CN100381482C - Adsorbing precipitant of anionic dye, its synthetic process and uses - Google Patents
Adsorbing precipitant of anionic dye, its synthetic process and uses Download PDFInfo
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- CN100381482C CN100381482C CNB2005100493777A CN200510049377A CN100381482C CN 100381482 C CN100381482 C CN 100381482C CN B2005100493777 A CNB2005100493777 A CN B2005100493777A CN 200510049377 A CN200510049377 A CN 200510049377A CN 100381482 C CN100381482 C CN 100381482C
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Abstract
The present invention relates to a negative ion dye absorbing precipitating agent, the synthetic method and the application thereof. The present invention uses epoxy resin to generate polymerization reaction with ethylene diamine and epoxy chloropropane to generate polyamine molecules with hydrophobic chain segments. Polyamine generates quaterisation with benzyl chloride and dimethyl sulphate to generate polycations used to generate stable insoluble complexes together with anionic dye in water, and dye waste water is purified through precipitating action. The polyamine molecule structure contains aromatic hydrophobic chain segments and base groups, and thus, the polyamine molecules generate self-emulsifying action to form stable emulsion or micro emulsion. When meeting anions, cation aggregates with the structure have stronger absorbing action than ordinary cations. As a result, the polycations can purify more than 95% of anionic dye in dye waste water. The present invention has the advantages of favorable effect, rapidness and no secondary pollution.
Description
Technical field
The invention relates to a kind of novel high polymer quaternary ammonium salt and its synthetic method and the application in dye wastewater treatment thereof, use this cationic polymers that the method for a kind of not only convenient and swift but also the removal anionic dyestuffs that effect is splendid can be provided.
Background technology
Waste water from dyestuff is mainly derived from dye well dyestuff intermediate production industry, is made up of the material that runs off in various products and intermediate crystalline mother liquor, the production process and the sewage that washes away ground etc.Because DYE PRODUCTION is wide in variety, and develops, thereby the dye wastewater treatment difficulty is strengthened towards anti-photodissociation, anti-oxidant, antibiont oxidation direction.The difficulty in treatment of waste water from dyestuff: the one, the COD height, and the BOD/COD value is less, biodegradability is poor; The 2nd, colourity height, and component complexity.Removal and the decolouring of COD have dependency, but the decolouring problem hard is bigger.Industrial method commonly used has methods such as biological degradation, chemical oxidation, flocculation sediment at present.
The biological degradation method cycle is long, also is subjected to the restriction of dyestuff biodegradability simultaneously, and the salinity in the waste water also can produce restraining effect to bacterium, has limited the usefulness of microorganism, so biological treatment COD clearance is not high.Aspect decolouring, biological treatment has certain decolorization to basic dyestuff and the waste water from dyestuff that contains the anthraquinone ring fast eolor base, but in general, percent of decolourization is not high, and about about 50%; Chemical oxidization method is the main method of decoloring dye waste water, utilize oxygenants such as ozone, chlorine and oxygenatedchemicals thereof that the chromophoric group oxidation of dyestuff is destroyed and decolour, the normal employing made up oxidation and catalytic oxidation, but its processing cost height has particular requirement to equipment; It is short that the chemical flocculation precipitation method has the treatment time, advantages such as processing cost is low, and equipment is simple, but relatively poor to the coagulation decoloration efficient of anionic dyestuffs, need to use the positively charged ion coagulant aids, as dodecyl benzyl dimethyl ammonium chloride, form mixture earlier, again with Tai-Ace S 150 or PAC coagulation, decolorizing effect can be arranged, but its treatment effect is subjected to the water miscible restriction of coagulant aids, and the removal effect of dyestuff is not good, can't reach the purpose of thoroughly removing dyestuff.In view of the advantage that the limitation and the chemical flocculation precipitation method of present dye wastewater treatment using the whole bag of tricks itself has, development of new dyestuff flocculating settling agent efficiently is the starting point of this patent research.
Summary of the invention
Primary technical problem to be solved by this invention be at existing background technology provide a kind of easy to operate, respond well, handle adsorbing precipitant of anionic dye rapid, convenient to use.
Another technical problem to be solved by this invention provides the synthetic method of above-mentioned adsorbing precipitant of anionic dye, and it is practical, and is easy and simple to handle, is easy to produce in batches.
Another technical problem to be solved by this invention provides a kind of application of above-mentioned adsorption precipitant.
The present invention solves the technical scheme that primary technical problem adopts: a kind of adsorbing precipitant of anionic dye, it is characterized by macromolecule cation, and contain the hydrophobic side group of Resins, epoxy hydrophobic segment and benzyl, polymkeric substance has following general structure:
Wherein EPOX represents the Resins, epoxy segment, and its structure can be expressed as:
M is from 1 to 5 integer
0＜x＜1，0＜y＜1。
What be highly profitable is, its Resins, epoxy of above-mentioned polymkeric substance and quadrol weight ratio are 1: 1 to 3: 1 scope, thereby the main chain that makes polycation has stronger hydrophobicity, benzyl on the nitrogen-atoms can be regulated the hydrophobicity of side chain, the volume ratio of quaternized used benzyl chloride and methyl-sulfate was 5: 1 to 1: 7 scope, above-mentioned polymkeric substance is insoluble to cold water, this helps removing the inorganic salt that produce in the dereaction, polymkeric substance can be dissolved in and be transformed into stable emulsion or microemulsion in the hot water and after cooling, this microemulsion is cationic aggregate, and it has very strong irreversible adsorption precipitation effect to the water-soluble anionic dyestuff.
The present invention solves the technical scheme that another technical problem adopts: a kind of above-mentioned adsorbing precipitant of anionic dye synthetic method, its characterization step is followed successively by: with quadrol and Resins, epoxy is to mix gradually in 1: 1～1: 3 by weight, and react completely at 70～80 ℃, drip the chainextender epoxy chloropropane afterwards gradually, epoxy chloropropane and quadrol weight ratio are 1: 0.65～1: 1.15, obtain versamid 900 at 85～95 ℃ of following sufficient reactings; Described versamid 900 reacts with benzyl chloride earlier after being dissolved in ethanol, reaction times was controlled at 0.5-2 hour, temperature is 75-85 ℃, add solid NaOH then, treat its fully dissolve after with the system cool to room temperature, splash into methyl-sulfate gradually, after adding reaction system is incubated 0.2-1 hour down at 55-65 ℃, after the cooling reaction solution is poured in the cold water, the flush away inorganic salt are also collected macromolecule product, dehydrate the back sealing and preserve.
Above-mentioned benzyl chloride is 5: 1 to 1: 7 scopes with the ratio of methyl-sulfate volume, and its theoretical molar number should satisfy following relational expression: benzyl chloride mole number+methyl-sulfate mole number * 2=quadrol mole number * 4.The mole number of solid NaOH should be two times of quadrol.The solvability of macromolecule product in water improves with the minimizing of benzyl chloride consumption, but can guarantee that in above-mentioned amount ranges polymer can not be dissolved in cold water.Be convenient to the salt that generated in the flush away reaction like this.
The present invention solves the technical scheme that another technical problem adopts: a kind of above-mentioned adsorbing precipitant of anionic dye is used, it is characterized in that with the co-precipitation form remove anhydrate in various anionic dyestuffs.
The application method of above-mentioned polycation, it is characterized in that polycation is dissolved in the solution of making 10～5wt% in the hot water, be transformed into emulsion (wetting ability is weak) or microemulsion (wetting ability is stronger) after being cooled to room temperature, join in the pending water, with form precipitation after the dyestuff negatively charged ion effect in the water at once, if add commercially available flocculation agent (as the polyacrylamide of the partial hydrolysis) aqueous solution again, precipitation that can very fast formation bulk also sinks to the water layer bottom, and the upper strata stillness of night with the naked eye be can't see color.
What be highly profitable is, above-mentioned treatment process is simple to operate, need not special equipment, and sedimentation speed is fast, handles waste water efficient height, satisfactory for result, does not introduce other objectionable impuritiess in the treating processes, can not cause secondary pollution.
The invention has the advantages that: we have stronger hydrophobicity by the synthetic polycation, and it can make positively charged ion be present in the water with state of aggregation, form very strong positivity electric field around it, can produce irreversible adsorption to the dyestuff negatively charged ion.Existing small molecules positively charged ion or macromolecule cation do not have such character, thereby can not produce the dye adsorption effect of ideal.Interaction meeting at the aqueous phase positive and negative charge is destroyed (ionizing event) by the strong polarity of water, just must water molecules be repelled away with hydrophobic grouping so want to produce strong electrostatic interaction.We have used a kind of practical way to synthesize the polycation that has strong hydrophobic grouping, it is a kind of high molecular quaternary, not only contain quaternary ammonium cation but also on main chain and side group, contain strong hydrophobic grouping, this high molecular quaternary be easy to matching stain in negatively charged ion produce adsorption and form insoluble polymer composite, the precipitation of coacervating large particle rapidly of assisting down at general flocculation agent, the residual concentration of removing dyestuff in the post precipitation waste water significantly reduces or reaches the degree that can't detect with instrument, use this scavenging agent to need not special equipment, there is not chemical reaction yet, efficient and convenient, effect is remarkable, simplified the process of conventional dyes wastewater treatment greatly, and can not cause detrimentally affect,, can obtain the ideal effect so it is used to contain the purification of waste water of anionic dyestuff to environment.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The Resins, epoxy (trade mark E-44) and quadrol (being dissolved in 6ml methyl alcohol) that in the four-hole boiling flask that agitator, reflux condensing tube, dropping funnel and thermometer are housed, add Different Weight respectively by table 1.Mix back (having a large amount of heats to emit, the cooling of palpus cold water), reacted 1 hour down at 70-80 ℃.After treating that resin and reacting ethylenediamine are fully, press the epoxy chloropropane that table 1 drips different amounts, after in 0.5 hour, dripping off, be incubated 0.5 hour at 100 ℃ again, abundant to guarantee polymerization, obtain the versamid 900 of high temperature thickness low-temperature curing at last.The solvability of versamid 900 is relevant with the composition of reactant, its solubleness in water reduces with the increase of Resins, epoxy add-on, the acidity of water also has bigger influence to dissolving resin simultaneously, secondary amine on the versamid 900 (pH≤4) under acidic conditions forms quaternary ammonium salt easily, thereby water-soluble raising.In addition, versamid 900 is relevant with temperature with the solvability in the alcoholic acid at methyl alcohol, in general temperature rising solvability increases, epoxy resin content is high more, the solvent temperature of versamid 900 is also high more, listed the solvent temperature of three kinds of versamid 900s in ethanol and methyl alcohol in the table 1, be higher than the just dissolving of this temperature resin, be lower than this temperature and just separate out.These three kinds of resins have solvability preferably in dimethyl formamide, so we have measured their viscosity in DMF.
Synthetic and the solvability of the different versamid 900s of table 1
* viscosity is to measure in the 30wt% dimethyl formamide solution, and temperature is 25 ℃
The versamid 900 that above-mentioned example is obtained carries out quaterisation, and concrete reaction process is as follows:
In above-mentioned attached fat, add the 30ml dehydrated alcohol, under agitation drip benzyl chloride after the heating for dissolving, have heat release in the reaction, add the back and continue reaction 1 hour down at 80 ℃, and then add solid NaOH 18g and stir and make its dissolving, drip methyl-sulfate after the question response liquid cooling but gradually, strong heat release in the reaction process, adding the back continues down to react half an hour at 60 ℃, after reaction finishes reaction solution is cooled to room temperature and pours in the cold water, institute's inorganic salt that generate and unreacted micromolecular compound are all gone by washing, and the polycation of generation is insoluble to cold water, through fully dewatering again behind the agitator treating, just obtain product after the drying.The gained polycation can be dissolved in the hot water of differing temps, forms clear soln, and as can be seen from Table 2, along with the solvent temperature of increase polymkeric substance in water of benzyl chloride consumption improves gradually, this wetting ability that shows polymkeric substance can be regulated by benzyl quantity.Polycation after the dissolving can not separated out from aqueous phase by reversible after cooling, be transformed into emulsion or microemulsion but regulate by the conformation of self, the aggregate (emulsion) of the formation micron-scale that wetting ability is weak, the aggregate that then forms nano-scale (microemulsion) that wetting ability is strong.For different parent versamid 900s, its quaterisation process is basic identical, but in order to keep the balance of hydrophilic/hydrophobic, the consumption of benzyl chloride should suitably be adjusted, and for the high versamid 900 of epoxy resin content, the consumption of benzyl chloride should suitably reduce; Otherwise should strengthen the consumption of benzyl chloride.Because polycation is in state of aggregation in the water of room temperature, the viscosity of system can not reflect its real molecular weight, so we do not measure its viscosity in water.
The preparation condition of the different polycations of table 2 and in water solvability
In order to study the removing effect of each polycation to anionic dyestuff, we have implemented a series of precipitation experiment.Select the anionic dyestuff of different colours in four, they are respectively Congo red, ponceau 6R, fast green FCF and solid Huang, and every kind of dyestuff is made into the 2000ml aqueous solution and with their light absorption values under maximum absorption wavelength of spectrophotometric determination.Polycation is dissolved in the solution of making 5wt% in the hot water, be transformed into emulsion (wetting ability is weak) or microemulsion (wetting ability is stronger) after being cooled to room temperature, get respectively in the dye solution that 10ml under agitation joins above-mentioned 100ml, become the muddy liquid of band solid particulate at once, dripping a little concentration for preparing in advance is the flocculant aqueous solution (polyacrylamide of partial hydrolysis of 5wt%, commercially available), the precipitation of very fast formation bulk sinks to water layer bottom (precipitation all has very dark color after the stirring, and the color of ducking in drink can not taken off), in most of the cases, supernatant liquid with the naked eye be can't see color substantially.Measure the light absorption value of supernatant under maximum absorption wavelength, its result is as showing 3-1 to showing shown in the 3-3.The concentration of handling dyestuff in the water of back with polycation descends greatly, has originally very that dark colour water has become clear water, and except that a few cases, their light absorption value is all below 0.1, sees to have at least 98% dye molecule to be eliminated from the light absorption value data.Different dyestuff experiment effects is not had tangible difference, different polycations is then demonstrated general regularity: the polycation hydrophobicity is strong more, and the effect of its adsorpting anion dyestuff is good more.So the hydrophilic/hydrophobic ratio of control polycation is very important, if wetting ability is crossed strong its adsorptivity meeting variation to dyestuff; If hydrophobicity is strong excessively, polycation is water-soluble just relatively poor so, will make troubles during use.
We do identical test with small molecules positively charged ion dodecyl benzyl dimethyl ammonium chloride and find, it can not show a candle to above-mentioned polycation to the adsorption of dye molecule, water after it is handled still keeps certain color, and its light absorption value all is greater than 0.5, and sedimentation speed is slower.Generally in use, used polycation is all excessive than theoretical value, that is to say that cationic sum is greater than anionic sum, just can produce good sedimentation effect with a small amount of polyanion flocculation again after the absorption like this, therefore will determine the usage quantity of polycation in actual use according to the concrete concentration of dyestuff.
Table 3-1 polycation is to the decontamination effect improving of anionic dyestuff
Table 3-2 polycation is to the decontamination effect improving of anionic dyestuff
Table 3-3 polycation is to the decontamination effect improving of anionic dyestuff
Test the structure of used anionic dyestuff:
Congo red
Ponceau 6R
Fast green FCF
Gu it is yellow
Claims (6)
1. an adsorbing precipitant of anionic dye is characterized in that being macromolecule cation, contains the hydrophobic side group of Resins, epoxy hydrophobic segment and benzyl, and polymkeric substance has following general structure:
Wherein EPOX represents the Resins, epoxy segment, and its structure can be expressed as:
M is from 1 to 5 integer
0＜x＜1，0＜y＜1。
2. precipitation agent according to claim 1 is characterized in that described polymkeric substance can form stable emulsion or microemulsion in cold water.
3. described adsorbing precipitant of anionic dye synthetic method of claim 1 is characterized in that steps in sequence is:
(1) be to mix gradually in 1: 1～1: 3 by weight with quadrol and Resins, epoxy, heat release during mixing, react completely at 70～80 ℃, obtain prepolymer, drip the chainextender epoxy chloropropane gradually, epoxy chloropropane and quadrol weight ratio are 1: 0.65～1: 1.15, obtain versamid 900 at 85～95 ℃ of following sufficient reactings;
(2) described versamid 900 reacts with benzyl chloride earlier in ethanol, temperature of reaction is 75-85 ℃, reaction times was controlled at 0.5-2 hour, then with solid NaOH neutralization, last and methyl-sulfate reacts, after dripping, normal temperature reacted 0.2-1 hour at 55-65 ℃ again, generate adsorbing precipitant of anionic dye, above-mentioned benzyl chloride is 5: 1 to 1: 7 scopes with the ratio of methyl-sulfate volume, its theoretical molar number should satisfy following relational expression: benzyl chloride mole number+methyl-sulfate mole number * 2=quadrol mole number * 4, the mole number of solid NaOH are two times of quadrol.
4. synthetic method according to claim 3 is characterized in that temperature of reaction is 80 ℃, and the reaction times was controlled at 1 hour.
5. the described adsorbing precipitant of anionic dye of claim 1 is used, and it is characterized in that with the co-precipitation form except that various anionic dyestuffs in anhydrating.
6. application according to claim 5, it is characterized in that the precipitation agent polycation is dissolved in the solution of making 10～5wt% in the hot water, be transformed into emulsion or microemulsion after being cooled to room temperature, join in the pending water, with form precipitation after the dyestuff negatively charged ion effect in the water at once, if add commercially available flocculation agent again, precipitation that can very fast formation bulk also sinks to the water layer bottom, and the upper strata stillness of night with the naked eye be can't see color.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100493777A CN100381482C (en) | 2005-03-16 | 2005-03-16 | Adsorbing precipitant of anionic dye, its synthetic process and uses |
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| CN100381482C true CN100381482C (en) | 2008-04-16 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5247087A (en) * | 1992-05-13 | 1993-09-21 | Baker Hughes Incorporated | Epoxy modified water clarifiers |
| CN1093342A (en) * | 1993-04-06 | 1994-10-12 | 中国矿业大学 | Cation coagulant |
| CN1290658A (en) * | 2000-07-06 | 2001-04-11 | 沈阳经济技术开发区环境保护监测站 | Epoxy polyamine flocculant produced by using adipamine residue |
| CN1375466A (en) * | 2001-03-21 | 2002-10-23 | 中国科学院沈阳应用生态研究所 | Cationic fluocculant and its synthesis method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5247087A (en) * | 1992-05-13 | 1993-09-21 | Baker Hughes Incorporated | Epoxy modified water clarifiers |
| CN1093342A (en) * | 1993-04-06 | 1994-10-12 | 中国矿业大学 | Cation coagulant |
| CN1290658A (en) * | 2000-07-06 | 2001-04-11 | 沈阳经济技术开发区环境保护监测站 | Epoxy polyamine flocculant produced by using adipamine residue |
| CN1375466A (en) * | 2001-03-21 | 2002-10-23 | 中国科学院沈阳应用生态研究所 | Cationic fluocculant and its synthesis method |
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