CN109231603A - The method and device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique - Google Patents
The method and device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique Download PDFInfo
- Publication number
- CN109231603A CN109231603A CN201811392351.6A CN201811392351A CN109231603A CN 109231603 A CN109231603 A CN 109231603A CN 201811392351 A CN201811392351 A CN 201811392351A CN 109231603 A CN109231603 A CN 109231603A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- freezing
- acid
- electrodialysis
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- 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
-
- 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
Abstract
The method and device of the invention discloses a kind of in cellulose viscose manufacturing technique cooperative disposal acid waste liquid, the characteristics of for acid waste liquid in viscose rayon industry, principle is utilized as with recycling, cooperate with its production technology, make full use of sulfuric acid, aluminum sulfate, the sulfuric acid zinc material in waste liquid, material balance new in system is established simultaneously, fully consider the heat in waste water, realize the low energy consumption high-recovery disposition of acid waste liquid, only have electrodialysis fresh water to be emitted into sewage treatment plant in spent acid disposing technique, the near-zero release of waste water is realized, Matter Transfer utilizes.
Description
Technical field
The present invention relates to a kind of sublevel resource recycle methods of valuable element in viscose rayon industry spinning waste liquid, can
The near-zero release for realizing waste water, belongs to utilization of wastewater resource field.
Background technique
Process that there are two viscose rayon productions mainly, first is that glue process, second is that spinning process.Become have one from viscose glue
The process for determining the regenerated cellulose strand of quality is completed by acid solidification acid bath.The component master of viscose rayon solidification
There are sulfuric acid, sodium sulphate, zinc sulfate, for the physical mechanical property of certain technique purposes and raising fiber, often in coagulating bath
A small amount of auxiliary agent containing aluminium is added.Therefore, this strand of waste water is a kind of highly acid high-salt wastewater, contains a large amount of sulfuric acid, sodium sulphate, sulfuric acid
Zinc, contains a certain amount of organic matter simultaneously, and water quality indicator is as shown in table 1.
1 waste water quality index of table
The content of sulfuric acid has reached 15000mg/L, about 1.5% in waste water it can be seen from the data in table 1；Sodium sulphate
Content is 45000mg/L, about 4.5%, secondly there are also a small amount of zinc sulfate and aluminum sulfate, total salt in waste water is divided into 6.8%, belongs to
In high slat-containing wastewater.In addition, there are also a certain amount of organic matter (main ingredient are cellulose sulfonate) in waste water, it can be to subsequent
Treatment process produces bigger effect.
Currently, the treatment process of viscose rayon filature wastewater is to mix the alkaline water generated in glue process, using one
Grade materialization+secondary biochemical treatment process, level-one materialization measure mainly have neutralization, aeration stripping, except the processes such as again, secondary biochemical
Mainly organic matter and other impurity elements are removed using the effect of microorganism.But prior art be primarily present it is following
Problem:
(1) a large amount of sulfuric acid resource is wasted, and consumes a large amount of alkali, treatment process is rough.In filature wastewater acid waste water with
After the alkaline waste water mixing of adhesive-preparing technology, waste water is still acid waste water, and pH is about 2-3, needs to consume a large amount of alkali for waste water
PH be adjusted to alkalinity, reach the basicity of removing heavy metals.In and during alkali tune, by a large amount of sulfuric acid in filature wastewater
Waste, consumes a large amount of alkali, has thereby resulted in the waste of resource and the increase of reagent cost, is a kind of thick mad environmental protection treatment
Technique.
(2) a large amount of waste residue is generated, dangerous waste cost of disposal is increased.Except weight the stage, mainly removal waste water in zinc and
Aluminium can generate a large amount of waste residue during recycling alkali precipitation, and the waste residue of generation is a kind of danger wastes, is needed according to danger
The processing standard of dangerous waste goes to dispose, costly, considerably increases the environmentally friendly cost of enterprise.
(3) salinity in waste water is exceeded, and biochemical process is unstable.Contain a large amount of salinity in filature wastewater, it is useless at two strands
Salinity is also higher after water mixing, can influence to microorganism it is very big, and microorganism is poor to the treatment effect of salinity, and country is to row
The increasingly tighter of the salt index control in waste water is put, causes the salinity in water outlet not up to standard.
(4) waste of sodium sulphate resource in waste water is caused.Contain a large amount of sodium sulphate in filature wastewater, content is up to
4.5%, waste water mixing biochemical treatment will cause into a large amount of wasting of resources, it also can the very big negative shadow of biochemical treatment generation
It rings.
(5) heat in waste water does not utilize, and causes to waste.The temperature of filature wastewater is and biochemical within the scope of 70-80 DEG C
The temperature of processing is needed in normal temperature condition, this partial heat does not make full use of, and causes the wasting of resources.
(6) during removing heavy metals, since the precipitating pH range of zinc is narrow (pH8-9), condition is difficult to control, and
Disturbing factor is more, and often the zinc in water outlet cannot be up to standard.
Summary of the invention
Technical problem: the present invention provides a kind of high recycling disposals of the low energy consumption for realizing acid waste liquid, meet sodium sulphate
The balance of salt avoids the accumulation of sodium sulfate salt in systems, establish spent acid disposition and production technology newly balance viscous
The method of cooperative disposal acid waste liquid in glue fiber production technology, only electrodialysis fresh water discharge in spent acid disposing technique, significantly
System energy consumption is reduced, realizes waste water near-zero release.The a kind of in viscose glue fibre of the above method is realized present invention simultaneously provides a kind of
The device of cooperative disposal acid waste liquid in terylene short fiber production technology.
Technical solution: the method for the cooperative disposal acid waste liquid of the invention in cellulose viscose manufacturing technique, including it is following
Step:
(1) by viscose rayon industry spinning acid waste liquid deliver into filter device (2) removal waste liquid in solid it is insoluble
Object；
(2) to step (1), treated, and waste liquid is evaporated concentration, obtain volume for former waste liquid volume 10%~
50% concentrate；
(3) by the concentrate that step (2) obtains and the acid recalled from the acid bath production process outlet in spinning production technology
Solution mixing is bathed, the sal glauberi crystal in mixed liquor is recycled by the way of freezing and crystallizing, while generating freezing raffinate；
(4) electrodialysis is carried out to the freezing raffinate that step (3) freezing and crystallizing generates, the organic matter in removal freezing raffinate,
Simultaneously the sal glauberi crystal of step (3) recycling is carried out being refining to obtain anhydrous sodium sulfate；
(5) acid bath apparatus by the NF concentrated water reuse obtained after step (4) electrodialysis process into spinning production technology.
Further, the reception in the method for the present invention, in the electrodialysis of step (4), using pure water as electrodialysis fresh water
The volume ratio of liquid, freezing raffinate and pure water receiving liquid is 1:(2~5), when salinity in the fresh water of electrodialysis plant generation and concentrated water
Ratio be 1:(5~15) when, complete electrodialysis removal organic matter work.
Further, in the method for the present invention, in the step (3), the acid bath solution recalled is exported from acid bath production process
Water is freeze raffinate water 10~30%.
Further, in the method for the present invention, the acid bath solution quality in the acid bath apparatus is freezing raffinate quality
20%.
Further, in the method for the present invention, it is the dense of former waste liquid volume 15%~30% that volume is obtained in the step (2)
Contracting liquid.
Further, in the method for the present invention, the freezing and crystallizing in the step (3) is using two-stage cooling freezing: the first order
The temperature of concentrate is reduced to 40~50 degrees Celsius by 75~100 degrees Celsius by freezing and crystallizing, and is stablized under the conditions of the temperature
20~60min；Temperature is reduced to -10~0 degree Celsius by 40~50 degrees Celsius by second level freezing and crystallizing, and in the temperature condition
Under stablize 20~60min, by be separated by solid-liquid separation, obtain sal glauberi crystal.
Further, in the method for the present invention, acid bath apparatus of the reuse into spinning production technology is cold in the step (3)
Freeze raffinate and meet following reuse standard:
| Sulfuric acid (g/L) | Zinc sulfate (g/L) | Aluminum sulfate (g/L) |
| 115-120 | ≥7.5 | ≥2.5 |
Further, in the method for the present invention, the filter device (2) in the step (1) uses accurate filter.
A kind of device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique of the invention, including it is sequentially connected
Filter device (2), evaporation concentration device (4), freezing and crystallizing device (5), the electricity being connect respectively with the freezing and crystallizing device (5)
Electrodialysis system (3) and refining system (1), the import of freezing and crystallizing device (5) and the acid bath production process in spinning production technology
The concentrated water outlet of outlet connection, the electrodialysis system (3) is connect with the acid bath production process import in spinning production technology.
Further, in apparatus of the present invention, the electrodialysis plant (3) is arranged in series two-stage or two-stage or more.
In a kind of embodiment of the method for the present invention, comprising the following steps:
For step (1) viscose rayon industry spinning waste liquid temperature within the scope of 70~80 DEG C, waste liquid enters accurate filter, goes
Except the solid insoluble in waste liquid；
In preferred embodiment, the filtering accuracy of accurate filter is 5 μm；
Step (2) takes the water outlet of step (1) accurate filter to enter evaporation concentration device, and the temperature control of evaporation and concentration exists
75-100 degrees Celsius, when the volume of evaporation concentrated solution is the 10%~50% of former waste liquid volume, into subsequent processing；
In preferred embodiment, the volume of evaporation concentrated solution is the 15%~30% of former waste liquid volume；
Step (3) takes the evaporation concentrated solution of step (2) to enter freezing and crystallizing device, and it is cold that evaporation concentrated solution is divided into two-stage cooling
Freeze recycling crystal, avoids equipment blocking.The temperature of concentrate is reduced to by first order freezing and crystallizing by 75~100 degrees Celsius
40~50 degrees Celsius, and stablize 20~60min under the conditions of the temperature；Second level freezing and crystallizing is by temperature by 40~50 degrees Celsius
It is reduced to -10~0 degree Celsius, and stablizes 20~60min under the conditions of the temperature, by being separated by solid-liquid separation, obtains sal glauberi
Crystal and freezing raffinate；
In preferred embodiment, solid-liquid separation method is centrifuge separation；
In preferred embodiment, collect refrigeration crystallization process in heat exchange heat to evaporation concentration device or (and) sodium sulphate essence
Device processed；
The freezing raffinate that step (4) takes step (3) freezing and crystallizing device to generate enters electrodialysis plant, electrodialysis plant
Main function is the organic matter in removal freezing raffinate, causes to have in production technology after avoiding freezing residual liquid recycling to production technology
The enrichment of machine object eventually leads to the paralysis of production technology.In freezing raffinate when by electrodialysis plant, use pure water for electric osmose
The receiving liquid of fresh water is analysed, the volume ratio for freezing raffinate and pure water receiving liquid is 1:(2~5), when the fresh water that electrodialysis plant generates
Be 1:(5~15 with the ratio of salinity in concentrated water) when (can be characterized with conductivity), complete the work of electrodialysis separation organic matter.
Fresh water (being rich in organic matter) is delivered to the Sewage Disposal processing of on-site after electrodialysis plant processing, and concentrated water (is rich in sulfuric acid, sulphur
The salinities such as sour sodium, zinc sulfate) recycled to acid bath apparatus import, made full use of in acid bath apparatus sulfuric acid in concentrated water,
The resources such as sodium sulphate, zinc sulfate realize the purpose of resource utilization in waste liquid；
In preferred embodiment, two-stage or more is arranged in electrodialysis plant；
In preferred embodiment, the fresh water of the generation of electrodialysis plant carries out Treated sewage reusing after Sewage Disposal is handled；
The sal glauberi crystal that step (5) takes step (3) freezing and crystallizing device to generate, using 50-70 degree celsius temperature
Under the cleaning of sodium sulphate saturated solution, according to sal glauberi crystal (moisture content is 70~90%) and be saturated metabisulfite solution
Mass volume ratio is 1:(1~5) mixing, sodium hydroxide is added and is adjusted to neutrality solution, 30~60min of stirring and washing, solid-liquid
Separation, crystal obtain the anhydrous sodium sulfate of Product-level (reaching a kind of Grade A purity) by baking process, and saturation cleaning solution returns
With to freezing and crystallizing process；
In preferred embodiment, sodium sulphate process for refining uses two-stage cleaning process, cleans according to same cleaning way
Twice；
In preferred embodiment, the saturation sodium sulfate crystal after cleaning can reuse in batches；
In preferred embodiment, pure water dissolution+neutralization precipitation+evaporative crystallization mode is can also be used in sodium sulphate process for refining
Obtain anhydrous sodium sulfate；
Step (6) takes the acid bath solution in acid bath apparatus exit to call to freezing and crystallizing device, calls acid bath exit acid
Bath solution water be freeze raffinate 10-30%, with realize the sodium sulfate salt in whole system balance, it is ensured that whole system it is steady
Fixed operation.
The present invention is directed to the characteristics of acid waste liquid in viscose rayon industry, is utilized as principle with recycling, cooperates with its life
Production. art makes full use of sulfuric acid, sodium sulphate, sulfuric acid zinc material in waste liquid, while establishing material balance new in system, sufficiently
Consider the heat in waste water, realizes the high recycling disposal of the low energy consumption of acid waste liquid, there was only electrodialysis fresh water in spent acid disposing technique
It is emitted into sewage treatment plant, realizes the near-zero release of waste water.
The utility model has the advantages that compared with prior art, the present invention having the advantage that
1, processing technique of the invention makes full use of wastewater characteristics, greatly reduces system energy consumption.The water outlet of acid waste liquid
Temperature is 70~80 degrees Celsius, and usually between 70~100 degrees Celsius, the technology of the present invention makes full use of out the temperature of evaporative crystallization
The heat of water, is directly entered vapo(u)rization system, and the zero calory supply in evaporation process almost may be implemented, substantially reduce and be processed into
This, realizes energy conservation disposition truly.
2, the present invention combines production technology, and cooperative achievement resource maximally utilizes.In cellulose viscose manufacturing technique, acid
Bathing process is a critically important process, needs that a large amount of sulfuric acid, sodium sulphate, zinc sulfate and aluminum sulfate is added in acid bath process
Medicament, to realize the purpose of acid bath.In the present invention, freezing raffinate is after electrodialysis plant removes organic matter, sulfuric acid, sulfuric acid
Zinc, aluminum sulfate concentration reached the reuse standard of acid bath process in production technology.Organic matter is a kind of for acid bath process
Unnecessary substance, if bringing organic matter into freezing raffinate will cause the enrichment of acid bath process organic matter, organic matter tires out for a long time
Product can generate irreversible influence to production technology.Therefore, freezing residual night can direct reuse after electrodialysis removes organic matter
To acid bath process, maximally utilizing for recycling is realized.
3, the technology of the present invention establishes spent acid disposition and the material of production technology newly balances.In the present invention, freezing raffinate is returned
It uses in the acid bath process in production technology, the small part sodium sulphate freezed in raffinate can be taken back, in order to guarantee at acid pickle
The balance of sodium sulfate salt during reason, needs to recall a part of acid bath solution from acid bath process exit to freezing and crystallizing system,
To meet the balance of sodium sulfate salt, while the accumulation of sodium sulfate salt in systems is also avoided, establishes spent acid disposition and production
The new balance of technique has significant innovative.
4, what the present invention was innovative removes useless Organic substance in water using electrodialysis plant, and it is rich in system to avoid organic matter
Collection.In existing film device, ultrafiltration membrane, reverse osmosis membrane using the principle separation fresh water and concentrated water intercepted, therefore in concentrated water containing from
Alite point and organic matter are very high, fresh water can Treated sewage reusing, salinity and organic matter do not separate；And the charge that electrodialytic membranes utilizes
Shifting principle separates salinity and organic matter, and the low organic matter of salinity is high in the fresh water of generation, meets the flow condition of biochemical treatment,
The high organic concentration of salinity is low in concentrated water, realizes the separation of salinity and organic matter.
5, present invention process recycles crystals of sodium salt using process for freezing and crystallizing.In viscose rayon industry, it is general to recycle sodium salt
By the way of direct evaporative crystallization, this mode substantially reduces the purity of recycling sodium salt, because of the content of organics in waste water
More, directly evaporation will cause in the organic matter entrainment crystals of sodium salt of the overwhelming majority, and purity and quality to sodium salt generate very
It is big to influence, and the water evaporated is larger.And sodium salt is recycled by the way of freezing and crystallizing in the present invention, it can effectively shield organic
The interference of object, the decrease temperature crystalline in the lesser situation of cycles of concentration, significantly reduces the entrainment of organic matter, improves the quality of sodium salt.
Simultaneously as the sal glauberi that decrease temperature crystalline is precipitated, takes 10 crystallizations water out of, can considerably reduce the water of evaporative crystallization
Amount.Therefore, crystal is improved while the water by reducing evaporative crystallization by the novelty of technique in present invention process
Purity is innovative very significant.
Detailed description of the invention
Fig. 1 is the process flow chart of the method for the present invention.
Have in figure: 1-refining system；2-filter devices；3-electrodialysis systems；4-evaporation concentration devices；5-freezings
Crystallization apparatus.
Specific embodiment
Below with reference to embodiment and Figure of description, the present invention is further illustrated.
Embodiment 1
(1) the spinning acid waste liquid of certain viscose rayon company is taken to be tested, the Raw performance of acid waste liquid such as table 1-1
It is shown.
Table 1-1 original waste liquid achievement data
The sodium sulphate content highest in waste liquid it can be seen from the data in table, it is dense at concentrations up to being 5%, followed by sulfuric acid
Degree has reached 1.5%, and zinc sulfate and sulfuric acid aluminium content are lower, and the concentration of sum of the two reaches 0.13%, the concentration of organic matter compared with
Height is 2000ppm, and long-term enrichment can generate irreversible influence to acidic treatment and production technology.
(2) it takes 5000ml acid waste liquid to enter accurate filter, removes the solid matter in waste liquid；
(3) water outlet of 5000ml accurate filter is taken to enter Rotary Evaporators, evaporating temperature is 85 degrees Celsius, works as evaporation and concentration
When the volume of liquid is 500ml (volume of concentrate be former waste liquid volume 10%), stop evaporation；
(4) acid bath process outlet solution 50ml in evaporation concentrated solution 500ml and production technology is taken (to freeze raffinate water for reuse
The 20% of amount) it mixes, the total 550ml of mixed liquor, freezing and crystallizing is carried out, the first stage is cooled to 40 degrees Celsius, and at 40 degrees Celsius
At a temperature of maintain 20min；Second stage is cooled to 0 degree Celsius, and maintains temperature 20min, and solid-liquid is mixed and is centrifugated,
Obtain sal glauberi crystal and freezing raffinate；
(5) the freezing raffinate 500ml of step (4) is taken to enter electrodialysis plant, it is (cold as absorbing liquid using 1000ml pure water
The volume ratio for freezing raffinate and pure water receiving liquid is 1:2), when the electrical conductivity ratio in the conductivity and concentrated water in fresh water is 1:5,
Complete the process.Electrodialysis fresh water (about 1250ml) is discharged into the processing of sewage treatment plant of plant area, electrodialysis concentrated water (about 250ml) reuse
Acid bath process into production technology；
(6) the sal glauberi crystal 25g (weight in wet base, moisture content 80%) in step (4) is taken to be dissolved in 50ml saturation sulphur
In sour sodium, solution temperature maintains 60 degrees Celsius, and the pH to 8.23 or so that sodium hydroxide solution adjusts solidliquid mixture is added,
30min is stirred, centrifuge separation, by solid again in 50ml saturation sodium sulphate, solution temperature maintains 60 degrees Celsius, stirs again
30min is mixed, is centrifugated, solid obtains the purity of a kind of Grade A in anhydrous sodium sulfate industrial goods standard by drying.
Detection data in experimental procedure is as shown in table 1-2.
The index concentration of water sample in table 1-2 various processes
The purity detecting index of the anhydrous slufuric acid sodium crystal of recycling is as shown in table 1-3.
Table 1-3 anhydrous sodium sulfate crystal purity achievement data and relevant criterion
Unit: %, pH dimensionless
Embodiment 2
(1) the spinning acid waste liquid of certain viscose rayon company is taken to be tested, the Raw performance of acid waste liquid such as table 2-1
It is shown.
Table 2-1 original waste liquid achievement data
The sodium sulphate content highest in waste liquid it can be seen from the data in table, it is dense at concentrations up to being 5%, followed by sulfuric acid
Degree has reached 1.5%, and zinc sulfate and sulfuric acid aluminium content are lower, and the concentration of sum of the two reaches 0.13%, the concentration of organic matter compared with
Height is 2000ppm, and long-term enrichment can generate irreversible influence to acidic treatment and production technology.
(2) it takes 5000ml acid waste liquid to enter accurate filter, removes the solid matter in waste liquid；
(3) water outlet of 5000ml accurate filter is taken to enter Rotary Evaporators, evaporating temperature is 95 degrees Celsius, works as evaporation and concentration
When the volume of liquid is 750ml (volume of concentrate be former waste liquid volume 15%), stop evaporation；
(4) acid bath process outlet solution 70ml in evaporation concentrated solution 750ml and production technology is taken (to freeze raffinate water for reuse
The 20% of amount) it mixes, the total 820ml of mixed liquor, freezing and crystallizing is carried out, the first stage is cooled to 50 degrees Celsius, and at 50 degrees Celsius
At a temperature of maintain 60min；Second stage is cooled to -5 degrees Celsius, and maintains temperature 60min, and solid-liquid is mixed centrifugation point
From, obtain sal glauberi crystal and freezing raffinate；
(5) the freezing raffinate 700ml of step (4) is taken to enter electrodialysis plant, it is (cold as absorbing liquid using 2100ml pure water
The volume ratio for freezing raffinate and pure water receiving liquid is 1:3), when the electrical conductivity ratio in the conductivity and concentrated water in fresh water is 1:7,
Complete the process.Electrodialysis fresh water (about 2450ml) is discharged into the processing of sewage treatment plant of plant area, electrodialysis concentrated water (about 350ml) reuse
Acid bath process into production technology；
(6) the sal glauberi crystal 50g (weight in wet base, moisture content 80%) in step (4) is taken to be dissolved in 75ml saturation sulphur
In sour sodium, solution temperature maintains 70 degrees Celsius, and the pH to 7.86 that sodium hydroxide solution adjusts solidliquid mixture is added, stirring
60min, centrifuge separation, by solid again in 75ml saturation sodium sulphate, solution temperature maintains 70 degrees Celsius, is again stirring for
60min, centrifuge separation, solid obtain the purity of a kind of Grade A in anhydrous sodium sulfate industrial goods standard by drying.
Detection data in experimental procedure is as shown in table 2-2.
The index concentration of water sample in table 2-2 various processes
The purity detecting index of the anhydrous slufuric acid sodium crystal of recycling is as shown in table 2-3.
Table 2-3 anhydrous sodium sulfate crystal purity achievement data and relevant criterion
Unit: %, pH dimensionless
Embodiment 3
(1) the spinning acid waste liquid of certain viscose rayon company is taken to be tested, the Raw performance of acid waste liquid such as table 3-1
It is shown.
Table 3-1 original waste liquid achievement data
The sodium sulphate content highest in waste liquid it can be seen from the data in table, it is dense at concentrations up to being 5%, followed by sulfuric acid
Degree has reached 1.5%, and zinc sulfate and sulfuric acid aluminium content are lower, and the concentration of sum of the two reaches 0.13%, the concentration of organic matter compared with
Height is 2000ppm, and long-term enrichment can generate irreversible influence to acidic treatment and production technology.
(2) it takes 5000ml acid waste liquid to enter accurate filter, removes the solid matter in waste liquid；
(3) water outlet of 5000ml accurate filter is taken to enter Rotary Evaporators, evaporating temperature is 100 degrees Celsius, dense when evaporating
When the volume of contracting liquid is 1500ml (volume of concentrate be former waste liquid volume 30%), stop evaporation；
(4) acid bath process outlet solution 80ml in evaporation concentrated solution 1500ml and production technology is taken (to freeze raffinate for reuse
The 30% of water) it mixes, the total 1580ml of mixed liquor, freezing and crystallizing is carried out, the first stage is cooled to 45 degrees Celsius, and Celsius 45
45min is maintained at a temperature of degree；Second stage is cooled to -10 degrees Celsius, and maintains temperature 20min, and solid-liquid is mixed and is centrifuged
Separation obtains sal glauberi crystal and freezing raffinate；
(5) the freezing raffinate 700ml of step (4) is taken to enter electrodialysis plant, it is (cold as absorbing liquid using 3500ml pure water
The volume ratio for freezing raffinate and pure water receiving liquid is 1:5), when the electrical conductivity ratio in the conductivity and concentrated water in fresh water is 1:15
When, complete the process.Electrodialysis fresh water (about 3935ml) is discharged into the processing of sewage treatment plant of plant area, electrodialysis concentrated water (about 265ml)
Acid bath process of the reuse into production technology；
(6) the sal glauberi crystal 50g (weight in wet base) in step (4) is taken to be dissolved in 50ml saturation sodium sulphate, solution temperature
Degree maintains 50 degrees Celsius, and the pH to 7.86 that sodium hydroxide solution adjusts solidliquid mixture is added, and stirs 60min, centrifugation point
From by solid again in 50ml saturation sodium sulphate, solution temperature maintains 60 degrees Celsius, is again stirring for 30min, centrifugation point
From solid obtains the purity of a kind of Grade A in anhydrous sodium sulfate industrial goods standard by drying.
Detection data in experimental procedure is as shown in table 3-2.
The index concentration of water sample in table 3-2 various processes
The purity detecting index of the anhydrous slufuric acid sodium crystal of recycling is as shown in table 3-3.
Table 3-3 anhydrous sodium sulfate crystal purity achievement data and relevant criterion
Unit: %, pH dimensionless
Embodiment 4
(1) the spinning acid waste liquid of certain viscose rayon company is taken to be tested, the Raw performance of acid waste liquid such as table 4-1
It is shown.
Table 4-1 original waste liquid achievement data
The sodium sulphate content highest in waste liquid it can be seen from the data in table, it is dense at concentrations up to being 5%, followed by sulfuric acid
Degree has reached 1.5%, and zinc sulfate and sulfuric acid aluminium content are lower, and the concentration of sum of the two reaches 0.13%, the concentration of organic matter compared with
Height is 2000ppm, and long-term enrichment can generate irreversible influence to acidic treatment and production technology.
(2) it takes 5000ml acid waste liquid to enter accurate filter, removes the solid matter in waste liquid；
(3) water outlet of 5000ml accurate filter is taken to enter Rotary Evaporators, evaporating temperature is 75 degrees Celsius, works as evaporation and concentration
When the volume of liquid is 2500ml (volume of concentrate be former waste liquid volume 50%), stop evaporation；
(4) acid bath process outlet solution 60ml in evaporation concentrated solution 2500ml and production technology is taken (to freeze raffinate for reuse
The 10% of water) it mixes, the total 2560ml of mixed liquor, freezing and crystallizing is carried out, the first stage is cooled to 48 degrees Celsius, and Celsius 48
50min is maintained at a temperature of degree；Second stage is cooled to -3 degrees Celsius, and maintains temperature 30min, and solid-liquid is mixed centrifugation point
From, obtain sal glauberi crystal and freezing raffinate；
(5) the freezing raffinate 700ml of step (4) is taken to enter electrodialysis plant, it is (cold as absorbing liquid using 2800ml pure water
The volume ratio for freezing raffinate and pure water receiving liquid is 1:4), when the electrical conductivity ratio in the conductivity and concentrated water in fresh water is 1:5,
Complete the process.Electrodialysis fresh water (about 2920ml) is discharged into the processing of sewage treatment plant of plant area, electrodialysis concentrated water (about 580ml) reuse
Acid bath process into production technology；
(6) the sal glauberi crystal 50g (weight in wet base) in step (4) is taken to be dissolved in 100ml pure water, solution temperature maintains
At 65 degrees Celsius, and the pH to 7.86 that sodium hydroxide solution adjusts solidliquid mixture is added, stirs 45min, filtering removal neutralizes
Solid impurity in solution afterwards, filtrate obtain more thick solidliquid mixture by evaporative crystallization, are centrifugated, and solid passes through
Drying obtains the purity of a kind of Grade A in anhydrous sodium sulfate industrial goods standard.
Detection data in experimental procedure is as shown in table 4-2.
The index concentration of water sample in table 4-2 various processes
The purity detecting index of the anhydrous slufuric acid sodium crystal of recycling is as shown in table 4-3.
Table 4-3 anhydrous sodium sulfate crystal purity achievement data and relevant criterion
Unit: %, pH dimensionless
Claims (10)
1. a kind of method of the cooperative disposal acid waste liquid in cellulose viscose manufacturing technique, which is characterized in that this method include with
Lower step:
(1) viscose rayon industry spinning acid waste liquid is delivered into the solid insoluble in filter device (2) removal waste liquid；
(2) to step (1), treated, and waste liquid is evaporated concentration, and obtaining volume is former waste liquid volume 10%~50%
Concentrate；
(3) concentrate that step (2) obtains and the acid bath that recalls from the acid bath production process outlet in spinning production technology is molten
Liquid mixing, recycles the sal glauberi crystal in mixed liquor, while generating freezing raffinate by the way of freezing and crystallizing；
(4) electrodialysis is carried out to the freezing raffinate that step (3) freezing and crystallizing generates, the organic matter in separation freezing raffinate, simultaneously
The sal glauberi crystal of step (3) recycling is carried out being refining to obtain anhydrous sodium sulfate；
(5) acid bath apparatus by the NF concentrated water reuse obtained after step (4) electrodialysis process into spinning production technology.
2. the method for the cooperative disposal acid waste liquid according to claim 1 in cellulose viscose manufacturing technique, feature exist
In in the electrodialysis of the step (4), using pure water as electrodialysis receiving liquid, the volume of freezing raffinate and pure water receiving liquid
Than for 1:(2~5), when the ratio of salinity in the fresh water and concentrated water that electrodialysis plant generates is 1:(5~15) when, complete electrodialysis
Remove the work of organic matter.
3. the method for the cooperative disposal acid waste liquid according to claim 1 in cellulose viscose manufacturing technique, feature exist
In, in the step (3), from the outlet of acid bath production process the acid bath solution water that recalls be freezing raffinate water 10~
30%.
4. the method for the cooperative disposal acid waste liquid according to claim 3 in cellulose viscose manufacturing technique, feature exist
In the acid bath solution quality in the acid bath apparatus is freeze raffinate quality 20%.
5. the method for the cooperative disposal acid waste liquid according to claim 1,2,3 or 4 in cellulose viscose manufacturing technique,
It is characterized in that, the concentrate that volume is former waste liquid volume 15%~30% is obtained in the step (2).
6. the method for the cooperative disposal acid waste liquid according to claim 1,2,3 or 4 in cellulose viscose manufacturing technique,
It is characterized in that, the freezing and crystallizing in the step (3) is using two-stage cooling freezing: first order freezing and crystallizing is by the temperature of concentrate
40~50 degrees Celsius are reduced to by 75~100 degrees Celsius, and stablizes 20~60min under the conditions of the temperature；Second level freezing knot
Temperature is reduced to -10~0 degree Celsius by 40~50 degrees Celsius by crystalline substance, and stablizes 20~60min under the conditions of the temperature, by solid
Liquid separation, obtains sal glauberi crystal.
7. the method for the cooperative disposal acid waste liquid according to claim 1,2,3 or 4 in cellulose viscose manufacturing technique,
It is characterized in that, the freezing raffinate of acid bath apparatus of the reuse into spinning production technology meets following reuse mark in the step (3)
It is quasi-:
8. the method for the cooperative disposal acid waste liquid according to claim 1,2,3 or 4 in cellulose viscose manufacturing technique,
It is characterized in that, the filter device (2) in the step (1) uses accurate filter.
9. a kind of device of the cooperative disposal acid waste liquid in cellulose viscose manufacturing technique, which is characterized in that the device include according to
Filter device (2), evaporation concentration device (4), the freezing and crystallizing device (5) of secondary connection, respectively with the freezing and crystallizing device (5)
The electrodialysis system (3) and refining system (1) of connection, the import and the acid bath in spinning production technology of freezing and crystallizing device (5)
Production process outlet connection, the electrodialysis system (3) concentrated water outlet with spinning production technology in acid bath production process into
Mouth connection.
10. the device of the cooperative disposal acid waste liquid according to claim 9 in cellulose viscose manufacturing technique, feature exist
In the electrodialysis plant (3) is arranged in series two-stage or two-stage or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811392351.6A CN109231603A (en) | 2018-11-21 | 2018-11-21 | The method and device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811392351.6A CN109231603A (en) | 2018-11-21 | 2018-11-21 | The method and device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109231603A true CN109231603A (en) | 2019-01-18 |
Family
ID=65076293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811392351.6A Pending CN109231603A (en) | 2018-11-21 | 2018-11-21 | The method and device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109231603A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316892A (en) * | 2019-07-11 | 2019-10-11 | 马杰 | A kind of processing method and its application of high-temperature acidic zinc-containing water |
| CN111803995A (en) * | 2020-07-31 | 2020-10-23 | 北京神州瑞霖环境技术研究院有限公司 | Natural evaporation crystallization system for acid bath discharge liquid reflux removal part and application |
| CN112408431A (en) * | 2020-11-25 | 2021-02-26 | 赛得利(九江)纤维有限公司 | Method for preparing anhydrous sodium sulphate by acid bath evaporation of viscose |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016462A1 (en) * | 1996-10-11 | 1998-04-23 | Pulp And Paper Research Institute Of Canada | Treatment of chlorine dioxide generator effluent and feed streams with fixed-resin bed |
| CN2682090Y (en) * | 2004-01-14 | 2005-03-02 | 上海乐生医疗器械有限公司 | Apparatus for adjusting dry spinning path of dry-wet method spinning and controlling concentration of coagulation bath for hollow fiber film |
| CN201971934U (en) * | 2011-02-18 | 2011-09-14 | 许达人 | Acid bath cooling crystallization device with plate type heat exchanger |
| CN105417828A (en) * | 2016-01-05 | 2016-03-23 | 中南大学 | Resource recycling method for heavy metal wastewater containing low-boiling-point acid and acid radicals of low-boiling-point acid |
| CN105645644A (en) * | 2016-01-07 | 2016-06-08 | 浙江蓝极膜技术有限公司 | Technique for recovering sulfuric acid from sulfuric acid/sodium sulfate-containing wastewater by two-stage diffusion dialysis, two-stage electrodialysis and bipolar membrane |
| CN105692989A (en) * | 2014-11-27 | 2016-06-22 | 上海凯鑫分离技术股份有限公司 | A comprehensive utilization process for viscose fiber acidic waste water |
| CN107008027A (en) * | 2017-05-22 | 2017-08-04 | 许达人 | A kind of multiple-effect evaporation concentration technology, evaporative crystallization technique and the device of sulfur acid and its salting liquid |
| CN107758947A (en) * | 2016-08-22 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of recycling processing method of sodium alkali desulfurization liquid |
| CN207175684U (en) * | 2017-08-17 | 2018-04-03 | 无锡诚尔鑫环保装备科技有限公司 | The system that hydrochloric acid and metallic compound are reclaimed from hydrochloric acid pickling waste liquor |
-
2018
- 2018-11-21 CN CN201811392351.6A patent/CN109231603A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016462A1 (en) * | 1996-10-11 | 1998-04-23 | Pulp And Paper Research Institute Of Canada | Treatment of chlorine dioxide generator effluent and feed streams with fixed-resin bed |
| CN2682090Y (en) * | 2004-01-14 | 2005-03-02 | 上海乐生医疗器械有限公司 | Apparatus for adjusting dry spinning path of dry-wet method spinning and controlling concentration of coagulation bath for hollow fiber film |
| CN201971934U (en) * | 2011-02-18 | 2011-09-14 | 许达人 | Acid bath cooling crystallization device with plate type heat exchanger |
| CN105692989A (en) * | 2014-11-27 | 2016-06-22 | 上海凯鑫分离技术股份有限公司 | A comprehensive utilization process for viscose fiber acidic waste water |
| CN105417828A (en) * | 2016-01-05 | 2016-03-23 | 中南大学 | Resource recycling method for heavy metal wastewater containing low-boiling-point acid and acid radicals of low-boiling-point acid |
| CN105645644A (en) * | 2016-01-07 | 2016-06-08 | 浙江蓝极膜技术有限公司 | Technique for recovering sulfuric acid from sulfuric acid/sodium sulfate-containing wastewater by two-stage diffusion dialysis, two-stage electrodialysis and bipolar membrane |
| CN107758947A (en) * | 2016-08-22 | 2018-03-06 | 中国石油化工股份有限公司 | A kind of recycling processing method of sodium alkali desulfurization liquid |
| CN107008027A (en) * | 2017-05-22 | 2017-08-04 | 许达人 | A kind of multiple-effect evaporation concentration technology, evaporative crystallization technique and the device of sulfur acid and its salting liquid |
| CN207175684U (en) * | 2017-08-17 | 2018-04-03 | 无锡诚尔鑫环保装备科技有限公司 | The system that hydrochloric acid and metallic compound are reclaimed from hydrochloric acid pickling waste liquor |
Non-Patent Citations (1)
| Title |
|---|
| 邵刚: "《膜法水处理技术》", 30 June 1992, 冶金工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316892A (en) * | 2019-07-11 | 2019-10-11 | 马杰 | A kind of processing method and its application of high-temperature acidic zinc-containing water |
| CN111803995A (en) * | 2020-07-31 | 2020-10-23 | 北京神州瑞霖环境技术研究院有限公司 | Natural evaporation crystallization system for acid bath discharge liquid reflux removal part and application |
| CN112408431A (en) * | 2020-11-25 | 2021-02-26 | 赛得利(九江)纤维有限公司 | Method for preparing anhydrous sodium sulphate by acid bath evaporation of viscose |
| CN112408431B (en) * | 2020-11-25 | 2023-01-17 | 赛得利(九江)纤维有限公司 | Method for preparing anhydrous sodium sulphate by acid bath evaporation of viscose |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105540619B (en) | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio | |
| CN109231603A (en) | The method and device of cooperative disposal acid waste liquid in cellulose viscose manufacturing technique | |
| CN106145496B (en) | The comprehensive utilization process of viscose fiber acid waste water | |
| CN105692989B (en) | The comprehensive utilization process of viscose fiber acid waste water | |
| CN103979730B (en) | Purify penicillin production waste liquid and the method for reclaim(ed) sulfuric acid sodium | |
| CN107117755B (en) | High ammonia-nitrogen wastewater treatment and ammonia recovery system and method | |
| CN109457325A (en) | The method and apparatus of the recycling of viscose rayon spinning acid waste liquid sublevel and recycled | |
| CN106082516A (en) | A kind of point of salt-pepper noise technique and device | |
| CN204874164U (en) | Zero release processing system of desulfurization waste water | |
| CN114275750A (en) | Resource recycling method for waste etching solution in photoelectric industry | |
| CN207862094U (en) | A kind of electroplating waste-water reutilizing and the processing system of zero-emission | |
| CN101219946A (en) | Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof | |
| CN103723736A (en) | Resource recovery method in white carbon black production process | |
| CN107686204B (en) | Method for comprehensively utilizing heat energy in viscose fiber acid wastewater treatment process | |
| CN108821493A (en) | A kind of Environmentally-frielow-energy-consumptipolycarboxylic low-energy-consumptipolycarboxylic tar refining processing method of sodium sulfate wastewater containing phenol | |
| CN109485189A (en) | Ca in high concentration chaff interferent waste water2+And SO42-Intermediate processing | |
| CN216837160U (en) | Sodium carbonate waste salt recovery device system | |
| CN103466871B (en) | Treatment method and recycling system for industrial wastewater of polycrystalline silicon batteries | |
| CN205933496U (en) | Desulfurization waste water zero release processing apparatus based on electrodialysis | |
| CN113800701A (en) | Method for recycling methanol waste liquid containing magnesium sulfate solid | |
| CN112159019A (en) | Treatment method of high-salt high-COD wastewater | |
| CN106242186B (en) | A kind of recycling processing method of sulphur black technique waste water | |
| CN205313300U (en) | High zero release processing system who contains salt waste water | |
| CN115771972B (en) | Treatment method and treatment system for fluorine-containing wastewater discharge | |
| CN109607582A (en) | A kind of method and system recycling magnesium salts from desulfurization wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |
|
| RJ01 | Rejection of invention patent application after publication |