, it will cause damage to the liver and kidney, and will affect the central nerve of the human body. After the lead content in the human body exceeds the standard, firstly, the blood system of the human body can be damaged, and the synthesis of hemoglobin is influenced. Secondly, the nervous system and organs are damaged, and the cardiovascular and cerebrovascular diseases are damaged. After the accumulation of the dose, the liver and the kidney are damaged, the central nerve of a human body is influenced, and the accumulated dose is extremely difficult to discharge out of the body. Meanwhile, the heavy metal is a very precious resource, and if the heavy metal in the industrial wastewater is recycled, the industrial cost can be greatly reduced.
The traditional waste water treatment methods include chemical precipitation, ion exchange, membrane separation adsorption and flocculation. However, this kind of method is often accompanied by the disadvantages of complex process flow, many kinds of equipment, large total project investment, large floor area, long labor time, power consumption, large equipment loss, complex equipment maintenance, civil engineering requirement, long project delivery period, high daily operation complexity, inconvenient and unstable operation.
At present, the heavy metal flocculants studied and applied are mainly classified into three main categories: the first type: the inorganic flocculant has a long application history, and is widely applied to purification of drinking water and industrial water and dehydration treatment of underground water. They can be divided into two main groups according to molecular weight: low molecular systems and high molecular systems. The inorganic polymeric flocculant is a novel water treatment agent developed on the basis of traditional aluminum salt and iron salt in the 60 th century. After being added into water, the polymer is adsorbed on the surface of the particles within a certain period of time, and plays the roles of electrical neutralization and bonding and bridging by using higher charge and larger molecular weight of the polymer. The second type: organic flocculants, which have been used rapidly in recent 20 years, can be classified into natural polymeric flocculants and artificially synthesized polymeric flocculants. Natural polymers are increasingly being replaced by synthetic polymers with ever decreasing costs, since they are susceptible to degradation by enzymes. The artificial synthesized organic polymer flocculant is mainly characterized in that the length of a hydrocarbon chain can be changed by adopting a synthesis method according to the use requirement, and functional groups with different properties are introduced on the hydrocarbon chain. The natural modified polymeric flocculant can be roughly divided into amphoteric starch, amphoteric cellulose, amphoteric vegetable gum and the like. For the selection of modified raw materials, countries in the world focus on different points according to respective natural conditions, such as more researches on starch modified substances in the United states, more applications on alginic acid derivatives in the United kingdom, and earlier sewage treatment by using chitin modified products in Japan. In the third category: the bioflocculant is prepared from microorganisms or secretion thereof by modern biotechnology through processes of fermentation, extraction, refining and the like of the microorganisms to obtain cohesive metabolic products, and the cohesive metabolic products can connect suspended matter particles together and destabilize colloids to form flocs. The biological flocculant is widely applied to the fields of medicine, food, chemistry, environmental protection and the like. Foreign, commercial production of microbial flocculants began in the 90's of the 20 th century.
The inorganic flocculant in the flocculant has high cost, high corrosivity and unsatisfactory water purification effect, the microbial flocculant is not widely applied in China, the technology is laggard, and part of organic flocculants contain carcinogenic substances and have great harm to human bodies. Therefore, the green environment-friendly organic polymer heavy metal chelating flocculant and the preparation method and the application thereof are provided.
Disclosure of Invention
The invention aims to provide an organic polymer heavy metal chelating flocculant which is efficient, low in cost and practical, can recycle heavy metals in sewage and does not cause secondary pollution to the environment, and a preparation method and application thereof. Solves the problems that the prior flocculating agent has high cost, high corrosivity, unsatisfactory water purification effect, easy secondary pollution to the environment and incapability of recycling heavy metals.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic polymer heavy metal chelating flocculant has a chemical structural formula shown as a formula (I):
a preparation method of an organic polymer heavy metal chelating flocculant comprises the following reaction equation:
a preparation method of an organic polymer heavy metal chelating flocculant comprises the steps of introducing glutamic acid with two carboxyl groups in natural amino acid into a molecular chain of a high polymer Chitosan (CTS) to obtain an organic polymer heavy metal chelating flocculant GAC; the method specifically comprises the following steps:
(1) weighing glutamic acid, chitosan and EDCI, and weighing a dilute hydrochloric acid solution for later use;
(2) dissolving the chitosan in the step (1) in dilute hydrochloric acid, and then adding distilled water for dilution and stirring;
(3) adding EDCI while continuously stirring the mixed solution in the step (2), and adding glutamic acid after EDCI is completely dissolved;
(4) adding a pH regulator into the solution prepared in the step (3), and regulating the pH of the solution to 4-8;
(5) and (4) stirring the solution prepared in the step (4) at 25 ℃ for 0.5-2 h to obtain the organic polymer heavy metal chelating flocculant.
Further, the glutamic acid, the chitosan, the diluted hydrochloric acid, the pH regulator, the EDCI and the water are in percentage by weight: 1-20% of glutamic acid, 1-20% of chitosan, 5-30% of dilute hydrochloric acid, 1-5% of a pH regulator, 0.1-2% of EDCI and the balance of distilled water.
Further, the concentration of the dilute hydrochloric acid is 0.1-1 mol.L -1 。
Further, the pH regulator is selected from one of NaOH or HCl solution.
The invention discloses an application of an organic polymer heavy metal chelating flocculant in sewage treatment.
Preferably, the organic polymer heavy metal chelating flocculant is applied to sewage treatment containing heavy metal copper ions.
The invention discloses an application of an organic polymer heavy metal chelating flocculant in sewage treatment containing one or more of heavy metal zinc ions, nickel ions, lead ions and chromium ions.
The invention also discloses application of the organic polymer heavy metal chelating flocculant in reducing turbidity-causing substances in water.
Further, the turbidity-causing substance includes a heavy metal compound in a granular form.
In summary, due to the adoption of the technical scheme, the beneficial technical effects of the invention are as follows:
the organic polymer heavy metal chelating flocculant is a novel heavy metal chelating flocculant, and glutamic acid with strong heavy metal chelating capacity is introduced into chitosan of a natural polymer flocculant, so that the function of trapping heavy metal ions is given to the flocculant. Carboxyl and amino groups introduced on the molecular chain of the flocculant are polar groups, so that the flocculant is easy to dissolve in water, and the solubility of chitosan is improved; and the strong coordination of the two groups improves the coordination capacity of the flocculant and reduces the solubility of the complex. The high molecular property of the chitosan provides strong adsorption and bridging effects, and the settleability of flocs is improved, so that the efficiency of removing heavy metals by using the flocculant is improved.
The organic polymer heavy metal chelating flocculant has wide application range, can react with various heavy metal ions in the wastewater quickly, and chelate generated by the reaction is insoluble in water and has stable chemical property. Meanwhile, the turbidity of the water body can be reduced.
The organic polymer heavy metal chelating flocculant disclosed by the invention is convenient to store, has strong thermal stability, is slightly influenced by other external factors such as PH (potential of hydrogen), temperature and the like, and is convenient to store for a long time.
Compared with other types of flocculants, the organic polymer heavy metal chelating flocculant provided by the invention is safer and more environment-friendly, does not generate toxic substances in the reaction process, is nontoxic and harmless to chelate bodies generated by the reaction, meets the environment-friendly requirement, and does not cause secondary pollution to the environment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
In the embodiment, the organic polymer heavy metal chelating flocculant is prepared from the following components in percentage by weight:
| glutamic acid | 20％ |
| Chitosan | 2％ |
| Dilute hydrochloric acid | 5％ |
| NaOH solution | 2％ |
| EDCI | 0.5％ |
| Distilled water | Balance of |
The preparation method comprises the following steps:
(1) weighing glutamic acid, chitosan, dilute hydrochloric acid, a pH regulator, EDCI and water according to the weight percentage for standby.
(2) Dissolving the glutamic acid in the step (1) in dilute hydrochloric acid, adding distilled water for dilution and stirring.
(3) And (3) adding EDCI into the mixed solution obtained in the step (2) while continuously stirring, and then adding chitosan.
(4) Adding a pH adjusting agent to the obtained solution prepared in (3), and adjusting the pH of the solution to 4.
(5) And stirring the solution for 2 hours at 25 ℃ to obtain the organic polymer heavy metal chelating flocculant.
Example 2
In the embodiment, the organic polymer heavy metal chelating flocculant is prepared from the following components in percentage by weight:
| glutamic acid | 10％ |
| Chitosan | 15％ |
| Dilute hydrochloric acid | 10％ |
| NaOH solution | 4％ |
| EDCI | 0.1％ |
| Distilled water | Balance of |
The preparation method comprises the following steps:
(1) weighing glutamic acid, chitosan, dilute hydrochloric acid, a pH regulator, EDCI and water according to the weight percentage for standby.
(2) Dissolving the glutamic acid in the step (1) in dilute hydrochloric acid, adding distilled water for dilution and stirring.
(3) And (3) adding EDCI into the mixed solution obtained in the step (2) while continuously stirring, and then adding chitosan.
(4) Adding a pH adjusting agent to the obtained solution prepared in (3), and adjusting the pH of the solution to 6.
(5) And stirring the solution for 2 hours at 25 ℃ to obtain the organic polymer heavy metal chelating flocculant.
Example 3
In the embodiment, the organic polymer heavy metal chelating flocculant is prepared from the following components in percentage by weight:
the preparation method comprises the following steps:
(1) weighing glutamic acid, chitosan, dilute hydrochloric acid, a pH regulator, EDCI and water according to the weight percentage for standby.
(2) Dissolving the glutamic acid in the step (1) in dilute hydrochloric acid, adding distilled water for dilution and stirring.
(3) And (3) adding EDCI into the mixed solution obtained in the step (2) while continuously stirring, and then adding chitosan.
(4) Adding a pH adjusting agent to the obtained solution prepared in (3), and adjusting the pH of the solution to 8.
(5) And stirring the solution for 1h at 25 ℃ to obtain the organic polymer heavy metal chelating flocculant.
Example 4
In the embodiment, the organic polymer heavy metal chelating flocculant is prepared from the following components in percentage by weight:
| glutamic acid | 6％ |
| Chitosan | 5％ |
| Dilute hydrochloric acid | 3％ |
| HCl solution | 1.5％ |
| EDCI | 1％ |
| Distilled water | Balance of |
The preparation method comprises the following steps:
(1) weighing glutamic acid, chitosan, dilute hydrochloric acid, a pH regulator, EDCI and water according to the weight percentage for standby.
(2) Dissolving the glutamic acid in the step (1) in dilute hydrochloric acid, adding distilled water for dilution and stirring.
(3) And (3) adding EDCI into the mixed solution obtained in the step (2) while continuously stirring, and then adding chitosan.
(4) Adding a pH adjusting agent to the obtained solution prepared in (3), and adjusting the pH of the solution to 6.
(5) And stirring the solution for 1h at 25 ℃ to obtain the organic polymer heavy metal chelating flocculant.
Comparative example 1
The raw materials of the organic polymer heavy metal chelating flocculant in the comparative example are the same as those in example 1, and the difference is that natural chitosan is adopted as the heavy metal chelating flocculant in the comparative example, and chitosan modified by glutamic acid is adopted as the heavy metal chelating flocculant in example 1.
Comparative example 2
The difference between the raw materials and the preparation method of the organic polymer heavy metal chelating flocculant in the comparative example and the example 1 is that acetic acid is adopted in the comparative example, and glutamic acid is adopted in the example 1.
The organic polymeric heavy metal-integrated flocculant described in examples 1 to 4 and comparative examples 1 to 2 was applied to sewage treatment.
(1) Wastewater containing copper ions
The wastewater containing copper ions prepared in a laboratory is selected, the concentration of the copper ions is measured to be 34.15mg/L, the pH value is measured to be 5.4, and the treatment results are as follows (Table 1):
| the dosage is mg/L | Treatment time min | Concentration mg/L of copper ion after treatment | Removal rate% | |
| Example 1 | 400 | 2 | 0.61 | 98.2 |
| Example 2 | 500 | 3 | 0.58 | 98.3 |
| Example 3 | 600 | 4 | 0.76 | 97.8 |
| Example 4 | 700 | 5 | 0.33 | 99.0 |
| Comparative example 1 | 500 | 8 | 4.50 | 86.8 |
| Comparative example 2 | 500 | 8 | 21.60 | 36.3 |
TABLE 1
(2) Wastewater containing zinc ions and nickel ions
The wastewater containing zinc ions and nickel ions prepared in a laboratory is selected, the concentration of the zinc ions is 19.77mg/L, the concentration of the nickel ions is 13.13mg/L, the pH value is 5.4, and the treatment results are as follows (Table 2):
TABLE 2
(3) Wastewater containing lead ions and chromium ions
The laboratory-prepared sewage containing lead ions and chromium ions was selected, and the lead ion concentration was 21.53mg/L, the chromium ion concentration was 12.44mg/L, the pH was 6.0, and the treatment results were as follows (Table 3):
TABLE 3
(4) Sewage with higher turbidity
The laboratory-prepared sewage with higher turbidity was selected, and the treatment results were as follows (table 4):
| clarity of treated water | |
| Example 1 | Is stronger |
| Example 2 | High strength |
| Example 3 | Is stronger |
| Example 4 | High strength |
| Comparative example 1 | Is weaker than |
| Comparative example 2 | Is weaker |
TABLE 4
As can be seen from tables 1 to 4, the organic polymer heavy metal chelating flocculant has the advantages of high reaction speed, short treatment speed, high removal rate (up to 95%) of various heavy metal ions, reduction of turbidity of sewage and the like under the condition of the same dosage.
The above description is meant to be illustrative of the preferred embodiments of the invention and should not be taken as limiting the invention, but rather should be construed as broadly within the spirit and scope of the invention.
Claims (10)
1. An organic polymer heavy metal chelating flocculant is characterized by having a chemical structural formula shown as a formula (I):
2. the method for preparing the organic polymer heavy metal chelating flocculant according to claim 1, wherein the reaction equation is as follows:
3. the method for preparing the organic polymer heavy metal chelating flocculant according to claim 1, characterized in that glutamic acid having two carboxyl groups simultaneously in natural amino acid is introduced into a molecular chain of a high polymer Chitosan (CTS) to obtain an organic polymer heavy metal chelating flocculant GAC; the method specifically comprises the following steps:
(1) weighing glutamic acid, chitosan and EDCI, and measuring a dilute hydrochloric acid solution for later use;
(2) dissolving the chitosan in the step (1) in dilute hydrochloric acid, and then adding distilled water for dilution and stirring;
(3) adding EDCI while continuously stirring the mixed solution in the step (2), and adding glutamic acid after EDCI is completely dissolved;
(4) adding a pH regulator into the solution prepared in the step (3), and regulating the pH of the solution to 4-8;
(5) and (5) stirring the solution prepared in the step (4) at 25 ℃ for 0.5-2 h to obtain the organic polymer heavy metal chelating flocculant.
4. The method according to claim 3, wherein the weight percentages of the glutamic acid, the chitosan, the diluted hydrochloric acid, the pH regulator, the EDCI and the water are as follows: 1-20% of glutamic acid, 1-20% of chitosan, 5-30% of dilute hydrochloric acid, 1-5% of a pH regulator, 0.1-2% of EDCI and the balance of distilled water.
5. The method as claimed in claim 3, wherein the concentration of the dilute hydrochloric acid is 0.1-1 mol.L -1 。
6. The method as claimed in claim 3, wherein the pH regulator is selected from NaOH or HCl solution.
7. The use of the organic polymeric heavy metal chelating flocculant of claim 1 in sewage treatment.
8. Use of the organic polymeric heavy metal chelating flocculant of claim 1 in the treatment of wastewater containing one or more of heavy metal copper ions, zinc ions, nickel ions, lead ions and chromium ions.
9. Use of the organic polymeric heavy metal chelating flocculant of claim 1 for reducing turbidity-causing substances in water.
10. The use of an organic polymeric heavy metal chelating flocculant according to claim 9 for reducing turbidity-causing substances in water, wherein the turbidity-causing substances comprise particulate heavy metal compounds.
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| CN117813265A (en) * | 2023-11-19 | 2024-04-02 | 广东邦普循环科技有限公司 | Heavy metal capturing agent and preparation method and application thereof |
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| CN104785227A (en) * | 2015-04-30 | 2015-07-22 | 南京大学 | Chitosan-grafting amino acid magnetic composite microsphere as well as preparation method and application |
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