CN104774290A - PH and temperature dual-sensitive chitosan flocculating agent, and preparation method and application thereof - Google Patents
PH and temperature dual-sensitive chitosan flocculating agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a pH and temperature dual-sensitive chitosan flocculating agent, and a preparation method and an application thereof, and belongs to the field of polymer compounds. The flocculating agent is prepared through a grafting copolymerization reaction of carboxymethyl chitosan, dimethyl diallyl ammonium chloride and N-isopropylacrylamide under acidic conditions. The flocculating agent has pH sensitivity and temperature sensitivity, has increased molecular weight and enhanced bridging flocculation effect, can meet flocculating removal requirements on water pollutants with different characteristics under different environment conditions, and has excellent flocculation ability especially on surface-charged hydrophilic/hydrophobic easy-transition pollutants, has the advantages of wide source of the raw material chitosan, non-toxicity, degradability and no secondary pollution risk, has good heavy metal ion and micro-molecular organic pollutants flocculation characteristic, and has functions of bacteriostasis, deodorizing, decoloring and effective reduction of the COD value.
Description
Technical field
The invention belongs to macromolecular compound field, more particularly, relate to a kind of pH, temperature dual susceptibility chitosan flocculant and its preparation method and application.
Background technology
Water is Source of life.The existence of the mankind, life and production all be unable to do without water.But in recent years, China's water pollution problems is more and more serious, has become and has hindered the economic rapid and healthy of China, affect one of important problem that living standards of the people improve further.Water conservation, improvement water pollutions are extremely urgent.
In June, 2008, country revises and has issued and implemented " the Prevention and Cure Law on Water Pollution of the P.C.C. ", serves huge pushing effect for water prevention pollutes; After this, the new more strict industry sewage emission standard comprising the multiple industries such as pulping and paper-making, fermentation, plating is promulgated again in succession, has promoted the work ensureing water security further.The issuing and implementation of these policies, laws and rules, embody attitude and the resolution of the Party Central Committee and State Council's attention solution water pollution problems.Greatly developing sewage disposal technology has been trend of the times.
In order to solve water pollution problems, a series of comprise flocculation, absorption, membrane filtration, oxidation, chemical precipitation, biochemical treatment, electrochemical method etc. water treatment purification techniques and operation development rapidly.Wherein, flocculation operation, as the first step in water treatment, is also a very crucial step, is used in water treatment combination process of being everlasting.In flocculation operation, the selection of flocculation agent directly determines the quality of flocculating effect, further determines the treatment effect of subsequent handling and even whole combination process.For now, inorganic flocculating agent (as aluminium salt, molysite etc.) and synthetic polymeric flocculant (as polyacrylamide etc.), because having the advantages such as effective, relative low price, are the most frequently used two class flocculation agents of existing water treatment.But this two classes flocculation agent all exists the possibility of secondary pollution, along with the raising of whole society's environmental consciousness, its use is subject to increasing restriction.
In recent years, owing to having renewable, the advantage such as degradable, nontoxicity, biomass flocculation agent is subject to scientific research personnel and industrial community is more and more paid close attention to.Biological material is from animal and plant and Microbial resources, and as chitosan, Mierocrystalline cellulose, starch, Lalgine etc., they take from nature, itself have very strong biocompatibility; And after going out of use, being also easy to resolve into water, carbonic acid gas etc., is environment-friendly material.It will be further appreciated that, biological material is the class renewable resources departing from petroleum resources, inexhaustible.Since 20 century 70s, American and Britain, method, Deng developed country bring into use biomass flocculation agent in the treatment of waste water all gradually.China is vast in territory, and biomass resource is very abundant, but comparatively speaking, the research of this respect is abundant not enough, and practical application is just more rare.
Chitosan is one of biological material of superior performance.Its structure as shown in Figure 1.Its precursor chitin, be extensively present in the crustaceans such as shrimp crab and insect, algae, annual production is huge.Product after chitin deacetylase is chitosan, because containing a large amount of reactive primary amine groups-NH in its molecular chain
2with primary hydroxyl-OH, to inorganic oxide suspended particle, there is good flocculating property.But because the solvability of chitosan itself is not good, molecular weight is relatively low, when in the face of heavy metal ion and small molecules organic pollutant, Chang Wufa realizes effective elimination, and its practical application is also restricted.In addition, due to electrically charged single property (primary amine groups is positively charged in acid condition) in chitosan molecule and be hydroaropic substance, when in the face of charge property and parent/hydrophobicity changeable some heavy metal ion, small molecules organic pollutant, just more seem helpless.For these shortcomings, the method of normal employing chemical modification improves the performance of chitosan, if Chinese Patent Application No. is 201010223727.8, the applying date is the preparation method that the patent document of on 07 12nd, 2010 discloses a kind of grafting amphoteric chitosan flocculant, comprise the following steps: cm-chitosan and polyacrylamide carry out graft copolymerization, obtain grafting amphoteric chitosan flocculant, wherein, in grafting amphoteric chitosan flocculant, hydroxy-acid group substitution value is 5%-90%, the quality of polyacrylamide amine structure is the 40%-80% of grafting amphoteric chitosan flocculant quality.Cm-chitosan can be undertaken being separated after carboxylation reaction obtaining by chitosan and Mono Chloro Acetic Acid.Described chitosan can adopt commercially available various products, and preferably, chitosan molecule amount is not less than 50,000, and more preferably chitosan molecule amount is 750,000-85 ten thousand.Carboxymethyl chitosan grafted branch polyacrylamide flocculant prepared by this invention, improves the water-soluble of chitosan, can be suitable for processing the water body with different electric charge, but the amphoteric chitosan flocculant in this invention is to temperature-insensitive, and range of application is restricted.From the feature that pollutent charge property changes with environmental change, design has the variable chitosan flocculant of the surface charge of pH susceptibility, can meet the object that itself and pollutent electric charge match; From the feature that the parent/hydrophobicity of pollutent changes with environmental change, design has the convertible chitosan flocculant of parent/hydrophobicity of temperature sensitivity, can meet the object matched with itself and pollutent parent/hydrophobicity.Therefore, the ternary graft copolymer that design chitosan and pH sensitive groups and temperature sensitivity group form can provide solution.Although the synthesis of common ternary graft copolymer also has some to report, there is not yet the ternary chitose graft copolymer simultaneously comprising pH sensitive groups and temperature sensitivity group.As Ma Yongsheng (Ma Yongsheng, Qiu Huayu, Wang Shaoqiang, Wang Caiyou, the synthesis of chitosan-AM-DMDAAC ternary graft copolymer and application [J]. Chinese papermaking, 2004,23 (12): 22 ~ 25) etc. people have studied with ceric ammonium nitrate is initiator, the binary polymerization reaction of chitosan (CS) and acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC), discuss the impact of reaction conditions on sintetics reinforced effects, the three-component grafted product property of synthesis is stablized, and has good reinforced effects, Zhang Yanqiao (Zhang Yanqiao, chitosan and AM and DMDAAC graft copolymer Synthesis and application are studied [J]. environment protection and recycling economy, 2010:53 ~ 57) adopt free radical solution polymerization method, take ammonium persulphate as initiator system, have studied the graft copolymerization of chitosan and acrylamide and dimethyl diallyl ammonium chloride, investigate the reaction times, acrylamide and dimethyl diallyl ammonium chloride mass ratio, total monomer concentration, temperature of reaction, the conditions such as initiator concentration are on the impact of graft copolymerization, the graft copolymerization product of synthesis is good to the effect of settling of mud.But, in these bibliographical informations, still do not have temperature sensitivity group to be introduced into (polymkeric substance that AM and DADMAC is formed all shows hydrophilic characteristics at all temperatures, does not possess the temperature sensitivity that parent/hydrophobicity can be made to change); And the single initiator system all used in graft copolymerization, and do not use initiation auxiliary agent to play synergy.
Summary of the invention
1. the problem that will solve
Susceptibility can not be had to pH and temperature for existing flocculation agent simultaneously, the problems such as range of application is restricted, the invention provides a kind of pH, temperature dual susceptibility chitosan flocculant and its preparation method and application, it carries out graft copolymerization with dimethyl diallyl ammonium chloride and NIPA in acid condition by cm-chitosan and obtains, flocculation agent of the present invention has pH susceptibility and temperature sensitivity simultaneously, not only increase molecular weight, enhance bridge flocculation effect, also can meet under varying environment condition and the water pollutant of different characteristics is flocculated the requirement removed, especially to the pollutent that institute's belt surface electric charge and parent/hydrophobicity are easily changed, there is excellent flocculation ability.
2. technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A kind of pH, temperature dual susceptibility chitosan flocculant, the structural formula of described pH, temperature dual susceptibility chitosan flocculant is:
Wherein, the numerical range of n is the numerical range of 0.47-3.85, m is 0.36-1.38.
Preferably, it carries out graft copolymerization by cm-chitosan and dimethyl diallyl ammonium chloride and NIPA and obtains, wherein, in pH, temperature dual susceptibility chitosan flocculant, hydroxy-acid group substitution value is 7%-91%, quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are (0.10-0.93): 1, and quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are (0.25-2.30): 1.
The preparation method of above-mentioned a kind of pH, temperature dual susceptibility chitosan flocculant, the steps include:
(1) chitosan is dispersed in sodium hydroxide solution alkalizes, add chloroacetic acid solution after alkalization terminates and carry out carboxylation reaction;
(2) after carboxylation reaction terminates, using ethanol as precipitation agent, precipitate and separate, obtains cm-chitosan;
(3) cm-chitosan obtained in above-mentioned steps is dissolved in aqueous hydrochloric acid, then add initiator successively, cause auxiliary agent, add again and be pre-mixed sufficient dimethyl diallyl ammonium chloride and NIPA mixture, at 25-75 DEG C, react 1-24 hour;
(4) reaction terminate after using ethanol or acetone as precipitation agent, precipitate and separate product is also dried, and prepares pH, temperature dual susceptibility chitosan flocculant.
Preferably, the chitosan molecule amount in described step (1) is not less than 100,000, and deacetylation is not less than 65%.
Preferably, the chitosan molecule amount in described step (1) is 750,000-85 ten thousand, and deacetylation is not less than 80%.
Preferably, in described step (1), chitosan and sodium hydroxide solution mass ratio are 1:(5-40), the mass percent concentration of sodium hydroxide solution is 1-30%, the solvent of sodium hydroxide solution is water and isopropyl alcohol mixed solvent, and wherein the mass ratio of water and Virahol is 1:(1-10); Alkalization time is 0.5-2 hour; The mass percent concentration of described chloroacetic acid solution is 10-50%, and solvent is aqueous isopropanol, and the Mono Chloro Acetic Acid in solution and chitosan mass are than being (0.1-5): 1; Described carboxylation reaction condition is react 1-6 hour at 40-80 DEG C.
Preferably, in described step (3), the mass percent concentration of cm-chitosan in aqueous hydrochloric acid is 0.5%-3%, and the mass percent solubility of aqueous hydrochloric acid is 0.5-2.5%.
Preferably, initiator in described step (3) is Potassium Persulphate, ammonium persulphate or ceric ammonium nitrate, the mole number of the initiator added is the 1%-5% of chitosan unit mole number, described initiation auxiliary agent is disodium ethylene diamine tetraacetate, and the mole number of the disodium ethylene diamine tetraacetate added is the 1%-5% of chitosan unit mole number.
Preferably, in described step (3), the mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is (1-5): 1; The mass ratio of NIPA and cm-chitosan is (1-10): 1.
Above-mentioned a kind of pH, the application of temperature dual susceptibility chitosan flocculant in water treatment.
Difficult point of the present invention is: pH sensitive groups and Thermo-sensitive group are introduced chitosan molecule also there is not been reported at present simultaneously, is often very difficult because introduce two kinds of groups with different susceptibility in chitosan molecule simultaneously.Its difficult point mainly contains three aspects: (1) temperature sensitivity group itself not easily with sufficiently long segment graft copolymerization in chitosan molecule, if temperature of reaction is too low, speed of reaction is very slow, if and temperature of reaction is too high, the hydrophobic character produced after the graft copolymerization of a small amount of Thermo-sensitive group can stop again reaction to occur further, and grafting segment cannot be grown, (2) reaction monomers needed for pH sensitive groups and temperature sensitivity group has different reactive behavioies, if wherein a kind of monomer reactivity another kind less (typical temperature sensitive groups reactivity ratio pH sensitive groups is low) comparatively greatly, so, due to competing reaction, in obtained product, only have active large monomer (normally pH sensitive groups) can be introduced in chitosan molecule, (3) in addition, when adopting graft copolymerization technology to introduce different group, traditional initiator due to suitability single, the normal reaction meeting a class monomer causes demand and cannot meet another kind of monomer reaction, therefore be used alone a kind of initiator (as the ceric ammonium nitrate used in people's documents such as Ma Yongsheng, the ammonium persulphate used in Zhang Yanqiao document) be also difficult to the needs simultaneously meeting the dissimilar sensitive groups of introducing two kinds, now, need to act synergistically by suitable initiation auxiliary agent and initiator, to regulate and to balance the reaction velocity of initiation of dissimilar sensitive groups.Therefore, in order to the reaction difficulty reducing temperature sensitivity group, the monomers that make two kinds to have a different sensivity feature have close reactive behavior, make initiator, cause the reaction needed that auxiliary agent synergy can meet two class monomers simultaneously simultaneously, in the compounded combination synthetic route of the enormous amount formed at miscellaneous pH sensitive monomer, temperature sensitive monomeric, initiator, initiation auxiliary agent, synthesis condition, only have special conditional combination just may meet these requirements.Under special conditions combination, when synthesis has the chitosan of pH and temperature dual susceptibility, synthetic technology has the feature of following uniqueness: (1) pH sensitive groups and temperature sensitivity group not only remain self reaction characteristics separately, the pH sensitive groups that reaction difficulty is low also can play reaction synergy, during promotion graft copolymerization, free radical chain propagation process, reduces the reaction difficulty of the temperature sensitivity group of more difficult reaction originally; (2) controlled by reaction conditions (temperature, feed ratio, reaction times etc.) and select, achieving pH sensitive groups and temperature sensitivity radical reaction activity matches; (3) initiator plays with initiation auxiliary combination and acts synergistically, and the trigger rate controlling dissimilar sensitive groups matches.
In addition, there is the chitosan of pH and temperature dual susceptibility simultaneously, compare other modified chitosan material, also have the following advantages: (1) is water-soluble significantly improves; (2) possess anions and canons feature, salt resistance is better simultaneously, and the scope of application is wider; (3) molecular weight significantly promotes; (4) complex ability of metal ion is strengthened; (5) and between pollutent, there is multiplephase mutual effects such as comprising charge attraction, parent/hydrophobic interaction, hydrogen bond, coordination, stronger bridge flocculation ability is possessed.Therefore, pH, temperature dual susceptibility chitosan flocculant have broad application prospects.
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) pH of the present invention, temperature dual susceptibility chitosan flocculant, with pH susceptibility and temperature sensitivity dual characteristics; And by the method for grafting, copolymerization and modification, improve the molecular weight of chitosan, improve the water-soluble of chitosan, enhance its bridge flocculation effect; Due on Poly Dimethyl Diallyl Ammonium Chloride grafted chain with positive charge, and with negative charge on carboxymethyl, be applicable to the water body of process with different charge characteristic, there is good anti-salt property and complex ability; Wetting ability or hydrophobicity is produced because poly N-isopropyl acrylamide grafted chain can vary with temperature, its scope of application is wider, can meet under varying environment condition and the water pollutant of different characteristics is flocculated the requirement removed, all can use hydrophilic, hydrophobic pollutent;
(2) molecular chain of chitosan flocculant of the present invention is rich in anions and canons group, improves the solubility property of chitosan;
(3) the raw materials of chitosan wide material sources in the present invention, nontoxic, degradable, non-secondary pollution risk;
(4) the present invention introduces side chain by graft copolymerization technology on carboxymethyl chitosan sugar backbone, improves the bridge flocculation performance of material;
(5) what the present invention was used compared to synthesis conventional polymer flocculation agent polyacrylamide has neurovirulent monomer (acrylamide), the monomer added in product of the present invention is the dimethyl diallyl ammonium chloride that significantly reduces of toxicity and NIPA, and the mass ratio that the monomer added accounts for final flocculation agent significantly reduces, substantially reduce the Pollution risk of monomer;
(6) product of the present invention has good flocculation heavy metal ion, the characteristic of small molecules organic pollutant, and has antibacterial, deodorizing, decolouring and effectively reduce the various functions such as COD value;
(7) product of the present invention has efficient feature, and injected volume is low, and after heavy metal, the process of microbiotic pollutant effluents, heavy metal, microbiotic pollutent residual concentration can drop to original less than 8%, and optimum injected volume is ten thousand/left and right of the water yield;
(8) preparation method of pH of the present invention, temperature dual susceptibility chitosan flocculant, join again in reaction system after in advance dimethyl diallyl ammonium chloride and NIPA being mixed when carrying out graft copolymerization, after making two kinds of reaction monomers add reaction system, there is close reaction probabilities, can be grafted on cm-chitosan molecular skeleton simultaneously;
(9) preparation method of pH of the present invention, temperature dual susceptibility chitosan flocculant, simple to operate, generated time is short, main raw material used is the biomass product of abundance, with low cost, being applicable to large-scale industrial production, is a kind of preparation method of water conditioner of acquisition high-quality of economy.
Accompanying drawing explanation
Fig. 1 is chitosan structure schematic diagram;
Fig. 2 is preparation method's schematic flow sheet of the present invention;
Fig. 3 is the infrared spectrogram of chitosan, cm-chitosan and pH of the present invention, temperature dual susceptibility chitosan flocculant; Wherein: (a) represents chitosan, (b) represents cm-chitosan, and (c) represents pH of the present invention, temperature dual susceptibility chitosan flocculant;
Fig. 4 is the nmr spectrum chart of chitosan, cm-chitosan and pH of the present invention, temperature dual susceptibility chitosan flocculant; Wherein: (a) represents chitosan, (b) represents cm-chitosan, and (c) represents pH of the present invention, temperature dual susceptibility chitosan flocculant;
Fig. 5 is that pH of the present invention, temperature dual susceptibility chitosan flocculant are to the flocculating effect schematic diagram of cupric ion-tetracycline hydrochloride combined pollution water body;
Fig. 6 be water body pH change on pH, temperature dual susceptibility chitosan flocculant flocculating property affect schematic diagram;
Fig. 7 be temperature variation on pH, temperature dual susceptibility chitosan flocculant flocculating property affect schematic diagram.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Further illustrate the present invention by the following examples.It should be understood that these embodiments are explaination of the present invention and citing, do not limit the scope of the invention in any form.
In following examples, raw materials used chitosan is that aokang bio tech ltd, Shandong produces, and viscosity-average molecular weight is 11-84 ten thousand, and deacetylation is 65-95%.
Embodiment 1
As shown in Figure 2, by chitosan (viscosity-average molecular weight 800,000, deacetylation 85%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 20%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:2), wherein chitosan and sodium hydroxide solution mass ratio are 1:10, alkalize 1 hour; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 1.5:1) that quality of chloroacetic acid percentage concentration is 40%, react 4 hours at 50 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 1%, be configured to the solution that cm-chitosan mass percent concentration is 1%, after dissolution homogeneity, add Potassium Persulphate as initiator (mole number added is 2% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 2% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 2:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 6:1), react 2 hours at 70 DEG C, then using acetone as precipitation agent (volume ratio of acetone and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Chitosan, cm-chitosan, and pH, temperature dual susceptibility chitosan flocculant infrared spectrogram see Fig. 3.See from Fig. 3, in the infrared spectrogram of chitosan ((a) in Fig. 3), wave number about 3400,3200,1650,1320cm
-1be respectively O-H, N-H, C=O ,-NH
2charateristic avsorption band; In the infrared spectrogram of cm-chitosan ((b) in Fig. 3), 1732cm
-1for protonated carboxylic carbonyl charateristic avsorption band, thus prove that cm-chitosan successfully obtains; In the infrared spectrogram of pH, temperature dual susceptibility chitosan flocculant ((c) in Fig. 3), 1407,991cm
-1be respectively the N-C charateristic avsorption band in the C-H on methyl, quaternary ammonium salt cationic group, illustrate that Poly Dimethyl Diallyl Ammonium Chloride segment and poly N-isopropyl acrylamide segment have been grafted on chitosan molecule chain.Chitosan, cm-chitosan, and pH, temperature dual susceptibility chitosan flocculant nmr spectrum chart see Fig. 4.See from Fig. 4, in the nmr spectrum chart of chitosan ((a) in Fig. 4), chemical shift about 2.94,3.25-3.80,4.66ppm are the proton nuclei magnetic hill on chitosan sugar ring; In the nmr spectrum chart of cm-chitosan ((b) in Fig. 4), 3.90ppm is the methylene radical characteristic peak on carboxymethyl, thus also demonstrates cm-chitosan and successfully obtain; In the infrared spectrogram of pH, temperature dual susceptibility chitosan flocculant ((c) in Fig. 4), 1.00,2.68ppm is respectively the methyl in poly N-isopropyl acrylamide segment, the methyl characteristic peak in Poly Dimethyl Diallyl Ammonium Chloride segment, therefore, NMR (Nuclear Magnetic Resonance) spectrum also demonstrates Poly Dimethyl Diallyl Ammonium Chloride segment and poly N-isopropyl acrylamide segment has been grafted on cm-chitosan molecular chain.In addition, through using NMR (Nuclear Magnetic Resonance) spectrum quantitative analysis, in pH, temperature dual susceptibility chitosan flocculant, hydroxy-acid group substitution value is 55%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.42:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 1.70:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 8.0, and namely its iso-electric point (pH susceptibility switch) is 8.0; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 33 DEG C, from 33 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 33 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body for simulated water sample (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L), when pH is 7, is measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Fig. 5 is the actual flocculating effect figure that this flocculation agent is simulated water sample with cupric ion-tetracycline hydrochloride combined pollution water body.As we can see from the figure, to cupric ion-tetracycline hydrochloride combined pollution water body, when flocculant usage is at 75-100mg/L, flocculating effect reaches best, and cupric ion residual quantity is minimum is 6.0%, and tetracycline hydrochloride residual quantity is minimum is 1.7%.With cupric ion-tetracycline hydrochloride combined pollution water body for simulated water sample, within the scope of pH=5-8, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe the impact of water body pH change on pH, temperature dual susceptibility chitosan flocculant flocculating property, as shown in Figure 6, within the scope of pH=5-8, after process, in water sample, pollutent residual rate is all less than 8%.With cupric ion-tetracycline hydrochloride combined pollution water body for simulated water sample, be within the scope of 25-40 DEG C in temperature, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe the impact of water temperature change on pH, temperature dual susceptibility chitosan flocculant flocculating property, as shown in Figure 7, be within the scope of 34-40 DEG C in temperature, after process, in water sample, pollutent residual rate is all less than 8%.
Embodiment 2
By chitosan (viscosity-average molecular weight 110,000, deacetylation 82%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 5%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:10), wherein chitosan and sodium hydroxide solution mass ratio are 1:40, alkalize 1 hour; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 0.5:1) that quality of chloroacetic acid percentage concentration is 10%, react 1 hour at 70 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 2%, be configured to the solution that cm-chitosan mass percent concentration is 2%, after dissolution homogeneity, add ammonium persulphate as initiator (mole number added is 1% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 3% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 5:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 8:1), react 12 hours at 60 DEG C, then using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Through by nuclear magnetic resonance spectroscopy, wherein, hydroxy-acid group substitution value is 42%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.93:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 2.30:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 11.3, and namely its iso-electric point (pH susceptibility switch) is 11.3; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 36 DEG C, from 36 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 36 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L) for simulated water sample, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Table 1 is that pH in the present embodiment, temperature dual susceptibility chitosan flocculant are to the optimum flocculating effect under the flocculation optimum condition of cupric ion-tetracycline hydrochloride combined pollution water body and optimum condition.Be 5-8 at pH, temperature is within the scope of 37-40 DEG C, and when flocculant usage is at 50-200mg/L, flocculating effect reaches best, and after process, in water sample, pollutent residual rate is less than 8%.
Table 1 pH, temperature dual susceptibility chitosan flocculant are to the Flocculation Results of cupric ion-tetracycline hydrochloride combined pollution water body
Embodiment 3
By chitosan (viscosity-average molecular weight 290,000, deacetylation 70%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 25%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:10), wherein chitosan and sodium hydroxide solution mass ratio are 1:8, alkalize 2 hours; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 3:1) that quality of chloroacetic acid percentage concentration is 30%, react 2 hours at 80 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 1.5%, be configured to the solution that cm-chitosan mass percent concentration is 3%, after dissolution homogeneity, add ceric ammonium nitrate as initiator (mole number added is 5% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 5% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 4:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 10:1), react 4 hours at 50 DEG C, then using acetone as precipitation agent (volume ratio of acetone and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Through by nuclear magnetic resonance spectroscopy, wherein, hydroxy-acid group substitution value is 77%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.75:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 2.10:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 10.5, and namely its iso-electric point (pH susceptibility switch) is 10.5; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 32 DEG C, from 32 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 32 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L) for simulated water sample, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Table 2 is that pH in the present embodiment, temperature dual susceptibility chitosan flocculant are to the optimum flocculating effect under the flocculation optimum condition of cupric ion-tetracycline hydrochloride combined pollution water body and optimum condition.Be 5-8 at pH, temperature is within the scope of 34-40 DEG C, and when flocculant usage is at 75-200mg/L, flocculating effect reaches best, and after process, in water sample, pollutent residual rate is less than 8%.
Table 2 pH, temperature dual susceptibility chitosan flocculant are to the Flocculation Results of cupric ion-tetracycline hydrochloride combined pollution water body
Embodiment 4
By chitosan (viscosity-average molecular weight 530,000, deacetylation 92%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 25%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:1), wherein chitosan and sodium hydroxide solution mass ratio are 1:5, alkalize 0.5 hour; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 5:1) that quality of chloroacetic acid percentage concentration is 40%, react 6 hours at 45 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 0.5%, be configured to the solution that cm-chitosan mass percent concentration is 0.5%, after dissolution homogeneity, add ceric ammonium nitrate as initiator (mole number added is 2.5% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 4.5% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 1:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 4:1), react 3 hours at 55 DEG C, then using acetone as precipitation agent (volume ratio of acetone and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Through by nuclear magnetic resonance spectroscopy, wherein, hydroxy-acid group substitution value is 91%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.10:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 1.07:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 2.2, and namely its iso-electric point (pH susceptibility switch) is 2.2; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 39 DEG C, from 39 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 39 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L) for simulated water sample, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Table 3 is that pH in the present embodiment, temperature dual susceptibility chitosan flocculant are to the optimum flocculating effect under the flocculation optimum condition of cupric ion-tetracycline hydrochloride combined pollution water body and optimum condition.Be within the scope of 5-6 at pH, when temperature is 39-40 DEG C, when flocculant usage is at 100-150mg/L, flocculating effect reaches best, and after process, in water sample, pollutent residual rate is less than 8%.
Table 3 pH, temperature dual susceptibility chitosan flocculant are to the Flocculation Results of cupric ion-tetracycline hydrochloride combined pollution water body
Embodiment 5
By chitosan (viscosity-average molecular weight 750,000, deacetylation 78%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 15%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:6), wherein chitosan and sodium hydroxide solution mass ratio are 1:30, alkalize 1.5 hours; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 2:1) that quality of chloroacetic acid percentage concentration is 25%, react 5 hours at 40 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 2.5%, be configured to the solution that cm-chitosan mass percent concentration is 1.5%, after dissolution homogeneity, add ammonium persulphate as initiator (mole number added is 1.5% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 2.5% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 1.5:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 2:1), react 18 hours at 30 DEG C, then using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Through by nuclear magnetic resonance spectroscopy, wherein, hydroxy-acid group substitution value is 60%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.23:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 0.34:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 4.6, and namely its iso-electric point (pH susceptibility switch) is 4.6; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 31 DEG C, from 31 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 31 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L) for simulated water sample, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Table 4 is that pH in the present embodiment, temperature dual susceptibility chitosan flocculant are to the optimum flocculating effect under the flocculation optimum condition of cupric ion-tetracycline hydrochloride combined pollution water body and optimum condition.Be 5-6 at pH, temperature is within the scope of 31-40 DEG C, and when flocculant usage is at 100-200mg/L, flocculating effect reaches best, and after process, in water sample, pollutent residual rate is less than 8%.
Table 4 pH, temperature dual susceptibility chitosan flocculant are to the Flocculation Results of cupric ion-tetracycline hydrochloride combined pollution water body
Embodiment 6
By chitosan (viscosity-average molecular weight 840,000, deacetylation 65%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 10%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:8), wherein chitosan and sodium hydroxide solution mass ratio are 1:20, alkalize 2 hours; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 4:1) that quality of chloroacetic acid percentage concentration is 15%, react 3 hours at 60 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 2%, be configured to the solution that cm-chitosan mass percent concentration is 2.5%, after dissolution homogeneity, add Potassium Persulphate as initiator (mole number added is 4% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 1% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 3.5:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 1:1), react 1 hour at 75 DEG C, then using acetone as precipitation agent (volume ratio of acetone and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Through by nuclear magnetic resonance spectroscopy, wherein, hydroxy-acid group substitution value is 85%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.65:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 0.25:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 8.4, and namely its iso-electric point (pH susceptibility switch) is 8.4; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 29 DEG C, from 29 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 29 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L) for simulated water sample, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Table 5 is that pH in the present embodiment, temperature dual susceptibility chitosan flocculant are to the optimum flocculating effect under the flocculation optimum condition of cupric ion-tetracycline hydrochloride combined pollution water body and optimum condition.Be 5-8 at pH, when temperature is 31-40 DEG C, when flocculant usage is at 100-125mg/L, flocculating effect reaches best, and after process, in water sample, pollutent residual rate is less than 8%.
Table 5 pH, temperature dual susceptibility chitosan flocculant are to the Flocculation Results of cupric ion-tetracycline hydrochloride combined pollution water body
Embodiment 7
By chitosan (viscosity-average molecular weight 370,000, deacetylation 95%) to be dispersed in mass percent concentration be that in the sodium hydroxide solution of 25%, (solvent is water and isopropyl alcohol mixed solvent, wherein the mass ratio of water and Virahol is 1:4), wherein chitosan and sodium hydroxide solution mass ratio are 1:25, alkalize 0.5 hour; Afterwards, add the aqueous isopropanol (Mono Chloro Acetic Acid wherein in solution and chitosan mass are than being 0.1:1) that quality of chloroacetic acid percentage concentration is 50%, react 1.5 hours at 65 DEG C, using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 2:1) after having reacted, precipitate and separate, obtains cm-chitosan.Cm-chitosan being dissolved in mass percent concentration is in the aqueous hydrochloric acid of 1%, be configured to the solution that cm-chitosan mass percent concentration is 1.5%, after dissolution homogeneity, add Potassium Persulphate as initiator (mole number added is 3.5% of carboxymethyl chitosan sugar unit mole number), add disodium ethylene diamine tetraacetate for causing auxiliary agent (mole number added is 1.5% of carboxymethyl chitosan sugar unit mole number), (mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is 4.5:1 to add dimethyl diallyl ammonium chloride and NIPA mixture again, the mass ratio of NIPA and cm-chitosan is 5:1), react 24 hours at 25 DEG C, then using ethanol as precipitation agent (volume ratio of ethanol and reaction system solution is for 3:1), precipitate and separate product is also dried 12 hours at 45 DEG C, prepare pH, temperature dual susceptibility chitosan flocculant.Through by nuclear magnetic resonance spectroscopy, wherein, hydroxy-acid group substitution value is 7%, and quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are 0.62:1; Quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are 0.84:1.Zeta potential measurement result shows, along with the rising of pH value of solution, pH, temperature dual susceptibility flocculate with chitosan agent molecule institute static electrification lotus are negative by forward, zeta current potential reduces, gradually when zeta current potential is 0, pH is 13.7, and namely its iso-electric point (pH susceptibility switch) is 13.7; Solution transmitance measurement result shows, along with the rising of temperature, pH, the temperature dual susceptibility chitosan flocculant aqueous solution were in clear (transmitance is more than 98%) before 30 DEG C, from 30 DEG C, its aqueous solution becomes rapidly oyster white to transmitance below 1%, and namely its low critical transition temperature (temperature sensitivity switch) is 30 DEG C.By this flocculation agent, with cupric ion-tetracycline hydrochloride combined pollution water body (wherein cupric ion and tetracycline hydrochloride concentration are 100mg/L) for simulated water sample, measured by atomic absorption spectrum and ultra-violet absorption spectrum, observe its actual flocculating effect.Table 6 is that pH in the present embodiment, temperature dual susceptibility chitosan flocculant are to the optimum flocculating effect under the flocculation optimum condition of cupric ion-tetracycline hydrochloride combined pollution water body and optimum condition.When pH is 5-8, when temperature is 31-40 DEG C, flocculant usage is when 75-175mg/L, and flocculating effect reaches best, and after process, in water sample, pollutent residual rate is less than 8%.
Table 6 pH, temperature dual susceptibility chitosan flocculant are to the Flocculation Results of cupric ion-tetracycline hydrochloride combined pollution water body
Claims (10)
1. pH, a temperature dual susceptibility chitosan flocculant, is characterized in that: the structural formula of described pH, temperature dual susceptibility chitosan flocculant is:
Wherein, the numerical range of n is the numerical range of 0.47-3.85, m is 0.36-1.38.
2. a kind of pH according to claim 1, temperature dual susceptibility chitosan flocculant, it is characterized in that: it carries out graft copolymerization by cm-chitosan and dimethyl diallyl ammonium chloride and NIPA and obtains, wherein, pH, in temperature dual susceptibility chitosan flocculant, hydroxy-acid group substitution value is 7%-91%, quality and the cm-chitosan backbone structure mass ratio of Poly Dimethyl Diallyl Ammonium Chloride structure are (0.10-0.93): 1, quality and the cm-chitosan backbone structure mass ratio of poly N-isopropyl acrylamide structure are (0.25-2.30): 1.
3. the preparation method of a kind of pH according to claim 1, temperature dual susceptibility chitosan flocculant, the steps include:
(1) chitosan is dispersed in sodium hydroxide solution alkalizes, add chloroacetic acid solution after alkalization terminates and carry out carboxylation reaction;
(2) after carboxylation reaction terminates, using ethanol as precipitation agent, precipitate and separate, obtains cm-chitosan;
(3) cm-chitosan obtained in above-mentioned steps is dissolved in aqueous hydrochloric acid, then add initiator successively, cause auxiliary agent, add again and be pre-mixed sufficient dimethyl diallyl ammonium chloride and NIPA mixture, at 25-75 DEG C, react 1-24 hour;
(4) reaction terminate after using ethanol or acetone as precipitation agent, precipitate and separate product is also dried, and prepares pH, temperature dual susceptibility chitosan flocculant.
4. the preparation method of a kind of pH according to claim 3, temperature dual susceptibility chitosan flocculant, is characterized in that: the chitosan molecule amount in described step (1) is not less than 100,000, and deacetylation is not less than 65%.
5. the preparation method of a kind of pH according to claim 4, temperature dual susceptibility chitosan flocculant, is characterized in that: the chitosan molecule amount in described step (1) is 750,000-85 ten thousand, and deacetylation is not less than 80%.
6. the preparation method of a kind of pH according to claim 5, temperature dual susceptibility chitosan flocculant, it is characterized in that: in described step (1), chitosan and sodium hydroxide solution mass ratio are 1:(5-40), the mass percent concentration of sodium hydroxide solution is 1-30%, the solvent of sodium hydroxide solution is water and isopropyl alcohol mixed solvent, and wherein the mass ratio of water and Virahol is 1:(1-10); Alkalization time is 0.5-2 hour; The mass percent concentration of described chloroacetic acid solution is 10-50%, and solvent is aqueous isopropanol, and the Mono Chloro Acetic Acid in solution and chitosan mass are than being (0.1-5): 1; Described carboxylation reaction condition is react 1-6 hour at 40-80 DEG C.
7. the preparation method of a kind of pH according to claim 6, temperature dual susceptibility chitosan flocculant, it is characterized in that: in described step (3), the mass percent concentration of cm-chitosan in aqueous hydrochloric acid is 0.5%-3%, and the mass percent solubility of aqueous hydrochloric acid is 0.5-2.5%.
8. the preparation method of a kind of pH according to claim 7, temperature dual susceptibility chitosan flocculant, it is characterized in that: the initiator in described step (3) is Potassium Persulphate, ammonium persulphate or ceric ammonium nitrate, the mole number of the initiator added is the 1%-5% of chitosan unit mole number, described initiation auxiliary agent is disodium ethylene diamine tetraacetate, and the mole number of the disodium ethylene diamine tetraacetate added is the 1%-5% of chitosan unit mole number.
9. the preparation method of a kind of pH according to claim 8, temperature dual susceptibility chitosan flocculant, is characterized in that: in described step (3), the mass ratio of dimethyl diallyl ammonium chloride and cm-chitosan is (1-5): 1; The mass ratio of NIPA and cm-chitosan is (1-10): 1.
10. a kind of pH described in claim 1 or 2, the application of temperature dual susceptibility chitosan flocculant in water treatment.
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