CN109336270A - A kind of dye vat Liquid Residue resource utilization method and its system - Google Patents
A kind of dye vat Liquid Residue resource utilization method and its system Download PDFInfo
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- CN109336270A CN109336270A CN201811179293.9A CN201811179293A CN109336270A CN 109336270 A CN109336270 A CN 109336270A CN 201811179293 A CN201811179293 A CN 201811179293A CN 109336270 A CN109336270 A CN 109336270A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to sewage treatment and field is recycled, discloses a kind of dye vat Liquid Residue resource utilization method, includes the following steps: that S11, raffinate are collected；S12, by raffinate filtering and impurity removing；S13, it raffinate is passed through to extraordinary film separation system obtains producing water and concentrated water；S14, water reuse and concentrated water collection discharge are produced.Using feature, separation system does not decolourize to dye vat raffinate to the present invention, and the salt in raffinate is retained in and is produced in water, the salt in raffinate is recycled while purified treatment dyeing waste-water, alleviate the processing load of sewage plant and is more energy-saving and environmentally friendly, reduces production and rises this.
Description
Technical field
The present invention relates to a kind of dye vat Liquid Residue resource utilization method and its system, belongs to sewage treatment and recycle neck
Domain.
Background technique
It is excellent that reactive dye have that chromatography is complete, bright in colour, technique for applying is easy, strong applicability, price are relatively cheap etc.
Point becomes most important a class of dyes in cellulose dyestuff.But reactive dye dye-uptake and degree of fixation are low (60%-70%),
A large amount of nothing is generally added in dye vat in the dyeing of cellulose in order to improve its dye-uptake and colour fixation
Machine salt (sodium chloride or sodium sulphate) is cooked dyeing auxiliaries, and dosage is up to 30g/L-150g/L, the reason is that electrolyte can reduce active combustion
The cloud density for the carbon atom being connected in material with chlorine promotes the progress of reactive dye and cellulose bonding reaction, to guarantee
Dyeing effect.After above-mentioned dyeing course, the waste water of one high chroma, high salinity can be remained in dye vat, coloration is typically up to
To 10000-100000 degree, salt content generally has 3%-10% or so.Wherein coloration is mainly derived from the not upper reactive dye contaminated
With the product after dyestuff hydrolysis, salt is mainly the dyeing auxiliaries (Na added in dye vat2SO4), reactive dye and cellulose occur
The sodium carbonate of chloride ion and adjusting dye liquor PH under replacing after bonding reaction.
At present this strand of high chroma, high salinity waste water there are no good processing methods, at this stage mainly this stock is given up
Liquid enters sewage disposal system processing after converging other waste water.But since this waste liquid contains a large amount of salinity and dyestuff difficult to degrade
On the one hand Liquid Residue, direct emission cause the waste of a large amount of useful materials, on the other hand can greatly increase at sewage into sewage plant
The processing load of reason system, influences the normal operation of biochemical system, also increases difficulty for the advanced treatment system of rear end.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of dye vat Liquid Residue resource utilization side
Method can slough the reactive dye in the residual liquid after dyeing, while enter the salt in residual liquid and producing in water, with
Just it recycles.
Above-mentioned technical purpose of the invention has the technical scheme that a kind of dye vat Liquid Residue recycling
Using method, include the following steps: that S11, raffinate are collected；S12, by raffinate filtering and impurity removing；S13, raffinate is passed through to special membrane point
It obtains producing water and concentrated water from system；S14, water reuse and concentrated water collection discharge are produced.
By using above-mentioned technical proposal, first the residual liquid (hereinafter referred to as raffinate) after dyeing is collected, then
Collected raffinate is filtered, cloth waste, soft flocks and other solids in dyeing course in residual liquid is removed and suspends
Granule foreign prevents these impurity from blocking extraordinary film separation system；Using extraordinary film separation system by the dyestuff in residual liquid
It sloughs, and retains a part of salt, the liquid through special membrane is to produce water, is collected simultaneously reuse, the partially liq being trapped
For concentrated water, it is collected decoloration again or reuse or discharge.
Be further arranged to: the specific method of S12 includes: that raffinate is passed through cartridge filter to be filtered, the security personnel
The pore size filter of filter is 5 microns.
By using above-mentioned technical proposal, raffinate is filtered using cartridge filter, dyestuff is generally and glue in solution
There are more cloth waste, knitting wool and other solid suspended particle impurity, these impurity to be easy in cartridge filter for poly- mode
Product is pushed away at strainer and blocks filter hole, and the filtering accuracy that cartridge filter is arranged is 5 microns, and filtering accuracy is high, and effect is good, can
Cloth waste, soft flocks and other solid suspended particle impurity are largely removed, subsequent special membrane is protected not block.
Be further arranged to: the specific method of S13 includes: that raffinate filtered in S12 is passed through special membrane through high-pressure pump
Separation system, operating pressure 0.5-1Mpa, extraordinary film separation system are more than or equal to 95% to the removal rate of coloration, and desalination rate is big
In equal to 50%.
By using above-mentioned technical proposal, the filtering filters pressing of 0.5-1Mpa can play the performance of special membrane well, suitable
Raffinate is pressed through special membrane by sharp ground, and after extraordinary film separation system decolorization filtering, chroma removal rate is more than or equal to 95%, saturating salt
Rate is more than or equal to 50%.
Be further arranged to: the specific method of the S14 includes: S141, will produce water and squeeze into rear end adsorption system, carries out two
Secondary decoloration produces colority of water after secondary decolourization and is less than or equal to 20 degree, and absorption multiplying power is more than or equal to 100BV, is finally back to production water
Dyeing course；S142, concentrated water recycle and squeeze into extraordinary film separation system and separated, and recycle and squeeze into 3-5 times, then by concentrated water drainage
It puts.
By using above-mentioned technical proposal, it is relatively still too high that special membrane filters later production colority of water, direct reuse in
Again in dyeing course, the effect of dyeing will affect, so that color is impure, need to carry out secondary decolourization, the absorption of secondary decolourization
It is required that control is more than or equal to 100BV in absorption multiplying power, enables the production colority of water after secondary decolourization less than 20 degree, meet reuse
Color standard；There are also a large amount of dyestuffs and salt in concentrated water, salinity therein still has larger utility value, concentrated water is beaten again
When entering extraordinary film separation system, the concentration for liquid is successively increased, so that salt rejection rate is gradually reduced, produce water stays salt effect more
It is good, reduce the salt amount in concentrated water, reduces waste；When producing water and draining ratio is 3:1, recovery efficiency is on the left side 70-80%
The right side enables to the salt total amount produced in water almost the same with the salt content of raffinate, last concentrated water view coloration and salt
Situation is emitted into sewage plant and is handled.
A kind of dye vat Liquid Residue resource utilization system, including the material liquid tank, the first feed pump, security personnel's filtering being sequentially connected
The front end of device, high-pressure pump and extraordinary film separation system, the special type film separation system is connected with concentrated water pipeline, the concentrated water pipe
Road is connected with reflux line and discharge collection conduit far from one end of the extraordinary film separation system simultaneously, and the reflux line connects
It is connected between cartridge filter and high-pressure pump；The rear end of the special type film separation system is connected with water production pipeline, the water producing pipe
Road is connected in turn far from one end of extraordinary film separation system and produces pond, the second feed pump and rear end adsorption system, after described
End adsorption system is connected with reuse pipeline.
By using above-mentioned technical proposal, material liquid tank is used for the raffinate that store collected is come, and the first feed pump will be in material liquid tank
Raffinate squeeze into cartridge filter and provide pressure for the filtering of raffinate, high-pressure pump for increasing filtered raffinate hydraulic pressure,
Enabling raffinate, concentrated water pipeline is for concentrated water to be discharged in extraordinary film separation system, and reflux line is for concentrated water to be passed through again
In extraordinary film separation system, discharge collection conduit is used for concentrated water discharge or collection；Water production pipeline is used for extraordinary UF membrane
The production water that system is isolated, which is delivered to, produces pond collection, and the second feed pump is used to the water produced in pond squeezing into rear end adsorption system
Secondary decolourization is carried out, so that producing water reaches reuse standard.
Be further arranged to: be disposed between the high-pressure pump and extraordinary film separation system check valve, ball valve and
Raffinate flowmeter, the conducting direction of the check valve is high-pressure pump to ball valve direction, between the cartridge filter and high-pressure pump
Equipped with first pressure gauge, second pressure gauge, the reuse pipeline, row are provided between the flowmeter and extraordinary film separation system
It puts collection conduit, reflux line and water production pipeline and is provided with sample tap, the reflux line is equipped with return flow meter, institute
It states and is provided with production water ga(u)ge in water production pipeline, be provided with concentrated water flowmeter in the discharge collection conduit.
By using above-mentioned technical proposal, on the one hand check valve prevents the generation of water hammer, on the other hand anti-locking system
Liquid return filling in special membrane when stoppage in transit, ball valve are used for the inflow of adjusting film, and first pressure gauge, second pressure gauge are each for monitoring
The hydraulic pressure of section, sample tap produce water ga(u)ge, concentrated water flowmeter is respectively used to calculating production water and dense for facilitating each section to be sampled
The flow of water.
Be further arranged to: special membrane used in the special type film separation system is sulfonated polyether sulfone seperation film, after described
Holding resin used in adsorption system is large aperture adsorption resin.
By using above-mentioned technical proposal, sulfonated polyether sulfone separates the restorative height of Membrane cleaning, and resistance to oxidation chlorine-resistant, surface has
Strong negative electrical charge has good repulsive interaction to sulfate ion, the carbanion of divalent, has preferable repel to chloride ion
Effect, and as concentration increases, salt rejection rate can gradually decrease, and when the rate of recovery is accomplished 70%-80%, concentrated water has been concentrated 4-
6 times, the salt content for producing water and the variation of raffinate salt content less, have accomplished the effect for staying salt in producing water；Another aspect sulfonation is poly-
Ether sulfone seperation film has good removing to act on dyestuff, so that the dyestuff in raffinate is largely divested, so that producing colority of water more
It is low；Large aperture adsorption resin carries out secondary decolourization to water is produced, so that the coloration for producing water is less than or equal to 20 degree, meets and returns for producing water
The chromaticity requirements used and leave most of recyclable inorganic salt as auxiliary agent.
Be further arranged to: the sulfonated polyether sulfone seperation film the preparation method comprises the following steps: S21, take resin-grade PES be added quality
In the concentrated sulfuric acid that score is 98%, stirring and dissolving forms homogeneous solution at room temperature, then oleum is slowly added dropwise and stirs, and spends
Reaction mixture is simultaneously washed till PH=6-7 by ion water sedimentation, dry the sulfonated polyether sulfone in 80 DEG C of baking ovens；S22, sulfonation is gathered
Ether sulfone is dissolved in the mixed solution of NMP and NMF, is stirred evenly, and 15wt% preparation liquid is configured to, and is cast on clean glass plate
It forms a film, drying for 24 hours, then at 100 DEG C is dried in vacuo for 24 hours at 60 DEG C, obtains sulfonated polyether sulfone seperation film.
By using above-mentioned technical proposal, the sulfonated polyether sulfone seperation film prepared according to the above method, preparation method is simple
Efficiently, and the sulfonation degree of sulfonated polyether sulfone seperation film prepared is high, can possess biggish acid and alkali-resistance range, decolorizing effect
Good, operating pressure requirement is low, and oxidative resistance is strong.
Be further arranged to: the preparation method of the large aperture adsorption resin include: S31, by concentration be 2% polyphenyl second
7 parts of alkene-alt- maleic acid sodium salt solution, 110 parts of water mixing, stir and heat, and are heated to 70 DEG C of stopping heating, are passed through nitrogen
Gas 5 minutes；S32,35 parts of the styrene solution for the benzoyl peroxide that mass fraction is 1-2% and 7 parts of divinylbenzene are added
Enter in solution obtained in S31, stir and continue to be passed through nitrogen 5 minutes, be heated to 90 DEG C and react 2 hours；S33, reaction 2 are small
When after sample observation shape of particle and hardness with suction pipe within each 20 minutes, when sampling, suction pipe is close to bottom of bottle, by the slurries of sucking
It is put into the beaker for filling clear water, observes the sink-float of particle, if the bottom can be sunk to, take out the inspection particle of particle nail pressure
Soft or hard degree；S34, it is to be observed be hardened to particle after be continuously heating to 95 DEG C of reaction half an hour, then stop heating, water of going out
Bath is cooled to 50 DEG C under stiring and obtains suspension；S35, suspension obtained in S34 is imported in 1000 parts of water, upper layer of inclining
Liquid is simultaneously washed for several times with tap water and distilled water repeatedly, is filtered and is moved into filter cake in culture dish, does in 50 DEG C of vacuum drying ovens
Large aperture adsorption resin is obtained after dry 3 hours.
By using above-mentioned technical proposal, prepare according to the above method large aperture adsorption resin absorption multiplying power it is strong, it is easy to produce, easily
Regeneration further can carry out decolourizing and will not removing the salt produced in water to production water, and the quality of water outlet meets reuse requirement, no
Dyeing when can be to reuse has an impact.
Be further arranged to: the regeneration method of the large aperture resin specifically includes: S41, large aperture resin are packed into
After exchange column, with distilled water backwash large aperture resin layer, sheetage 50-70%, up to being discharged clear, odorlessness, without fine crushing
Until resin, then eluted at a slow speed with 10-15 times of volume of 50%-100% ethyl alcohol；S42, with the 4-5%HCl solution of about 2 times of volumes,
With 2m/h flow velocity by large aperture resin layer, after being all passed through, impregnate 4-8 hours, venting acid solution is rinsed with clean water to water outlet
It is in neutrality, irrigation flow rate 10-20m/h.S43, with the 2-5%NaOH solution of about 2 times of resin volumes, passed through with 2m/h flow velocity big
Aperture resin layer after being all passed through, impregnates 4-8 hours, venting lye is rinsed to water outlet with clean water and is in neutrality, irrigation flow rate
For 10-20m/h；S44, the large aperture resin of S32 and S33 two to after must regenerate three times is repeated.
By using above-mentioned technical proposal, regeneration is carried out to large aperture resin by the above method, favorable regeneration effect,
Repeated regeneration uses large aperture resin, more environmentally-friendly economy.
In conclusion the invention has the following advantages:
1, first raffinate is collected, is then filtered, remove cloth waste in dyeing course in residual liquid, soft flocks and its
His solid suspended particle impurity prevents these impurity from blocking extraordinary film separation system；Using extraordinary film separation system by Liquid Residue
Dyestuff in body is sloughed, and retains a part of salt, and the liquid through special membrane is to produce water, is collected simultaneously reuse, is trapped
Partially liq be concentrated water, be collected, be passed through extraordinary film separation system after collection again and make more salts through extraordinary
Film repeatedly makes there was only a small amount of salt in concentrated water later, and most of salt enters to produce to be utilized in water；
2, material liquid tank is used for the raffinate that store collected is come, and the raffinate in material liquid tank is squeezed into cartridge filter by the first feed pump
In and for the filtering of raffinate provide pressure, high-pressure pump enables raffinate in special membrane point for increasing filtered raffinate hydraulic pressure
It is used to for concentrated water being discharged from concentrated water pipeline in system, reflux line is arranged for concentrated water to be passed through again in extraordinary film separation system
Collection conduit is put to be used for concentrated water discharge or collection；The production water that water production pipeline is used to isolate extraordinary film separation system conveys
It is collected to is produced from pond, the second feed pump, which is used to the water produced in pond squeezing into rear end adsorption system, carries out secondary decolourization, so that producing
Water reaches reuse standard；
3, the sulfonated polyether sulfone seperation film prepared, preparation method are simple and efficient, and the sulfonated polyether sulfone separation prepared
The sulfonation degree of film is high, can possess biggish acid and alkali-resistance range, and good decolorizing effect, operating pressure requirement is low, and oxidative resistance is strong,
As solution salt concentration increases, the rejection of salt is greatly lowered in this sulfonated polyether sulfone seperation film；Prepare large aperture
It is strong to adsorb resin adsorption multiplying power, it is easy to produce, it easily regenerates, further production water can be carried out decolourizing and will not removing the salt produced in water
Part, the quality of water outlet meets reuse requirement, and dyeing when will not be to reuse has an impact.
Detailed description of the invention
Fig. 1 is the structural representation flow chart of dye vat Liquid Residue resource utilization system in embodiment 1.
Appended drawing reference: 1, material liquid tank；21, the first feed pump；22, high-pressure pump；23, the second feed pump；3, cartridge filter；
4, extraordinary film separation system；5, pond is produced；6, rear end adsorption system；71, concentrated water pipeline；72, reflux line；73, discharge is collected
Pipeline；74, water production pipeline；75, reuse pipeline；81, check valve；82, ball valve；83, first pressure gauge；84, second pressure gauge；
85, raffinate flowmeter；86, return flow meter；87, water ga(u)ge is produced；88, concentrated water flowmeter；9, sample tap.
Specific embodiment
Embodiment 1: a kind of dye vat Liquid Residue resource utilization method includes the following steps:
S11, raffinate are collected: the residual liquid flowed down after dyeing in the equipment such as dye vat, overflow dyeing machine is collected；
S12, by raffinate filtering and impurity removing: raffinate is passed through cartridge filter and is filtered, the filtering of the cartridge filter
Aperture is 5 microns；
S13, it raffinate is passed through to extraordinary film separation system obtains producing water and concentrated water: by raffinate filtered in S12 through height
Press pump is passed through extraordinary film separation system, operating pressure 0.5-1Mpa, and extraordinary film separation system is greater than the removal rate of coloration etc.
In 95%, desalination rate is more than or equal to 50%, and the liquid through extraordinary film separation system is to produce water, and the liquid of retention is concentrated water.
S14, water reuse and concentrated water collection discharge are produced: water will be produced and squeeze into rear end adsorption system, carry out secondary decolourization, it is secondary
Colority of water is produced after decoloration and is less than or equal to 20 degree, and absorption multiplying power is more than or equal to 100BV, will finally produce water and is back to dyeing course；It is dense
Water recycles and squeezes into extraordinary film separation system and separated, and recycling and squeezing into number is 4 times, is got over using special membrane with solution concentration
Height, this lower property of salt rejection rate are able to enter most of salt in production water, the salt total amount in concentrated water are reduced, through spy
After kind film is filtered for multiple times, the rate of recovery accomplishes 70-80%, and concentrated water is concentrated 4-6 times, so that raffinate salt is close with water salt is produced
Seemingly.The concentrated water finally obtained is collected or is emitted into sewage plant.
A kind of dye vat Liquid Residue resource utilization system, as shown in Figure 1, including the material liquid tank 1 being sequentially connected, the first water supply
Pump 21, cartridge filter 3, high-pressure pump 22 and extraordinary film separation system 4, the front end of extraordinary film separation system 4 is connected with concentrated water
Pipeline 71, the one end of concentrated water pipeline 71 far from extraordinary film separation system 4 are connected with reflux line 72 and discharge collection conduit simultaneously
73, reflux line 72 is connected between cartridge filter 3 and high-pressure pump 22；Special membrane used in extraordinary film separation system 4 is
Sulfonated polyether sulfone seperation film, the rear end of extraordinary film separation system 4 are connected with water production pipeline 74, and water production pipeline 74 is far from special membrane point
One end from system 4, which is connected in turn, produces pond 5, the second feed pump 23 and rear end adsorption system 6, and rear end adsorption system 6 connects
It is connected to for water will to be produced towards dyeing installation so that the reuse pipeline 75 of water reuse will be produced, the film that rear end adsorption system 6 uses is
Large aperture resin.
Check valve 81, ball valve 82 and raffinate flowmeter are disposed between high-pressure pump 22 and extraordinary film separation system 4
85, the conducting direction of check valve 81 is high-pressure pump 22 to 82 direction of ball valve, and first is equipped between cartridge filter 3 and high-pressure pump 22
Pressure gauge 83 is provided with second pressure gauge 84, reuse pipeline 75, discharge between raffinate flowmeter 85 and extraordinary film separation system 4
Collection conduit 73, reflux line 72 and water production pipeline 74 are provided with sample tap 9, and reflux line 72 is equipped with return flow meter
86, it is provided in water production pipeline 74 and produces water ga(u)ge 87, discharge and be provided with concentrated water flowmeter 88 in collection conduit 73.
Wherein, sulfonated polyether sulfone seperation film the preparation method comprises the following steps: S21, to take resin-grade PES that mass fraction is added be 98%
In the concentrated sulfuric acid, stirring and dissolving forms homogeneous solution at room temperature, then oleum is slowly added dropwise and stirs, simultaneously with deionized water precipitating
Reaction mixture is washed till PH=6-7, dry the sulfonated polyether sulfone in 80 DEG C of baking ovens；S22, sulfonated polyether sulfone is dissolved in NMP
It in the mixed solution of NMF, stirs evenly, is configured to 15wt% preparation liquid, cast on clean glass plate and form a film, at 60 DEG C
Drying for 24 hours, then at 100 DEG C is dried in vacuo for 24 hours, obtains sulfonated polyether sulfone seperation film.
Wherein, the preparation method of large aperture adsorption resin include: S31, by concentration be 2% polystyrene-alt- along fourth
7 parts of enedioic acid sodium salt solution, 110 parts of water mixing, stir and heat, and are heated to 70 DEG C of stopping heating, are passed through nitrogen 5 minutes；
S32, it will be obtained in the 7 parts of addition S31 of 35 parts of styrene solution and divinylbenzene for the benzoyl peroxide that mass fraction is 1-2%
To solution in, stir and continue to be passed through nitrogen 5 minutes, be heated to 90 DEG C and react 2 hours；It is S33, each after reaction 2 hours
Observation shape of particle and hardness is sampled with suction pipe within 20 minutes, when sampling, suction pipe is close to bottom of bottle, and the slurries of sucking are put into and are filled
In the beaker of clear water, the sink-float of particle is observed, if the bottom can be sunk to, takes out the soft or hard journey of the inspection particle of particle nail pressure
Degree；S34, it is to be observed be hardened to particle after be continuously heating to 95 DEG C of reaction half an hour, then stop heating, water-bath of going out stirring
Mix down be cooled to 50 DEG C suspension；S35, by suspension obtained in S34 import 1000 parts of water in, upper liquid of inclining and use oneself
Water and distilled water wash for several times repeatedly, filter and move into filter cake in culture dish, after 3 hours dry in 50 DEG C of vacuum drying ovens
Obtain large aperture adsorption resin.
Its large pore resin can be specifically included with regeneration, regeneration method: S41, large aperture resin, which are packed into, to be handed over
After changing column, with distilled water backwash large aperture resin layer, sheetage 50-70%, up to being discharged clear, odorlessness, without tree fine crushing
Until rouge, then eluted at a slow speed with 10-15 times of volume of 50%-100% ethyl alcohol；S42, with the 4-5%HCl solution of about 2 times of volumes, with
2m/h flow velocity is by large aperture resin layer, after being all passed through, impregnates 4-8 hours, venting acid solution, is rinsed with clean water to water outlet and is in
Neutrality, irrigation flow rate 10-20m/h.S43, with the 2-5%NaOH solution of about 2 times of resin volumes, macropore is passed through with 2m/h flow velocity
Diameter resin layer after being all passed through, impregnates 4-8 hours, venting lye is rinsed to water outlet with clean water and is in neutrality, and irrigation flow rate is
10-20m/h；S44, the large aperture resin of S32 and S33 two to after must regenerate three times is repeated.
Embodiment 2-3 and the difference of embodiment 1 are only that: dope recycle and be passed through in sulfonated polyether sulfone seperation film again into
The number of row filtering respectively is 3 times, 5 times.
Comparative example 1-4 and the difference of embodiment 1 are only that: dope recycle and be passed through in sulfonated polyether sulfone seperation film again into
The number of row filtering respectively is 0 time, 1 time, 2 times, 6 times.
Comparative example 5 and the difference of embodiment 1 are only that: in comparative example 5 raffinate without rear end adsorption system secondary decolourization at
Reason.
The difference of comparative example 6-8 and embodiment 1 is through being: film used in the adsorption system of rear end is respectively as follows: D201 macropore
Adsorb resin, X-5 macroporous absorbent resin, NKA macroporous absorbent resin.
It is tested using the dye vat Liquid Residue resource utilization system in embodiment 1, selecting coloration is 5000 degree, sulfur-bearing
Sour sodium molar concentration is the dye vat residual liquid of 0.01mol/L as feed liquid；Feed liquid total volume is 1000L, pressure 1Mpa, temperature
25 DEG C, the extraordinary film separation system rate of recovery is designed as 75%, is tested, and obtained data are as shown in the table:
By upper Biao Ke get: it is respectively 4 times, 3 that the number of extraordinary film separation system is squeezed into concentrated water recycling again in embodiment 1-3
It is secondary, 5 times, account for the 93.14% of total salt amount, the total salt amount of the production water measured in embodiment 2 accounts for total salt amount in 8.475mol
84.75%, the total salt amount of production water that the total salt amount of production water measured in embodiment 1 measures in 9.314mol, embodiment 3 exists
9.931mol accounts for the 99.31% of total salt amount, as the number that extraordinary film separation system is squeezed into concentrated water recycling gradually increases,
The ratio that the salt amount recycled in production water accounts for total salt amount is gradually increasing, and has just reached 99.31% height time in embodiment 3
Yield；It can be obtained in conjunction with the total salt amount data of production water of comparative example 1,2,3,4, recycled with concentrated water and squeeze into special membrane segregative line again
The number of system increases, and salt always stays salt rate to rise rapidly in feed liquid, and tends towards stability at 5 times or more, is further added by recycling and repeats
When squeezing into process, the residual quantity of the salt in concentrated water and few, the energy and the energy mismatch with cost, it is not necessary that.To sum up
It can obtain, recycling and squeeze into the number of extraordinary film separation system again concentrated water is preferably 3-5 times, and in the numbers range, benefit
After being handled with sulfonated polyether sulfone seperation film and dye vat Liquid Residue resource utilization system provided by the invention raffinate, take off
Color effect is good, and salt ratio is stayed to be up to 80-99%, so that builder salts in raffinate etc. can obtain good recycling.
By sulfonated polyether sulfone seperation film obtained in the present embodiment 1-3 for the rejection of sodium sulphate, sodium chloride, sodium carbonate
It tests, detailed process is as follows for experiment:
Keep feed liquid into film flow be 600L/H, pressure 1Mpa, 25 DEG C of temperature, for each electrolyte ultrapure water
The solution that (conductivity be 2.5us/cm or so) is configured to different molar concentrations is tested, using conductivity meter measurement film into
Feed liquid conductivity (μ filter) and permeate conductivity (μ is saturating).According to apparent rejection formula R=1- (μ filter/μ is saturating), membrane is calculated
To rejection of the different electrolyte under various concentration.The data obtained is as shown in the table:
By upper Biao Ke get, with the increase of salt content in solution, sulfonated polyether sulfone separation obtained in the present embodiment 1-3
Film is gradually reduced the rejection of salt, and when salt content is higher, and this variation is rapider, and is gradually lowered to smaller
Rejection range, can concentration etc. increase salt concentration by way of so that salt overall in raffinate be in it is lower
Rejection is utilized again so that most of salt can have in the production water after decoloration.
It is put into the adsorption system of rear end after the large aperture adsorption resin of embodiment 1, comparative example 5-8 are film-made and carries out secondary take off
Color experiment, experiment condition are as follows:
Feed liquid formula is the mixed solution of Reactive Brilliant Blue KN-R and sodium sulphate, and wherein the mass fraction of sodium sulphate is 10%,
Mixed solution coloration is 50 degree.The flow for keeping feed liquid is 600L/H, pressure 1Mpa, 25 DEG C of temperature, adjusts PH=6.To implementation
Production water in example 1, comparative example 5-8 after the decoloration of rear end adsorption system carries out determination of colority, and utilizes titration measuring sulfuric acid
The mass fraction of sodium, obtained data are as shown in the table:
By upper Biao Ke get: large aperture adsorption resin obtained, D201 large aperture adsorption resin, the large aperture X-5 in embodiment 1
The final production water that absorption resin, NKA large aperture adsorption resin obtain after secondary decolourization to liquid meets coloration and is less than
20 degree of use standard, the absorbing film that could act as rear end adsorption system uses, but large aperture obtained in the present embodiment
The stronger for the decoloring ability of reactive dye of resin is adsorbed, and desalination rate is up to 98%, meets and water progress two is produced for raffinate
It decolourizes when secondary processing and stays the requirement of salt.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
1. a kind of dye vat Liquid Residue resource utilization method, which comprises the steps of:
S11, raffinate are collected；
S12, by raffinate filtering and impurity removing；
S13, it raffinate is passed through to extraordinary film separation system (4) obtains producing water and concentrated water；
S14, water reuse and concentrated water collection discharge are produced.
2. a kind of dye vat Liquid Residue resource utilization method according to claim 1, which is characterized in that the specific side of S12
Method includes: that raffinate is passed through cartridge filter (3) to be filtered, and the pore size filter of the cartridge filter (3) is 5 microns.
3. a kind of dye vat Liquid Residue resource utilization method according to claim 1, which is characterized in that the specific side of S13
Method includes: that raffinate filtered in S12 is passed through extraordinary film separation system (4), operating pressure 0.5- through high-pressure pump (22)
1Mpa, extraordinary film separation system (4) are more than or equal to 95% to the removal rate of coloration, and desalination rate is more than or equal to 50%.
4. a kind of dye vat Liquid Residue resource utilization method according to claim 1, which is characterized in that the tool of the S14
Body method includes:
S141, production water is squeezed into rear end adsorption system (6), carries out secondary decolourization, produces colority of water after secondary decolourization and be less than or equal to 20
Degree, absorption multiplying power are more than or equal to 100BV, will finally produce water and are back to dyeing course；
S142, concentrated water, which recycle and squeeze into extraordinary film separation system, is separated (4), is recycled and is squeezed into 3-5 times, then by concentrated water drainage
It puts.
5. a kind of dye vat Liquid Residue resource utilization system, which is characterized in that including be sequentially connected material liquid tank (1), first to
Water pump (21), cartridge filter (3), high-pressure pump (22) and extraordinary film separation system (4), the special type film separation system (4)
Front end be connected with concentrated water pipeline (71), the one end of the concentrated water pipeline (71) far from the extraordinary film separation system (4) is simultaneously
It is connected with reflux line (72) and discharge collection conduit (73), the reflux line (72) is connected to cartridge filter (3) and height
Between press pump (22)；The rear end of the special type film separation system (4) is connected with water production pipeline (74), and the water production pipeline (74) is remote
One end from extraordinary film separation system (4), which is connected in turn, produces pond (5), the second feed pump (23) and rear end adsorption system
(6), the rear end adsorption system (6) is connected with reuse pipeline (75).
6. a kind of dye vat Liquid Residue resource utilization system according to claim 5, which is characterized in that the high-pressure pump
(22) check valve (81), ball valve (82) and raffinate flowmeter (85), institute are disposed between extraordinary film separation system (4)
The conducting direction for stating check valve (81) is high-pressure pump (22) to ball valve (82) direction, the cartridge filter (3) and high-pressure pump
(22) first pressure gauge (83) are equipped between, are provided with second pressure gauge between the flowmeter and extraordinary film separation system (4)
(84), the reuse pipeline (75), discharge collection conduit (73), reflux line (72) and water production pipeline (74) are provided with and take
Sample mouth (9), the reflux line (72) are equipped with return flow meter (86), are provided with production water flow on the water production pipeline (74)
It counts (87), is provided with concentrated water flowmeter (88) on the discharge collection conduit (73).
7. a kind of dye vat Liquid Residue resource utilization system according to claim 5, which is characterized in that the special membrane point
It is sulfonated polyether sulfone seperation film from special membrane used in system, resin used in the rear end adsorption system is large aperture absorption tree
Rouge.
8. a kind of dye vat Liquid Residue resource utilization system according to claim 7, which is characterized in that the sulfonated polyether
Sulfone seperation film the preparation method comprises the following steps:
S21, resin-grade PES is taken to be added in the concentrated sulfuric acid that mass fraction is 98%, stirring and dissolving forms homogeneous solution at room temperature, then
Oleum is slowly added dropwise and stirs, precipitated with deionized water and reaction mixture is washed till PH=6-7, is done in 80 DEG C of baking ovens
It is dry to obtain sulfonated polyether sulfone；
S22, sulfonated polyether sulfone is dissolved in the mixed solution of NMP and NMF, is stirred evenly, be configured to 15wt% preparation liquid, cast
It forms a film on clean glass plate, drying for 24 hours, then at 100 DEG C is dried in vacuo for 24 hours at 60 DEG C, obtains sulfonated polyether sulfone seperation film.
9. a kind of dye vat Liquid Residue resource utilization system according to claim 7, which is characterized in that inhale the large aperture
The preparation method of attached resin includes:
S31,7 parts of the polystyrene-alt- maleic acid sodium salt solution by concentration for 2%, 110 parts of water mixing, stir and simultaneously add
Heat is heated to 70 DEG C of stopping heating, is passed through nitrogen 5 minutes；
S32, by mass fraction be 1-2% benzoyl peroxide 7 parts of addition S31 of 35 parts of styrene solution and divinylbenzene
Obtained in solution, stir and continue to be passed through nitrogen 5 minutes, be heated to 90 DEG C and react 2 hours；
S33, observation shape of particle and hardness is sampled with suction pipe within each 20 minutes after reaction 2 hours, when sampling, suction pipe is close to bottle
The slurries of sucking are put into the beaker for filling clear water by bottom, observe the sink-float of particle, if the bottom can be sunk to, take out particle with referring to
The soft or hard degree of the inspection particle of first pressure；
S34, it is to be observed be hardened to particle after be continuously heating to 95 DEG C of reaction half an hour, then stop heating, water-bath of going out stirring
Mix down be cooled to 50 DEG C suspension；
S35, suspension obtained in S34 is imported in 1000 parts of water, upper liquid of inclining simultaneously is washed with tap water and distilled water repeatedly
It washs for several times, filter and moves into filter cake in culture dish, absorption tree in large aperture is obtained after 3 hours dry in 50 DEG C of vacuum drying ovens
Rouge.
10. a kind of dye vat Liquid Residue resource utilization system according to claim 9, which is characterized in that the macropore
The regeneration method of diameter resin reproducible utilization, the large aperture resin specifically includes:
After S41, large aperture resin are packed into exchange column, with distilled water backwash large aperture resin layer, sheetage 50-70%, until out
Water is clear, odorlessness, without resin fine crushing until, then eluted at a slow speed with 10-15 times of volume of 50%-100% ethyl alcohol；
S42, after being all passed through, 4- is impregnated with 2m/h flow velocity by large aperture resin layer with the 4-5%HCl solution of about 2 times of volumes
8 hours, venting acid solution was rinsed to water outlet with clean water and is in neutrality, irrigation flow rate 10-20m/h；
S43, with the 2-5%NaOH solution of about 2 times of resin volumes, with 2m/h flow velocity by large aperture resin layer, after being all passed through,
It impregnates 4-8 hours, venting lye is rinsed to water outlet with clean water and is in neutrality, irrigation flow rate 10-20m/h；
S44, the large aperture resin of S32 and S33 two to after must regenerate three times is repeated.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113324585A (en) * | 2021-05-27 | 2021-08-31 | 苏州汇博龙环保科技有限公司 | Automatic online detection, color measurement and color matching instrument and method for recycling residual dyeing liquid |
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| CN113324585A (en) * | 2021-05-27 | 2021-08-31 | 苏州汇博龙环保科技有限公司 | Automatic online detection, color measurement and color matching instrument and method for recycling residual dyeing liquid |
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