CN102977227B - Method for preparing chitosan-like efficient flocculant - Google Patents
Method for preparing chitosan-like efficient flocculant Download PDFInfo
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- CN102977227B CN102977227B CN201210530889.5A CN201210530889A CN102977227B CN 102977227 B CN102977227 B CN 102977227B CN 201210530889 A CN201210530889 A CN 201210530889A CN 102977227 B CN102977227 B CN 102977227B
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Abstract
The invention discloses a method for preparing chitosan-like efficient flocculant, which comprises the following steps of: (1) pre-treatment of chitosan and derivatives of chitosan: dissolving chitosan and derivatives of chitosan in an acetic acid solution with pH value being 5, uniformly stirring, adding alkali until the pH value is 9 and chitosan separates out, and carrying out suction filtration for later use; (2) preparation of efficient flocculant: adding 1-2 parts of the pre-treated chitosan and derivatives of chitosan, 3-5 parts of cross-linking agents, 1 part of carbamide and 1.5-3 parts of aluminum sulfate in a four-port flask, stirring, pre-reacting for 0.5-1h in a water bath at 60-80 DEG C, then adding 3-8 parts of a dicyandiamide and carbamide mixed modifier, continuing to react for 2-4h, to obtain carbamide-chitosan-dicyandiamide like composite flocculant; and (3) purification of the product: after the reaction, separating out the product by using acetone; carrying out suction filtration; washing the product with ethanol; carrying out suction filtration, and drying in an oven at 90 DEG C for further use.
Description
Technical field
The invention belongs to technical field of sewage, specifically relate to a kind of preparation method of chitosan-like efficient flocculant.
Background technology
China is textile printing and dyeing big country, and have every day number to discharge in the waste water of ten thousand tons, dyeing waste water has that the water yield is large, colourity is high, COD value is high and be difficult to biodegradable feature, and intractability is large, and the effect of process is poor.At present, the comparatively easy Coagulation Method of operation is usually adopted to carry out treatment of dyeing and printing, main with aluminium salt, molysite and polyacrylamide coagulating agent.But there is the shortcoming of self with not enough in these coagulating agent, when aluminium ion concentration is greater than 0.5 mg/L in water, salmon can be made lethal, there is toxic effect to soil, plant and microorganism; And molysite itself is with light green or yellow, not obvious to the decolorizing effect of dyeing waste water; And acrylamide monomer has neurotoxicity, carinogenicity and genetoxic especially, the second stage employ of waste water is restricted, and does not meet the high request of environmental protection.Along with the development of society and the progress of science and technology, increasing new and effective coagulating agent is developed and carries out suitability for industrialized production, and they progressively instead of the position of traditional coagulating agent, and this has great significance to the energy-saving and emission-reduction of wastewater treatment and environmental protection.
Dicandiamide-formaldehyde polymkeric substance is cationic efficient organic floculant emerging in the last few years, and to the process of dyeing waste water, especially decolorizing effect is very remarkable.The people such as Zhang Wenyi are with Dyhard RU 100, formaldehyde for raw material, and Tai-Ace S 150 is catalyzer, prepared this type of high-efficiency decolorant, and the optimum process condition of synthesis is Dyhard RU 100: formaldehyde: Tai-Ace S 150=1:2.58:0.35 (mol ratio), 8O DEG C, react 3 h.Made discoloring agent processes Red 167, BES indigo plant, Disperse Blue-79 three kinds of typical dye waste water, its percent of decolourization all reaches more than 98%, under the condition of pH=8, dosage position l7.5 mL/L, percent of decolourization can reach more than 96%, and effluent color dilution reduces to 1O doubly from 360 times.
Chitosan is a kind of natural high score subclass polysaccharide material, is widely used in the every field such as medicine, food, water treatment.As a kind of polymeric flocculant, except having its structural advantage, chitosan is nontoxic, harmless, the advantage such as readily biodegradable, non-secondary pollution in addition, have practical application, and treatment effect is better in the field such as treatment of dyeing and printing, food wastewater.The people such as An Zhongjun are with chitosan and Dyhard RU 100 for raw material, and Tai-Ace S 150 is catalyzer, has prepared chitosan-Dyhard RU 100 discoloring agent by addition reaction.Research shows: when synthesis temperature is 50 DEG C, n (chitosan structure unit): n (Dyhard RU 100): n (Tai-Ace S 150)=l:4:1.5, reaction times are when being 2.5 h, the discoloring agent of synthesis to reactive orange, red, the neutral 2V25 of slightly acidic Kapp human relations in black and acid 5GS green 4 percent of decolourization of waste water from dyestuff all reach more than 90%, the clearance of COD also can reach 50%, and effect is more obvious.
Current existing dicandiamide-formaldehyde class and chitosan class flocculation agent are with glutaraldehyde as cross linker, and make chitosan and Dyhard RU 100 generation crosslinking reaction, its production cost is higher.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides a kind of preparation method of chitosan-like efficient flocculant, comprise the steps: the pre-treatment of (1) Chitosan-phospholipid complex: be dissolved in by Chitosan-phospholipid complex in the acetic acid solution of pH=5, stir, adding alkali makes chitosan separate out to pH=9, and suction filtration is for subsequent use; (2) preparation of efficient flocculant: get above-mentioned pretreated Chitosan-phospholipid complex 1-2 part, linking agent 3-5 part, 1 part, urea, Tai-Ace S 150 1.5-3 part, in four-hole boiling flask, is stirred, pre-reaction 0.5-1 hour in 60-80 DEG C of water-bath.Then add Dyhard RU 100 and urea admixture properties-correcting agent 3-8 part, continue reaction 2-4 hour, obtain urea-chitosan-Dyhard RU 100 class composite flocculation agent; (3) purifying of product: after question response completes, separates out product acetone, suction filtration, then uses washing with alcohol product, after suction filtration in 90 DEG C of baking ovens dry for standby.
Further, described chitosan-like efficient flocculant is used for decolouring and the flocculation treatment of dyeing waste water.
Further, described Chitosan-phospholipid complex is chitosan, cm-chitosan, 0-HACC, 0-hydroxyethyl chitosan or 0-sulfated chitosan.
Further, described linking agent is oxalic dialdehyde or glutaraldehyde.
Further, described properties-correcting agent is the mixture of Dyhard RU 100 and urea, and the two mol ratio is 0.7:0.3-0.8:0.2.
Of the present invention with the chitosan reclaimed in sericin waste water-silk gum flocculation for polyfunctional finishing composition prepared by basic raw material, there is following advantage and disadvantage:
First, Chitosan-phospholipid complex is polymeric flocculant, remarkable to the adsorption bridging effect of impurity, modified water-soluble reinforcement, and application is convenient, to the decolouring of dyeing waste water and flocculating effect good.
Secondly, the Dyhard RU 100 of introducing and urea contain more amino or imino-, the positive polarity of chitosan macromolecular chain is strengthened, is conducive to carrying out charge neutrality effect to electronegative impurity; Meanwhile, a large amount of amino and imino-contribute to forming hydrogen bond between flocculation agent and impurity, improve Van der Waals force, improve flocculating effect.
Again, making linking agent with glutaraldehyde etc. can increase molecular chain length to a certain extent, is conducive to strengthening adsorption bridging effect.
Finally, part urea substitutes Dyhard RU 100 and can reduce costs, and is conducive to suitability for industrialized production.
The present invention adopts Dyhard RU 100 and urea admixture as properties-correcting agent, prepare chitosan-urea-Dyhard RU 100 class composite flocculation agent, not only can reduce costs, be conducive to suitability for industrialized production, and increase chitosan active group kind, be more suitable for the process of the dyeing waste water containing complicated contaminant ion, have good effect to the decolouring of dyeing waste water and the removal of other impurity.
Accompanying drawing explanation
Fig. 1 is the structural formula of the chitosan-like efficient flocculant that the present invention prepares.
Embodiment
Below in conjunction with accompanying drawing, to the present embodiment, the present invention is further illustrated, and " part " in following examples all refers to " molar part ".
Embodiment one
The preparation method of chitosan-like efficient flocculant, carries out following steps successively:
1) pre-treatment of chitosan: chitosan is dissolved in the acetic acid solution of pH=5, stirs, add alkali and to pH=9, chitosan is separated out, suction filtration is for subsequent use;
2) preparation of efficient flocculant: get above-mentioned chitosan 1 part, glutaraldehyde cross-linking agent 3 parts, 1 part, urea, 1.5 parts, Tai-Ace S 150 is placed in four-hole boiling flask, stirs, pre-reaction 1 hour in 60 DEG C of water-baths; Then add Dyhard RU 100 2.1 parts, 0.9 part, urea, continue reaction 2 hours, obtain urea-chitosan-Dyhard RU 100 class composite flocculation agent;
3) purifying of product: after having reacted, separated out by product acetone, suction filtration, then uses washing with alcohol product, after suction filtration in 90 DEG C of baking ovens dry for standby.
Adopt the flocculation agent treatment of dyeing and printing of above-described embodiment one gained, technique is: the pH=8 regulating waste water, temperature is 30 DEG C, adds the flocculation agent of 0.5g/L, stir process 5min.After completing, the percent of decolourization of waste water is 93%, and turbidity removal rate is 95%, COD clearance be 78%, BOD clearance is 83%.
Contrast experiment 1-1, select chitosan as flocculant, process waste water according to above-mentioned technique, effect is: percent of decolourization reaches 89%, and turbidity removal rate is 91%, COD clearance be 62%, BOD clearance is 53%.
Contrast experiment 1-2, select Tai-Ace S 150 to make flocculation agent, process waste water according to above-mentioned technique, effect is: percent of decolourization reaches 90%, and turbidity removal rate is 92%, COD clearance be 71%, BOD clearance is 65%.
Embodiment two
The preparation method of chitosan-like efficient flocculant, carries out following steps successively:
1) pre-treatment of cm-chitosan: cm-chitosan be dissolved in the acetic acid solution of pH=5, stir, adds alkali and to pH=9, cm-chitosan is separated out, suction filtration.
2) preparation of efficient flocculant: get above-mentioned cm-chitosan 2 parts, oxalic dialdehyde linking agent 5 parts, 1 part, urea, 3 parts, Tai-Ace S 150, in four-hole boiling flask, stirs, pre-reaction 0.5 hour in 80 DEG C of water-baths.Then add Dyhard RU 100 2.4 parts, 0.6 part, urea, continue reaction 4 hours, obtain urea-chitosan-Dyhard RU 100 class composite flocculation agent;
3) purifying of product: after having reacted, separated out by product acetone, suction filtration, then uses washing with alcohol product, after suction filtration in 90 DEG C of baking ovens dry for standby.
Adopt the flocculation agent treatment of dyeing and printing of above-described embodiment two gained, technique is: the pH=8 regulating waste water, temperature is 30 DEG C, adds the flocculation agent of 0.4g/L, stir process 5min.After completing, the percent of decolourization of waste water is 92%, and turbidity removal rate is 94%, COD clearance be 83%, BOD clearance is 86%.
Contrast experiment 2-1, select chitosan as flocculant, process waste water according to above-mentioned technique, effect is: percent of decolourization reaches 89%, and turbidity removal rate is 91%, COD clearance be 62%, BOD clearance is 53%.
Flocculation agent made by contrast experiment 2-2, selective chlorination iron, and process waste water according to above-mentioned technique, effect is: percent of decolourization reaches 77%, and turbidity removal rate is 90%, COD clearance be 63%, BOD clearance is 58%.
Embodiment three
The preparation method of chitosan-like efficient flocculant, carries out following steps successively:
1) pre-treatment of 0-hydroxyethyl chitosan: be dissolved in the acetic acid solution of pH=5 by 0-hydroxyethyl chitosan, stir, adds alkali and to pH=9, O-hydroxyethyl chitosan is separated out, suction filtration.
2) preparation of efficient flocculant: get above-mentioned O-hydroxyethyl chitosan 1.5 parts, glutaraldehyde cross-linking agent 4 parts, 1 part, urea, 2 parts, Tai-Ace S 150, in four-hole boiling flask, stirs, pre-reaction 0.8 hour in 70 DEG C of water-baths.Then add Dyhard RU 100 2.4 parts, 0.6 part, urea, continue reaction 3 hours, obtain urea-chitosan-Dyhard RU 100 class composite flocculation agent;
3) purifying of product: after having reacted, separated out by product acetone, suction filtration, then uses washing with alcohol product, after suction filtration in 90 DEG C of baking ovens dry for standby.
Adopt the flocculation agent treatment of dyeing and printing of above-described embodiment three gained, technique is: the pH=8 regulating waste water, temperature is 30 DEG C, adds the flocculation agent of 0.3g/L, stir process 5min.After completing, the percent of decolourization of waste water is 94%, and turbidity removal rate is 96%, COD clearance be 83%, BOD clearance is 86%.
Contrast experiment 2-1, select chitosan as flocculant, process waste water according to above-mentioned technique, effect is: percent of decolourization reaches 89%, and turbidity removal rate is 91%, COD clearance be 62%, BOD clearance is 53%.
Flocculation agent made by contrast experiment 2-2, selective chlorination iron, and process waste water according to above-mentioned technique, effect is: percent of decolourization reaches 77%, and turbidity removal rate is 90%, COD clearance be 63%, BOD clearance is 58%.
What enumerate it is also to be noted that above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (3)
1. a preparation method for chitosan-like efficient flocculant, comprises the steps:
(1) pre-treatment of Chitosan-phospholipid complex: Chitosan-phospholipid complex is dissolved in the acetic acid solution of pH=5, stirs, add alkali and to pH=9, chitosan is separated out, suction filtration is for subsequent use;
(2) preparation of efficient flocculant: get above-mentioned pretreated Chitosan-phospholipid complex 1-2 part, linking agent 3-5 part, 1 part, urea, Tai-Ace S 150 1.5-3 part, in four-hole boiling flask, is stirred, pre-reaction 0.5-1 hour in 60-80 DEG C of water-bath; Then add Dyhard RU 100 and urea admixture properties-correcting agent 3-8 part, continue reaction 2-4 hour, obtain urea-chitosan-Dyhard RU 100 class composite flocculation agent;
(3) purifying of product: after question response completes, separates out product acetone, suction filtration, then uses washing with alcohol product, after suction filtration in 90 DEG C of baking ovens dry for standby;
Described chitosan-like efficient flocculant is used for decolouring and the flocculation treatment of dyeing waste water;
Described properties-correcting agent is the mixture of Dyhard RU 100 and urea, and the two mol ratio is 0.7:0.3-0.8:0.2.
2. the preparation method of chitosan-like efficient flocculant as claimed in claim 1, is characterized in that: described Chitosan-phospholipid complex is chitosan, cm-chitosan, O-HACC, O-hydroxyethyl chitosan or O-sulfated chitosan.
3. the preparation method of chitosan-like efficient flocculant as claimed in claim 1, is characterized in that: described linking agent is oxalic dialdehyde or glutaraldehyde.
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| CN104229961B (en) * | 2014-09-15 | 2016-05-11 | 武汉理工大学 | The running water composite flocculation agent of environment-friendly chitosan quaternary ammonium salt and aluminium polychloride |
| CN104262504B (en) * | 2014-10-24 | 2016-08-17 | 广东汇群中药饮片股份有限公司 | The preparation of Fructus Phyllanthi polysaccharide and application |
| CN105217765B (en) * | 2015-09-24 | 2017-09-15 | 福州大学 | A kind of composite macromolecular flocculant and preparation method thereof |
| CN106749585B (en) * | 2016-11-18 | 2021-02-23 | 辽东学院 | Biomass extraction method of sericin, extract and application thereof |
| CN106633213A (en) * | 2016-12-15 | 2017-05-10 | 李华玲 | Preparation method of chitosan gel |
| CN107556434B (en) * | 2017-09-25 | 2019-09-03 | 陕西科技大学 | A kind of DMDAAC grafting hydroxyethyl chitosan and preparation method thereof |
| CN107879447B (en) * | 2017-12-25 | 2020-09-08 | 菏泽衡巽环保科技有限公司 | Preparation method of flocculant for treating oily sewage |
| CN109095579A (en) * | 2018-08-01 | 2018-12-28 | 广州振清环保技术有限公司 | A kind of biochemical modified soybean protein-carboxymethyl chitosan composite flocculation agent and its preparation method and application |
| CN111253502A (en) * | 2018-12-03 | 2020-06-09 | 中国科学院理化技术研究所 | Water-soluble natural polysaccharide antibacterial derivative and preparation method thereof |
| CN111115782B (en) * | 2020-01-09 | 2022-05-20 | 江西省地质环境监测总站(鄱阳湖生态环境研究所) | Sewage treatment flocculant and preparation method thereof |
| CN112645418B (en) * | 2020-12-01 | 2024-11-01 | 安徽鸿昌糖业科技有限公司 | Composite flocculant for stevioside purification |
| CN112939177B (en) * | 2021-02-04 | 2023-07-04 | 扬州工业职业技术学院 | Environment-friendly dicyandiamide-formaldehyde-based decolorizing flocculant |
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