CN103992413B - The synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent - Google Patents
The synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent Download PDFInfo
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Abstract
The present invention relates to the synthetic method of a kind of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent. First first W-Gum is carried out esterification and crosslinking with negatively charged ion esterification linking agent, the doublemodified starch treatment of dyeing wastewater agent being then obtained by reacting with chloro-2 hydroxypropyl-trimethyl ammonium chlorides of positively charged ion etherifying reagent 3-; Described negatively charged ion esterification linking agent is the mixed anhydride that diacetyl oxide and hexanodioic acid are made. The acetic ester positively charged ion doublemodified starch cation group that the method obtains ionizes completely in water, positive charge density height, the suspended particles of energy pull-in range negative charge, and anionic group can promote the sedimentation of mineral suspensions, plaing a part to build bridge, it is solidifying to help, two kinds of groups play different adsorption-flocculation performances, complement each other, obtain desirable flocculating decoloring effect.
Description
Technical field
The present invention relates to the synthetic method of a kind of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, belong to chemical technology field.
Background technology
Along with the fast development of China's economy, problem of environmental pollution is day by day serious, the focus that wherein air is administered, water conservation is just becoming people's concern. Water pollutions comprises trade effluent and sanitary wastewater pollutes two kinds, and in trade effluent, the waste water of textile industry, Pulp industry occupies sizable ratio, and dyeing year, waste discharge was about about 3,000,000,000 tons. Dyeing waste water belongs to the organic waste water of high density, poisonous and harmful, difficult degradation, containing residual dye, dyeing auxiliary, soda acid and some heavy metal, wherein residual dye and auxiliary agent constitute the main component of useless Organic substance in water, and make waste water with special color, therefore, how making the major issue that decolorizing printing and dyeing waste water becomes currently pending, the research of decoloring method also becomes the important topic for the treatment of of dyeing wastewater.
For a long time, Coagulation Method has that investment cost is low, equipment takes up an area less, process capacity is big, percent of decolourization advantages of higher, is still now the method for wastewater treatment that the middle-size and small-size printing and dyeing enterprise of China generally adopts. Efficient flocculation agent and effective coagulation decoloration technique is selected to be the keys of this technology, it is the main flocculation agent of current decolorizing printing and dyeing waste water based on the synthesis polymer of polyacrylamide PAM, but the toxicity problem of synthetic polymeric flocculant, difficult degradation problem are paid close attention to day by day, and the superiority of natural macromolecule flocculating agent is also favored gradually. Since the nineties in 20th century, new interest to natural macromolecule flocculating agent research and development occurs within the scope of the world, the research fields such as starch derivative, vegetable jelly modified water treatment agent, microbial flocculant and chitin derivativ become new research focus all gradually, the water conditioner that natural high moleculer eompound modification obtains, show incomparable advantage in this respect, it is nontoxic to environment, and process residue is easily biodegradable, and environment can not be caused secondary pollution.
Summary of the invention
It is an object of the invention to provide the synthetic method of a kind of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, the crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater that the method is obtained, in flocculation, there is stronger decoloring ability simultaneously, have more when treatment of dyeing and printing that wadding body is big, separation soon, the advantage such as higher loading capacity.
The object of the present invention is achieved like this: the synthetic method of a kind of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, first W-Gum is carried out esterification and crosslinking, the doublemodified starch treatment of dyeing wastewater agent being then obtained by reacting with chloro-2 hydroxypropyl-trimethyl ammonium chlorides of positively charged ion etherifying reagent 3-with negatively charged ion esterification linking agent (aceticanhydride, hexanodioic acid mixed anhydride).
Described negatively charged ion esterification linking agent is mixed by diacetyl oxide and hexanodioic acid mixed anhydride.
The preferred version of the synthetic method of a kind of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent is, take a certain amount of W-Gum, add deionized water, it is warming up to 40 DEG C��50 DEG C, adjust in the scope of PH value to 7��9 with NaOH solution, add self-control esterification and crosslinking agent (diacetyl oxide and hexanodioic acid mixed anhydride), insulation reaction 1��3 hour, product is poured in deionized water, leaving standstill 3 hours, remove supernatant liquid, washing is to neutral, dehydration, puts into baking oven and dries at 55 DEG C and must be cross-linked acetate starch in 20 hours;
Then crosslinked acetate starch is taken, add deionized water, taking NaOH solution regulation system pH value as 9��11, heating makes reaction system be warming up to 40 DEG C��50 DEG C, adds the mixed solution of the chloro-2 hydroxypropyl-trimethyl ammonium chloride etherifying agents of 3-and NaOH while stirring, the reaction times 4 10h, reaction is adjusted to pH value with rare HCl after terminating and equals 7, filter, with ethanol/water mixing solutions repetitive scrubbing, drying, grind broken, and sieve with 100 orders/25.4mm sub-sieve.
Described esterification and crosslinking agent: the ratio of diacetyl oxide and hexanodioic acid 10��20:1 in mass ratio is mixed, leaves standstill, after spending stirring 10��20min with magnetic stirring apparatus at 20��35 DEG C, the esterification and crosslinking agent mixed anhydride that water white transparency can be obtained.
NaOH solution concentration is 5��20%.
Starch, deionized water bath raio equal 200��1000g/L.
The throwing material mass ratio of esterification and crosslinking reagent mixed anhydride and W-Gum is: 0.1��0.4:100
The throwing material mass ratio of cationic etherifying agent and crosslinked acetate starch is: 5��20:100
Preferred version is: takes a certain amount of W-Gum, adds deionized water, bath raio 650g/L, it is warming up to 45 DEG C, about adjusting PH value to 8 with 10%NaOH solution, drips the self-control esterification and crosslinking agent (diacetyl oxide and hexanodioic acid mixed anhydride) adding starch quality 0.2%, PH value is kept to be 8 during reaction, insulation reaction 1.5h, pours in doubling dose ionized water by product, leaves standstill 3 hours, remove supernatant liquid, washing is to neutral, and dehydration, puts into baking oven and dry at 55 DEG C and must be cross-linked acetate starch in 20 hours.
Take crosslinked acetate starch, adding deionized water; bath raio 650g/L, taking 10%NaOH solution regulation system pH value as 11, heating makes reaction system be warming up to 45 DEG C; add the mixed solution of the chloro-2 hydroxypropyl-trimethyl ammonium chloride etherifying agents of 3-and NaOH while stirring; reaction times 6h, and it is neutral that reaction is adjusted to pH value with rare HCl after terminating, filtration; with ethanol/water (1:1) mixing solutions repetitive scrubbing, drying, grinds broken, and sieves with 100 orders/25.4mm sub-sieve.
The invention has the beneficial effects as follows:
1, crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, during for cotton waste water from dyestuff (substantive dyestuff, reactive dyestuffs, bipseudoindoxyl dye, dispersed dye etc.) is carried out flocculation decoloration, usage quantity is that 0.2g/L dyeing waste water chroma removal rate can reach more than 90%, it may also be useful to measure as during 0.4g/L, dyeing waste water chroma removal rate can reach more than 98%.
2, crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent is from flocculation decoloration water technology relatively, what enterprise adopted now is PAM flocculation and clorox decolouring recombining process, and amphoteric starch treatment of dyeing wastewater agent treatment process prepared by this method is simple; And PAM process residue may produce micro-poison carcinogens, secondary pollution is caused after entering environment, the water conditioner that amphoteric starch obtains as natural high moleculer eompound modification, show incomparable advantage in this respect, it is nontoxic to environment, and process residue is easily biodegradable, environment can not be caused secondary pollution.
Embodiment
Embodiment 1:
The present invention relates to the synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, and described method comprises following processing step:
Take a certain amount of W-Gum, add deionized water, bath raio 650g/L, it is warming up to 45 DEG C, about adjusting PH value to 8 with 10%NaOH solution, drip the self-control esterification and crosslinking agent (mixed anhydride that diacetyl oxide and hexanodioic acid reaction are made adding starch quality 0.15%, the ratio of diacetyl oxide and hexanodioic acid 10:1 in mass ratio is mixed, leave standstill, after 20 DEG C of degree stir 15min, the esterification and crosslinking agent mixed anhydride that water white transparency can be obtained) with magnetic stirring apparatus, PH value is kept to be 8 during reaction, insulation reaction 1h, product is poured in doubling dose ionized water, leave standstill 3 hours, remove supernatant liquid, washing is to neutral, dehydration, put into baking oven to dry at 55 DEG C and must be cross-linked acetate starch in 20 hours.
Take crosslinked acetate starch, adding deionized water; bath raio 650g/L, crosslinked acetate starch and etherifying agent (chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-) mass ratio are 10:1, temperature of reaction 40 DEG C; pH value is 11; 2.5 hours reaction times, and reaction is adjusted to pH value to neutral, filtration with rare HCl after terminating; with ethanol/water (1:1) mixing solutions repetitive scrubbing, drying, grind broken, and sieve with 100 orders/25.4mm sub-sieve. Obtained crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, Anion substituting degree is 0.0739, and degree ofacationic substitution is 0.0085.
Embodiment 2:
The present invention relates to the synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, and described method comprises following processing step
Take a certain amount of W-Gum, add deionized water, bath raio 650g/L, it is warming up to 45 DEG C, with about 10%NaOH solution adjust pH to 9, drip the self-control esterification and crosslinking agent (mixed anhydride that diacetyl oxide and hexanodioic acid reaction are made adding starch quality 0.20%, the ratio of diacetyl oxide and hexanodioic acid 10:1 in mass ratio is mixed, leave standstill, after 20 DEG C of degree stir 15min, the esterification and crosslinking agent mixed anhydride that water white transparency can be obtained) with magnetic stirring apparatus, pH value is kept to be 9 during reaction, insulation reaction 1.5h, product is poured in doubling dose ionized water, leave standstill 3 hours, remove supernatant liquid, washing is to neutral, dehydration, put into baking oven to dry at 55 DEG C and must be cross-linked acetate starch in 20 hours.
Take crosslinked acetate starch, adding deionized water; bath raio 650g/L, crosslinked acetate starch and etherifying agent (chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-) mass ratio are 8:1, temperature of reaction 45 DEG C; pH value is 11; 6 hours reaction times, and reaction is adjusted to pH value to neutral, filtration with rare HCl after terminating; with ethanol/water (1:1) mixing solutions repetitive scrubbing, drying, grind broken, and sieve with 100 orders/25.4mm sub-sieve. Obtained crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, Anion substituting degree is 0.0745, and degree ofacationic substitution is 0.0131.
Embodiment 3:
Take a certain amount of W-Gum, add deionized water, bath raio 650g/L, it is warming up to 50 DEG C, with about 10%NaOH solution adjust pH to 8, drip the self-control esterification and crosslinking agent (mixed anhydride that diacetyl oxide and hexanodioic acid reaction are made adding starch quality 0.15%, the ratio of diacetyl oxide and hexanodioic acid 10:1 in mass ratio is mixed, leave standstill, after 20 DEG C of degree stir 15min, the esterification and crosslinking agent mixed anhydride that water white transparency can be obtained) with magnetic stirring apparatus, pH value is kept to be 8 during reaction, insulation reaction 2h, product is poured in doubling dose ionized water, leave standstill 3 hours, remove supernatant liquid, washing is to neutral, dehydration, put into baking oven to dry at 55 DEG C and must be cross-linked acetate starch in 20 hours.
Take crosslinked acetate starch, adding deionized water; bath raio 650g/L, crosslinked acetate starch and etherifying agent (chloro-2 hydroxypropyl-trimethyl ammonium chlorides of 3-) mass ratio are 5:1, temperature of reaction 45 DEG C; pH value of reaction system is 11; 6 hours reaction times, and reaction is adjusted to pH value to neutral, filtration with rare HCl after terminating; with ethanol/water (1:1) mixing solutions repetitive scrubbing, drying, grind broken, and sieve with 100 orders/25.4mm sub-sieve. Obtained crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, Anion substituting degree is 0.0705, and degree ofacationic substitution is 0.0220.
Get respectively crosslinked acetate starch (Anion substituting degree 0.0745), cationic starch (the chloro-2 hydroxypropyl-trimethyl ammonium chloride degree ofacationic substitution 0.0130 of 3-), crosslinked acetic ester amphoteric starch (embodiment 1: Anion substituting degree is 0.0739, degree ofacationic substitution is 0.0085; Embodiment 2: Anion substituting degree is 0.0745, degree ofacationic substitution is 0.0131; Embodiment 3: Anion substituting degree is 0.0705, degree ofacationic substitution is 0.0220. ) carrying out dyeing waste water (containing matching stain, reactive dyestuffs, substantive dyestuff, bipseudoindoxyl dye) Decolorant Test, decolorizing effect sees the following form
Table all kinds starch water conditioner dyeing waste water chroma removal rate contrast table
As can be seen from the above table, the crosslinked acetate starch of identical Anion substituting degree is compared with crosslinked acetate starch amphoteric starch, reinforced be all 0.2g/L time, it is 90.64% that dyeing waste water chroma removal rate raises by 28.91%, crosslinked acetate starch amphoteric starch effect is better than crosslinked acetic ester anionic starch greatly, the cationic starch of identical degree ofacationic substitution and crosslinked acetate starch amphoteric starch, reinforced be all 0.2g/L time, it is 90.64% that dyeing waste water chroma removal rate raises by 50.13%, crosslinked acetate starch amphoteric starch decolorizing effect is significantly better than cationic ion starch. when reaching 0.4g/L when feeding in raw material, the dyeing waste water chroma removal rate of crosslinked acetate starch amphoteric starch can reach 98.83%.
This is because in dyeing waste water containing the dyestuff such as matching stain, reactive dyestuffs, substantive dyestuff, bipseudoindoxyl dye have in water in positively charged ion, have in water in negatively charged ion, and because the amphoteric starch pollution system that is applicable to anions and canons coexists because having. Amphoteric starch flocculation agent cation group ionizes completely in water, positive charge density height, the suspended particles of energy pull-in range negative charge, and anionic group can promote the sedimentation of mineral suspensions, plaing a part to build bridge, it is solidifying to help, two kinds of groups play different adsorption-flocculation performances, complement each other, obtain desirable flocculating decoloring effect.
Claims (5)
1. the synthetic method of a crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent, it is characterized in that: first first W-Gum is carried out esterification and crosslinking with negatively charged ion esterification linking agent, the doublemodified starch treatment of dyeing wastewater agent being then obtained by reacting with chloro-2 hydroxypropyl-trimethyl ammonium chlorides of positively charged ion etherifying reagent 3-; Described negatively charged ion esterification linking agent is the mixed anhydride that diacetyl oxide and hexanodioic acid are made;
Described preparation process comprises:
Take a certain amount of W-Gum, add deionized water, it is warming up to 40 DEG C��50 DEG C, with in the scope of NaOH solution adjust pH to 7��9, add negatively charged ion esterification linking agent, insulation reaction 1��3 hour, pours into product in deionized water, leaves standstill, remove supernatant liquid, washing is to neutral, and dehydration, puts into oven for drying and must be cross-linked acetate starch;
Take crosslinked acetate starch, add deionized water, taking NaOH solution regulation system pH value as 9��11, heating makes reaction system be warming up to 40 DEG C��50 DEG C, add the mixed solution of the chloro-2 hydroxypropyl-trimethyl ammonium chloride etherifying agents of 3-and NaOH while stirring, in the reaction times 4 10h, reaction is extremely neutral by rare HCl adjusted to ph after terminating.
2. the synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent according to claim 1, it is characterised in that: in described negatively charged ion esterification linking agent, diacetyl oxide and hexanodioic acid mass ratio are 10��20:1.
3. according to the synthetic method of the described crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent of one of claim 1-2, it is characterized in that: diacetyl oxide is mixed with hexanodioic acid by described negatively charged ion esterification linking agent preparation method, leave standstill, after spending stirring 10��20min with magnetic stirring apparatus at 20��35 DEG C, the esterification and crosslinking agent that water white transparency can be obtained.
4. the synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent according to claim 1, it is characterized in that: the technique of crosslinked acetate starch esterification and crosslinking is: pH value is 8, W-Gum, deionized water bath raio are 650g/L, the add-on of esterification and crosslinking agent is the 0.2% of W-Gum, temperature of reaction 45 DEG C, the reaction times is 1.5h.
5. the synthetic method of crosslinked acetic ester positively charged ion doublemodified starch treatment of dyeing wastewater agent according to claim 1, it is characterized in that: the technique of crosslinked acetic ester positively charged ion doublemodified starch positively charged ion etherificate is: pH value is 11, crosslinked acetate starch, deionized water bath raio are 650g/L, the add-on of chloro-2 hydroxypropyl-trimethyl ammonium chlorides of etherifying agent 3-is crosslinked acetate starch 8%, temperature of reaction 45 DEG C, the reaction times is 6h.
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