CN205473142U - Device of industry salt is prepared in strong brine zero release - Google Patents
Device of industry salt is prepared in strong brine zero release Download PDFInfo
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- CN205473142U CN205473142U CN201620035312.0U CN201620035312U CN205473142U CN 205473142 U CN205473142 U CN 205473142U CN 201620035312 U CN201620035312 U CN 201620035312U CN 205473142 U CN205473142 U CN 205473142U
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- strong brine
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- 239000012267 brine Substances 0.000 title claims abstract description 85
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 80
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 48
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 230000003139 buffering effect Effects 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000005416 organic matter Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 150000001768 cations Chemical class 0.000 claims description 25
- 238000001728 nano-filtration Methods 0.000 claims description 21
- 239000002699 waste material Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000010802 sludge Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000005341 cation exchange Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 56
- 238000000034 method Methods 0.000 description 52
- 230000008569 process Effects 0.000 description 40
- 230000000694 effects Effects 0.000 description 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 239000011780 sodium chloride Substances 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003245 coal Substances 0.000 description 11
- 229910001425 magnesium ion Inorganic materials 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000004148 unit process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 nano-filtration unit Chemical compound 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Treatment Of Water By Ion Exchange (AREA)
Abstract
The utility model provides a device of industry salt is prepared in strong brine zero release, include: a receive and strain the unit for the preliminary treatment strong brine for the compound oxidation unit of degradation organic matter is used for getting rid of the chemical removal impurity unit of various metal ion impurity, is used for the special membrane unit of concentrated strong brine, is used for getting rid of once more organic pollutant's activated carbon filter, is used for getting rid of once more the cation exchange ware of metal ion impurity, is used for the buffering to evaporate the middle pond that the crystallization unit was intake, and is used for preparing the evaporation crystallization unit of industry salt. Receive and strain unit, compound oxidation unit, chemical removal impurity unit, special membrane unit, activated carbon filter, cation exchange ware, middle pond and the order connection in proper order of evaporation crystallization unit. The utility model discloses the zero release of strong brine processing can be realized, the problem that the strong brine pollutes is thoroughly solved, the industry salt purity of producing simultaneously is higher, can regard as industry salt to use, realizes waste water zero release and utilization.
Description
Technical field
This utility model belongs to sewage treatment area, is specifically related to a kind of strong brine zero-emission and produces the device of Nacl.
Background technology
The strong brine that the industry such as Coal Chemical Industry, petrochemical industry produces, different water quality sources, different pretreating process is dense
Saline water quality difference is very big, wherein NaSO4The biggest with the ratio of NaCl also difference.Strong brine processes the key issue faced at present
It is: 1. reduce the content of organics in strong brine that strong brine is carried out innoxious and minimizing process；2. pair strong brine is carried out
Recycling, produces Nacl；3. select the low-cost processes technique of mature and reliable, it is achieved strong brine processes real zero
Discharge.
The water quality characteristics of the industry strong brine such as Coal Chemical Industry, petrochemical industry is summarized as follows: 1, the usual water yield of strong brine is big, saliferous
Amount height, containing Na+、K+、Ca2+、Mg2+、Fe3+、Cl·、SO4 2-、F-, the inorganic impurity such as Si, TDS total content after membrance concentration
At least at more than 50000mg/L.2, strong brine organism kinds is many and content high, it is difficult to biochemical degradation.3, strong brine has
The harm of machine thing: 1) easily cause solution foaming, cause secondary vapour to carry secretly seriously, affect condensed water index.If using MVR to steam
Send out, also can make compressor impeller salt crust, cause compressor to shake, it has to shut down cleaning.2) affect crystal salt crystal grain to grow up, make
Become centrifuge cannot divide salt.3) crystallization mixed salt is carried Organic substance secretly and is exceeded standard that to be classified as danger useless, can affect salt during the crystallization of salt sub-prime
Whiteness.
Strong brine generally uses the method for evaporative crystallization to process, and the problem of this processing method and existence thereof has: 1, strong brine
Mixed salt crystallizes, and does the useless process of danger.The method crystallization processes flow process is the shortest, but mixed salt processing cost is high.2, strong brine salt sub-prime knot
Crystalline substance, salt resource, minimizing process.Evaporative crystallisation process technological process is longer, but final carnallite processing cost is relatively low.Wherein
The method of sub-prime crystallization can have two kinds: 1) crystallize NaSO respectively4With NaCl mono-salt, it is useless that danger made by a small amount of carnallite；2) crystallize respectively
NaSO4Or NaCl mono-salt, other carnallites do the useless process of danger.
Entitled " a kind of method that Coal Chemical Industry strong brine separation evaporative crystallization prepares Nacl " Chinese invention patent application
(publication number 104071808A, publication date on October 1st, 2014), discloses a kind of Coal Chemical Industry strong brine separation evaporative crystallization and prepares
The method of Nacl, concrete grammar is: one, adds lime cream, coagulant and magnesia mixture in Coal Chemical Industry strong brine, is passed into clarification
Pond or coagulative precipitation tank carry out chemical precipitation process；Two, regulation pH；Three, hyperfiltration treatment；Four, nanofiltration processes；Five, single-action is steamed
Send out crystallization or multiple-effect evaporation crystallization, obtain Nacl.This technology solves and has two in existing Coal Chemical Industry strong brine processing procedure
The problem that secondary pollution and resource are not recycled utilization, it is provided that a kind of Coal Chemical Industry strong brine separation evaporative crystallization preparation industry
The method of salt;In Coal Chemical Industry strong brine, isolated sodium chloride can use as Nacl, turns waste into wealth, it is achieved that waste water
Zero-emission and recycling.But the weak point of this technology is: 1. the nanofiltration water outlet not only water yield is very big, and TDS content
The lowest (total salinity TDS is less than 10000mg/L), if being directly evaporated crystallization treatment, investment and operating cost are the highest；2.
Entering the saline solution of crystallizing evaporator, still contain a small amount of Organic substance, the Nacl of preparation often purity is relatively low, Nacl
Purity requirement is more than 80%.
Utility model content
In place of the deficiencies in the prior art, the purpose of this utility model is to propose a kind of strong brine zero-emission to produce industry
The device of salt.
The technical scheme realizing this utility model purpose is:
The device of Nacl is produced in a kind of strong brine zero-emission, including:
For the nano-filtration unit of pretreatment strong brine, for the combined oxidation unit of degradation of organic substances, it is used for removing various
The chemical subtraction unit of impurity metal ion, for concentrating the special membrane unit of strong brine, for again removing removal organic polluter
Active carbon filter, for again removing the cation exchanger of impurity metal ion, be used for buffering evaporative crystallization unit and enter
The intermediate pool of water, and for producing the evaporative crystallization unit of Nacl；
Described nano-filtration unit, described combined oxidation unit, described chemical subtraction unit, described special membrane unit, described work
Property carbon filter, described cation exchanger, described intermediate pool and described evaporative crystallization unit by pipeline successively order
Connect.
Wherein, described combined oxidation unit, chemical subtraction unit are connected by pipeline sludge treating block；Described activity
Carbon filter is provided with counter-flushing pipeline, the counter-flushing pipeline of described active carbon filter and the regeneration water outlet of cation exchanger
Pipeline connects has waste collection pond, described sludge treating block to be connected by pipeline with waste collection pond.
Wherein, described waste collection pond connects described combined oxidation unit by reflux pipe.
Wherein, described evaporative crystallization unit uses the one in single effect evaporator or multi-effect evaporator.
The beneficial effects of the utility model are:
1. this utility model utilizes NF membrane tentatively to remove the Organic substance in strong brine and heavy metal ion.This way
Benefit be: optimize the technological process that strong brine processes, improve Organic substance and the overall removal efficiency of inorganic matter, reduce follow-up place
The burden of reason unit.The water outlet of nanofiltration again by combined oxidation unit and chemical subtraction unit remove in strong brine respectively organic
Thing and inorganic impurity, result shows that treatment effect is good, to COD, SiO in strong brine2, total hardness, the clearance of calcium hardness divide
Do not reach: 90 ~ 98%, 95 ~ 99%, 90 ~ 96% and 95 ~ 98%.
2. this utility model uses special membrane unit that pretreated strong brine is carried out reconcentration.On the one hand special membrane list
The product water of unit carries out reuse, had both saved the consumption of fresh water, and had achieved again the zero-emission in strong brine processing procedure；The opposing party
Face, the dense water end (W.E.) of special membrane unit obtains TDS more than 100, the concentration solution of 000mg/L, thus greatly reduces evaporative crystallization
The process water yield of unit, reduces investment and the cost run.
3. this utility model uses active carbon filter and cation exchanger purified concentration saline again, removes low molecule
Organic substance and impurity metal ion, thus substantially increase purity and the whiteness producing Nacl.
4. this utility model uses multiple-effect evaporation crystallization, gives full play to the repeatedly utilization to steam thermal energy, saves energy consumption.
5. the processing unit in this utility model, all uses the wastewater processing technology of mature and reliable, to Coal Chemical Industry, oil
The strong adaptability of the strong brine of the industries such as chemical industry, can effectively process various types of strong brine.The pre-of Nacl produced by strong brine
Processing technique, method is simple, and effect stability, capacity of resisting impact load is strong.
6. this utility model is capable of the zero-emission that strong brine processes, and thoroughly solves the industry such as Coal Chemical Industry, petrochemical industry
Strong brine pollute problem；The Nacl purity simultaneously produced is higher.Isolated inorganic salt can use as Nacl,
Turn waste into wealth, it is achieved wastewater zero discharge and recycling.
Accompanying drawing explanation
Fig. 1 is the device each unit annexation figure that Nacl is produced in the strong brine zero-emission that the utility model proposes.
Detailed description of the invention
Now with following example, this utility model is described, but is not limited to scope of the present utility model.In embodiment
The means used, if no special instructions, all use the means that this area is conventional.
Below in conjunction with the accompanying drawing in this utility model embodiment, the technical scheme in this utility model embodiment is carried out
Clearly and completely describe, it is clear that described embodiment is only a part of embodiment of this utility model rather than whole
Embodiment.Based on the embodiment in this utility model, those of ordinary skill in the art are not under making creative work premise
The every other embodiment obtained, broadly falls into the scope of this utility model protection.
As shown in Figure 1: the utility model proposes a kind of strong brine zero-emission and produce the device of Nacl, including: be used for
The nano-filtration unit of pretreatment strong brine, for the combined oxidation unit of degradation of organic substances, is used for removing various impurity metal ion
Chemical subtraction unit, for concentrating the special membrane unit of strong brine, for again going the activated carbon of removal organic polluter to filter
Device, for again removing the cation exchanger of impurity metal ion, for buffering the intermediate pool of evaporative crystallization unit water inlet,
And for producing the evaporative crystallization unit of Nacl；
Nano-filtration unit, combined oxidation unit, chemical subtraction unit, special membrane unit, active carbon filter, cation exchange
Device, intermediate pool and evaporative crystallization unit are linked in sequence successively.
The workflow of whole device is: strong brine initially enters nano-filtration unit, passes sequentially through compound after preliminary treatment
Oxidation unit, chemical subtraction unit, special membrane unit, active carbon filter and cation exchanger, eventually through evaporative crystallization
Unit produces Nacl.This utility model uses membrane filtration process, advanced oxidation processes, and Calx magnesia mixture is soft except silicon, Calx soda
The physical and chemical process such as change, activated carbon filtration, ion exchange and evaporative crystallization.Nano-filtration unit is used for removing larger molecular organics
With highly charged ions, but to small organic molecule and the poor removal effect of persistent organic pollutants；Then, combined oxidation list
Unit uses advanced oxidation processes to remove the most organic in strong brine, and hardly degraded organic substance is decomposed into little molecule simultaneously
Organic substance；In strong brine, the beavy metal impurity of the overwhelming majority is removed by chemical subtraction unit；Strong brine is entered by special membrane unit
Row concentrates, thus causes the concentration of the small organic molecule in strong brine and inorganic ion to be all multiplied；Use activated carbon
Small organic molecule in strong brine and inorganic ions impurity are processed by filter and cation exchanger respectively again；Finally adopt
Producing Nacl from the strong brine of purification with evaporative crystallization unit, the mother solution amount of evaporative crystallization is little, dense with nanofiltration system
Mummification landfill is carried out after hydration also.
As the preferred technical scheme of one, another embodiment of the present utility model, the nanofiltration membranous type that nano-filtration unit uses
Number being HYDRAPRO402, molecular cut off scope is 150 ~ 200nm, operates pressure limit 15 ~ 30bar, and the response rate is about 90%.
Described NF membrane is 50-60% to rejection organic in strong brine, and the clearance to total hardness is 60 ~ 70%.
The purpose that nano-filtration unit processes is the Organic substance retaining the molecular weight in strong brine more than 150 ~ 200nm, goes simultaneously
Except the bivalence in strong brine and high valence ion, the rejection of bivalence and high valence ion is reached 80% ~ 95%.
The dense water of nano-filtration unit is mainly composed of Organic substance and high valence ion, the most all has high salinity, high rigidity and height
The feature of organic concentration, carries out mummification landfill after collection.
As the preferred technical scheme of one, another embodiment of the present utility model, combined oxidation unit uses height
Level oxidation technology.One or more during pH adjusting agent is sulphuric acid or hydrochloric acid, Calx or caustic soda in advanced oxidation processes, use
Composite oxidant be H2O2And FeSO4, flocculant uses the one in iron-based flocculating agent or AlSnSi alloy.
Before advanced oxidation reaction, pH is adjusted to 3.0 ~ 5.0, H2O2Dosage is 1 ~ 2 times of influent COD, H2O2With Fe2+Mole
Ratio is 2 ~ 16, and the response time is 1 ~ 2h, and after reaction, pH is adjusted to 5 ~ 11, uses middling speed or quickly stir in course of reaction.Reaction
Add flocculant after completing, quickly stir 5 ~ 10min, standing sedimentation 10 ~ 30min.
Combined oxidation unit is 90% ~ 95% to the clearance of COD in strong brine, and water outlet COD is less than 20mg/L.
As the preferred technical scheme of one, another embodiment of the present utility model, chemical subtraction unit uses Calx magnesium
Agent removes silicon, Calx soda softening process, needs point three steps to complete.
The first step, feeding lime and magnesia mixture in the product water of chemical subtraction unit, it is therefore an objective to remove SiO2, simultaneously by heavy
Mn is removed in reaction of forming sediment2+、Sr2+、Zn2+、Fe3+Etc. numerous metal ions.Add MgO and SiO in strong brine3 2-Mass ratio be (0.4
~ 1): 1, moderate-speed mixer reaction 30 ~ 40min.
Second step, adds soda and lime cream softens, it is therefore an objective to remove the Ca in strong brine2+、Mg2+、CO3 2-Deng
Ion.The dosage of soda and Calx is according to CO free in the total alkalinity of strong brine, strong brine2Concentration, Ca2+And Mg2+Hardness etc.
Parameter calculates and determines.
3rd step, coagulation clarification, it is therefore an objective to accelerate the flocculation sediment process of float so that delivery turbidity reduces.Chemistry
Soften after reaction completes and add flocculant, quickly stir 5 ~ 10min, then add the flocculation aid of 1 ~ 4mg/L, low rate mixing 5 ~
10min, standing sedimentation 10 ~ 30min.
As the preferred technical scheme of one, another embodiment of the present utility model, special membrane unit, design two-stage is extraordinary
Film unit processes strong brine.Special membrane unit maximum influent COD is several ten thousand ppm, TDS 5000 ~ 7000mg/L of intaking, inlet flow-patterm
Scope is 6 ~ 9.
Special membrane unit is divided into two-stage, the response rate of two-stage special membrane unit can reach 80 ~ 88%, and wherein one-level is extraordinary
Film unit allows pressure 90Bar, the response rate 60 ~ 70%；Two grades of special membrane unit allow pressure 160Bar, the response rate 50 ~ 60%.Cause
This water yield entering into subsequent processing units greatly reduces, and saves investment and operating cost.Two grades of special membrane unit generations
In dense water, TDS is about 140000mg/L, COD content and is about 300 ~ 500mg/L.
The film post water outlet of special membrane unit is divided into two parts: concentrated solution and permeate, concentrated solution enters intermediate water tank, more defeated
Delivering to secondary membrane post process further, reconcentration liquid enters concentrated solution reservoir, enters follow-up processing unit.Above two-stage is extraordinary
The permeate that film produces enters permeate degassing tower, removes in water the gases such as carbon dioxide through stripping, makes pH reach 6 ~ 9,
After enter product pond, enter plant area reuse unit.
As the preferred technical scheme of one, another embodiment of the present utility model, cation exchanger uses advanced
Fixed bed counter-current regeneration technique, and be designed by without top pressure regeneration, both eliminate the source of the gas of pneumatic jack, save again loss.Warp
After cation exchanger process, in water, total hardness is minimum can be to 0.04mg/L.
Cation exchanger built with the sodium ion exchange resin of certain altitude as exchanger.Unboiled water is from top to down
By exchange oxidant layer, the sodium ion on exchanger has been replaced the calcium in unboiled water, magnesium ion, has been made water be softened.React as follows:
Ca2++2NaR → CaR+2Na+ Mg2++2NaR → MgR+2Na+
Cation exchanger needs to use regenerated liquid regular regeneration.When the sodium ion on exchanger is gradually by calcium, magnesium ion
Replaced, after using a period of time, calcium, magnesium ion will be leaked out, when going out the numerical value that hardness of water reaches defined, i.e.
Out of service, regenerate.By the saline (or dilute hydrochloric acid) of 4-10% from bottom to top by exchange oxidant layer during regeneration.In saline solution
Sodium ion displace again the calcium on exchanger, magnesium ion, make exchanger be regenerated, recover its exchange capacity.React as follows:
CaR+2Na+→ Ca2++2NaR MgR+2Na+→ Mg2++2NaR
As the preferred technical scheme of one, another embodiment of the present utility model, active carbon filter uses product water fixed
Phase backwash, cation exchanger add regenerated liquid regular regeneration, in backwash liquid waste and regeneration liquid waste containing a certain amount of metal from
Son, waste collection pond delivered to combined oxidation unit after collecting and processed further.
As the preferred technical scheme of one, another embodiment of the present utility model, evaporative crystallization unit uses single-action to steam
Send out the one in device or multi-effect evaporator.Vaporizer uses in forward feed, salt-draining of parallel flow or adverse current feeding, countercurrently salt discharge
One, obtain under conditions of vapor (steam) temperature is 80 DEG C ~ 140 DEG C separate out NaCl crystal salt slurry.
Multi-effect evaporator can be the one in two effects, triple effect, quadruple effect, five effects, six effects and seven single-effect evaporators.Multiple-effect is steamed
Send out device using the steam of previous effect as rear one effect add vapours, so multiple-effect evaporation can save give birth to steam consumption.Multiple-effect
Evaporating the increase with effect number, when total evaporation is identical, required raw quantity of steam then reduces, and operating cost reduces.But effect number is the most,
Its cost of equipment is the highest, and along with the increase of effect number, the raw quantity of steam saved is the most fewer and feweri.Effect number is too much in theory,
Evaporator operation will be difficult to.
As the preferred technical scheme of one, another embodiment of the present utility model, Multi-effect evaporation crystallizer centrifugation
Go out the slurry of the salt after NaCl and return the product water mixing circulation utilization of I single-effect evaporator and cation exchanger；Salt is starched through repeatedly circulating
After utilization, heteroion enrichment concentrates, and concentration is gradually increased, such as COD, NO3 -、NO2 -Deng, now salt slurry is entered chemistry again
Impurity removing unit processes.The mother solution amount that evaporative crystallization unit produces is little, carries out mummification landfill after the dense hydration with nanofiltration system also.
As the preferred technical scheme of one, another embodiment of the present utility model, evaporative crystallization unit includes that preheating is single
Unit, evaporation element, crystallisation by cooling unit, solid-liquid separation unit four part.
Brine waste preheating unit is made up of condensed water preheater and vapor preheater.It is pre-that brine waste is introduced into condensed water
Hot device, enters vapor preheater after preliminary preheating.Condensed water preheater and vapor preheater all use plate type heat exchanger, heating to be situated between
Matter is respectively indirect steam condensed water and the indirect steam of this device generation or gives birth to steam, controls to enter the material of evaporative crystallization unit
Liquid temp is more than 50 DEG C.
Enter evaporation element after brine waste is preheated, carry out forced-circulation evaporation crystallization.Evaporation element by heater, point
Form from device and circulating pump.In separator, material evaporates under the temperature conditions set, when the density of material reaches setting value
Discharging pump starts to deliver to the concentrated solution containing solid solid-liquid separation unit one isolated NaCl solid.
Crystallisation by cooling unit is mainly made up of crystallizer, cooler and circulating pump etc..In crystallizer, there is a guide shell at middle part,
A cylindrical baffle is had in surrounding.Brine waste forms the condition of good mixing under guide shell internal propeller stirring action.Circle
Crystallizer is divided into crystal growth district and settling section by cylindrical baffle.Brine waste is able to from mother solution sedimentation at settling section crystal
Separating, only the crystallite of excess can be with mother solution outside the top displacer of settling section.
Solid-liquid separation unit is made up of centrifuge, mother liquor tank and mother solution pump.Centrifuge can use continuous operation filter from
Scheming.Can under full-speed operation, be carried out continuously charging, separate, wash, the operation such as discharging.
Evaporation element water outlet sequentially enters crystallisation by cooling unit one, solid-liquid separation unit two, by regulation crystallisation by cooling
Temperature is by Na in brine waste2SO4Solid separates out, and finally gives purity and reaches technical grade NaCl and Na of more than 96%2SO4Solid
Salt.The mother solution that solid-liquid separation unit produces is stored in mother liquor tank, is finally back to evaporation element and processes further.
It is exemplified below several example so that effect of the present utility model to be described, but protection domain of the present utility model the most only limits
In this.
Embodiment 1:
Certain Coal Chemical Industry strong brine processing item, influent COD be 600mg/L, TDS be 9000mg/L, Na+For 2500mg/L,
Cl-For 3500mg/L, SO4 2-For 800mg/L.
Strong brine zero-emission is used to produce the device (Fig. 1) of Nacl, including nano-filtration unit, combined oxidation unit, chemistry
Impurity removing unit, special membrane unit, active carbon filter, cation exchanger, for buffer evaporative crystallization unit water inlet centre
Pond, and for producing the evaporative crystallization unit of Nacl.Described nano-filtration unit, described combined oxidation unit, described chemistry
Impurity removing unit, described special membrane unit, described active carbon filter, described cation exchanger, described intermediate pool and institute
State evaporative crystallization unit to be linked in sequence successively by pipeline.
Wherein, combined oxidation unit, chemical subtraction unit are connected by pipeline sludge treating block；Described activated carbon mistake
Filter is provided with counter-flushing pipeline, the counter-flushing pipeline of described active carbon filter and cation exchanger regenerate water lines
Connecting has waste collection pond, described sludge treating block to be connected by pipeline with waste collection pond.
The first step, strong brine enters nano-filtration unit preliminary treatment, and NF membrane model is HYDRAPRO402, molecular cut off
Scope is 150 ~ 200nm, operates pressure limit 15 ~ 30bar, and the response rate is about 90%.Described NF membrane is to Organic substance in strong brine
Rejection be 50%, the clearance to total hardness is 60%.
Second step, the product water after the first step processes enters combined oxidation unit, with sulphuric acid, pH is adjusted to 4.0, adds multiple
Conjunction oxidant is H2O2And FeSO4, H2O2Dosage is 1.5 times of influent COD, H2O2With Fe2+Mol ratio be 10:1, during reaction
Between be 2h, with sodium hydroxide, pH is adjusted to 10 after reaction, course of reaction uses middling speed or quickly stirs.Throw after having reacted
Adding flocculant, flocculant uses iron-based flocculating agent ferrous sulfate, quickly stirs 10min, standing sedimentation 30min.To in strong brine
The clearance of COD is 95%, and water outlet COD is 20mg/L；
The bottom sediment of combined oxidation unit enters sludge treating block.The filtrate of sludge treating block enters waste liquid and receives
Ji Chi, dewatered sludge carries out security landfill.
3rd step, the product water after second step processes enters chemical subtraction unit.First add MgO magnesia mixture and remove SiO2,
Control precipitation in the basic conditions and remove strontium, zinc, iron metal ion, then add flocculant (ibid step).Chemical subtraction unit
Bottom sediment enter sludge treating block.Add MgO and SiO in strong brine3 2-Mass ratio be 0.5:1.
4th step, the product water after described three step process enters special membrane unit.Described special membrane unit uses
DTRO film.The dense water of special membrane dense water side is saline.Special membrane unit is divided into two-stage, wherein one-level membrane operations pressure 90Bar, returns
Yield 60 ~ 70%；Secondary membrane operation pressure 160Bar, response rate 50-60%.Thus into subsequent processing units the water yield significantly
Reduce, save investment and operating cost.In the dense water of two grades of special membrane unit generations, TDS is about 140000mg/L, COD content
It is about 400mg/L.
5th step, the dense water after described 4th step processes enters active carbon filter, and effect is by absorption and to filter
The Organic substance in demineralized water is removed in effect.
6th step, the dense water after described 5th step processes enters cation exchanger, and effect is in displacement strong brine
Ca2+、Mg2+、Mn2+、Sr2+、Zn2+、Fe3+Cation, reduces the total hardness of strong brine.Cation exchanger uses fixed bed adverse current
Regeneration technology, uses without top pressure regeneration.
7th step, the dense water after described 6th step processes enters intermediate pool buffering, and effect is to be adjusted into evaporation knot
The water quality of brilliant unit and the water yield.
8th step, the dense water after described 7th step processes is evaporated crystallization, uses single effect evaporator, and effect is to salt
Solution is evaporated crystallization, produces Nacl.Under conditions of temperature is 120 DEG C, obtain separating out the salt slurry of NaCl crystal.
Finally, the NaCl and least a portion of Na of technical grade are obtained2SO4, the purity of Nacl can reach 94%.
Embodiment 2:
The device used is with embodiment 1.Difference is: evaporative crystallization unit uses four-effect evaporator.
Certain strong brine processing item, influent COD be 200mg/L, TDS be 20000mg/L, Na+For 2000mg/L, Cl-For
4000mg/L, SO4 2-It is 500 mg/L.
The first step, strong brine enters nano-filtration unit preliminary treatment, and NF membrane model is HYDRAPRO402, in strong brine
Organic rejection is 60%, and the clearance to total hardness is 60%.
Second step, the product water after the first step processes enters combined oxidation unit, with hydrochloric acid, pH is adjusted to 5.0, adds multiple
Conjunction oxidant is H2O2And FeSO4, H2O2Dosage is 2 times of influent COD, H2O2With Fe2+Mol ratio be 8:1, the response time
For 1.5h, with sodium hydroxide, pH is adjusted to 8 after reaction, course of reaction uses middling speed or quickly stirs.Throw after having reacted
Adding flocculant, flocculant uses Alumen, quickly stirs 10min, standing sedimentation 30min.To the clearance of COD in strong brine it is
95%, water outlet COD are 20mg/L.
3rd step, the product water after second step processes enters chemical subtraction unit.First add magnesia magnesia mixture to remove
SiO2, then add flocculant (ibid step).Add magnesia mixture and SiO in strong brine3 2-Mass ratio be 0.5:1.
4th step, the product water after described three step process enters special membrane unit.Described special membrane unit uses
DTRO film.The dense water of special membrane dense water side is saline.Special membrane unit is divided into two-stage, wherein one-level membrane operations pressure 90Bar, returns
Yield 70%；Secondary membrane operation pressure 160Bar, the response rate 60%.In the dense water of two grades of special membrane dense water side generations, TDS is about
150000mg/L, COD content is about 200mg/L.
5th step, the dense water after described 4th step processes enters active carbon filter, and effect is by absorption and to filter
The Organic substance in demineralized water is removed in effect.
6th step, the dense water after described 5th step processes enters cation exchanger, and effect is in displacement strong brine
Ca2+、Mg2+、Mn2+、Sr2+、Zn2+、Fe3+Cation, reduces the total hardness of strong brine.
7th step, the dense water after described 6th step processes enters intermediate pool buffering, and effect is to be adjusted into evaporation knot
The water quality of brilliant unit and the water yield.
8th step, the dense water after described 7th step processes is evaporated crystallizing, employing four-effect evaporator, adverse current feeding,
Countercurrently salt discharge.Wherein after four-effect evaporator evaporative crystallization, centrifugation is remaining salt slurry return I single-effect evaporator after going out NaCl, with
The product water mixing circulation of cation exchanger utilizes；Salt is starched after 5 times recycle, and again enters at chemical subtraction unit
Reason.Finally, the NaCl and least a portion of Na of technical grade are obtained2SO4, the purity of Nacl reaches 98%.
Above embodiment is only to be described preferred implementation of the present utility model, not to this utility model
Scope be defined, without departing from this utility model design spirit on the premise of, this area ordinary skill technical staff to this
Various modification that the technical scheme of utility model is made and improvement, all should fall into the guarantor that claims of the present utility model determine
In the range of protecting.
Claims (4)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481160A (en) * | 2016-01-15 | 2016-04-13 | 北京清大国华环境股份有限公司 | Method and device for preparing industrial salt with zero emission of concentrated brine |
| CN108128916A (en) * | 2017-11-21 | 2018-06-08 | 清华大学 | Water treatment method and device |
-
2016
- 2016-01-15 CN CN201620035312.0U patent/CN205473142U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481160A (en) * | 2016-01-15 | 2016-04-13 | 北京清大国华环境股份有限公司 | Method and device for preparing industrial salt with zero emission of concentrated brine |
| CN105481160B (en) * | 2016-01-15 | 2022-05-24 | 清大国华环境集团股份有限公司 | Method and device for preparing industrial salt by strong brine with zero discharge |
| CN108128916A (en) * | 2017-11-21 | 2018-06-08 | 清华大学 | Water treatment method and device |
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Address after: 100085 C404, Building C, Jiahua Building, 9 Shangdi Third Street, Haidian District, Beijing Patentee after: GO HIGHER ENVIRONMENT GROUP Co.,Ltd. Address before: 100085 C404, Building C, Jiahua Building, 9 Shangdi Third Street, Haidian District, Beijing Patentee before: GO HIGHER ENVIRONMENT CO.,LTD. |
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Granted publication date: 20160817 |