CN109970232A - A kind of processing method and processing device of effluent brine - Google Patents
A kind of processing method and processing device of effluent brine Download PDFInfo
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- CN109970232A CN109970232A CN201711455266.5A CN201711455266A CN109970232A CN 109970232 A CN109970232 A CN 109970232A CN 201711455266 A CN201711455266 A CN 201711455266A CN 109970232 A CN109970232 A CN 109970232A
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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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- 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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- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- 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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C02F2001/007—Processes including a sedimentation step
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/131—Reverse-osmosis
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Abstract
The present invention provides a kind of processing method and processing device of abraum salt, this method comprises: selecting abraum salt waste water is raw material, calcium and magnesium ion is removed by adding medicine, then ceramic membrane filter is used, the clear liquid of filtering carries out advanced treating using resin, then monovalence is carried out using nanofiltration and divalent ion separates, be concentrated twice using reverse osmosis membrane and high pressure resistant reverse osmosis membrane, refined liquid is transformed into bronsted lowry acids and bases bronsted lowry solution by Bipolar Membrane by obtained final concentrate.Method described in through the invention handles abraum salt, compared with the conventional evaporation, produced soda acid can reuse, realize the resource utilization of abraum salt.
Description
Technical field
The present invention relates to a kind of processing method and processing devices of effluent brine, belong to abraum salt processing technology field.
Background technique
It is reported that China and the related average daily discharge amount of industry waste water of weaving be substantially at 500~5,500,000 tons, these enterprises
The textile of every 100 meters of processing, just can accordingly produce 3~4.5 tons of waste water.Unprocessed or processing is directly discharged into not up to standard
The waste water of rivers and lakes substantially has few hundred thousand tonnes of daily.Since the salt content of dyeing waste water is very high, TDS is likely to be breached 4000~
11000mg/L.If direct emission can make pollution of estuary, river water is caused to cannot be used for agricultural irrigation.
Currently, printing and dyeing enterprise generally uses ozone oxidation+biological aerated filter+multi-medium filtering+active carbon filtering+ultrafiltration
+ reverse osmosis treatment process can achieve recycle-water requirement, and the high-salt wastewater generated in processing uses " electrodialysis+mechanical vapour
The target of zero-emission may be implemented in Compression Evaporation (MVR) " technique.But evaporative crystallization route is used, not only processing cost is high, and steams
It sends out in obtained a large amount of solid waste and is mixed with solid sodium chloride, the processing for these sodium chloride waste residues, producer is usually will
It is buried or hazardous waste processing center is transferred to be handled that it transports to soot, but since the processing cost at fixed-end forces center is higher.
In addition, largely useless Nacl can be also generated, especially at many paper making wastewater zero discharges in paper industry
In science and engineering journey, reverse osmosis concentrated water can obtain mainly containing the useless of sodium chloride by way of evaporative crystallization after after post treatment
Salt, for example, patent CN105174587A provide slurrying tail water Treated sewage reusing technique of zero discharge method, use including pretreatment,
Membranous system, evaporative crystallization, pretreatment include cooling tower, homogeneous pond, mechanical accelerating purifying pool, manganese sand filter, ozone bioactivity
Carbon filtering pool, rapid filter, more medium filter, melded system, membranous system include ultrafiltration, reverse osmosis, electrodialytic integrated technique,
Middle evaporative crystallization includes evaporator, crystallizer, centrifuge, drying bed, obtains crystalline solid and takes out as industrial products.But this
Contain more divalent ion and organic pollutant in the useless sodium chloride salt of kind, is not easy to realize utilization again.
Salt is a kind of important industrial chemicals, and extremely valuable national strategy resource, if by physically or chemically
Method, mixing effluent brine is comprehensively utilized, not only can increase income for enterprise's save the cost, while chlorination can also be reduced
Pollution of the sodium waste residue to environment, to realize economy and the double profits of environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of processing method for mixing effluent brine, this method utilizes the collection of membrane technology and resin
At so that the mixing effluent brine that generates of printing and dyeing paper mill after processing reuse can be obtained, and realize the resource of salt in effluent brine
Change and utilize, is enterprise's save the cost, also pollution of the reduction waste residue to environment.
A kind of processing method of abraum salt, includes the following steps:
NaOH and Na is added in step 1 in the effluent brine for mainly containing NaCl2CO3Precipitation reaction is carried out to impurity cationic；
Step 2 carries out the salt water after step 1 precipitation reaction to be separated by solid-liquid separation removal precipitating；
Step 3 further removes impurity cationic by the way of resin desalination to the salt water that step 2 obtains；
Step 4 is filtered the resin clear liquid that step 3 obtains using nanofiltration membrane；
Step 5 successively uses reverse osmosis concentration, high pressure reverse osmosis concentration to the nanofiltration membrane clear liquid that step 4 obtains, after obtaining concentration
Purifying salt water.
In one embodiment, the effluent brine for mainly containing NaCl refers to from dyeing and papermaking row
The mixing of the effluent brine of industry.
In one embodiment, the effluent brine refers to the effluent brine obtained after abraum salt is dissolved in water.
In one embodiment, mainly contain in the effluent brine of NaCl and include: COD concentration is 60~200mg/L,
SO4 2-Concentration is 400~2000mg/L, Ca2+Concentration is 40~80mg/L, Mg2+Concentration is 30~50mg/L.
In one embodiment, it is Ca that impurity cationic, which is selected from,2+、Mg2+、Fe3+Or Si etc..
In one embodiment, NaOH adds concentration than precipitating the Mg in salt water completely2+Big 0.1~the 0.5g/ of concentration
L, Na2CO3Add concentration than precipitating the Ca in salt water completely2+Big 0.2~0.6g/L of concentration.
In one embodiment, the mode of the separation of solid and liquid is selected from centrifuge separation mode, expression separation mode, pottery
One of porcelain filter membrane separate mode, floating separate mode, sedimentation separation mode or several combinations；It is preferred that using ceramic filtering
Membrane separator is separated.
In one embodiment, ceramic filtration membrane separator is using ceramic super-filtering film, and average pore size is 20~
200nm, filtration temperature is at 50~80 DEG C, using cross-flow filtration mode, 1~6m/s of crossflow velocity, operating pressure 0.1~
0.6Mpa。
In one embodiment, the resin used in the step 2 is ion exchange resin.
In one embodiment, ion exchange resin refers to strongly acidic cation-exchange, more preferably sodium form sun
Ion exchange resin, 2~5BV/h of upper prop flow velocity.
In one embodiment, nanofiltration molecular cut off be 100~1000Da nanofiltration membrane, more preferably 200~
500Da；When using nanofiltration process, 1.5~4.0Mpa of operating pressure, 5~45 DEG C of operation temperature.
In one embodiment, osmosis filtration temperature is at 30~50 DEG C in step 5, operating pressure 2.0~4.0
Mpa；High pressure osmosis filtration temperature is at 30~50 DEG C, 8.0~10.0 Mpa of operating pressure, 2 times of high pressure reverse osmosis concentration.
In one embodiment, the purifying salt water that step 5 obtains by bipolar membrane electrodialysis treatment, obtain NaOH and
Cl2。
In one embodiment, bipolar membrane electrodialysis equipment is three cell structures of Bipolar Membrane, anode membrane and cavity block, is
Homogeneous membrane, Bipolar Membrane membrane stack voltage≤35V, electric current≤4.4A.
A kind of processing unit of effluent brine, comprising:
Precipitation tank in term, for carrying out precipitation reaction to the impurity cationic in effluent brine；
Precipitating reagent adds tank, makes impurity cationic that precipitation reaction occur for precipitating reagent to be added into precipitation tank in term；
Equipment for separating liquid from solid is connected to precipitation tank in term, for having carried out the removal precipitating of the material after precipitation reaction；
Ion exchange resin column is connected to equipment for separating liquid from solid, de- for carrying out ion-exchange to the clear liquid after separation of solid and liquid
Salt；
Nanofiltration membrane is connected to ion exchange resin column, for carrying out nanofiltration desalination to the material after ion exchange exchange process desalination；
Reverse osmosis membrane is connected to the per-meate side of nanofiltration membrane, for the clear liquid that nanofiltration membrane obtains to be concentrated；
High pressure reverse osmosis membrane is connected to the retention side of reverse osmosis membrane, and the concentrate for obtaining to reverse osmosis membrane is further concentrated.
In one embodiment, further includes: bipolar membrane electrodialysis device is connected to high pressure reverse osmosis membrane, for high pressure
Dope in reverse osmosis membrane carries out bipolar membrane electrodialysis treatment, obtains NaOH and HCl.
In one embodiment, the equipment for separating liquid from solid is selected from whizzer, expression separation device, ceramic filtration membrane
One of separator, floating separator, settlement separator or several combinations；It is preferred that using ceramic filtration membrane.
In one embodiment, the ceramic filtration membrane is ultrafiltration membrane, and average pore size is 20~200nm.
In one embodiment, that fills in ion exchange resin column refers to strongly acidic cation-exchange, more excellent
Choosing is sodium form cation exchange resin.
In one embodiment, the molecular cut off of the nanofiltration membrane is 100~1000Da, more preferably 200~
500Da。
It in one embodiment, include three cell structures of Bipolar Membrane, anode membrane and cavity block in bipolar membrane electrodialysis device,
For homogeneous membrane.
Beneficial effect
1) a kind of processing method for mixing effluent brine provided by the invention, treated, and water can achieve recycle-water requirement, and keep away
Exempt to handle the costly problem of subsequent waste water using electrodialysis and evaporation, and the solid slag after crystallization may be as danger
Great number processing cost problem caused by useless.2) a kind of processing method for mixing effluent brine provided by the invention, may be implemented abraum salt
The resource utilization of abraum salt in water, the alkali generated in technique can save dyer with direct reuse in the dyeing process of printing and dyeing
The dosage of sequence alkali, the acid of generation can be used for the processes such as dyeing waste water pH adjusting, resin regeneration.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the device of the invention figure.
Wherein, 1, precipitation tank in term；2, precipitating reagent adds tank；3, equipment for separating liquid from solid；4, ion exchange resin column；5, it receives
Filter membrane；6, reverse osmosis membrane；7, high pressure reverse osmosis membrane；8, bipolar membrane electrodialysis device.
Specific embodiment
Below by specific embodiment, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person described technology or conditions or carry out according to the literature in the art according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only including clearly enumerating as range in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as not only including clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Heretofore described percentage in the absence of special instructions,
Refer to weight percent.
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiments
Sign, structure or feature are also fallen in the application scope of the claimed.
Present invention effluent brine to be dealt with comes from the abraum salt of dyeing and paper industry, usually in dyeing
In the process, it needs to be added a large amount of inorganic salts and carries out assisting-dyeing processing, improve dyeing effect, but resulted in a large amount of inorganic salts
It resides in printing and dyeing waste liquid, dyeing waste water needs after biochemical treatment, concentration, has just obtained a large amount of printing and dyeing abraum salt or salt
Water, water quality characteristics are containing a large amount of inorganic salts (such as sodium chloride), and since the biodegradability of dyestuff is poor, these are useless
Also contain the compound of a large amount of bio-refractories in salt.For paper industry, a large amount of chlorine is also contained in paper waste
Change sodium, is passing through biochemical treatment, after concentration, also obtaining strong brine or abraum salt, more divalent is contained in these abraum salts
Salt ion, such as calcium, magnesium etc..Therefore, during processing, there is more technical difficulty for above-mentioned mixing abraum salt.
Above-mentioned effluent brine, either the strong brine directly obtained, is also possible to the abraum salt that crystallization obtains and adds water again
The salt water obtained after dissolution.
Processing method of the invention is:
Na is added in the mixing effluent brine of step 1, printing and dyeing and papermaking2CO3Metal cation impurity precipitate with NaOH anti-
It answers；
Step 2 carries out ultrafiltration to the effluent brine that step 1 obtains, can get rid of sediment therein, sediment is by concentration
Afterwards, it as industrial salty slurry, obtains that liquid and ultrafiltrated permeation liquid is concentrated by ultrafiltration after hyperfiltration treatment；
Step 3, ultrafiltrated permeation liquid are removed impurity cationic by ion exchange resin；
The permeate of step 4, ion exchange resin carries out a divalent and organic matter separation by nanofiltration, and nanofiltration clear liquid is mainly one
Valence solion；
The clear liquid of step 4, nanofiltration is concentrated using reverse osmosis membrane, obtains a concentrate, and clear liquid can be with direct reuse；
Step 5, concentrate are concentrated again by high pressure is reverse osmosis, obtain secondary concentration liquid, clear liquid can in step 4 clearly
Liquid mixing direct reuse；
Secondary concentration liquid is sent into bipolar membrane electrodialysis treatment, obtains NaOH solution and HCl solution, a small amount of NaOH is molten by step 7
Liquid send into step 1 reuse.Added NaOH need to only be added once before bipolar membrane electrodialysis treatment method, and required NaOH comes later
From the subsequent generation of bipolar membrane electrodialysis.
In the step 1 and step 6, impurity cationic is not Na+Ion, mainly Ca2+、Mg2+、Fe3+, Si etc..
In the step 1, include in the mixing effluent brine of printing and dyeing and papermaking: COD concentration is 60~200mg/L,
SO4 2-Concentration is 400~2000mg/L, Ca2+Concentration is 40~80mg/L, Mg2+Concentration is 30~50mg/L.
In one embodiment, in the step 1, NaOH's adds concentration than precipitating the Mg in salt water completely2+It is dense
Spend big 0.1~0.5g/L, Na2CO3Add concentration than precipitating the Ca in salt water completely2+Big 0.2~0.6g/L of concentration.
In one embodiment, in the step 2, the filter element of ultrafiltration is inorganic membrane element, and average pore size is
20~200nm, filtration temperature is at 50~80 DEG C, using cross-flow filtration mode, 1~6m/s of crossflow velocity, operating pressure 0.1~
0.6Mpa。
In one embodiment, in the step 3, nanofiltration molecular cut off is 100~1000Da nanofiltration membrane, more excellent
It is selected as 200~500Da；When using nanofiltration process, 1.5~4.0Mpa of operating pressure, 5~45 DEG C of operation temperature.
In one embodiment, in the step 4, osmosis filtration temperature at 30~50 DEG C, operating pressure 2.0~
4.0 Mpa。
In one embodiment, in the step 5, high pressure osmosis filtration temperature is at 30~50 DEG C, operating pressure
8.0~10.0 Mpa, 2 times of high pressure reverse osmosis concentration.
In one embodiment, in the step 6, ion exchange resin refers to strongly acidic cation-exchange,
More preferably sodium form cation exchange resin, 2~5BV/h of upper prop flow velocity.
In one embodiment, handled printing and dyeing abraum salt is by containing the chloro- 6- carboxyl acyl chloride quinoxaline activity of 2,3- bis-
Dyestuff dyed after the effluent brine that is obtained after biochemical treatment, ultrafiltration, reverse osmosis concentration of dyeing waste water；Contain in salt water
The chloro- 6- carboxyl acyl chloride quinoxaline of about 0.1~0.3wt%2,3- bis-, biochemical degradability is poor, and water-disintegrable difference is difficult.It uses
Processing method is that the method for first passing through Fe-C micro electrolysis is handled, can be with since Fe-C filler will form small primary battery
It is effectively facilitated the hydrolysis of acyl chlorides, generates carboxylic acid and hydrogen chloride, then carry out Fenton oxidation processing, at this time due to can be effective
Ground keeps acyl chlorides hydrolyzed, obtains in the case where electrolysis, the obtained hydrogen chloride of hydrolysis close waste water can be effective in acidity
Ground promotes the progress of Fenton oxidation, due to can also enter more Fe in salt water during Fe-C micro electrolysis2+And Fe3+From
Son, these ions can pass through charge balance Donnan effect in the Interception process of nanofiltration membrane, generate nanofiltration membrane to sodium chloride
Repulsive force improves nanofiltration membrane to the transmitance of sodium chloride；Meanwhile in the process of subsequent precipitation method removal impurity cationic
In, Fe2+And Fe3+Ion can generate floccule again, can be to preferably capture CaCO3With Mg (OH)2Precipitating is generated, precipitating is made
Grain becomes larger, and reduces the small particles of pollution of ceramic filtration membrane filtering, improves membrane flux.Furthermore it is possible to by bipolar membrane electrodialysis
Acidity is adjusted during being back to Fenton oxidation in obtained hydrochloric acid solution, realizes the overall coordination of front and back process section.
Based on above-mentioned method, device provided by the invention is as shown in Figure 2, comprising:
Precipitation tank in term 1, for carrying out precipitation reaction to the impurity cationic in effluent brine；
Precipitating reagent adds tank 2, makes impurity cationic that precipitation reaction occur for precipitating reagent to be added into precipitation tank in term 1；
Equipment for separating liquid from solid 3 is connected to precipitation tank in term 1, for having carried out the removal precipitating of the material after precipitation reaction；
Ion exchange resin column 4 is connected to equipment for separating liquid from solid 3, for carrying out ion-exchange to the clear liquid after separation of solid and liquid
Desalination；
Nanofiltration membrane 5 is connected to ion exchange resin column 4, removes for carrying out nanofiltration to the material after ion exchange exchange process desalination
Salt；
Reverse osmosis membrane 6 is connected to the per-meate side of nanofiltration membrane 5, and the clear liquid for obtaining to nanofiltration membrane 5 is concentrated；
High pressure reverse osmosis membrane 7, is connected to the retention side of reverse osmosis membrane 6, and the concentrate for obtaining to reverse osmosis membrane 5 is further dense
Contracting.
In one embodiment, further includes: bipolar membrane electrodialysis device 8 is connected to high pressure reverse osmosis membrane 7, for height
It presses the dope in reverse osmosis membrane 7 to carry out bipolar membrane electrodialysis treatment, obtains NaOH and HCl.
In one embodiment, the equipment for separating liquid from solid 3 is selected from whizzer, expression separation device, ceramic filtering
One of membrane separator, floating separator, settlement separator or several combinations；It is preferred that using ceramic filtration membrane.
In one embodiment, the ceramic filtration membrane is ultrafiltration membrane, and average pore size is 20~200nm.
In one embodiment, that fills in ion exchange resin column refers to strongly acidic cation-exchange, more excellent
Choosing is sodium form cation exchange resin.
In one embodiment, the molecular cut off of the nanofiltration membrane 5 is 100~1000Da, more preferably 200~
500Da。
It in one embodiment, include three cell structures of Bipolar Membrane, anode membrane and cavity block in bipolar membrane electrodialysis device 8,
It is homogeneous membrane.
Embodiment 1
Handled waste water is that the blue anthraquinone disperse dyestuff waste water of certain printing and dyeing mill is dense by biochemical, oxidation, film in the present embodiment
The mixing effluent brine that the effluent brine obtained after contracting and paper mill generate.Effluent brine water quality: ammonia nitrogen concentration average out to 1.06mg/L,
COD concentration is 164.5mg/L, sodium chloride content 1800mg/L, sulfate ion concentration 850mg/L, and calcium ion concentration is
65mg/L, magnesium ion concentration 50mg/L.
(1) mixing effluent brine is discharged into slurry pool, and adds agent mixing, reaction, NaOH containing sodium hydroxide and sodium carbonate
Add concentration than precipitating the Mg in salt water completely2+Concentration big 0.1g/L, Na2CO3Add concentration than completely precipitating salt water in
Ca2+And Ba2+The big 0.2g/L of concentration.Waste water after reaction enters ultrafiltration, and the ultrafiltration membrane of use is the pottery of average pore size 50nm
Porcelain film retains the suspended matters such as the magnesium hydroxide of generation and calcium carbonate, realizes and is separated by solid-liquid separation, ceramic membrane operational process stabilized flux
It is 243.4L/m2·h；
(2) ultrafiltrated permeation liquid carries out resin system, carries out the metal ions such as depth removing calcium and magnesium, exchanges using sodium form cation
Resin, upper prop flow velocity 3BV/h；
(3) permeate of ion exchange resin is carried out a divalent and organic matter separation, is controlled by valve by being pumped into nanofiltration system
Flow and pressure are operated, pressure control is in 2.0Mpa, and filtration temperature is 35 DEG C, and nanofiltration clear liquid is mainly monovalent ion solution, is received
Filter membrane is 88.4% to the transmitance of NaCl, and nanofiltration membrane operating flux is 27.4L/m3·h；
(4) clear liquid of nanofiltration is concentrated by being pumped into counter-infiltration system, by valve control operation flow and pressure, pressure control
In 3.0Mpa, filtration temperature is 35 DEG C, and reverse osmosis dope is a concentrate；
(5) one times concentrate is concentrated by being pumped into high pressure counter-infiltration system again, is concentrated 2 times, pressure is controlled in 9.0Mpa, mistake
Filtering temperature is 35 DEG C, is concentrated 2 times, the reverse osmosis dope of high pressure is secondary concentration liquid, and partial concentration obtains after condensing crystallizing
The sodium chloride for being 95.5wt% to purity；
(6) secondary concentration liquid carries out the processing of bipolar membrane electrodialysis equipment, obtains the sodium hydroxide and hydrochloric acid solution of 2mol/L, bipolar
80 mA/cm of membrane electrodialysis equipment membrance current intensity2。
Embodiment 2
Handled waste water is that the blue anthraquinone disperse dyestuff waste water of certain printing and dyeing mill is dense by biochemical, oxidation, film in the present embodiment
The mixing effluent brine that the effluent brine obtained after contracting and paper mill generate.Effluent brine water quality: ammonia nitrogen concentration average out to 1.06mg/L,
COD concentration is 164.5mg/L, sodium chloride content 1800mg/L, sulfate ion concentration 850mg/L, and calcium ion concentration is
65mg/L, magnesium ion concentration 50mg/L.
(1) mixing effluent brine is discharged into slurry pool, and adds agent mixing, reaction, NaOH containing sodium hydroxide and sodium carbonate
Add concentration than precipitating the Mg in salt water completely2+Concentration big 0.20g/L, Na2CO3Add concentration than completely precipitating salt water in
Ca2+And Ba2+The big 0.15g/L of concentration.Waste water after reaction enters ultrafiltration, and the ultrafiltration membrane of use is average pore size 50nm
Ceramic membrane retains the suspended matters such as the magnesium hydroxide of generation and calcium carbonate, realizes and is separated by solid-liquid separation, and ceramic membrane operational process is stablized logical
Amount is 221.8L/m2·h；
(2) ultrafiltrated permeation liquid carries out resin system, carries out the metal ions such as depth removing calcium and magnesium, exchanges using sodium form cation
Resin, upper prop flow velocity 4BV/h；
(3) permeate of ion exchange resin is carried out a divalent and organic matter separation, is controlled by valve by being pumped into nanofiltration system
Flow and pressure are operated, pressure control is in 2.5Mpa, and filtration temperature is 35 DEG C, and nanofiltration clear liquid is mainly monovalent ion solution, is received
Filter membrane is 89.3% to the transmitance of NaCl, and nanofiltration membrane operating flux is 28.5L/m3·h；
(4) clear liquid of nanofiltration is concentrated by being pumped into counter-infiltration system, by valve control operation flow and pressure, pressure control
In 3.0Mpa, filtration temperature is 35 DEG C, and reverse osmosis dope is a concentrate, clear liquid reuse；
(5) one times concentrate is concentrated by being pumped into high pressure counter-infiltration system again, is concentrated 2 times, pressure is controlled in 8.5Mpa, mistake
Filtering temperature is 35 DEG C, is concentrated 2 times, and the reverse osmosis dope of high pressure is secondary concentration liquid, partial concentration liquid after condensing crystallizing,
Obtain the sodium chloride that purity is 95.5wt%；
(6) secondary concentration liquid carries out the processing of bipolar membrane electrodialysis equipment, obtains the sodium hydroxide and hydrochloric acid solution of 2mol/L, bipolar
75 mA/cm of membrane electrodialysis equipment membrance current intensity2。
Embodiment 3
Handled waste water is that the chloro- 6- carboxyl acyl chloride quinoxaline active dye wastewater of 2,3- bis- of certain printing and dyeing mill passes through in the present embodiment
The mixing effluent brine that the effluent brine and paper mill obtained after biochemical, oxidation, film concentration generates.Effluent brine water quality: ammonia nitrogen concentration is flat
It is 1.55mg/L, COD concentration is 198.2mg/L, sodium chloride content 1950mg/L, sulfate ion concentration 1040mg/
L, calcium ion concentration 78mg/L, the chloro- 6- carboxyl acyl chloride quinoxaline of 2,3- bis- of magnesium ion concentration 65mg/L and 0.15wt%.
(1) mixing effluent brine is discharged into slurry pool, and adds agent mixing, reaction, NaOH containing sodium hydroxide and sodium carbonate
Add concentration than precipitating the Mg in salt water completely2+Concentration big 0.15g/L, Na2CO3Add concentration than completely precipitating salt water in
Ca2+And Ba2+The big 0.25g/L of concentration.Waste water after reaction enters ultrafiltration, and the ultrafiltration membrane of use is average pore size 50nm
Ceramic membrane retains the suspended matters such as the magnesium hydroxide of generation and calcium carbonate, realizes and is separated by solid-liquid separation, and ceramic membrane operational process is stablized logical
Amount is 186.3L/m2·h；
(2) ultrafiltrated permeation liquid carries out resin system, carries out the metal ions such as depth removing calcium and magnesium, exchanges using sodium form cation
Resin, upper prop flow velocity 2BV/h；
(3) permeate of ion exchange resin is carried out a divalent and organic matter separation, is controlled by valve by being pumped into nanofiltration system
Flow and pressure are operated, pressure control is in 2.0Mpa, and filtration temperature is 35 DEG C, and nanofiltration clear liquid is mainly monovalent ion solution, is received
Filter membrane is 86.6% to the transmitance of NaCl, and nanofiltration membrane operating flux is 18.7L/m3·h；
(4) clear liquid of nanofiltration is concentrated by being pumped into counter-infiltration system, by valve control operation flow and pressure, pressure control
In 3.0Mpa, filtration temperature is 35 DEG C, and reverse osmosis dope is a concentrate；
(5) one times concentrate is concentrated by being pumped into high pressure counter-infiltration system again, is concentrated 2 times, pressure is controlled in 9.0Mpa, mistake
Filtering temperature is 35 DEG C, is concentrated 2 times, the reverse osmosis dope of high pressure is secondary concentration liquid, and partial concentration obtains after condensing crystallizing
The sodium chloride for being 92.4wt% to purity；
(6) secondary concentration liquid carries out the processing of bipolar membrane electrodialysis equipment, obtains the sodium hydroxide and hydrochloric acid solution of 2mol/L, bipolar
80 mA/cm of membrane electrodialysis equipment membrance current intensity2。
Embodiment 4
Handled waste water is that the chloro- 6- carboxyl acyl chloride quinoxaline active dye wastewater of 2,3- bis- of certain printing and dyeing mill passes through in the present embodiment
The mixing effluent brine that the effluent brine and paper mill obtained after biochemical, oxidation, film concentration generates.Effluent brine water quality: ammonia nitrogen concentration is flat
It is 1.55mg/L, COD concentration is 198.2mg/L, sodium chloride content 1950mg/L, sulfate ion concentration 1040mg/
L, calcium ion concentration 78mg/L, the chloro- 6- carboxyl acyl chloride quinoxaline of 2,3- bis- of magnesium ion concentration 65mg/L and 0.15wt%.
(1) mixing effluent brine is discharged into slurry pool, is sent into Fe-C micro electrolysis tower and carries out microelectrolysis processing, temperature 30~32
DEG C, residence time 40min, then Fenton oxidation processing is carried out, control H2O2: FeSO4Molar ratio is 2:1, and hydrogen peroxide (30%) adds
Enter amount for 2%, reaction time 2h, precipitating reagent processing is added after processing in salt water, wherein the concentration that adds of NaOH is precipitated than complete
Mg in salt water2+Concentration big 0.15g/L, Na2CO3Add concentration than precipitating the Ca in salt water completely2+And Ba2+Concentration it is big
0.25g/L.Waste water after reaction enters ultrafiltration, and the ultrafiltration membrane of use is the ceramic membrane of average pore size 50nm, by the hydrogen-oxygen of generation
Change the retention of the suspended matters such as magnesium and calcium carbonate, realizes and be separated by solid-liquid separation, ceramic membrane operational process stabilized flux is 251.2L/m2·h；
(2) ultrafiltrated permeation liquid carries out resin system, carries out the metal ions such as depth removing calcium and magnesium, exchanges using sodium form cation
Resin, upper prop flow velocity 2BV/h；
(3) permeate of ion exchange resin is carried out a divalent and organic matter separation, is controlled by valve by being pumped into nanofiltration system
Flow and pressure are operated, pressure control is in 2.0Mpa, and filtration temperature is 35 DEG C, and nanofiltration clear liquid is mainly monovalent ion solution, is received
Filter membrane is 93.2% to the transmitance of NaCl, and nanofiltration membrane operating flux is 30.4L/m3·h；
(4) clear liquid of nanofiltration is concentrated by being pumped into counter-infiltration system, by valve control operation flow and pressure, pressure control
In 3.0Mpa, filtration temperature is 35 DEG C, and reverse osmosis dope is a concentrate；
(5) one times concentrate is concentrated by being pumped into high pressure counter-infiltration system again, is concentrated 2 times, pressure is controlled in 9.0Mpa, mistake
Filtering temperature is 35 DEG C, is concentrated 2 times, the reverse osmosis dope of high pressure is secondary concentration liquid, and partial concentration obtains after condensing crystallizing
The sodium chloride for being 96.3wt% to purity；
(6) secondary concentration liquid carries out the processing of bipolar membrane electrodialysis equipment, obtains the sodium hydroxide and hydrochloric acid solution of 2mol/L, bipolar
80 mA/cm of membrane electrodialysis equipment membrance current intensity2。
Claims (9)
1. a kind of processing method of abraum salt, which comprises the steps of:
NaOH and Na is added in step 1 in the effluent brine for mainly containing NaCl2CO3Precipitation reaction is carried out to impurity cationic；
Step 2 carries out the salt water after step 1 precipitation reaction to be separated by solid-liquid separation removal precipitating；
Step 3 further removes impurity cationic by the way of resin desalination to the salt water that step 2 obtains；
Step 4 is filtered the resin clear liquid that step 3 obtains using nanofiltration membrane；
Step 5 successively uses reverse osmosis concentration, high pressure reverse osmosis concentration to the nanofiltration membrane clear liquid that step 4 obtains, after obtaining concentration
Purifying salt water.
2. the processing method of abraum salt according to claim 1, which is characterized in that the effluent brine for mainly containing NaCl
Refer to the mixing of the effluent brine from dyeing and paper industry；The effluent brine refers to be obtained after abraum salt is dissolved in water
Effluent brine；Mainly contain in the effluent brine of NaCl and include: COD concentration is 60~200mg/L, SO4 2-Concentration be 400~
2000mg/L, Ca2+Concentration is 40~80mg/L, Mg2+Concentration is 30~50mg/L；It is Ca that impurity cationic, which is selected from,2+、Mg2+、Fe3 +Or Si etc..
3. the processing method of abraum salt according to claim 1, which is characterized in that NaOH's adds concentration than complete deposited salt
Mg in water2+Concentration big 0.1~0.5g/L, Na2CO3Add concentration than precipitating the Ca in salt water completely2+Concentration it is big by 0.2~
0.6g/L；The mode of the separation of solid and liquid be selected from centrifuge separation mode, expression separation mode, ceramic filtration membrane separate mode, on
One of floating separate mode, sedimentation separation mode or several combinations；It is preferred that being separated using ceramic filtration membrane separator；
For ceramic filtration membrane separator using ceramic super-filtering film, average pore size is 20~200nm, and filtration temperature is used at 50~80 DEG C
Cross-flow filtration mode, 1~6m/s of crossflow velocity, 0.1~0.6Mpa of operating pressure.
4. the processing method of abraum salt according to claim 1, which is characterized in that the resin used in the step 2 is
Ion exchange resin；Ion exchange resin refers to strongly acidic cation-exchange, more preferably sodium form cation exchange resin,
2~5BV/h of upper prop flow velocity.
5. the processing method of abraum salt according to claim 1, which is characterized in that nanofiltration molecular cut off be 100~
1000Da nanofiltration membrane, more preferably 200~500Da；When using nanofiltration process, 1.5~4.0Mpa of operating pressure, operation temperature
5~45 DEG C；Osmosis filtration temperature is at 30~50 DEG C in step 5,2.0~4.0 Mpa of operating pressure；High pressure osmosis filtration temperature
Degree is at 30~50 DEG C, 8.0~10.0 Mpa of operating pressure, 2 times of high pressure reverse osmosis concentration；The purifying salt water that step 5 obtains passes through
Bipolar membrane electrodialysis treatment obtains NaOH and HCl；Bipolar membrane electrodialysis equipment is that three rooms of Bipolar Membrane, anode membrane and cavity block are tied
Structure is homogeneous membrane, Bipolar Membrane membrane stack voltage≤35V, electric current≤4.4A.
6. a kind of processing unit of effluent brine characterized by comprising
Precipitation tank in term (1), for carrying out precipitation reaction to the impurity cationic in effluent brine；
Precipitating reagent adds tank (2), makes impurity cationic that precipitation reaction occur for precipitating reagent to be added into precipitation tank in term (1)；
Equipment for separating liquid from solid (3) is connected to precipitation tank in term (1), for having carried out the removal precipitating of the material after precipitation reaction；
Ion exchange resin column (4) is connected to equipment for separating liquid from solid (3), for carrying out ion friendship to the clear liquid after separation of solid and liquid
Change method desalination；
Nanofiltration membrane (5) is connected to ion exchange resin column (4), for receiving to the material after ion exchange exchange process desalination
Filter out salt；
Reverse osmosis membrane (6), is connected to the per-meate side of nanofiltration membrane (5), and the clear liquid for obtaining to nanofiltration membrane (5) is concentrated；
High pressure reverse osmosis membrane (7) is connected to the retention side of reverse osmosis membrane (6), and the concentrate for obtaining to reverse osmosis membrane (5) is into one
The concentration of step.
7. the processing unit of effluent brine according to claim 6, which is characterized in that further include: bipolar membrane electrodialysis device
(8), high pressure reverse osmosis membrane (7) are connected to, for carrying out bipolar membrane electrodialysis treatment to the dope in high pressure reverse osmosis membrane (7),
Obtain NaOH and HCl；The equipment for separating liquid from solid (3) be selected from whizzer, expression separation device, ceramic filtration membrane separator,
One of floating separator, settlement separator or several combinations；It is preferred that using ceramic filtration membrane；The ceramic filtration membrane is
Ultrafiltration membrane, average pore size are 20~200nm；That fills in ion exchange resin column (4) refers to strongly acidic cation-exchange,
More preferably sodium form cation exchange resin.
8. the processing unit of effluent brine according to claim 6, which is characterized in that the retention of the nanofiltration membrane (5) point
Son amount is 100~1000Da, more preferably 200~500Da.
9. the processing unit of effluent brine according to claim 6, which is characterized in that bipolar membrane electrodialysis device includes in (8)
Three cell structures of Bipolar Membrane, anode membrane and cavity block, are homogeneous membrane.
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