CN103408092A - Treatment method for production wastewater of sulfonic acid group dye and dye intermediate of sulfonic acid group dye - Google Patents
Treatment method for production wastewater of sulfonic acid group dye and dye intermediate of sulfonic acid group dye Download PDFInfo
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Abstract
The invention belongs to the technical field of treatment of dye chemical engineering production wastewater and provides a treatment method for production wastewater of sulfonic acid group dye and dye intermediate of the sulfonic acid group dye to solve the problem of treatment of production wastewater of the sulfonic acid group dye and the dye intermediate of the sulfonic acid group dye. The treatment method comprises the steps as follows: (1), extracting the production wastewater; (2), performing absorption treatment on an aqueous layer after extraction; (3), recovering and reusing inorganic salt; (4), regenerating an extractant, recovering and reusing organisms, recovering the inorganic salt sodium sulfate contained in the production wastewater, and taking the sodium sulfate as a commercialized thinner and a dyeing accelerant used in the process of dyeing to enable the sodium sulfate to be applied to practical production of active dyes so as to realize wastewater treatment and recovery comprehensive utilization.
Description
Technical field
The invention belongs to dye chemical industry Wastewater Treatment field, in particular to p-sulfonic acid base class dyestuff and sulfonic acid base class intermediate production process waste water commonly used, carry out the method for the comprehensive regulation and recycling.
Background technology
Dyestuff is as a kind of important fine chemical product, in daily life and industry application extremely extensive, the dyestuffs such as activity, acidity that wherein contain the sulfonic acid base class are fastest-rising dye species in recent years.Contain sulfonic acid base class dyestuff intermediate and be the indispensable starting material of dyestuff such as producing the activity that contains the sulfonic acid base class, acidity, output is quite large.Due to this type of dyestuff and its intermediate complex structure, Production Flow Chart is long, side reaction is many, causes in production process and produces the waste water that a large amount of complicated components, concentration are high, contain a large amount of salinities, is difficult to biochemical treatment.
Method about this type of production wastewater treatment, mainly contain at present Wet Catalytic Oxidation Method, photocatalytic oxidation, resin adsorption method etc., these methods exist respectively equipment complexity, special substance difficult quality guarantee, reagent costliness, operational condition harsh (as high temperature, high pressure etc.) and secondary pollution problems are arranged.
Chinese patent CN1309092 discloses and a kind ofly with complexometric extraction p-sulfonic acid base class dyestuff intermediate, has carried out pretreatment method for wastewater, and the method is to adopt multi-stage counter current extraction to process.There is following deficiency in this technical scheme: 1) extraction efficiency is not high, and effect is poor, needs multi-stage counter current extraction and carries out continually oil phase regeneration, long flow path; 2) organic materials reclaimed for extraction does not have further resource recycling scheme, and the discharge water after extraction treatment does not further utilize scheme simultaneously.
Chinese patent CN1073536C discloses a kind of method that reclaims organic matter in naphthalene series dye intermediate waste liquor with the trialkyl tertiary amine, though this technical scheme can solve the goal of the invention of this patent, but following deficiency is arranged still: 1) sewage should have a large amount of inorganic salinities in the gained aqueous layer extracted after extraction treatment, its scheme as discharge of wastewater, is not further processed recovery scheme for directly; 2) its extraction agent is that the trialkyl tertiary amine adds diluent kerosene, owing in kerosene, containing a small amount of unsaturated alkane, easily causes the extraction agent lamination problem, affects the homogeneous of extraction agent, also may produce engineering problem simultaneously.Its extraction efficiency is not high in addition, and effect of extracting is poor, and extraction phase is higher.
At present in the complexometric extraction treatment process about this type of waste water, for the water layer after extraction treatment, be all to put into production as discharge of wastewater or as water at the bottom of production, and in fact in this part water layer, should contain a large amount of inorganic salinities, as discharge of wastewater, having equally part pollutes, and put into production to recycle as water at the bottom of production, wherein salinity accumulative total can be caused, finally normal production can be had a strong impact on.
Summary of the invention
For solve sulfonic acid base class dyestuff with and the problem of dyestuff intermediate production wastewater treatment, the present invention propose a kind of sulfonic acid base class dyestuff with and the treatment process of dyestuff intermediate factory effluent, reclaim the inorganic salt sodium sulfate contained in waste water, and using its dyeing accelerant as commercialization thinner, dyeing course, be applied to, in the reactive dyestuffs actual production, realize the wastewater treatment comprehensive utilization of resources.
The present invention is achieved by the following technical solutions: a kind for the treatment of process of its dyestuff intermediate factory effluent of sulfonic acid base class dye well is following steps:
(1) extraction of waste water: its dyestuff intermediate factory effluent of sulfonic acid base class dye well is mixed in extraction plant with extraction agent, the volume ratio of extraction agent and waste water is 1:2 ~ 20, described its dyestuff intermediate factory effluent of sulfonic acid base class dye well pH is 1.0 ~ 5.0, it is 35 ~ 65 ℃ that temperature is controlled in extraction, then standing, layering, obtain organic layer and water layer;
As preferably, selecting mass concentration is that 30% ~ 70% dilute sulphuric acid is regulated its dyestuff intermediate factory effluent of sulfonic acid base class dye well pH value.
As preferably, pH regulator is 1.5 ~ 2.5, and extraction temperature is 50 ~ 55 ℃.
Described extraction agent is mixed by complexing agent, chaotropic agent and catalyst aid, the preparation method of extraction agent for: chaotropic agent under agitation is warming up to 50 ~ 60 ℃, then add catalyst aid, after 0.5 ~ 1 hour, add complexing agent 50 ~ 60 ℃ of maintenances, namely be extracted agent;
Described complexing agent is selected from the tertiary amine of belt length paraffinic hydrocarbons group, and structural formula is N-[C
nH
2n+1]
3, wherein, n=8 ~ 10; As preferably, complexing agent is selected from trioctylamine (being n=8).
Described chaotropic agent is selected from toluene, dimethylbenzene, dodecylbenzene a kind of; As preferably, chaotropic agent is selected from dodecylbenzene.
Described catalyst aid is selected from chlorination trialkyl methylamine, and structural formula is [CH
3-N-(C
8 ~ 10H
17 ~ 21)
3]
+Cl
-
The mass percent of described each component of extraction agent is: complexing agent 15% ~ 45%, chaotropic agent 55% ~ 85%, catalyst aid 0% ~ 5%, each constituent mass sum is 100%, as preferably, in extraction agent, the mass percent of each component is: complexing agent 20%, chaotropic agent 78%, catalyst aid 2%.
(2) adsorption treatment of water layer after the extraction: the water layer obtained in step (1) is added to sorbent material, and the adsorption process temperature is 30 ~ 60 ℃, and the mass volume ratio of sorbent material add-on and water layer is 40 ~ 202g/m
3, after absorption, filter, obtain filtrate; The inorganic salt that gained filtrate is carried out next step reclaim.Described sorbent material is selected from silica gel, activated alumina, gac, molecular sieve a kind of.
(3) recycling of inorganic salt: from reclaiming sodium sulfate crystal the filtrate of step (2);
Reclaim the sodium sulfate crystal treatment process and have two kinds:
A) carry out that underpressure distillation is concentrated, cooling, the filtered and recycled sodium sulfate crystal, distillation condensation water outlet can be made washing water, water of productive use is used.
B) naturally cooling, crystallization, then filtered and recycled sodium sulfate crystal.
The sodium sulfate crystal quality index reclaimed is good, can be using it as reactive dyestuffs commercial thinner, gained dyestuff property indices is normal; Also can as dyeing accelerant, be applied to linen-cotton, dyeing keratin-fiber using reclaiming sodium sulfate crystal, dyeing cloth specimen performance index are normal.Reclaim sodium sulfate crystal process institute effluent clear, colorless, can directly do production at the bottom of water use.
(4) extractant regeneration and organic recycling: it is 40 ~ 65 ℃ that resulting organic layer in step (1) is controlled to temperature, adds dilute alkaline soln under stirring state, regulates pH value to 5.5 ~ 9.5, carries out the layering processing after standing 0.5 ~ 2 hour.
Separating lower floor is the organism concentrated solution, can directly apply to production; Upper strata is the extraction agent of reclaiming, and the rate of recovery, can be for the present invention more than 99%.If the waste water of processing is for containing sulfonic acid base class waste water in dye production, directly blending is in conventional variety reactive black series for the organism concentrated solution of recovery, and the products obtained therefrom application performance is good; If the waste water of processing is for containing sulfonic acid base class dyestuff intermediate factory effluent, the organism concentrated solution reclaimed is by analysis after effective content, according to Workshop Production technique composite reactive or matching stain, blending conventional variety reactive black series by a certain percentage, the products obtained therefrom application performance is good.
The mass concentration of described diluted alkaline is 10% ~ 25%, and as preferably, dilute alkaline soln is selected from liquid caustic soda.
As preferably, the organic layer temperature is 55 ~ 60 ℃, and regulating the pH value is 7.5 ~ 8.
Compared with prior art, the invention has the beneficial effects as follows:
(1) scope of application is wide, and practicality is good.For the waste water from dyestuff of sulfonic acid base class, and sulfonic acid base class Intermediate Wastewater, all can apply present method and process, and treatment effect is not subjected to the impact of organic concentration in waste water and inorganic salt.
(2) extraction agent stable performance of the present invention, p-sulfonic acid base class dyestuff and Intermediate Wastewater extraction efficiency are high, and percentage extraction, more than 99%, does not produce secondary pollution, and the rate of recovery of back extraction regenerating extracting agent, more than 99%, can recycle long service life.
(3) present method p-sulfonic acid base class waste water is processed simultaneously, to comprehensive utilization of resources, turns waste into wealth.Pollutent in waste water mostly is raw material, intermediate or the product run off in production.Adopt the recyclable wherein organism of this method and be applied to produce reactive dyestuffs.Reclaim simultaneously the inorganic salt sodium sulfate contained in waste water, and, using its dyeing accelerant as commercialization thinner, dyeing course, be applied to, in the reactive dyestuffs actual production, realize the wastewater treatment comprehensive utilization of resources.
The accompanying drawing explanation
Fig. 1 is extraction agent preparation technology schematic diagram in the present invention;
Fig. 2 is schematic flow sheet of the present invention.
Embodiment
Below by embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
Extraction agent, according to preparation technology's preparation shown in Figure 1, under agitation is warming up to 50 ℃ by chaotropic agent, then adds catalyst aid, after 1 hour, adds complexing agent 60 ℃ of maintenances, namely is extracted agent; Wherein complexing agent is tridecylamine, and mass percent is 15%, and chaotropic agent is toluene, and mass percent is 85%, and the catalyst aid mass percent is 0%.
Factory effluent is taken from company's reactive dyestuffs production plant wastewater collection pond, and this stage, this Workshop Production dye species mainly contained the kinds such as reactive black KNB, reactive yellow W, reactive red 090329, active yellow 3 R FN and Acid Black 1 #.The factory effluent outward appearance of getting is chocolate, pH=6.8, and wherein total amount of organic is 19700mg/L.
According to method shown in Figure 2, by getting 5L factory effluent, adding slowly mass concentration, be 70% dilute sulphuric acid, regulating the pH value is 2.5.And then add the extraction agent 250ml prepared, and at 35 ~ 45 ℃, fully mixed 10 minutes, after standing 30 minutes, separate the about 4750ml of lower floor's extraction water.
Add gac 0.19g to carry out adsorption treatment the about 4750ml of lower floor's aqueous layer extracted, control 30 ~ 35 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate outward appearance is as clear as crystal, analyzes sodium sulfate and organism total content data in Table 1.
Extraction water filtrate is carried out to underpressure distillation concentrated, cooling, reclaim the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as dyeing accelerant, be applied to active yellow 3 R FN and draw a design in process, use normal.
Under abundant stirring state, adding slowly massfraction is 10% liquid caustic soda by the upper strata organic layer, and adjusting temperature is 40 ~ 45 ℃, and regulating pH is 7.0 ~ 7.5, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's Waste water concentrating liquid, obtaining solid content is the assorted dyestuff M-1 of 10% left and right.The dyestuff M-1 that will mix take massfraction as 12% ratio for blending commodity reactive black G2RC, the products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.7%.
Embodiment 2
Extraction agent, according to preparation technology's preparation shown in Figure 1, under agitation is warming up to 60 ℃ by chaotropic agent, then adds catalyst aid, after 0.5 hour, adds complexing agent 50 ℃ of maintenances, namely is extracted agent; Wherein complexing agent is trioctylamine, and mass percent is 45%, and chaotropic agent is dimethylbenzene, and mass percent is 50%, and the mass percent of catalyst aid chlorination trialkyl methylamine is 5%.
Factory effluent is taken from color-forming intermediate H acids production plant H acid mother liquor collecting tank, and the factory effluent outward appearance of getting is brown, pH=2.9, and wherein total amount of organic is 39600mg/L.
According to method shown in Figure 2, by getting 2L waste water, adding slowly mass concentration, be 30% dilute sulphuric acid, regulating the pH value is 1.5.And then with the extraction agent 1000ml prepared, at 55 ~ 65 ℃, fully mixed 10 minutes, after standing 30 minutes, separate the about 1860ml of lower floor's extraction water.
To in the about 1860ml of lower floor's extraction water, add gac 0.37g to carry out adsorption treatment, control 50 ~ 55 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.
Extraction water filtrate is carried out to naturally cooling and place more than 12 hours, namely have sodium sulfate crystal to separate out, reclaim the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as dyeing accelerant, be applied to reactive orange W and draw a design, use normal.
Under abundant stirring state, adding slowly massfraction is 25% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 55 ~ 65 ℃, and regulating pH is 9.0 ~ 9.5, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's concentrated solution, detect and analyze its amino content, carry out the composite reactive dyestuff according to the existing reactive black KNB technique in workshop, final that solid content is the assorted dyestuff M-2 of 18% left and right.Assorted dyestuff M-2 be take to the ratio of massfraction as 15% for blending reactive black WM, and the products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.8%.
Embodiment 3
Extraction agent, according to preparation technology's preparation shown in Figure 1, under agitation is warming up to 55 ℃ by chaotropic agent, then adds catalyst aid, after 45 minutes, adds complexing agent 55 ℃ of maintenances, namely is extracted agent; Wherein complexing agent is trioctylamine, and mass percent is 20%, and chaotropic agent is dodecylbenzene, and mass percent is 78%, and the mass percent of catalyst aid chlorination trialkyl methylamine is 2%.
Waste water is taken from company's reactive dyestuffs production plant wastewater collection pond, and this Workshop Production of this stage mainly contains the kinds such as reactive black KNB, Acid Black 1 # and active yellow 3 R FN.The waste water outward appearance of getting is blue brown, pH=2.9, and wherein total amount of organic is 22600mg/L.
According to method shown in Figure 2, institute gets in 2L waste water that to add slowly mass concentration be 50% dilute sulphuric acid, and regulating the pH value is 1.0.And then with the extraction agent 200ml prepared, at 40 ~ 45 ℃, fully mixed 10 minutes, after standing 30 minutes, separate the about 1900ml of lower floor's extraction water.
Add gac 0.1g to carry out adsorption treatment the about 1900ml of lower floor's extraction water, control 55 ~ 60 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.The extraction water outward appearance is as clear as crystal, analyzes sodium sulfate and organism total content data in Table 1.
Extraction water filtrate is carried out to underpressure distillation concentrated, cooling, reclaim the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as thinner, be applied to the adjustment of reactive black KNB product intensity, the dyestuff quality is normal.
Under abundant stirring state, adding slowly massfraction is 15% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 50 ~ 55 ℃, and regulating pH is 5.5 ~ 6.5, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's concentrated solution, obtaining solid content is the assorted dyestuff M-3 of 8% left and right.The dyestuff M-3 that will mix take massfraction as 13% ratio for blending reactive black GLP.The products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.4%.
Embodiment 4
Extraction agent, according to preparation technology's preparation shown in Figure 1, under agitation is warming up to 58 ℃ by chaotropic agent, then adds catalyst aid, after 1 hour, adds complexing agent 53 ℃ of maintenances, namely is extracted agent; Wherein complexing agent is TNA trinonylamine, and mass percent is 19%, and chaotropic agent is dodecylbenzene, and mass percent is 80%, and the white percentage ratio of quality of catalyst aid chlorination trialkyl methylamine is 1%.
Waste water is got the amino K acid mother liquor of intermediate collecting tank, and the waste water outward appearance of getting is brown, pH=1.0, and wherein total amount of organic is 45180mg/L.
According to method shown in Figure 2, the 2L waste water of getting adds the extraction agent 150ml prepared, and fully mixes 10 minutes at 55 ~ 65 ℃, after standing 30 minutes, separates the about 1820ml of lower floor's extraction water.
To in the about 1820ml of lower floor's extraction water, add gac 0.3g to carry out adsorption treatment, control 50 ~ 55 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.It is concentrated that extraction water filtrate is carried out underpressure distillation, cooling, reclaims the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as thinner, be applied to the adjustment of reactive red E-XF product intensity, the dyestuff quality is normal.
Under abundant stirring state, adding slowly mass concentration is 12% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 50 ~ 55 ℃, and regulating pH is 7.5 ~ 8.0, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's concentrated solution, detect and analyze its amino content, carry out synthetic dyestuff according to the existing active yellow 3 R FN technique in workshop, final that solid content is the assorted dyestuff M-4 of 20% left and right.Assorted dyestuff M-4 be take to the ratio of massfraction as 15% for blending reactive black EDG.The products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.6%.
Embodiment 5
Extraction agent, according to preparation technology's preparation shown in Figure 1, under agitation is warming up to 54 ℃ by chaotropic agent, then adds catalyst aid, after 0.5 hour, adds complexing agent 58 ℃ of maintenances, namely is extracted agent; Wherein complexing agent is trioctylamine, and mass percent is 25%, and chaotropic agent is dodecylbenzene, and mass percent is 74%, and the mass percent of catalyst aid chlorination trialkyl methylamine is 1%.
Waste water is taken from intermediate mother liquor collecting tank, and wherein contained component has H acid, m-sulfanilic acid, amino K acid etc. by analysis, and the waste water outward appearance of getting is Vandyke brown, pH=1.1, and wherein total amount of organic is 34500mg/L.
According to method shown in Figure 2, the 2L waste water of getting adds the extraction agent 1000ml prepared, and fully mixes 10 minutes at 55 ~ 65 ℃, after standing 30 minutes, separates the about 1850ml of lower floor's extraction water.In lower floor's extraction water, add activated alumina 0.2g to carry out adsorption treatment, control 45 ~ 50 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.It is concentrated that extraction water filtrate is carried out underpressure distillation, cooling, reclaims the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as dyeing accelerant, be applied to reactive black KNB and draw a design in process, according to the cloth specimen situation, use normal.
Under abundant stirring state, adding slowly mass concentration is 12% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 50 ~ 55 ℃, and regulating pH is 8.5 ~ 9.0, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's concentrated solution, detect and analyze its amino content, carry out synthetic dyestuff according to the existing reactive black KNB technique in workshop, final that solid content is the assorted dyestuff M-5 of 18% left and right.Assorted dyestuff M-5 be take to the ratio of massfraction as 8% for blending reactive black WM, and the products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.5%.
Embodiment 6
The regenerating extracting agent that extraction agent adopts embodiment 2 to reclaim.
Waste water is with embodiment 1.
According to method shown in Figure 2, institute gets in 2L waste water that to add slowly mass concentration be 40% dilute sulphuric acid, and regulating the pH value is 3.5.And then with embodiment 2 in the extraction agent 150ml that reclaims, at 40 ~ 45 ℃, fully mixed 10 minutes, after standing 30 minutes, separate the about 1860ml of lower floor's extraction water.
In the about 1860ml of lower floor's extraction water, add silica gel 0.15g to carry out adsorption treatment, control 45 ~ 50 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.It is concentrated that extraction water filtrate is carried out underpressure distillation, cooling, reclaims the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as dyeing accelerant, be applied to active yellow 3 R FN and draw a design in process, according to the cloth specimen situation, use normal.
Under abundant stirring state, adding slowly mass concentration is 12% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 50 ~ 55 ℃, and regulating pH is 7.5 ~ 8, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's concentrated solution, obtaining solid content is the assorted dyestuff M-1 of 8% left and right.The dyestuff M-1 that will mix take massfraction as 5% ratio for blending reactive black G2RC, the products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.8%.
Embodiment 7
The regenerating extracting agent that extraction agent adopts embodiment 3 to reclaim.
Waste water is with embodiment 2.
According to method shown in Figure 2, get in 2L waste water add slowly mass concentration be 50% dilute sulphuric acid to regulate pH value be 2.0 ~ 2.2, then add the extraction agent 180ml reclaimed in embodiment 3,55 ~ 65 ℃ of fully mixing 10 minutes, after standing 30 minutes, separate the about 1860ml of lower floor's extraction water.
In the extraction water 1860ml of lower floor, add gac 0.3g to carry out adsorption treatment, control 55 ~ 60 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.It is concentrated that extraction water filtrate is carried out underpressure distillation, cooling, reclaims the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as thinner, be applied to the adjustment of reactive red E-XF product intensity, the dyestuff quality is normal.
By upper layer of extraction liquid under abundant stirring state, slowly adding mass concentration is 20% liquid caustic soda, adjusting temperature is 50 ~ 55 ℃, and regulating pH is 8.0 ~ 8.5, after fully stirring 30 minutes, standing 1 little layered, upper strata is regenerating extracting agent, separates lower floor's concentrated solution, detects and analyzes its amino content, according to the existing reactive black KNB technique in workshop, carry out the composite reactive dyestuff, final that solid content is the assorted dyestuff M-2 of 15% left and right.Assorted dyestuff M-2 be take to the ratio of massfraction as 10% for blending reactive black WM.The products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.2%.
Embodiment 8
The regenerating extracting agent that extraction agent adopts embodiment 4 to reclaim.
Waste water is with embodiment 1.
According to method shown in Figure 2, get in 2L waste water that to add slowly mass concentration be 30% dilute sulphuric acid, regulating the pH value is 2.0.And then add the extraction agent 140ml reclaimed in embodiment 4, and at 35 ~ 45 ℃, fully mixed 10 minutes, after standing 30 minutes, separate the about 1850ml of lower floor's extraction water.
In the about 1850ml of lower floor's extraction water, add molecular sieve 0.37g to carry out adsorption treatment, control 40 ~ 45 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.It is concentrated that extraction water filtrate is carried out underpressure distillation, cooling, reclaims the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as thinner, be applied to the adjustment of reactive red E-XF product intensity, the dyestuff quality is normal.
Under abundant stirring state, adding slowly mass concentration is 15% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 50 ~ 55 ℃, and regulating pH is 6.5 ~ 7, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's Waste water concentrating liquid, obtaining solid content is the assorted dyestuff M-1 of 10% left and right.The dyestuff M-1 that will mix take massfraction as 5% ratio for blending reactive black WM, the products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.9%.
Embodiment 9
The regenerating extracting agent that extraction agent adopts embodiment 6 to reclaim.
Waste water is with embodiment 4.
According to method shown in Figure 2, get in 2L waste water and add the extraction agent 250ml reclaimed in embodiment 6, at 40 ~ 45 ℃, fully mixed 10 minutes, after standing 30 minutes, separate the about 1820ml of lower floor's extraction water.
In the about 1820ml of lower floor's extraction water, add gac 0.08g to carry out adsorption treatment, control 40 ~ 45 ℃ of temperature, stir and keep filtering after 30 minutes.Gained extraction water filtrate appearance transparent is colourless, analyzes sodium sulfate and organism total content data in Table 1.It is concentrated that extraction water filtrate is carried out underpressure distillation, cooling, reclaims the sodium sulfate crystal quality index in Table 1.Reclaim sodium sulfate crystal as thinner, be applied to the adjustment of reactive black KNB product intensity, the dyestuff quality is normal.
Under abundant stirring state, adding slowly mass concentration is 12% liquid caustic soda by upper layer of extraction liquid, and adjusting temperature is 50 ~ 55 ℃, and regulating pH is 8 ~ 8.5, after fully stirring 30 minutes, and standing 1 little layered, upper strata is regenerating extracting agent, lower floor is Waste water concentrating liquid.Separate lower floor's concentrated solution, detect and analyze its amino content, carry out synthetic dyestuff according to the existing active yellow 3 R FN technique in workshop, final that solid content is the assorted dyestuff M-4 of 15% left and right.Assorted dyestuff M-4 be take to the ratio of massfraction as 10% for blending reactive black EDG, and the products obtained therefrom application data is in Table 2.The upper strata regenerating extracting agent rate of recovery is 99.7%.
Comparative Examples 1
Waste water is with embodiment 2.According to embodiment 2 described in Chinese patent CN1309092, adopt volumetric concentration 30% trialkylamine+40% octanol+30% kerosene as extraction agent, the H acid producing waste water is carried out to multi-stage solvent extraction, the volume of take is compared (extraction phase/waste water) and is joined in separating funnel as 0.75:1 compares, at normal temperatures, acutely shake extraction 30 minutes, make two-phase reach extraction equilibrium; Standing at normal temperatures by after balance, obtaining solution again, phase-splitting, separate organic phase and water after 10 minutes.Analyze water phase organic matters total amount concentration, sodium sulphate content data in Table 1.Then water adds in separating funnel and carries out second stage extraction according to compare identical with the first step equally, and wherein extraction phase is lean solvent, reaches phase-splitting after balance, and then carries out third stage extraction.After three grades of cross current solvent extractions were processed, the waste water outward appearance was water white transparency, and analyzing organic substance total amount concentration, sodium sulphate content data are in Table 1.According to the described sodium sulfate recovery method of this patent, to after three grades of cross current solvent extractions, waste water being pressed to distillation and concentration, cooling, reclaim the sodium sulfate crystal quality index in Table 1.
Although the comparative example also has water treatment effect, process in waste water and still have more inorganic salt not reclaim, organism is also residual more; Organic concentrated solution after processing does not further utilize yet.
Comparative Examples 2
Waste water is with embodiment 2.According to method described in Chinese patent CN1073536C, extraction agent trialkyl tertiary amine (N253) dilutes with kerosene, and Dilution ratio is kerosene: trialkyl tertiary amine=1:0.35.According to its method, extraction agent is added in waste water, carry out wastewater treatment in strict accordance with its processing condition, the aqueous phase extracted analyzing organic substance total amount concentration, the sodium sulphate content that obtain, data are in Table 1.According to the described sodium sulfate recovery method of this patent, the water after extraction is pressed to distillation and concentration, cooling, reclaim the sodium sulfate crystal quality index in Table 1.In strict accordance with its processing condition back extraction resulting organic concentrated solution, analyzing organic substance total amount concentration conversion, the organic substance extraction rate of recovery 97.5% in waste water.
In embodiment, the organism total content measuring method of waste water and aqueous layer extracted is with reference to GB 13193-91.In aqueous layer extracted, the sodium sulphate content measuring method is with reference to GB/T 6366-1992.Reclaim the sodium sulfate crystal quality index, wherein arsenic (As) content assaying method adopts GB/T 23947.1-2009, and heavy metal (in lead) content assaying method adopts GB/T 23946-2009, and all the other indexs are with reference to GB/T6009-2003.The results are shown in Table 1:
In embodiment, gained dye product dyeing process carries out with reference to the method in GB/T 2387-2006, the mensuration of degree of fixation, colour fastness to rubbing, washing fastness and colour fastness to perspiration is carried out according to the method in GB/T 2391-2006, GB/T 3920-1997, GB/T 3921.4-1997 and GB/T 3922-1995 respectively, the results are shown in following table 2
Claims (7)
1. the treatment process of its dyestuff intermediate factory effluent of sulfonic acid base class dye well, is characterized in that, described treatment process is following steps:
(1) extraction of waste water: its dyestuff intermediate factory effluent of sulfonic acid base class dye well is mixed in extraction plant with extraction agent, the volume ratio of extraction agent and waste water is 1:2 ~ 20, described its dyestuff intermediate factory effluent of sulfonic acid base class dye well pH is 1.0 ~ 5.0, it is 35 ~ 65 ℃ that temperature is controlled in extraction, then standing, layering, obtain organic layer and water layer;
(2) adsorption treatment of water layer after the extraction: the water layer obtained in step (1) is added to sorbent material, and the adsorption process temperature is 30 ~ 60 ℃, and the mass volume ratio of sorbent material add-on and water layer is 40 ~ 202g/m
3, after absorption, filter, obtain filtrate;
(3) recycling of inorganic salt: from reclaiming sodium sulfate crystal the filtrate of step (2);
(4) extractant regeneration and organic recycling: it is 40 ~ 65 ℃ that resulting organic layer in step (1) is controlled to temperature, adds dilute alkaline soln under stirring state, regulates pH value to 5.5 ~ 9.5, carries out the layering processing after standing 0.5 ~ 2 hour.
2. the treatment process of a kind of its dyestuff intermediate factory effluent of sulfonic acid base class dye well according to claim 1, it is characterized in that, in step (1), selecting mass concentration is that 30% ~ 70% dilute sulphuric acid is regulated its dyestuff intermediate factory effluent of sulfonic acid base class dye well pH value, pH is 1.5 ~ 2.5, and extraction temperature is 50 ~ 55 ℃.
3. the treatment process of a kind of its dyestuff intermediate factory effluent of sulfonic acid base class dye well according to claim 1, it is characterized in that, extraction agent described in step (1) is mixed by complexing agent, chaotropic agent and catalyst aid, the preparation method of extraction agent for: chaotropic agent under agitation is warming up to 50 ~ 60 ℃, then add catalyst aid, 50 ~ 60 ℃ of maintenances, add complexing agent after 0.5 ~ 1 hour, namely be extracted agent;
Described complexing agent is selected from the tertiary amine of belt length paraffinic hydrocarbons group, and structural formula is N-[C
nH
2n+1]
3, wherein, n=8 ~ 10;
Described chaotropic agent is selected from toluene, dimethylbenzene, dodecylbenzene a kind of;
Described catalyst aid is selected from chlorination trialkyl methylamine, and structural formula is [CH
3-N-(C
8 ~ 10H
17 ~ 21)
3]
+Cl
-
The mass percent of described each component of extraction agent is: complexing agent 15% ~ 45%, chaotropic agent 55% ~ 85%, catalyst aid 0% ~ 5%, each constituent mass sum is 100%.
4. the treatment process of a kind of its dyestuff intermediate factory effluent of sulfonic acid base class dye well according to claim 3, it is characterized in that, complexing agent is selected from trioctylamine (being n=8), chaotropic agent is selected from dodecylbenzene, and in extraction agent, the mass percent of each component is: complexing agent 20%, chaotropic agent 78%, catalyst aid 2%.
5. the treatment process of a kind of its dyestuff intermediate factory effluent of sulfonic acid base class dye well according to claim 1, is characterized in that, in step (2), sorbent material is selected from silica gel, activated alumina, gac, molecular sieve a kind of.
6. the treatment process of a kind of its dyestuff intermediate factory effluent of sulfonic acid base class dye well according to claim 1, is characterized in that, in step (4), the organic layer temperature is 55 ~ 60 ℃, and the diluted alkaline mass concentration is 10% ~ 25%, and regulating the pH value is 7.5 ~ 8.
7. the treatment process of a kind of its dyestuff intermediate factory effluent of sulfonic acid base class dye well according to claim 1, is characterized in that, dilute alkaline soln is selected from liquid caustic soda.
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