CN1843951A - Method for treating printing/dyeing waste water - Google Patents
Method for treating printing/dyeing waste water Download PDFInfo
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- CN1843951A CN1843951A CN 200610050424 CN200610050424A CN1843951A CN 1843951 A CN1843951 A CN 1843951A CN 200610050424 CN200610050424 CN 200610050424 CN 200610050424 A CN200610050424 A CN 200610050424A CN 1843951 A CN1843951 A CN 1843951A
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- waste water
- dyeing
- trimethyl ammonium
- printing
- dyestuff
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Abstract
The invention provides a method for treating printing and dyeing wastewater. It comprises following steps: (1) adding 0.001-0.1 g cationic surface active agent into said wastewater for per liter; (2) adding natural alta-mud for 0.25-2.5 g, stirring for reaction for 0.5-2 hours. The invention is characterized in that the adsorbent is natural mineral, which is easy to get. The surface active agent in wastewater and added alta-mud generate organic alta-mud, which realizes colorant and surface active agent removing from wastewater. The soild-liquid separation is fast and effective, and the used alta-mud can be reused after simple treatment.
Description
Technical field
The invention belongs to technical field of waste water processing, relate in particular to a kind of treatment process of printing and dyeing/waste water from dyestuff.
Background technology
Textile printing and dyeing industry is the industrial wastewater discharge rich and influential family, and according to incompletely statistics, national dyeing waste water quantity discharged every day is 300～4,000,000 tons.Waste water contains auxiliary agents such as multiple dyestuff and tensio-active agent.This waste water characteristic is organic concentration height, complicated component, biodegradability is poor, colourity is high and changeable, water quality and quantity changes greatly, belongs to more unmanageable trade effluent
[1]It is aromatic hydroxy compound and heterogeneous ring compound that the raw material major part that drops into is produced in printing and dyeing, thereby the waste water overwhelming majority who makes in the production process to be discharged is with the organism of aromatophores such as benzene, naphthalene, anthracene, quinone as parent, have the colour developing group, color is very dark, colourity reaches 500-500000, has a strong impact on urban look
[2]Water body bubbles, toxigenicity because the tensio-active agent that is rich in the dyeing waste water can cause simultaneously, reduces reoxygenation speed and oxygenation degree in the water, causes water quality deterioration, influences hydrobiological existence, reduces water body self-purification ability.In addition, other pollution substance increases its solubleness in the tensio-active agent energy emulsification water body, influences pollutants transfer and transforms and ecologic effect.Therefore, research printing and dyeing/waste water from dyestuff processing to preserve the ecological environment and human health have very important significance.Industrial printing and dyeing/dye waste water treatment method commonly used has absorption method, flocculent precipitation, electrolytic process, oxidation style and biological degradation method etc.Shortcomings such as but the some of them method has the cost height, and timeliness is short.Absorption method is to remove the effective ways of this pollutant, but the most key be to seek high-efficiency adsorbent.
Wilkinite be a kind of be the tonstein of essential mineral with montmorillonite (Montmorillonite).At present, organobentonite adsorption treatment organic waste water technology commonly used both at home and abroad comprises two self-contained process of the synthetic absorption of organobentonite.Wherein building-up process is that natural montmorillonite and tensio-active agent (as quaternary ammonium salt) are mixed, constant temperature stirs for some time, the back use of sieving is dried, activates, ground to product after washing, filtration, complex process, consuming time, power consumption, and there is the waste water that contains tensio-active agent in a large number to produce, needs further to handle; To directly influence quality after bentonite modified if synthesis technique stability is bad.In addition, in the adsorption process, because the wilkinite surface hydrophobicity strengthens after the modification, difficulties in dispersion in water and utilization ratio is low, and handle back solid-liquid separation difficulty, and influence delivery turbidity, be unfavorable for the recycling of wilkinite mud.At above deficiency, utilize the adsorptive power of natural montmorillonite to tensio-active agent, realize the synthetic and waste water adsorption treatment of organobentonite simultaneously, and remove dyestuff and tensio-active agent in the waste water simultaneously, reduced the sequence of operations process in synthesizing and avoided the isolating difficulty of solid-liquid.Then only need add a small amount of wilkinite as treatment of dyeing and printing and utilize the tensio-active agent that itself exists in the waste water to realize that organobentonite is synthetic and adsorption treatment of dye is integrated, realize the treatment of wastes with processes of wastes against one another, greatly reduce processing cost.
[1] Zhang Jianying etc., Flocculant of Modified Bentonite S
CpbTreatment of dyeing and printing, Environmental Pollution and Control, 1994,16 (2), 37～40.
[2] Wang Kaimin etc., dyeing water treatment technical progress, environmental science, 1991,12 (4), 62～67.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is low, the treatment process of the printing and dyeing/waste water from dyestuff of applied range.
The step of method is as follows:
(1) in every liter of printing and dyeing/waste water from dyestuff, adds 0.001g～0.1g cats product;
(2) add 0.25g～2.5g natural montmorillonite, stirring reaction got final product in 0.5～2 hour.
Described cats product is a quaternary surfactant.Quaternary ammonium salt surface active agent is that the alkyl carbon number is at the long chain type cats product more than 10.The alkyl carbon number at the long chain type cats product more than 10 is: ten alkyl trimethyl ammonium bromides, Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, ten alkyl trimethyl ammonium chlorides, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride.
The particle diameter of natural montmorillonite is 50～200 orders.
Advantage of the present invention and positively effect: the sorbent material that purifying method of the present invention adopted is a natural mineral, and raw material is easy to get.China's bentonite resource is very abundant, occupies first place in the world, and total reserves is greater than 7,000,000,000 tons, bentonite ore 23 provinces that spread all over the country, more than 20 of large ore deposits.Utilize the tensio-active agent of existence in the waste water own and the wilkinite of adding to generate organobentonite in the treating processes, realize the synthetic and waste water adsorption treatment of organobentonite simultaneously, and remove dyestuff and tensio-active agent in the waste water simultaneously.Solid-liquid separates rapidly, and treatment effect is good.And through simple process, the wilkinite behind the processing waste water can reuse.
Description of drawings
Fig. 1 be traditional organobentonite and the used natural montmorillonite of the present invention turbidity after to wastewater treatment relatively.
Fig. 2 is the amount of cats product of waste water and the graph of a relation of toluylene red 2GL clearance;
Embodiment
Purification mechanism of the present invention is:
Wilkinite be a kind of be the tonstein of main component with the montmorillonite.The Si-O tetrahedron and the Al-O of montmorillonite
4(OH)
2Silicon in the octahedron, aluminium are made the net charge of the structure cell band 0.66 of each montmorillonite by other cation replacement at a low price.So montmorillonite has the ability of absorption positively charged ion and polarity organic molecule.The cation exchange capacity of natural montmorillonite is at 70～140mmol/100g.Organic cation can be replaced the inorganic cation between bentonite bed, and the organobentonite of generation has hydrophobicity, and organic carbon content improves, and the removal ability of hydrophobic organic pollutant in the water is significantly strengthened.Particularly after quaternary cationics and wilkinite generation ion-exchange, the energy force rate natural montmorillonite that wilkinite is adsorbed with organic pollutants improves tens to hundred times, has reduced the migration of organic pollutant in environment effectively.In the dyeing waste water owing to there are a large amount of various types of tensio-active agents, can with the Ca of natural montmorillonite sheet interlayer
2+, Na
+Deng positively charged ion generation replacement(metathesis)reaction, the organobentonite that the reaction back generates has extremely strong absorption property to other pollutents such as dyeing waste water dyestuffs.And because bentonite clay particle is a charged particle, can interacts with tensio-active agent and form flco, promote settlement separate thereby become coagulant aids.Therefore improved effluent quality greatly.Treatment process of the present invention is used very extensive, different dyeing waste waters is all had good treatment effect, and be not subjected to the influence of waste water acid-basicity.
Used natural montmorillonite sample is standby after pre-treatment such as seasoning, fragmentation, screening.The simulation dyeing waste water is industrial common dyes and deionized water.Test used instrument and mainly contain Tianjin, island UV-2450 type spectrophotometer, DHZ-DA type constant temperature oscillator, Biofuge P.R. whizzer etc.
In the finite concentration scope, the concentration of dyestuff and its absorbancy meet lambert-law of Beer: the concentration and the relation between the liquid layer thickness of absorbancy, solution are as follows:
The unit of A=ε bc concentration c is mol.L
-1, b is a liquid layer thickness, and unit is cm, and ε is called molar absorptivity, and unit is L.mol
-1Cm
-1
This experiment utilizes this principle concentration with dyestuff in the solution of measurement of ultraviolet-visible spectrophotometer absorption back in certain concentration range.
Calculate the dyestuff clearance according to following formula:
Y=((C
0-C
e)/C
0Y represents clearance in) * 100% formula; C
0And C
eRepresent the concentration of initial and final dyestuff respectively.
Embodiment 1
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the toluylene red 2GL waste water of 20mg/L, adds the 0.25g grain again through being auxiliary agent cetyl trimethylammonium bromide (CTMAB) commonly used in 150 purpose wilkinite powder and the 0.01g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 0.5 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result toluylene red 2GL dyeing waste water reaches 95%.
Under nitrogen protection, 500 ℃ of calcinations obtain black powder with the wilkinite after the absorption; be used further to the purifying treatment of dyeing waste water, waste strength and consumption are the same, and clearance reaches 95%; result shows that through simple process the wilkinite behind the processing waste water can repeatedly use.
Compare organobentonite and the used natural montmorillonite of the present invention turbidity (accompanying drawing 1) after handling waste water, it is limpid to find that the present invention handles back water quality, and solid-liquid separates rapidly.
Embodiment 2
In the 2L Erlenmeyer flask, add the dyeing waste water that 1L picks up from Ningbo Jin Hui woollen blanket factory, this waste water composition mainly contains reactive red APS, reactive brilliant bule APSN, reactive golden yellow RNL, acid blue 25, Acid Blue 40, Basic Blue 3 24 and toluylene red etc., adds the 2.5g grain through being 200 purpose wilkinite powder and 0.1g cetyl trimethylammonium bromide in this waste water.Put into constant temperature oscillator, at 25 ℃, vibration is 2 hours under the 200rpm condition, takes out the back centrifugation, COD
CrPercent of decolourization reaches 91.1%.Simple to operate, effective.
Embodiment 3
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the toluylene red 2GL waste water of 20mg/L, adds the 0.25g grain again through being auxiliary agent ten alkyl trimethyl ammonium bromides commonly used in 100 purpose wilkinite powder and the 0.001g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 1.5 hours under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result toluylene red 2GL dyeing waste water reaches 90%.
Embodiment 4
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the acid blue waste water of 20mg/L, adds the 0.15g grain again through being auxiliary agent Trimethyllaurylammonium bromide commonly used in 200 purpose wilkinite powder and the 0.02g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 0.5 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 90%.
Embodiment 5
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the acid blue waste water of 20mg/L, adds the 2.5g grain again through being auxiliary agent Dodecyl trimethyl ammonium chloride commonly used in 200 purpose wilkinite powder and the 0.01g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 0.5 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 95%.
Embodiment 6
Experimentation: in the 2L Erlenmeyer flask, add 1L, concentration be 40mg/L contain reactive golden yellow RNL waste water, add the 0.3g grain again through being auxiliary agent Tetradecyl Trimethyl Ammonium Bromide commonly used in 100 purpose wilkinite powder and the 0.01g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 0.5 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 93%.
Embodiment 7
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the acid blue waste water of 20mg/L, adds the 0.4g grain again through being auxiliary agent tetradecyl trimethyl ammonium chloride commonly used in 50 purpose wilkinite powder and the 0.01g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 0.5 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 99%.
Embodiment 8
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the acid blue waste water of 20mg/L, adds the 0.5g grain again through being auxiliary agent palmityl trimethyl ammonium chloride commonly used in 100 purpose wilkinite powder and the 0.01g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 2 hours under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 98%.
Embodiment 9
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the acid blue waste water of 20mg/L, adds the 1g grain again through being auxiliary agent octadecyl trimethylammonium bromide commonly used in 200 purpose wilkinite powder and the 0.1g dyeing process.Put into constant temperature oscillator then, at 25 ℃, vibration is 0.5 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 90%.
Embodiment 10
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the reactive brilliant bule waste water of 20mg/L, adds the 1g grain again through being auxiliary agent octadecyl trimethyl ammonium chloride commonly used in 150 purpose wilkinite powder and the 0.1g dyeing process.Put into constant temperature oscillator then, at 25 ℃, 0.5 time of vibration under the 200rpm condition, take out the back centrifugation, supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 98%.
Embodiment 11
Experimentation: add 1L in the 2L Erlenmeyer flask, concentration is the reactive brilliant bule waste water of 20mg/L, adds the 2g grain again through being 200 purpose wilkinite powder and 0.05g ten alkyl trimethyl ammonium chlorides.Put into constant temperature oscillator then, at 25 ℃, vibration is 1 hour under the 200rpm condition, takes out the back centrifugation, and supernatant liquor is measured the concentration of excess dye with ultraviolet-visible pectrophotometer.Calculate the clearance (percent of decolourization) of dyestuff.The clearance of experimental result acid blue waste water reaches 99%.
Discover that cats product bigger to influential effect is as accompanying drawing 2.When bentonitic amount is certain, the amount of CTMAB is during near 100% cation exchange capacity (CEC), and it is maximum that clearance reaches.
Claims (5)
1. the treatment process of a printing and dyeing/waste water from dyestuff is characterized in that the step of method is as follows:
(1) in every liter of printing and dyeing/waste water from dyestuff, adds 0.001g～0.1g cats product;
(2) add 0.25g～2.5g natural montmorillonite, stirring reaction got final product in 0.5～2 hour.
2. the treatment process of a kind of printing and dyeing/waste water from dyestuff according to claim 1 is characterized in that described cats product is a quaternary surfactant.
3. the treatment process of a kind of printing and dyeing/waste water from dyestuff according to claim 2 is characterized in that described quaternary ammonium salt surface active agent is that the alkyl carbon number is at the long chain type cats product more than 10.
4. the treatment process of a kind of printing and dyeing/waste water from dyestuff according to claim 3 is characterized in that described alkyl carbon number at the long chain type cats product more than 10 is: ten alkyl trimethyl ammonium bromides, Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, ten alkyl trimethyl ammonium chlorides, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride.
5. the treatment process of a kind of printing and dyeing/waste water from dyestuff according to claim 1, the particle diameter that it is characterized in that described natural montmorillonite is 50～200 orders.
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|---|---|---|---|
| CN 200610050424 CN1843951A (en) | 2006-04-19 | 2006-04-19 | Method for treating printing/dyeing waste water |
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|---|---|---|---|
| CN 200610050424 CN1843951A (en) | 2006-04-19 | 2006-04-19 | Method for treating printing/dyeing waste water |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320708A (en) * | 2011-08-30 | 2012-01-18 | 吉首大学 | Method for degrading synthetic dye through compound system |
| CN102328977A (en) * | 2011-06-08 | 2012-01-25 | 广西大学 | Method for discoloring printing and dyeing wastewater by using granulated composite bentonite material |
| CN102335586A (en) * | 2011-09-13 | 2012-02-01 | 常州大学 | Preparation method of printing and dyeing wastewater treating material |
| CN102796397A (en) * | 2012-08-23 | 2012-11-28 | 楚源高新科技集团股份有限公司 | Method for synthesis of active printing dye from T acid mother liquor wastewater |
| CN102863044A (en) * | 2012-09-19 | 2013-01-09 | 常州大学 | Method for synchronously processing washing wastewater and organic chemical industrial wastewater |
| CN103011340A (en) * | 2012-11-28 | 2013-04-03 | 常州大学 | Method for purifying washing waste water |
| CN104276693A (en) * | 2014-10-09 | 2015-01-14 | 常州大学 | Method for treating congo red in printing and dyeing waste water |
| CN105645635A (en) * | 2016-01-12 | 2016-06-08 | 浙江大学 | Physicochemical treatment method of disperse dye wastewater |
-
2006
- 2006-04-19 CN CN 200610050424 patent/CN1843951A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328977A (en) * | 2011-06-08 | 2012-01-25 | 广西大学 | Method for discoloring printing and dyeing wastewater by using granulated composite bentonite material |
| CN102320708A (en) * | 2011-08-30 | 2012-01-18 | 吉首大学 | Method for degrading synthetic dye through compound system |
| CN102320708B (en) * | 2011-08-30 | 2014-03-12 | 吉首大学 | Method for degrading synthetic dye through compound system |
| CN102335586A (en) * | 2011-09-13 | 2012-02-01 | 常州大学 | Preparation method of printing and dyeing wastewater treating material |
| CN102335586B (en) * | 2011-09-13 | 2013-03-13 | 常州大学 | Preparation method of printing and dyeing wastewater treating material |
| CN102796397A (en) * | 2012-08-23 | 2012-11-28 | 楚源高新科技集团股份有限公司 | Method for synthesis of active printing dye from T acid mother liquor wastewater |
| CN102796397B (en) * | 2012-08-23 | 2013-07-24 | 楚源高新科技集团股份有限公司 | Method for synthesis of active printing dye from T acid mother liquor wastewater |
| CN102863044A (en) * | 2012-09-19 | 2013-01-09 | 常州大学 | Method for synchronously processing washing wastewater and organic chemical industrial wastewater |
| CN103011340A (en) * | 2012-11-28 | 2013-04-03 | 常州大学 | Method for purifying washing waste water |
| CN104276693A (en) * | 2014-10-09 | 2015-01-14 | 常州大学 | Method for treating congo red in printing and dyeing waste water |
| CN105645635A (en) * | 2016-01-12 | 2016-06-08 | 浙江大学 | Physicochemical treatment method of disperse dye wastewater |
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