CN107758939A - A kind of recycling standard discharge method of sodium alkali desulfurization liquid - Google Patents
A kind of recycling standard discharge method of sodium alkali desulfurization liquid Download PDFInfo
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- CN107758939A CN107758939A CN201610701771.2A CN201610701771A CN107758939A CN 107758939 A CN107758939 A CN 107758939A CN 201610701771 A CN201610701771 A CN 201610701771A CN 107758939 A CN107758939 A CN 107758939A
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- C02F1/22—Treatment of water, waste water, or sewage by freezing
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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
- 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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- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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Abstract
The present invention relates to a kind of recycling standard discharge method of sodium alkali desulfurization liquid.This method is the method for realizing sodium alkali desulfurization liquid recycling treatment using ceramic membrane filter+efficient electrodialysis concentration+freezing and crystallizing technology.The recycling treatment of the achievable sodium alkali desulfurization liquid of the present invention, on the basis of the suspension in effectively removing doctor solution, realize the recycling recovery of salt in sodium alkali desulfurization liquid, solve the problems, such as that the processing of sodium alkali desulfurization liquid is difficult in petroleum chemical enterprise, on the basis of qualified discharge, the recycling of petroleum chemical enterprise's wastewater with high concentration of sulfide is realized.The efficient electrodialysis cell fresh water formed after treated by the present method can direct qualified discharge, realize the standard discharge of sodium alkali desulfurization liquid, at the same it is treated by the present method after obtain sodium sulfate in high purity crystal salt, utilization of the recycling of renewable resources can be used as, realize recycling.
Description
Technical field
The present invention relates to field of industrial waste water treatment, specifically a kind of recycling standard discharge side of sodium alkali desulfurization liquid
Method.Espespecially using ceramic membrane filter+efficient electrodialysis concentration+freezing and crystallizing technical finesse petroleum chemical enterprise sodium alkali desulfurization liquid, make it
Qualified discharge and the processing method for realizing recycling.
Background technology
With the continuous development of society, the mankind continue to increase to the demand of the energy, and fossil fuel can produce in combustion
The polluters such as raw a large amount of SOx and NOx and dust, these materials, which are largely discharged into air, to cause serious atmosphere pollution.China
To SO2, NOx and particulate matter discharge have strict limitation, petro chemical industry pollutant emission standard (GB31571-2015)
It is required that SO2Less than 100mg/m3, NOXLess than 150mg/m3, particulate matter is less than 20mg/m3.At present, nearly all petroleum chemical enterprise urges
Change cracking unit and all establish flue gas desulphurization system.
The EDV wet scrubbing technologies of Belco companies exploitation are widely used by Domestic Petrochemical Enterprises, and the method can be removed effectively
Oxysulfide in flue gas, while produce substantial amounts of doctor solution.With petro chemical industry pollutant emission standard (GB31571-
2015) discharge of implementation, especially certain areas to brine waste has strict limitation, as Beijing require efflux wastewater in can
Soluble solids content is less than 1600mg/L, therefore high concentration saliferous doctor solution is present at discharge caused by EDV wet scrubbing technologies
The problem of reason, it has also become technology uses a problem of unit.
The processing cost of doctor solution is higher, in some Large Scale Petrochemical Enterprises, generally mixes doctor solution and other waste water
General wastewater treatment is used as after converting, though temporarily solving environmental issue, reusing sewage enterprise quality of reused water salt is easily caused and contains
The problem of amount gradually increases, it is difficult to realize the salt balance of enterprise.Some enterprises are also individually handled doctor solution, such as double using sodium calcium
Alkaline process, the circulation technology such as sodium alkali take in alkali back and forth, but cost and long-term operation constrain the popularization and application of such technology.
It is effective method using the supporting evaporation technique of dual-membrane process, patent 201510275955.2 uses nanofiltration
Desulfurization wastewater is handled with the embrane method group technology of counter-infiltration, then realizes salt using ion exchange, freezing and crystallizing and evaporation technology
The separation and recovery of class, but the technique is present that operating pressure is high, softening chemical feeding quantity is big, high energy consumption and system complex equipment are various
The problem of.Patent 201610038282.3 discloses a kind of power plant desulfurization wastewater processing system, nanofiltration, counter-infiltration and electric drive film
Combination, afterwards plus evaporative crystallization realizes the processing of desulfurization wastewater, but it is more processing unit to be present, the problem of flow complexity.Patent
201010232059.5, using bipolar membrane electrodialysis method processing sodium alkali flue gas desulfurization liquid, realize the zero-emission of doctor solution, but be somebody's turn to do
The problem of investment is high, energy consumption is big be present in system.
The content of the invention
For defect present in prior art, it is an object of the invention to provide a kind of recycling of sodium alkali desulfurization liquid to reach
The outer discharge method of mark, this method realize the recovery of salts resources in sodium alkali desulfurization liquid on the basis of effectively processing sodium alkali desulfurization liquid,
Solve the problems, such as sodium alkali desulfurization liquid suspension content height, high energy consumption in processing procedure, finally realize the resource of sodium alkali desulfurization liquid
Change standard discharge processing.It is treated by the present method after formed efficient electrodialysis fresh water can direct qualified discharge, realize sodium alkali desulfurization
The standard discharge of liquid, at the same it is treated by the present method after obtained high-purity sulfuric acid sodium salt, utilization of the recycling of renewable resources can be used as.
To achieve the above objectives, the present invention adopts the technical scheme that：
A kind of recycling standard discharge method of sodium alkali desulfurization liquid, comprises the following steps：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell；
3rd step, efficient electrodialysis cell concentrated water isolate crystal and mother liquor, efficient electrodialysis into freezing and crystallizing unit
Unit fresh water standard discharge or reuse；
The sodium sulfate crystal (i.e. high-purity sulfuric acid sodium salt) that crystal obtains after processing reaches Nacl standard.
On the basis of above-mentioned technical proposal, the main water quality characteristic of the sodium alkali desulfurization liquid is：
60000~80000mg/L of total dissolved solid,
1000~3000mg/L of suspension,
0~1mg/L of oil content,
Na+18000~30000mg/L,
Cl-100~150mg/L,
SO4 2-42000~50000mg/L,
0~30mg/L of COD,
Mg2+15~25mg/L,
Ca2+100~150mg/L,
Molten 2~6mg/L of silicon.
On the basis of above-mentioned technical proposal, in the first step, in ceramic membrane filter water outlet suspension content 1mg/L with
Under.
On the basis of above-mentioned technical proposal, in the first step, after the solid suspension collection solidification of ceramic membrane filter removing
Concentrate outward transport processing.
On the basis of above-mentioned technical proposal, in the first step, ceramic membrane filter core aperture that ceramic membrane filter is selected for 50~
150nm, filter pressure are 0.08~0.15MPa.
On the basis of above-mentioned technical proposal, in second step, efficient electrodialysis cell is divided into two-stage electrodialysis, using equal
Phase amberplex membrane stack, the water inlet of efficient electrodialysis cell are the electrodialytic water inlet of the first order, the electrodialytic concentrated water of the first order
For efficient electrodialysis cell concentrated water, the electrodialytic fresh water of the first order is the electrodialytic water inlet in the second level, and the second level is electrodialytic dense
Water is used as the electrodialytic water inlet of the first order after being mixed with the water inlet of efficient electrodialysis cell, and the electrodialytic fresh water in the second level is efficient
Electrodialysis cell fresh water.
On the basis of above-mentioned technical proposal,
The electrodialytic service condition of the first order is：
0.02~0.20m/s of crossflow velocity,
15~40mA/cm of current density2,
The electrodialytic concentrated water concentration of the first order is 150~260g/L,
The electrodialytic fresh water concentration of the first order is 7~15g/L；
The electrodialytic service condition in the second level is：
0.02~0.20m/s of crossflow velocity,
0.1~1.0V/ of voltage to film,
The electrodialytic concentrated water concentration in the second level is 60~80g/L,
The electrodialytic fresh water concentration in the second level is less than 1.6g/L, reaches outer row and requires that (such as Beijing requires can in efflux wastewater
Soluble solids content is less than 1600mg/L).
On the basis of above-mentioned technical proposal, in the 3rd step, the temperature of freezing and crystallizing unit is -2~-5 DEG C.
On the basis of above-mentioned technical proposal, in the 3rd step, it is more than 99.3% that crystal obtains purity after separation is dried
Sodium sulfate crystal, reach the class high-class product standard of industrial anhydrous sodium sulfate I.
On the basis of above-mentioned technical proposal, in the 3rd step, as Cl in mother liquor-When concentration is less than or equal to 40g/L, mother liquor
Efficient electrodialysis cell is reentered after being mixed with ceramic membrane filter water outlet；As Cl in mother liquor-When concentration is higher than 40g/L, collect
Mother liquor is disposed in addition.
Beneficial effects of the present invention are as follows：
The recycling standard discharge method of sodium alkali desulfurization liquid of the present invention, on the basis of effectively processing sodium alkali desulfurization liquid
On, the recovery of salts resources in sodium alkali desulfurization liquid is realized, solves sodium alkali desulfurization liquid suspension content height, energy consumption in processing procedure
The problem of high, finally realize the recycling standard discharge processing of sodium alkali desulfurization liquid.The efficient electric osmose formed after treated by the present method
Analyse unit fresh water can direct qualified discharge, realize the standard discharge of sodium alkali desulfurization liquid, at the same it is treated by the present method after obtained height
Purity sodium sulfate salt, utilization of the recycling of renewable resources can be used as.
Brief description of the drawings
The present invention has drawings described below：
Fig. 1 is the process chart of the present invention.
Embodiment
As shown in figure 1, the recycling standard discharge method of sodium alkali desulfurization liquid of the present invention, using " ceramic membrane filter+
Efficient electrodialysis concentration+freezing and crystallizing " technology path, comprises the following steps：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell；
3rd step, efficient electrodialysis cell concentrated water isolate crystal and mother liquor, efficient electrodialysis into freezing and crystallizing unit
Unit fresh water standard discharge or reuse；
The sodium sulfate crystal that crystal obtains after processing reaches Nacl standard.
On the basis of above-mentioned technical proposal, the main water quality characteristic of the sodium alkali desulfurization liquid is：
60000~80000mg/L of total dissolved solid,
1000~3000mg/L of suspension,
0~1mg/L of oil content,
Na+18000~30000mg/L,
Cl-100~150mg/L,
SO4 2-42000~50000mg/L,
0~30mg/L of COD,
Mg2+15~25mg/L,
Ca2+100~150mg/L,
Molten 2~6mg/L of silicon.
On the basis of above-mentioned technical proposal, in the first step, in ceramic membrane filter water outlet suspension content 1mg/L with
Under.
On the basis of above-mentioned technical proposal, in the first step, after the solid suspension collection solidification of ceramic membrane filter removing
Concentrate outward transport processing.
On the basis of above-mentioned technical proposal, in the first step, the ceramic membrane filter core aperture that the ceramic membrane filter is selected is
50~150nm, filter pressure are arranged to 0.08~0.15MPa.
On the basis of above-mentioned technical proposal, in second step, efficient electrodialysis cell is divided into two-stage electrodialysis, using equal
Phase amberplex membrane stack, the water inlet of efficient electrodialysis cell are the electrodialytic water inlet of the first order, the electrodialytic concentrated water of the first order
For efficient electrodialysis cell concentrated water, the electrodialytic fresh water of the first order is the electrodialytic water inlet in the second level, and the second level is electrodialytic dense
Water is used as the electrodialytic water inlet of the first order after being mixed with the water inlet of efficient electrodialysis cell, and the electrodialytic fresh water in the second level is efficient
Electrodialysis cell fresh water.
On the basis of above-mentioned technical proposal,
The electrodialytic service condition of the first order is：
0.02~0.20m/s of crossflow velocity,
15~40mA/cm of current density2,
The electrodialytic concentrated water concentration of the first order is 150~260g/L,
The electrodialytic fresh water concentration of the first order is 7~15g/L；
The electrodialytic service condition in the second level is：
0.02~0.20m/s of crossflow velocity,
0.1~1.0V/ of voltage to film,
The electrodialytic concentrated water concentration in the second level is 60~80g/L,
The electrodialytic fresh water concentration in the second level is less than 1.6g/L.
On the basis of above-mentioned technical proposal, in the 3rd step, the temperature of freezing and crystallizing unit is set as -2~-5 DEG C.
On the basis of above-mentioned technical proposal, in the 3rd step, it is more than 99.3% that crystal obtains purity after separation is dried
Sodium sulfate crystal, reach the class high-class product standard of industrial anhydrous sodium sulfate I.
On the basis of above-mentioned technical proposal, as Cl in mother liquor-When concentration is less than or equal to 40g/L, mother liquor and ceramic membrane
Efficient electrodialysis cell is reentered after filtering water outlet mixing；As Cl in mother liquor-When concentration is higher than 40g/L, mother liquor is collected in addition
Disposal.
The essential distinction of the present invention and prior art are：For the technological deficiency of prior art, the present invention is using pottery
Porcelain membrane filtration+efficient electrodialysis concentration+freezing and crystallizing technical finesse sodium alkali desulfurization liquid.By using the technology, soda is realized
The qualified discharge of doctor solution, while the salts resources in sodium alkali desulfurization liquid are recycled, realize its recycling treatment.
Compared to the prior art, technical equipment of the present invention is simple, operation maintenance is easy, strong environmental adaptability, desulfuration efficiency
High, achievable skid processing, Technical Economy are good.
Its advantage is：
1st, the present invention is compared, the present invention using ceramic membrane filter processing sodium alkali desulfurization liquid with sedimentation basin, secondary filter technology
The technical equipment that is related to is simple, automaticity is high, operation maintenance is easy, strong environmental adaptability, floor space are few, and ceramics
Film anti-pollution ability is strong, flux is big；The ceramic membrane filter that the present invention uses is particularly suitable for use in place and auxiliary facility haltingly
The sodium alkali desulfurization liquid processing in area；
2nd, the present invention uses efficient electrodialysis, can one-level sodium alkali desulfurization liquid is concentrated into more than 20%, disposal ability and effect
Rate is significantly better than that conventional electrodialysis, and operating cost substantially reduces；
3rd, the present invention, by the electrodialytic fresh water secondary concentration of the first order, is made whole using second level electrodialysis as supplement
Technological process is more perfect, improves overall desalting efficiency, reduces overall equipment investment and operating cost；
4th, the recycling treatment of sodium alkali desulfurization liquid is carried out using the method for the present invention, solves petroleum chemical enterprise's sodium alkali desulfurization liquid
The problem of difficult is handled, while realizes salts resources and waste liquid standard discharge.
It is some specific embodiments below.
Embodiment 1
The main water quality characteristic of sodium alkali desulfurization liquid is：Total dissolved solid 60000mg/L, suspension 1000mg/L, oil contain
Measure 0mg/L, Na+18000mg/L, Cl-100mg/L, SO4 2-42000mg/L, COD 0mg/L, Mg2+15mg/L, Ca2+100mg/L,
Molten silicon 2mg/L.
Processing step is as follows：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed, ceramic membrane filter selection
The ceramic membrane filter core in 50nm apertures, filter pressure are arranged to 0.08MPa, and the solid suspension content of ceramic membrane filter water outlet is
1.0mg/L；Outward transport processing is concentrated after the solid suspension that ceramic membrane filter is isolated collects solidification；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell, and efficient electrodialysis cell is divided into two-stage electricity
Dialysis, using homogeneous ion-exchange membrane membrane stack, the water inlet of efficient electrodialysis cell is the electrodialytic water inlet of the first order, the first order
Electrodialytic concentrated water is efficient electrodialysis cell concentrated water, and the electrodialytic fresh water of the first order is the electrodialytic water inlet in the second level, second
The electrodialytic concentrated water of level is used as the electrodialytic water inlet of the first order, second level electrodialysis after being mixed with the water inlet of efficient electrodialysis cell
Fresh water be efficient electrodialysis cell fresh water；
First order electrodialysis service condition is set as：Crossflow velocity 0.02m/s, current density 15mA/cm2；Second level electricity
Dialysis service condition is set as：Crossflow velocity 0.02m/s, voltage 0.1V/ is to film；The electrodialytic fresh water concentration of the first order is 7g/
L, the electrodialytic concentrated water concentration in the second level are 60/L, and efficient electrodialysis cell concentrated water (i.e. the electrodialytic concentrated water of the first order) concentration is
150g/L, efficient electrodialysis cell fresh water (i.e. the electrodialytic fresh water in the second level) concentration is 1.6g/L, meets discharge standard or returns
Use standard；
3rd step, efficient electrodialysis cell concentrated water enter freezing and crystallizing unit, efficient electrodialysis cell fresh water standard discharge；
Freezing and crystallizing unit isolates crystal and mother liquor, and freezing and crystallizing temperature is set as -2 DEG C, obtained sodium sulfate crystal
Purity reaches 99.3% after separation is dried, and reaches the class high-class product standard of industrial anhydrous sodium sulfate I；Mother liquor goes out with ceramic membrane filter
Efficient electrodialysis cell is reentered after water mixing, if Cl in mother liquor-When concentration is higher than 40g/L, collects mother liquor and dispose in addition.
Embodiment 2
The main water quality characteristic of sodium alkali desulfurization liquid is：Total dissolved solid 65000mg/L, suspension 1500mg/L, oil contain
Measure 0.3mg/L, Na+20000mg/L, Cl-120mg/L, SO4 2-45000mg/L, COD 10mg/L, Mg2+17mg/L, Ca2+
110mg/L, molten silicon 4mg/L.
Processing step is as follows：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed, ceramic membrane filter selection
The ceramic membrane filter core in 100nm apertures, filter pressure are arranged to 0.10MPa, and the solid suspension content of ceramic membrane filter water outlet is
0.7mg/L；Outward transport processing is concentrated after the solid suspension that ceramic membrane filter is isolated collects solidification；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell, and efficient electrodialysis cell is divided into two-stage electricity
Dialysis, using homogeneous ion-exchange membrane membrane stack, the water inlet of efficient electrodialysis cell is the electrodialytic water inlet of the first order, the first order
Electrodialytic concentrated water is efficient electrodialysis cell concentrated water, and the electrodialytic fresh water of the first order is the electrodialytic water inlet in the second level, second
The electrodialytic concentrated water of level is used as the electrodialytic water inlet of the first order, second level electrodialysis after being mixed with the water inlet of efficient electrodialysis cell
Fresh water be efficient electrodialysis cell fresh water；
First order electrodialysis service condition is set as：Crossflow velocity 0.05m/s, current density 25mA/cm2；Second level electricity
Dialysis service condition is set as：Crossflow velocity 0.05m/s, voltage 0.3V/ is to film；The electrodialytic fresh water concentration of the first order is 9g/
L, the electrodialytic concentrated water concentration in the second level are 65/L, and efficient electrodialysis cell concentrated water (i.e. the electrodialytic concentrated water of the first order) concentration is
170g/L, efficient electrodialysis cell fresh water (i.e. the electrodialytic fresh water in the second level) concentration is 1.2g/L, meets discharge standard or returns
Use standard；
3rd step, efficient electrodialysis cell concentrated water enter freezing and crystallizing unit, efficient electrodialysis cell fresh water standard discharge；
Freezing and crystallizing unit isolates crystal and mother liquor, and freezing and crystallizing temperature is set as -3 DEG C, obtained sodium sulfate crystal
Purity reaches 99.4% after separation is dried, and reaches the class high-class product standard of industrial anhydrous sodium sulfate I；
Mother liquor reenters efficient electrodialysis cell after being mixed with ceramic membrane filter water outlet, if Cl in mother liquor-Concentration is higher than
During 40g/L, collect mother liquor and dispose in addition.
Embodiment 3
The main water quality characteristic of sodium alkali desulfurization liquid is：Total dissolved solid 75000mg/L, suspension 2500mg/L, oil contain
Measure 0.8mg/L, Na+23000mg/L, Cl-140mg/L, SO4 2-52000mg/L, COD 20mg/L, Mg2+23mg/L, Ca2+
135mg/L, molten silicon 5mg/L.
Processing step is as follows：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed, ceramic membrane filter selection
The ceramic membrane filter core in 100nm apertures, filter pressure are arranged to 0.12MPa, and the solid suspension content of ceramic membrane filter water outlet is
0.8mg/L；Outward transport processing is concentrated after the solid suspension that ceramic membrane filter is isolated collects solidification；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell, and efficient electrodialysis cell is divided into two-stage electricity
Dialysis, using homogeneous ion-exchange membrane membrane stack, the water inlet of efficient electrodialysis cell is the electrodialytic water inlet of the first order, the first order
Electrodialytic concentrated water is efficient electrodialysis cell concentrated water, and the electrodialytic fresh water of the first order is the electrodialytic water inlet in the second level, second
The electrodialytic concentrated water of level is used as the electrodialytic water inlet of the first order, second level electrodialysis after being mixed with the water inlet of efficient electrodialysis cell
Fresh water be efficient electrodialysis cell fresh water；
First order electrodialysis service condition is set as：Crossflow velocity 0.09m/s, current density 34mA/cm2；Second level electricity
Dialysis service condition is set as：Crossflow velocity 0.09m/s, voltage 0.5V/ is to film；The electrodialytic fresh water concentration of the first order is 11g/
L, the electrodialytic concentrated water concentration in the second level are 75/L, and efficient electrodialysis cell concentrated water (i.e. the electrodialytic concentrated water of the first order) concentration is
200g/L, efficient electrodialysis cell fresh water (i.e. the electrodialytic fresh water in the second level) concentration is 0.9g/L, meets discharge standard or returns
Use standard；
3rd step, efficient electrodialysis cell concentrated water enter freezing and crystallizing unit, efficient electrodialysis cell fresh water standard discharge；
Freezing and crystallizing unit isolates crystal and mother liquor, and freezing and crystallizing temperature is set as -4 DEG C, obtained sodium sulfate crystal
Purity reaches 99.3% after separation is dried, and reaches the class high-class product standard of industrial anhydrous sodium sulfate I；
Mother liquor reenters efficient electrodialysis cell after being mixed with ceramic membrane filter water outlet, if Cl in mother liquor-Concentration is higher than
During 40g/L, collect mother liquor and dispose in addition.
Embodiment 4
The main water quality characteristic of sodium alkali desulfurization liquid is：Total dissolved solid 80000mg/L, suspension 3000mg/L, oil contain
Measure 1.0mg/L, Na+30000mg/L, Cl-150mg/L, SO4 2-50000mg/L, COD 30mg/L, Mg2+25mg/L, Ca2+
150mg/L, molten silicon 6.0mg/L.
Processing step is as follows：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed, ceramic membrane filter selection
The ceramic membrane filter core in 150nm apertures, filter pressure are arranged to 0.15MPa, and the solid suspension content of ceramic membrane filter water outlet is
0.9mg/L；Outward transport processing is concentrated after the solid suspension that ceramic membrane filter is isolated collects solidification；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell, and efficient electrodialysis cell is divided into two-stage electricity
Dialysis, using homogeneous ion-exchange membrane membrane stack, the water inlet of efficient electrodialysis cell is the electrodialytic water inlet of the first order, the first order
Electrodialytic concentrated water is efficient electrodialysis cell concentrated water, and the electrodialytic fresh water of the first order is the electrodialytic water inlet in the second level, second
The electrodialytic concentrated water of level is used as the electrodialytic water inlet of the first order, second level electrodialysis after being mixed with the water inlet of efficient electrodialysis cell
Fresh water be efficient electrodialysis cell fresh water；
First order electrodialysis service condition is set as：Crossflow velocity 0.20m/s, current density 40mA/cm2；Second level electricity
Dialysis service condition is set as：Crossflow velocity 0.20m/s, voltage 1.0V/ is to film；The concentration of the electrodialytic fresh water of the first order is
15g/L, the concentration of the electrodialytic concentrated water in the second level is 80/L, efficient electrodialysis cell concentrated water (i.e. the electrodialytic concentrated water of the first order)
Concentration is 260g/L, and efficient electrodialysis cell fresh water (the electrodialytic fresh water in the second level) concentration is 1.3g/L, meets discharge standard
Or reuse standard；
3rd step, efficient electrodialysis cell concentrated water enter freezing and crystallizing unit, efficient electrodialysis cell fresh water standard discharge；
Freezing and crystallizing unit isolates crystal and mother liquor, and freezing and crystallizing temperature is set as -5 DEG C, obtained sodium sulfate crystal
Purity reaches 99.5% after separation is dried, and reaches the class high-class product standard of industrial anhydrous sodium sulfate I；
Mother liquor reenters efficient electrodialysis cell after being mixed with ceramic membrane filter water outlet, if Cl in mother liquor-Concentration is higher than
During 40g/L, collect mother liquor and dispose in addition.
The preferable possible embodiments of the present invention are the foregoing is only, not thereby limit to the scope of the claims of the present invention, thus it is all
It is the equivalence changes made with description of the invention and accompanying drawing content, is both contained in protection scope of the present invention.
The content not being described in detail in this specification belongs to prior art known to professional and technical personnel in the field.
Claims (10)
1. a kind of recycling standard discharge method of sodium alkali desulfurization liquid, it is characterised in that comprise the following steps：
The first step, using ceramic membrane filter, the solid suspension in sodium alkali desulfurization liquid is removed；
Second step, ceramic membrane filter water outlet concentrate into efficient electrodialysis cell；
3rd step, efficient electrodialysis cell concentrated water isolate crystal and mother liquor, efficient electrodialysis cell into freezing and crystallizing unit
Fresh water standard discharge or reuse；
The sodium sulfate crystal that crystal obtains after processing reaches Nacl standard.
2. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that the sodium alkali desulfurization
The main water quality characteristic of liquid is：
60000~80000mg/L of total dissolved solid,
1000~3000mg/L of suspension,
0~1mg/L of oil content,
Na+18000~30000mg/L,
Cl-100~150mg/L,
SO4 2-42000~50000mg/L,
0~30mg/L of COD,
Mg2+15~25mg/L,
Ca2+100~150mg/L,
Molten 2~6mg/L of silicon.
3. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that in the first step, pottery
Suspension content is in below 1mg/L in porcelain film filtration effluent.
4. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that in the first step, pottery
The solid suspension of porcelain membrane filtration removing concentrates outward transport processing after collecting solidification.
5. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that in the first step, pottery
The ceramic membrane filter core aperture that porcelain membrane filtration is selected is 50~150nm, and filter pressure is 0.08~0.15MPa.
6. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that high in second step
Effect electrodialysis cell is divided into two-stage electrodialysis, and using homogeneous ion-exchange membrane membrane stack, the water inlet of efficient electrodialysis cell is the
The electrodialytic water inlet of one-level, the electrodialytic concentrated water of the first order are efficient electrodialysis cell concentrated water, and the electrodialytic fresh water of the first order is
The electrodialytic water inlet in the second level, the electrodialytic concentrated water in the second level are electric as the first order after being mixed with the water inlet of efficient electrodialysis cell
The water inlet of dialysis, the electrodialytic fresh water in the second level are efficient electrodialysis cell fresh water.
7. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 6, it is characterised in that
The electrodialytic service condition of the first order is：
0.02~0.20m/s of crossflow velocity,
15~40mA/cm of current density2,
The electrodialytic concentrated water concentration of the first order is 150~260g/L,
The electrodialytic fresh water concentration of the first order is 7~15g/L；
The electrodialytic service condition in the second level is：
0.02~0.20m/s of crossflow velocity,
0.1~1.0V/ of voltage to film,
The electrodialytic concentrated water concentration in the second level is 60~80g/L,
The electrodialytic fresh water concentration in the second level is less than 1.6g/L, reaches outer row and requires.
8. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that cold in the 3rd step
The temperature for freezing crystalline element is -2~-5 DEG C.
9. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that brilliant in the 3rd step
Body obtains the sodium sulfate crystal that purity is more than 99.3% after separation is dried.
10. the recycling standard discharge method of sodium alkali desulfurization liquid as claimed in claim 1, it is characterised in that in the 3rd step, when
Cl in mother liquor-When concentration is less than or equal to 40g/L, mother liquor reenters efficient electrodialysis list after being mixed with ceramic membrane filter water outlet
Member；
As Cl in mother liquor-When concentration is higher than 40g/L, collects mother liquor and dispose in addition.
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| CN113003826A (en) * | 2021-03-01 | 2021-06-22 | 新疆佳宇恒能源科技有限公司 | Harmless treatment method of desulfurization waste alkali liquor |
| CN114394712A (en) * | 2022-01-27 | 2022-04-26 | 安徽中科莘阳膜科技有限公司 | Integrated device and method for extracting high-purity mirabilite from white carbon black production wastewater |
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| CN114394712A (en) * | 2022-01-27 | 2022-04-26 | 安徽中科莘阳膜科技有限公司 | Integrated device and method for extracting high-purity mirabilite from white carbon black production wastewater |
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