CN105197965A - Method of extracting mirabilite and industrial salt from high salinity wastewater - Google Patents
Method of extracting mirabilite and industrial salt from high salinity wastewater Download PDFInfo
- Publication number
- CN105197965A CN105197965A CN201510630167.0A CN201510630167A CN105197965A CN 105197965 A CN105197965 A CN 105197965A CN 201510630167 A CN201510630167 A CN 201510630167A CN 105197965 A CN105197965 A CN 105197965A
- Authority
- CN
- China
- Prior art keywords
- salt
- waste water
- saltcake
- add
- industrial
- 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.)
- Granted
Links
Abstract
The invention relates to the technical field of wastewater treatment, extraction and recycling, in particular to a method of extracting mirabilite and industrial salt from high salinity wastewater. The method includes a series of steps: advanced oxidation, deep softening, membrane concentration, refrigeration denitration, deep denitration and preparation of the industrial salt; the method has the advantages that the mirabilite and industrial salt in the high salinity wastewater can be extracted for industrial reutilization, purification rate is high, and wastewater finally obtained is directly dischargeable and is free of environmental pollution.
Description
Technical field
The present invention relates to wastewater treatment and extract recovery technology field, be specifically related to a kind of method extracting saltcake and Industrial Salt from high-salt wastewater.
Background technology
High-salt wastewater refers to that the waste water that saltiness is greater than 10%, essential characteristic are total dissolved salt TDS>10 ~ 15%, simultaneously containing saltcake (Na
2sO
4), salt (NaCl) two kinds of components and various pollutent.
It mainly results from trade effluent and implements in Treated sewage reusing or zero release process, the dense water of film film workshop section produces: concrete process as shown in Figure 1;
Also the situation directly being produced this high-salt wastewater by technological process is had.Such as dyestuffs industries Salting-Out Waste Water, preserved szechuan pickle waste water or electroplating sludge acid-soluble go out Cu-Ni, then neutralization precipitation Cu (OH)
2, Ni (OH)
2the waste water produced, but this situation is few, and also the water yield is few.
This high-salt wastewater can not directly discharge.Its feature is three high: COD is high, and total salt is high, heavy metal or ammonium nitrogen high, direct discharge directly can cause the problem of environmental pollutions such as saline Land, heavy metal, water body eutrophication, and current universal process method is evaporation just, reclaims water of condensation.Detailed process as shown in Figure 2.
By traditional method by crystalline salt mainly saltcake (Na remaining after waste water evaporation
2sO
4) and salt (NaCl) two kinds of mixtures, not only without any marketable value, and be organic pollutant, heavy metal concentration is high, even reaches keep under strict control refuse or Hazardous wastes rank.Regulation can only be entrusted to specify has the Wei Fei company of qualification to process, and not only charges high, and the also not more good method process of Wei Fei company.This just increases the cost of wastewater treatment widely, makes most of Treated sewage reusing or zero release environmental protection facility become ornaments.
This problem is very severe in China, China's scale 10,000 m
3the industry park waste water station of/d has more than thousand.Waste water saliferous is generally TDS>3000mg/L, total salt that then each waste water station brings environment into has 30T/d or 10000T/, the salt bringing environment because of waste water into has ten million ton of each year, this is to the salinization heavy metal in river, territory, eutrophication harm is huge, if but implement zero release, these ten million ton of mixing salt is dealt with improperly, and its harm is larger.
At present with saltcake (Na in the total salt of waste water
2sO
4) and salt (NaCl) accounting classification, have two kinds:
1. the low salt form of high nitre: Na
2sO
4>70 ~ 90%, NaCl<10 ~ 30%, this is common situation.
2. the low nitre type of high salt: NaCl>70 ~ 90%, Na
2sO
4<10 ~ 30%, this fewer.
Except mine or salt pan production of water (being commonly called as bittern), in nature water body, always Cl
->SO
4 2+, namely containing NaCl>Na
2sO
4, consequent trade effluent is also generally NaCl>Na
2sO
4.But in wastewater treatment process, there is acid always---alkali N-process.Due to sulfuric acid H
2sO
4price always lower than hydrochloric acid HCl, therefore generally all uses H
2sO
4as acid-base modifier.Therefore always SO in waste water
4 2+>>Cl
-, namely most cases is high nitre low-solids water absolutely.
Saltcake (Na is extracted from strong brine bittern, glass gall etc.
2sO
4) or the Technology of salt (NaCl), existing centuries history:
From mirabilite ore, exploit glass gall, be exactly high nitre low-solids water, usual saltcake accounting (Na
2sO
4) >90 ~ 95%, salt accounting (NaCl) <10 ~ 5%, just crystallization can go out saltcake (Na with freezing or evaporation
2sO
4).
Mining brine from salt mine is exactly the low glass gall of high salt, usual salt (NaCl) >90 ~ 95%, saltcake <10 ~ 5%, just crystallization can go out salt (NaCl) with vacuum-evaporation.
But for high-salt wastewater, above-mentionedly adopt salt technology if directly applied mechanically, salt made from earth containing a comparatively high percentage of sodium chloride can not be realized and be separated, also cannot obtain qualified nitre or salt industrial product.
Therefore will implement Treated sewage reusing, go on wastewater zero discharge, this difficult problem does not solve, and will strongly limit the enforcement of this policy.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of method extracting saltcake and Industrial Salt from high-salt wastewater, it has and the saltcake in high-salt wastewater and Industrial Salt separation and Extraction out can be carried out industrialization recycling, purification rate is high, the waste water finally obtained can directly discharge, the feature of environmentally safe.
Object of the present invention is achieved through the following technical solutions:
From high-salt wastewater, extract a method for saltcake and Industrial Salt, mainly comprise the following steps:
Step one: oxidation: use H
2sO
4regulate the pH value of waste water to 3-5, add flocculation agent simultaneously, remove the organic pollutant in waste water.
Step 2: softening: regulate the pH value of waste water to 9-11, adds supernatant after sorbent material and PAM, removal heavy metal hardness simultaneously.
Step 3: membrane concentration: first carry out microfiltration membrane, then carry out electrodialysis, obtain colorless clear liquid.
Step 4: freezing denitration: colorless clear liquid step 3 obtained is refrigerated to less than-5 DEG C, slowly stirs, after crystallization reaction completes, centrifugation goes out Na
2sO
410H
2o crystal.
Step 5: denitration again: centrifugal for the step 4 mother liquor obtained is added containing Ca
2+material, then add BaCl
2rear until again without BaSO
4white precipitate then adds flocculation agent and makes Ca till generating
2+and Ba
2+flocculate agglomerating, namely supernatant until obtain colourless salt solution without white precipitate.
Step 6: evaporation salt manufacturing: colourless salt solution evaporative crystallization step 5 obtained, obtains Industrial Salt NaCl.
Except above-mentioned committed step, the conventional waste water treatment step such as filtration, precipitation can also be comprised.
Applicant be experimental studies have found that by a large amount of, traditional extraction saltcake (Na
2sO
4) or the basic reason of Technology weak effect of salt (NaCl) be: the high-salt wastewater produced by commercial run, the hardness pollutents such as organic pollutant COD, heavy metal, ammonia nitrogen, Ca-Mg-Si are very high, again through film concentration, organic concentration can reach 1 ~ 30,000 mg/L, heavy metal concentration can reach 5 ~ 50mg/L, and ammonia nitrogen and hardness respectively can more than 200 ~ 1000mg/L.
These pollutents, to saltcake (Na
2sO
4) and salt (NaCl) separating-purifying impact interference have:
1. pollutent changes salt made from earth containing a comparatively high percentage of sodium chloride and to coexist saturation value.
In existing historical document, under having a large amount of differing temps, Na
2sO
4-NaCl coexists saturation data.But these data are with distilled water+reagent N a
2sO
4under constant temperature, acquisition is tested with NaCl.This compares with the data under actual industrial wastewater conditions, and difference is great.
2. pollutent is wrapped in outside nucleus, and crystal cannot be grown up, and temperature slightly changes, dissolving crystallized again, and actual percent crystallization in massecuite is very low, also can only obtain micro-crystal powder, and whizzer separation efficiency is low, and crystal total recovery is lower than 30%.
3. pollutent hinders CaCO
3or Mg (OH)
2crystal generates, and make the conventional softening method except Ca-Mg invalid, salt made from earth containing a comparatively high percentage of sodium chloride liquid is difficult to purify.
4. intergranular is carried secretly seriously.
Countless microcrystals is assembled mutually, and various impurity is all wrapped in druse, and result obtains saltcake (Na
2sO
4) and salt (NaCl) component seriously impure, cannot qualified product be obtained.
Technical scheme of the present invention is utilized effectively to solve the problem.
As preferably, the flocculation agent that described step one is added is FeSO
4be the H of 30% with concentration
2o
2mixed flocculation agent, the reaction times is 1-3 hour.In the strict control reaction times, by fully oxidized for the organic pollutant in waste water removal, reduce Organic Pollutants in Wastewater to the impact of later steps, improve the pick-up rate preparing saltcake and Industrial Salt, can raise the efficiency simultaneously.
Wherein, FeSO in described step one
4add-on be 300-800mg/L, described H
2o
2add-on utilize detect waste water Eo+ value control, this Eo+ value controls between 500-800mv.H
2o
2and FeSO
4be combined as the Fenton reagent of Fenton's reaction, its addition needs strict control, guarantee fully oxidized while can not excessively add.
Wherein, described step 2 utilizes mixed base to regulate the pH value of waste water, and the composition of described mixed base is NaOH30-70%, Na
2cO
370-30%, both summations are 100%.Utilize the Mg that NaOH can effectively regulate the pH value of waste water can make in waste water simultaneously
2+generate MgOH
2precipitation, Na
2cO
3by the Ca in waste water
2+precipitation, add the micromolecular organism of diatomite adsorption, PMM, as flocculation agent, can strengthen the effect of removing impurity by means of precipitation, and save time, raise the efficiency simultaneously.
Wherein, the sorbent material in described step 2 is diatomite, and diatomaceous add-on is the 0.5-1% of wastewater flow rate, and the add-on of described PAM is 1-15ppm.Because most larger molecular organics is removed by step one, remain a small amount of micromolecular organic pollutant in waste water and utilize diatomite to remove, the effect of purification & isolation can be improved.
Wherein, the reaction times of described step 2 is 1-2 hour, reacted salt solution Clear colourless, and pH value is 9-11.
Wherein, the stirring velocity of described step 4 is 30-60r/min, and crystallization time is 1-2 hour.
Wherein, what add in described step 5 contains Ca
2+material is CaCl
2or Ca(OH)
2, described Ca
2+add-on be SO in waste water
4 2+1.05-1.1 doubly, by SO in waste water
4 2+precipitation complete.
Wherein, the flocculation agent in described step 5 is AlCl
3.
Wherein, pending in described step one waste water Na
2sO
4content be greater than 5g/L, the content of NaCl is greater than 150-300g/L, is particularly useful for method of the present invention.
Beneficial effect of the present invention is:
Applicant is found by research, and utilize traditional method cannot obtain qualified saltcake or salt industrial product, reason is:
If 1. directly high-salt wastewater evaporative crystallization, the organism of lark, bois de rose or grey black and the very high mixing salt made from earth containing a comparatively high percentage of sodium chloride of heavy metal can only be obtained, also cannot obtain in the most people imagination can high-purity water of condensation of reuse.
If 2. use cold method crystallization, can mirabilite hydrate be obtained, but obtain brilliant rate lower than 30%, even uncrystallizable.Crystal outward appearance can white, colourless or pure color, but organism and heavy metal and NaCl cannot reach the technical grade product specification of quality that can sell.
If 3. with conventional lime Method of Soda or two alkaline process (NaOH+Na
2cO
3) tenderizer removes Ca, Mg in high-salt wastewater, purification salt made from earth containing a comparatively high percentage of sodium chloride quality, then softening efficiency is very low, and generally only 30%, even sometimes can not generate CaCO
3or Mg (OH)
2precipitation produces bating effect.
The present invention by carrying out to high-salt wastewater that advanced oxidation, the degree of depth are softening, membrane concentration, freezing denitration, degree of depth denitration, finally prepare this series of steps process of Industrial Salt, in the current industrial high-salt wastewater of effective solution, pollutant load is complicated, salt made from earth containing a comparatively high percentage of sodium chloride content ratio difference is larger, cannot the technical problem of high efficiency extraction Industrial Salt and saltcake, its advantage has:
1. wide accommodation:
As long as 1.. the composition state point of high-salt wastewater is total on saturation curves at 0 DEG C, i.e. Na
2sO
4>5g/L, NaCl>150 ~ 300g/L can operate.
2.. alleged state point refers to Na in haline water
2sO
4, the point of crossing of content on common saturation curves figure of NaCl.
2. can obtain saltcake or salt, organism, the ammonia nitrogen of technical grade specification, heavy metal can within technical grade product set quota, and recovery utilization rate is high, very big to the meaning of environment protection.
3. the evaporative process of salt solution, there will be no Ca-Mg hardness thing to scab, also there will not be salt crust scar, water of condensation COD and NH
3-N is very low, and reuse utilization ratio is high.
Accompanying drawing explanation
Fig. 1 is that in prior art, trade effluent is implemented in Treated sewage reusing or zero release process, at the schema of the dense water of film that film workshop section produces;
Fig. 2 is the common method schema processing high-salt wastewater in prior art.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
embodiment 1
Treatment process of the present invention is utilized to process high nitre less salt waste water:
This be through the nanofiltration membrane limit concentrate after high-salt wastewater, feature is:
Saltcake (Na
2sO
4) 80g/L; Salt (NaCl) 20g/L; Total salt TDS100g/L;
Salt made from earth containing a comparatively high percentage of sodium chloride accounting in total salt TDS: nitre >80%, salt <20%, salt made from earth containing a comparatively high percentage of sodium chloride ratio is lower than 1:0.25.
The treatment step of the present invention to above-mentioned waste water is as follows:
Step one: oxidation: use H
2sO
4regulate the pH value to 3 of waste water, add FeSO simultaneously
4be the H of 30% with concentration
2o
2, react 2 hours, FeSO
4add-on be 500mg/L, Eo+ value controls at ORP500mv, removes the organic pollutant in waste water.
Step 2: softening: the Na adding 30%NaOH and 70%
2cO
3regulate the pH value to 9 of waste water, add simultaneously 1% diatomite and 1ppmPAM after supernatant, removal heavy metal hardness.
Step 3: membrane concentration: first carry out microfiltration membrane, then carry out electrodialysis, obtain colorless clear liquid.
Step 4: freezing denitration: colorless clear liquid step 3 obtained is refrigerated to-5 DEG C, 30 revs/min are slowly stirred, and crystallization reaction is after 2 hours, and centrifugation goes out Na
2sO
410H
2o crystal;
Step 5: denitration again: the CaCl centrifugal for the step 4 mother liquor obtained being added 1.05 times of parts
2, then add BaCl
2rear until again without BaSO
4white precipitate then adds AlCl till generating
3make Ca
2+and Ba
2+flocculate agglomerating, namely supernatant until obtain colourless salt solution without white precipitate.
Step 6: evaporation salt manufacturing: colourless salt solution evaporative crystallization step 5 obtained, obtains Industrial Salt NaCl.
Above-mentioned waste water, after pre-treatment organics removal of the present invention, makes COD<100mg/L, is refrigerated to-5 DEG C, and crystallization goes out mirabilite hydrate Na
2s0
410H
20, extraction yield is 200g/L, amounts to anhydrous nitre Na
2sO
4, extraction yield is 5g/L, and residual solution is containing nitre Na
2sO
4<10g/L, salt NaCl>25g/L, the saltcake rate of recovery is greater than 85%, and the total salt TDS of waste water drops to 35g/L, and always decline 65%, residual solution can send to membrane concentration again, then freeze cycle reclaims nitre further---salt.
embodiment 2
Treatment process of the present invention is utilized to process high nitre less salt waste water:
This be through the nanofiltration membrane limit concentrate after high-salt wastewater, feature is:
Saltcake (Na
2sO
4) 120g/L; Salt (NaCl) 30g/L; Total salt TDS150g/L;
Salt made from earth containing a comparatively high percentage of sodium chloride accounting in total salt TDS: nitre >80%, salt <20%, salt made from earth containing a comparatively high percentage of sodium chloride ratio is lower than 1:0.25.
The treatment step of the present invention to above-mentioned waste water is as follows:
Step one: oxidation: use H
2sO
4regulate the pH value to 3 of waste water, add FeSO simultaneously
4be the H of 30% with concentration
2o
2, react 2 hours, FeSO
4add-on be 500mg/L, Eo+ value controls at ORP600mv, removes the organic pollutant in waste water.
Step 2: softening: the Na adding 30%NaOH and 70%
2cO
3regulate the pH value to 9 of waste water, add simultaneously 1% diatomite and 1ppmPAM after supernatant, removal heavy metal hardness.
Step 3: membrane concentration: first carry out microfiltration membrane, then carry out electrodialysis, obtain colorless clear liquid.
Step 4: freezing denitration: colorless clear liquid step 3 obtained is refrigerated to-5 DEG C, 30 revs/min are slowly stirred, and crystallization reaction is after 2 hours, and centrifugation goes out Na
2sO
410H
2o crystal;
Step 5: denitration again: the CaCl centrifugal for the step 4 mother liquor obtained being added 1.05 times of parts
2, then add BaCl
2rear until again without BaSO
4white precipitate then adds AlCl till generating
3make Ca
2+and Ba
2+flocculate agglomerating, namely supernatant until obtain colourless salt solution without white precipitate.
Step 6: evaporation salt manufacturing: colourless salt solution evaporative crystallization step 5 obtained, obtains Industrial Salt NaCl.
Above-mentioned waste water, after pre-treatment organics removal of the present invention, makes COD<300mg/L, is refrigerated to-5 DEG C, and crystallization goes out mirabilite hydrate Na
2s0
410H
20, extraction yield is 200g/L, amounts to anhydrous nitre Na
2sO
4, extraction yield is 5g/L, and residual solution is containing nitre Na
2sO
4<10g/L, salt NaCl>28g/L, the saltcake rate of recovery is greater than 85%, and the total salt TDS of waste water drops to 38g/L, and always decline 75%, residual solution can send to membrane concentration again, then freeze cycle reclaims nitre further---salt.
embodiment 3
Treatment process of the present invention is utilized to process the low nitre waste water of high salt:
Salt mine adopt bittern water, implement mother liquor reconcentration in, more freezing out of stock after secondary mother liquid, all belong to the low nitre waste water of high salt, feature is:
Salt (NaCl) 200g/L; Nitre (Na
2sO
4) 20g/L; Total salt TDS220g/L;
Salt made from earth containing a comparatively high percentage of sodium chloride accounting in total salt TDS: nitre <10%, salt >90%, salt made from earth containing a comparatively high percentage of sodium chloride ratio is higher than 1:9.
The treatment step of the present invention to above-mentioned waste water is as follows:
Step one: oxidation: use H
2sO
4regulate the pH value to 5 of waste water, add FeSO simultaneously
4be the H of 30% with concentration
2o
2, react 1 hour, FeSO
4add-on be 800mg/L, Eo+ value controls at ORP800mv, removes the organic pollutant in waste water.
Step 2: softening: the Na adding 70%NaOH and 30%
2cO
3regulate the pH value to 11 of waste water, add simultaneously 0.5% diatomite and 15ppmPAM after supernatant, removal heavy metal hardness.
Step 3: membrane concentration: first carry out microfiltration membrane, then carry out electrodialysis, obtain colorless clear liquid.
Step 4: freezing denitration: colorless clear liquid step 3 obtained is refrigerated to-5 DEG C, 60 revs/min are slowly stirred, and crystallization reaction is after 1 hour, and centrifugation goes out Na
2sO
410H
2o crystal;
Step 5: denitration again: the CaCl centrifugal for the step 4 mother liquor obtained being added 1.1 times of parts
2, then add BaCl
2rear until again without BaSO
4white precipitate then adds AlCl till generating
3make Ca
2+and Ba
2+flocculate agglomerating, namely supernatant until obtain colourless salt solution without white precipitate.
Step 6: evaporation salt manufacturing: colourless salt solution evaporative crystallization step 5 obtained, obtains Industrial Salt NaCl.
This waste water, after pre-treatment organics removal of the present invention, makes COD<100 (mg/L), is refrigerated to-5 DEG C, then crystallization goes out mirabilite hydrate Na
2sO
410H
2o, extraction yield is that 30g/L (rolls over anhydrous nitre Na
2sO
413g/L), residual solution is still Na containing nitre
2sO
4<10g/L, salt NaCl>250g/L, mother liquor, can directly as production liquid salt or Industrial Salt raw material due to low containing nitre.
embodiment 4
Treatment process of the present invention is utilized to process the low nitre waste water of high salt:
Salt mine adopt bittern water, implement mother liquor reconcentration in, more freezing out of stock after secondary mother liquid, all belong to the low nitre waste water of high salt, feature is:
Salt (NaCl) 300g/L; Nitre (Na
2sO
4) 30g/L; Total salt TDS330g/L;
Salt made from earth containing a comparatively high percentage of sodium chloride accounting in total salt TDS: nitre <10%, salt >90%, salt made from earth containing a comparatively high percentage of sodium chloride ratio is higher than 1:10.
The treatment step of the present invention to above-mentioned waste water is as follows:
Step one: oxidation: use H
2sO
4regulate the pH value to 4 of waste water, add FeSO simultaneously
4be the H of 30% with concentration
2o
2, react 3 hours, FeSO
4add-on be 500mg/L, Eo+ value controls at ORP700mv, removes the organic pollutant in waste water.
Step 2: softening: the Na adding 50%NaOH and 50%
2cO
3regulate the pH value to 10 of waste water, add simultaneously 0.5% diatomite and 8ppmPAM after supernatant, removal heavy metal hardness.
Step 3: membrane concentration: first carry out microfiltration membrane, then carry out electrodialysis, obtain colorless clear liquid.
Step 4: freezing denitration: colorless clear liquid step 3 obtained is refrigerated to-5 DEG C, 40 revs/min are slowly stirred, and crystallization reaction is after 2 hours, and centrifugation goes out Na
2sO
410H
2o crystal;
Step 5: denitration again: the CaCl centrifugal for the step 4 mother liquor obtained being added 1.1 times of parts
2, then add BaCl
2rear until again without BaSO
4white precipitate then adds AlCl till generating
3make Ca
2+and Ba
2+flocculate agglomerating, namely supernatant until obtain colourless salt solution without white precipitate.
Step 6: evaporation salt manufacturing: colourless salt solution evaporative crystallization step 5 obtained, obtains Industrial Salt NaCl.
This waste water, after pre-treatment organics removal of the present invention, makes COD<300 (mg/L), is refrigerated to-5 DEG C, then crystallization goes out mirabilite hydrate Na
2sO
410H
2o, extraction yield is that 50g/L (rolls over anhydrous nitre Na
2sO
415g/L), residual solution is still Na containing nitre
2sO
4<10g/L, salt NaCl>250g/L, mother liquor, can directly as production liquid salt or Industrial Salt raw material due to low containing nitre.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. from high-salt wastewater, extract a method for saltcake and Industrial Salt, it is characterized in that: mainly comprise the following steps:
Step one: oxidation: use H
2sO
4regulate the pH value of waste water to 3-5, add flocculation agent simultaneously, remove the organic pollutant in waste water;
Step 2: softening: regulate the pH value of waste water to 9-11, adds supernatant after sorbent material and PAM, removal heavy metal hardness simultaneously;
Step 3: membrane concentration: first carry out microfiltration membrane, then carry out electrodialysis, obtain colorless clear liquid;
Step 4: freezing denitration: colorless clear liquid step 3 obtained is refrigerated to less than-5 DEG C, slowly stirs, after crystallization reaction completes, centrifugation goes out Na
2sO
410H
2o crystal;
Step 5: denitration again: centrifugal for the step 4 mother liquor obtained is added containing Ca
2+material, then add BaCl
2rear until again without BaSO
4white precipitate then adds flocculation agent and makes Ca till generating
2+and Ba
2+flocculate agglomerating, namely supernatant until obtain colourless salt solution without white precipitate;
Step 6: evaporation salt manufacturing: colourless salt solution evaporative crystallization step 5 obtained, obtains Industrial Salt NaCl.
2. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: the flocculation agent that described step one is added is FeSO
4be the H of 30% with concentration
2o
2mixed flocculation agent, the reaction times is 1-3 hour.
3. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 2, is characterized in that: FeSO in described step one
4add-on be 300-800mg/L, described H
2o
2add-on utilize detect waste water Eo+ value control, this Eo+ value controls between 500-800mv.
4. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: described step 2 utilizes mixed base to regulate the pH value of waste water, and the composition of described mixed base is NaOH30-70%, Na
2cO
370-30%, both summations are 100%.
5. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, it is characterized in that: the sorbent material in described step 2 is diatomite, diatomaceous add-on is the 0.5-1% of wastewater flow rate, and the add-on of described PAM is 1-15ppm.
6. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: the reaction times of described step 2 is 1-2 hour, reacted salt solution Clear colourless, and pH value is 9-11.
7. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: the stirring velocity of described step 4 is 30-60r/min, and crystallization time is 1-2 hour.
8. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: what add in described step 5 contains Ca
2+material is CaCl
2or Ca(OH)
2, described Ca
2+add-on be SO in waste water
4 2+1.05-1.1 doubly.
9. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: the flocculation agent added in described step 5 is AlCl
3.
10. a kind of method extracting saltcake and Industrial Salt from high-salt wastewater according to claim 1, is characterized in that: waste water Na pending in described step one
2sO
4content be greater than 5g/L, the content of NaCl is greater than 150-300g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510630167.0A CN105197965B (en) | 2015-09-29 | 2015-09-29 | A kind of method that saltcake and Nacl are extracted from high-salt wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510630167.0A CN105197965B (en) | 2015-09-29 | 2015-09-29 | A kind of method that saltcake and Nacl are extracted from high-salt wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105197965A true CN105197965A (en) | 2015-12-30 |
| CN105197965B CN105197965B (en) | 2017-11-07 |
Family
ID=54946001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510630167.0A Expired - Fee Related CN105197965B (en) | 2015-09-29 | 2015-09-29 | A kind of method that saltcake and Nacl are extracted from high-salt wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105197965B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585194A (en) * | 2016-01-07 | 2016-05-18 | 王文领 | Comprehensive utilization method of high-concentration waste saline water containing Na<+>, Ka<+>, NH<4+>, Cl<->, SO4<2-> and NO<3-> in coal chemical industry |
| CN109592698A (en) * | 2018-12-12 | 2019-04-09 | 天津大学 | A method of preparing funnel-form sodium sulphate from high-salt wastewater |
| CN110065957A (en) * | 2018-09-29 | 2019-07-30 | 内蒙古博源工程有限责任公司 | A kind of deep refining system of complexity brine |
| CN112978767A (en) * | 2021-02-26 | 2021-06-18 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for recycling and reusing industrial mixed salt in caustic soda plant |
| CN113023753A (en) * | 2021-02-26 | 2021-06-25 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for producing high-purity industrial salt and anhydrous sodium sulphate by using industrial miscellaneous salt |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616891A (en) * | 2011-12-31 | 2012-08-01 | 广东先导稀材股份有限公司 | Method for treating sewage containing sodium sulfate and sodium chloride |
| CN102887533A (en) * | 2012-09-28 | 2013-01-23 | 天津中科化工有限公司 | Method for producing anhydrous Na2SO3 by using alkali-containing waste mother liquor |
| CN104071808A (en) * | 2014-07-24 | 2014-10-01 | 哈尔滨工业大学 | Method for preparing industrial salt through separation, evaporation and crystallization of coal chemical strong brine |
| CN104609633A (en) * | 2015-02-16 | 2015-05-13 | 阮氏化工（常熟）有限公司 | Method and device for utilizing sewage containing ammonia and sodium |
| CN104843927A (en) * | 2015-05-26 | 2015-08-19 | 中国华电工程(集团)有限公司 | Desulfurization waste water zero discharging process and system |
-
2015
- 2015-09-29 CN CN201510630167.0A patent/CN105197965B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616891A (en) * | 2011-12-31 | 2012-08-01 | 广东先导稀材股份有限公司 | Method for treating sewage containing sodium sulfate and sodium chloride |
| CN102887533A (en) * | 2012-09-28 | 2013-01-23 | 天津中科化工有限公司 | Method for producing anhydrous Na2SO3 by using alkali-containing waste mother liquor |
| CN104071808A (en) * | 2014-07-24 | 2014-10-01 | 哈尔滨工业大学 | Method for preparing industrial salt through separation, evaporation and crystallization of coal chemical strong brine |
| CN104609633A (en) * | 2015-02-16 | 2015-05-13 | 阮氏化工（常熟）有限公司 | Method and device for utilizing sewage containing ammonia and sodium |
| CN104843927A (en) * | 2015-05-26 | 2015-08-19 | 中国华电工程(集团)有限公司 | Desulfurization waste water zero discharging process and system |
Non-Patent Citations (5)
| Title |
|---|
| 严进等: "《化工环境保护及安全技术》", 30 June 2011, 化学工业出版社 * |
| 周全法等: "《废旧家电与材料的回收利用》", 30 November 2004, 化学工业出版社 * |
| 李培元等: "《发电厂水处理及水质控制》", 30 September 2012, 中国电力出版社 * |
| 杨慧芬等: "《环境工程材料》", 31 May 2008, 化学工业出版社 * |
| 王光辉等: "《水处理工程（上册）》", 31 January 2015, 中国环境出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585194A (en) * | 2016-01-07 | 2016-05-18 | 王文领 | Comprehensive utilization method of high-concentration waste saline water containing Na<+>, Ka<+>, NH<4+>, Cl<->, SO4<2-> and NO<3-> in coal chemical industry |
| CN105585194B (en) * | 2016-01-07 | 2018-02-27 | 王文领 | One kind contains Na+、K+、NH4+、Cl‑、SO42‑、NO3‑The highly concentrated effluent brine method of comprehensive utilization of coal chemical industry |
| CN110065957A (en) * | 2018-09-29 | 2019-07-30 | 内蒙古博源工程有限责任公司 | A kind of deep refining system of complexity brine |
| CN109592698A (en) * | 2018-12-12 | 2019-04-09 | 天津大学 | A method of preparing funnel-form sodium sulphate from high-salt wastewater |
| CN112978767A (en) * | 2021-02-26 | 2021-06-18 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for recycling and reusing industrial mixed salt in caustic soda plant |
| CN113023753A (en) * | 2021-02-26 | 2021-06-25 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for producing high-purity industrial salt and anhydrous sodium sulphate by using industrial miscellaneous salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105197965B (en) | 2017-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4634533A (en) | Method of converting brines to useful products | |
| CN108698827B (en) | Process for producing phosphorus products from wastewater | |
| CN105197965A (en) | Method of extracting mirabilite and industrial salt from high salinity wastewater | |
| CN101555053B (en) | Compound coagulant used for treating rare-earth highly concentrated ammonian wastewater to recover industry ammonium chloride and treatment method | |
| CN105585194A (en) | Comprehensive utilization method of high-concentration waste saline water containing Na<+>, Ka<+>, NH<4+>, Cl<->, SO4<2-> and NO<3-> in coal chemical industry | |
| US9102555B2 (en) | Method for removing phosphorus and nitrogen contained in sewage or wastewater using iron ore wastewater | |
| CN108472695B (en) | Method and apparatus for recovering salt | |
| CN101979350B (en) | Physical and chemical sludge recycling and reducing method | |
| CN102674593A (en) | Method for treating waste water generated in ionic rare earth production | |
| CN105948359B (en) | A kind of processing method of rare-earth industry waste water | |
| CN106007093A (en) | Zero discharge method for heavy metal waste water | |
| US8282690B2 (en) | Process for the preparation of solar salt having high purity and whiteness | |
| CN105668754A (en) | Method for removing trace of heavy metal and nonmetal impurities in waste acid cleaning liquor | |
| CN111072052A (en) | Method and system for recovering calcium carbonate and magnesium hydroxide from high-magnesium wastewater | |
| CN111252978A (en) | Method for recovering high-purity sodium sulfate in regenerated lead waste liquid | |
| CN114538486A (en) | Magnesium recovery method and system based on chlor-alkali salt mud | |
| CN108947012A (en) | A method of separating and recovering ammonia from ammonia nitrogen waste water | |
| CN110683622A (en) | Method for extracting aluminum in sludge to prepare aluminum-containing flocculant | |
| CN206927750U (en) | A kind of power plant waste water processing system | |
| CN114715926A (en) | Method for cooperative recycling of incineration ash of excess sludge in sewage treatment and seawater desalination brine | |
| CN112194298B (en) | System and method for recycling wastewater of whole power plant | |
| CN114105349A (en) | Zero-emission resource utilization system and process method of fracturing flow-back fluid | |
| CN115626773B (en) | Comprehensive utilization method of sludge containing calcium, iron and chromium | |
| CN114195328B (en) | Advanced treatment method for steel industry sewage and wastewater | |
| CN116253470A (en) | Zero-emission treatment method and system for wastewater containing mixed salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171107 Termination date: 20190929 |