CN110104865A - Spent acid, salkali waste, the wastewater zero discharge system of crystal salt recycling and method can be achieved - Google Patents
Spent acid, salkali waste, the wastewater zero discharge system of crystal salt recycling and method can be achieved Download PDFInfo
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- CN110104865A CN110104865A CN201910511422.8A CN201910511422A CN110104865A CN 110104865 A CN110104865 A CN 110104865A CN 201910511422 A CN201910511422 A CN 201910511422A CN 110104865 A CN110104865 A CN 110104865A
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- waste
- exchange resin
- water
- spent acid
- salt
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- 239000002253 acid Substances 0.000 title claims abstract description 83
- 150000003839 salts Chemical class 0.000 title claims abstract description 74
- 239000002699 waste material Substances 0.000 title claims abstract description 68
- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 239000013078 crystal Substances 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001728 nano-filtration Methods 0.000 claims abstract description 41
- 238000012545 processing Methods 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 36
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 33
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 29
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 21
- 230000001172 regenerating effect Effects 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000012267 brine Substances 0.000 claims abstract description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000008929 regeneration Effects 0.000 claims description 20
- 238000011069 regeneration method Methods 0.000 claims description 20
- 238000000909 electrodialysis Methods 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- 239000012141 concentrate Substances 0.000 claims description 15
- 238000000502 dialysis Methods 0.000 claims description 15
- 238000009792 diffusion process Methods 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 14
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- -1 salt ion Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005345 coagulation Methods 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 4
- 238000011033 desalting Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 239000010808 liquid waste Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000010612 desalination reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 230000003134 recirculating effect Effects 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 235000012489 doughnuts Nutrition 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 239000012492 regenerant Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 4
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A kind of achievable spent acid, salkali waste, the wastewater zero discharge system of crystal salt recycling and method, wastewater zero discharge system include that sequentially connected cation exchange resin system and anion change resin system；The waste liquid outlet of the cation exchange resin system is connected to regenerating spent acid processing system, and the waste liquid outlet of the anion exchange resin system is connected to regenerated alkali process system；The waste liquid outlet of the regenerating spent acid processing system and regenerated alkali process system is connected to waste water treatment system, the outlet of the waste water treatment system is connected to reverse osmosis membrane system, the waste liquid outlet of the reverse osmosis membrane system is connected to strong brine nanofiltration point salt system, which is respectively connected to monovalent salt vapo(u)rization system and multivalent salts vapo(u)rization system.Present invention process is reasonable, system run all right, it can be achieved that spent acid, salkali waste, crystal salt resource utilization utilize while generating high-quality pure water.
Description
Technical field
The invention belongs to while technical field of waste water processing more particularly to a kind of generation high-quality pure water, it can be achieved that useless
Acid, salkali waste, the wastewater zero discharge system of crystal salt recycling and method.
Background technique
Growing tension and economic continuous development along with water resource, industrial enterprise is in water resource utilization, environmental protection
Increase increasingly with the pressure in terms of discharge of wastewater, realizing wastewater zero discharge gradually becomes the primary choosing of current industrial enterprise
It selects.
Ion exchange resin desalinating process is in all conglomeraties such as electric power, steel, chemical industry, papermaking, microelectronics, biofermentation
It is applied, is the important link that these industrial trades prepare desalted water.However, ion exchange resin is in use, need
The resin of failure is regenerated using certain density chemical regenerant, such as acid, alkali, thus generated chemical regeneration
Waste liquid can not recycle for a long time, can only simply carry out entering waste water treatment system or Zero discharging system after acid-base neutralization.
Above-mentioned simple Neutralisation treatment method not only increases the water load of waste water treatment system, while ion exchange
The high salinity of resin regeneration waste water, which can also be constituted original waste water treatment system, impacts, and is unfavorable for its normal, stable operation,
Also the processing difficulty of Zero discharging system downstream is thereby increased.
There is partial monopoly (such as CN103755082A, CN206467016U etc.) to refer to ion exchange resin regeneration in recent years
The technique of zero discharge of waste water.However, these techniques are still limited to first carry out the neutralization of acid waste water and alkaline waste water, Zhi Houzai
For the neutral waste water after mixing, waste water recycling is carried out using such as the methods of reverse osmosis membrane or electrodialysis, technique is final
It can be only done Sewage treatment, and be unable to complete effective recycling of bronsted lowry acids and bases bronsted lowry.
In addition, also there is partial monopoly (such as CN207121452U, CN204298109U etc.) using switch valve pair in recent years
The regeneration liquid waste of ion exchange switches over segmentation.However, this switching segmentation was discharged only in waste water in flowing
Simple cutting in journey is not the substance transmitting and separation process carried out on molecular scale, cannot achieve spent acid yet and give up
The concentration and purity of lye are adjusted, and it is even more impossible to realize the effective recycling of the chemical resources such as acid/base.
Summary of the invention
The object of the present invention is to provide a kind of achievable spent acid, salkali waste, crystal salt recycling wastewater zero discharge system and
Method, rational technology, system run all right, it can be achieved that spent acid, salkali waste, crystal salt money while generating high-quality pure water
Sourceization recycles.
To achieve the above object, the present invention takes following technical scheme:
A kind of achievable spent acid, salkali waste, crystal salt recycling wastewater zero discharge system, including sequentially connected cation
Exchanger resin system and anion change resin system；The waste liquid outlet of the cation exchange resin system is connected at regenerating spent acid
Reason system, the waste liquid outlet of the anion exchange resin system are connected to regenerated alkali process system；The regenerating spent acid processing system
System and the waste liquid outlet of regenerated alkali process system are connected to waste water treatment system, and the outlet of the waste water treatment system is connected to
Reverse osmosis membrane system, the waste liquid outlet of the reverse osmosis membrane system are connected to strong brine nanofiltration point salt system, the strong brine nanofiltration point
Salt system is respectively connected to monovalent salt vapo(u)rization system and multivalent salts vapo(u)rization system.
Further, the net liquid of the regenerating spent acid processing system and regenerated alkali process system outlet is connected to boiler
Smoke processing system, recirculating cooling water system, ion exchange resin system, full factory's makeup Water System.
Further, the waste liquid outlet of the anion exchange resin system is connected to the waste water treatment system simultaneously,
The entrance of the waste water treatment system is connect with desulfurization wastewater pipeline and comprehensive wastewater pipeline.
Further, the achievable spent acid, salkali waste, crystal salt recycling wastewater zero discharge system, further include pre-
Processing system and product processing system, the pretreatment system are arranged before the cation exchange resin system, the product system
System is arranged after the monovalent salt vapo(u)rization system and multivalent salts vapo(u)rization system.
Further, the pretreatment system includes coagulation system, settling system, biochemistry treatment system, advanced oxygen
Change at least one of processing system, air-flotation system, filtration system, melded system, the product processing system includes reverse osmosis
Water producing tank system, drying system and at least one of mix ash system.
Further, the regenerating spent acid processing system and regenerated alkali process system include nanofiltration membrane system, electric osmose
One of analysis system, diffusion dialysis system are a variety of；The waste water treatment system includes filtration system, flocculation system, clarification
One of system is a variety of.
Further, the reverse osmosis membrane of the reverse osmosis membrane system is polyamide or poly- piperazine material；The reverse osmosis membrane
For wound membrane element, flat membrane component or hollow fibre membrane component；The strong brine nanofiltration divides the nanofiltration membrane of salt system to be polyamides
Amine, polyacrylonitrile, polysulfones, polyether sulfone or poly- piperazine material, the nanofiltration membrane can for wound membrane element, flat membrane component, in
Empty fiber membrane element.
A kind of achievable spent acid, salkali waste, crystal salt recycling zero emission method of wastewater, utilize the wastewater zero discharge
System, the zero emission method of wastewater the following steps are included:
S1, industrial raw water, is pre-processed by pretreatment system, which includes coagulation, precipitating, biology
It is chemical treatment, advanced oxidation processing, air bearing, filtering, chemical tendering, one or more in UF membrane, by pretreated original
Water enters cation exchange resin system and anion changes resin system and carries out desalination or depth polishing desalting processing；
S2, the product water by anion and cation exchange resin system, which enters next stage purification system or is supplied to, uses water spot；
S3, anion and cation exchange resin system carry out resin regeneration using alkali/acid after a duty cycle terminates；
The acid regeneration waste liquid of S4, cation exchange resin system use nanofiltration membrane system, electrodialysis system and diffusion dialysis
One of system or a variety of impurity separated in waste liquid simultaneously recycle pure acid；The alkali regeneration liquid waste of anion exchange resin system is adopted
With the impurity in one of nanofiltration membrane system, electrodialysis system and diffusion dialysis system or a variety of separation waste liquids and recycle pure
Alkali；
S5, residual solution caused by above-mentioned nanofiltration membrane system, electrodialysis or diffusion dialysis system are infused as pH adjusting agent
Enter waste water treatment system；
S6, the waste water in waste water treatment system after pretreatment by reverse osmosis membrane system recycling pure water, and to salinity
It carries out concentrate and forms strong brine；
S7, strong brine, which enters strong brine nanofiltration point salt system, to carry out point salt and operates, and obtains the concentrated water containing high price salt ion
With the production water of enrichment monovalence salt ion；
S8, the concentrated water and the production water carry out concentrate again again by reverse osmosis membrane system respectively, then respectively into
Enter corresponding multivalent salts vapo(u)rization system and pure salt is prepared in monovalent salt vapo(u)rization system.
It further, further include purification step and/or concentrate step in S4；
The purification step is that Reusability nanofiltration membrane or resin technology carry out acid/base purifying；
The concentrate step is that Reusability reverse osmosis membrane or evaporation carry out acid/base concentrate.
Further, the anion and cation exchange resin system selects the ion of polystyrene or polyacrylic acid substrate
Exchanger resin；The anion and cation exchange resin system is regenerated using acid or alkaline regenerative agent, the regenerative agent be hydrochloric acid,
Sulfuric acid, nitric acid, phosphoric acid, sodium hydroxide, potassium hydroxide or ammonium hydroxide.
The beneficial effects of the present invention are: the wastewater zero discharge system of the achievable spent acid of the present invention, salkali waste, crystal salt recycling
And method, rational technology, system run all right, it can be achieved that spent acid, salkali waste, crystal salt while generating high-quality pure water
Resource utilization utilizes.
Detailed description of the invention
Fig. 1 be the achievable spent acid of the present invention, salkali waste, crystal salt recycling wastewater zero discharge system embodiment 1 knot
Structure schematic diagram.
Fig. 2 be the achievable spent acid of the present invention, salkali waste, crystal salt recycling wastewater zero discharge system embodiment 2 knot
Structure schematic diagram.
Fig. 3 be the achievable spent acid of the present invention, salkali waste, crystal salt recycling wastewater zero discharge system embodiment 3 knot
Structure schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing, to the present invention into
Row is further described.It should be appreciated that the specific embodiments described herein are only used to explain the present invention, it is not used to
Limit the present invention.
As shown in Figure 1, the present invention provide a kind of achievable spent acid, salkali waste, crystal salt recycling wastewater zero discharge system,
Resin system 2 is changed including sequentially connected cation exchange resin system 1 and anion.The cation exchange resin system 1
Waste liquid outlet 11 is connected to regenerating spent acid processing system 3, and the waste liquid outlet 21 of the anion exchange resin system 2 is connected to regeneration
Salkali waste processing system 4.The waste liquid outlet 31,41 of the regenerating spent acid processing system 3 and regenerated alkali process system 4 is connected to useless
The outlet 51 of water treatment system 5, the waste water treatment system 5 is connected to reverse osmosis membrane system 6, the waste liquid of the reverse osmosis membrane system 6
Outlet 61 is connected to strong brine nanofiltration point salt system 7, which is respectively connected to monovalent salt vapo(u)rization system
8 and multivalent salts vapo(u)rization system 9.
Anion and cation exchange resin system 2,1 utilizes ion exchange principle for becoming the further desalting and purifying of water
High-quality pure water is for industrial application；And after a cycle of operation of ion exchange resin terminates, it needs using bronsted lowry acids and bases bronsted lowry
Equal chemical regenerations reagent is regenerated, and regenerated acid enters the regenerating spent acid processing system 3, and regenerating alkali enters the regenerated alkali process
System 4, the regenerating spent acid processing system 3 and regenerated alkali process system 4 can use the nanofiltration principle of nanofiltration membrane system to not
Ion or molecule with component are separated, and are obtained purifying acid and purifying alkali, are sent to factory's other processes respectively and are returned
With；The waste liquid of the regenerating spent acid processing system 3 and regenerated alkali process system 4 contains original spent acid and the concentration of salkali waste is miscellaneous
Matter, is discharged into full factory's comprehensive wastewater treatment system 5 after decrement concentration, and waste water treatment system 5 utilizes filtering, flocculation, clarification etc.
Principle pre-processes waste water, can using the pure water that principle of reverse osmosis is filtered water into reverse osmosis membrane system 6
Reuse is carried out with reuse to factory's other processes；The waste liquid of reverse osmosis membrane system 6 is to mix high strong brine, mainly organize become with
Sodium chloride is the monovalent salt of representative and using sodium sulphate as multivalent salts of representative etc., respectively enters monovalent salt vapo(u)rization system 8 and multivalence
Salt vapo(u)rization system 9 separates water and salinity using evaporating principle.Anion and cation exchange resin system, nanofiltration membrane system,
Waste water treatment system, reverse osmosis membrane system, monovalent salt vapo(u)rization system and multivalent salts vapo(u)rization system are no less than one.
As shown in Fig. 2, in the present embodiment, other than the main flow introduced in embodiment 1, also describing regeneration
The reuse place to go of bronsted lowry acids and bases bronsted lowry caused by waste acid treatment system 3 and regenerated alkali process system 4.In general industrial trade,
Spent acid salkali waste from ion exchange resin system can be back to use the smoke processing system A of boiler, follow after purifying
Ring cooling water system B, ion exchange resin system C, full factory's makeup Water System D etc..The bronsted lowry acids and bases bronsted lowry of reuse can be used as original useless
PH adjusting agent of water treatment system 5, or the preparation water as soda acid needed for it etc., the soda acid for thus saving related system disappear
Consumption and operating cost.
As shown in figure 3, other than the main flow introduced in embodiment 1 and embodiment 2, being also situated between in the present embodiment
The coupling case of the system that continued and power industry desulfurization wastewater.The waste liquid outlet 21 of the anion exchange resin system 2 is simultaneously
It is connected to the waste water treatment system 5, the entrance 52 and desulfurization wastewater pipeline 53 and comprehensive wastewater pipeline 54 of the waste water treatment system 5
Connection.The high rigidity feature as possessed by the desulfurization wastewater of power industry needs to be added in its preprocessing process a large amount of
Soften medicament, such as lime, calcium carbonate carry out chemical tendering.And in this step, from the dense of regenerated alkali process system 4
Contracting waste liquid or the pretreatment system that desulfurization wastewater can be supplemented into from the salkali waste of anion exchange resin system 2, and
It also can be used as the pH adjusting agent of desulfurization wastewater treatment system from the concentrating spent liquor of regenerating spent acid processing system 3.Complete chemistry
After hard, or enter full factory's comprehensive wastewater treatment system, enters after converging with full factory's comprehensive wastewater and being preprocessed complete
Factory's Zero discharging system, or the desulfurization wastewater completed after chemistry removes firmly can individually enter waste water reverse osmosis membranous system, complete
Desulfurization wastewater zero-emission.
In addition, the wastewater zero discharge system of achievable spent acid, salkali waste described in above three embodiments, crystal salt recycling
System, further includes pretreatment system and product processing system, pretreatment system setting the cation exchange resin system 1 it
Before, for removing waste water scale forming matter therein；Product systems setting is in the monovalent salt vapo(u)rization system 8 and multivalent salts evaporation system
After system 9, for being further processed to product.The pretreatment system includes coagulation system, settling system, biochemistry treatment
At least one of system, advanced oxidation processing system, air-flotation system, filtration system, melded system, the product processing system packet
At least one of include reverse osmosis produced water tank system, drying system and mix ash system.
The regenerating spent acid processing system 3 and regenerated alkali process system 4 include nanofiltration membrane system, electrodialysis system, expansion
Dissipate one of electrodialysis system or a variety of.The waste water treatment system 5 includes one in filtration system, flocculation system, clarification system
Kind is a variety of.
The reverse osmosis membrane of the reverse osmosis membrane system 6 is polyamide or poly- piperazine material.The reverse osmosis membrane is rolling membrane element
Part, flat membrane component or hollow fibre membrane component.The strong brine nanofiltration divide salt system 7 nanofiltration membrane be polyamide, polyacrylonitrile,
Polysulfones, polyether sulfone or poly- piperazine material, the nanofiltration membrane can be wound membrane element, flat membrane component, hollow fibre membrane component.
The present invention also provides a kind of achievable spent acid, salkali waste, crystal salt recycling zero emission method of wastewater, using described
Wastewater zero discharge system, the zero emission method of wastewater the following steps are included:
S1, industrial raw water, such as surface water, well water, seawater, municipal water supply, municipal wastewater or trade effluent, warp
Pretreatment system is crossed to be pre-processed, the pretreatment include coagulation, precipitating, biochemistry treatment, advanced oxidation processing, air bearing,
It is filtering, chemical tendering, one or more in UF membrane, enter 1 He of cation exchange resin system by pretreated raw water
Anion changes resin system 2 and carries out desalination or depth polishing desalting processing；
S2, the product water by anion and cation exchange resin system, which enters next stage purification system or is supplied to, uses water spot；
S3, anion and cation exchange resin system carry out resin regeneration using alkali/acid after a duty cycle terminates；
The acid regeneration waste liquid of S4, cation exchange resin system 1 use nanofiltration membrane system, electrodialysis system and diffusion dialysis
One of system or a variety of impurity separated in waste liquid simultaneously recycle pure acid, and pure acid can be used for terminal user's sale, industrial process
Produce or be multiplexed with regeneration of ion-exchange resin liquid etc.；The alkali regeneration liquid waste of anion exchange resin system 2 uses nanofiltration membrane
One of system, electrodialysis system and diffusion dialysis system or a variety of impurity separated in waste liquid simultaneously recycle soda ash, and soda ash can
Produce for terminal user's sale, industrial process or be multiplexed with regeneration of ion-exchange resin liquid etc.；Electric osmose may be selected in this step
Analysis perhaps diffusion dialysis technology and is interpreted as Reusability electrodialysis or diffusion dialysis technology, and is interpreted as using receiving
Two kinds in filter membrane, electrodialysis or diffusion dialysis technology or three kinds of technologies are combined, and realize useless acid/base purifying with final
Purpose；
S5, residual solution caused by above-mentioned nanofiltration membrane system, electrodialysis or diffusion dialysis system are infused as pH adjusting agent
Enter waste water treatment system 5；
S6, the waste water in waste water treatment system 5 recycle pure water by reverse osmosis membrane system 6 after pretreatment, and to salt
Divide and carries out concentrate formation strong brine；
S7, strong brine, which enters strong brine nanofiltration point salt system 7, to carry out point salt and operates, and obtains the concentrated water containing high price salt ion
With the production water of enrichment monovalence salt ion；
S8, the concentrated water and the production water carry out concentrate again again by reverse osmosis membrane system respectively, then respectively into
Enter corresponding multivalent salts vapo(u)rization system 9 and pure salt is prepared in monovalent salt vapo(u)rization system 8.
It further include purification step and/or concentrate step in S4；
The purification step is that Reusability nanofiltration membrane or resin technology carry out acid/base purifying；
The concentrate step is that Reusability reverse osmosis membrane or evaporation carry out acid/base concentrate.
The anion and cation exchange resin system selects the ion exchange resin of polystyrene or polyacrylic acid substrate,
Its type includes strongly acidic cation-exchange, weak-type cation exchange resin, strong basic type anion-exchange resin, weak base
Type anion exchange resin, chelating resin, absorption resin etc..
In all conglomeraties such as electric power, steel, chemical industry, papermaking, microelectronics, biofermentation, ion exchange resin is all wide
It is general to be applied to prepare desalted water, however, ion exchange resin then needs certain density chemical regeneration medicine after work saturation
Agent (such as acid, alkali) is regenerated and is transferred to next duty cycle.Resulting acid and alkaline waste water then need by
Enter waste water treatment system after acid-base neutralization processing.Anion and cation exchange resin system of the invention uses acid or alkaline again
Raw agent is regenerated, which is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium hydroxide, potassium hydroxide or ammonium hydroxide.
The present invention carries out acid and alkalinity with nanofiltration membrane (or group technology of electrodialysis, diffusion dialysis or three kinds of technologies)
Wastewater treatment simultaneously recycles the useful chemical substances such as acid therein, alkali, and the volume of residual solution and concentration obtain greatly after recycling
Width reduces, then the impact that while importing subsequent wastewater treatment system and Zero discharging system is constituted also is greatly reduced, while residual solution
(perhaps untreated acid waste water or untreated alkaline waste water) also can be used as the pH of waste water treatment system and Zero discharging system
Regulator, it is corresponding to save the chemical agent expense adjusted for pH, economic benefit is thus generated both ways.
Following experimental examples are tested with the system and method in above-described embodiment, select heterogeneity content waste water into
The experimental test of row nanofiltration membrane and reverse osmosis membrane:
Experimental example 1
Test film is rolling nanofiltration membrane, and simulation ion exchange regenerant spent acid water quality is as shown in table 1, operating flux 10L/
(m2.h), the operation rate of recovery is 75%, and 20 degrees Celsius of test temperature, test result is as shown in table 2.
Table 1. simulates ion exchange regenerant spent acid water quality water quality (unit: mg/L)
| Chloride ion | Sodium ion | Calcium ion | Magnesium ion | Sulfate radical | |
| Concentration (mg/L) | 5290 | 911 | 522 | 398 | 0 |
The nanofiltration concentrated water and producing water water quality (unit: mg/L) of the test waste acid recovery system of table 2.
| Chloride ion | Sodium ion | Calcium ion | Magnesium ion | Sulfate radical | |
| Concentrated water (mg/L) | 10648 | 2435 | 1994 | 1544 | 0 |
| It produces water (mg/L) | 3504 | 403 | 31 | 16 | 0 |
Experimental example 2
Test film is rolling nanofiltration membrane, and simulation ion exchange regenerant salkali waste water quality is as shown in table 1, operating flux 10L/
(m2.h), the operation rate of recovery is 75%, and 20 degrees Celsius of test temperature, test result is as shown in table 2.
Table 1. simulates ion exchange regenerant salkali waste water quality water quality (unit: mg/L)
| Chloride ion | Sulfate radical | Sodium ion | Calcium ion | Magnesium ion | |
| Concentration (mg/L) | 3498 | 871 | 4983 | 0 | 0 |
The nanofiltration concentrated water and producing water water quality (unit: mg/L) of the test waste acid recovery system of table 2.
| Chloride ion | Sulfate radical | Sodium ion | Calcium ion | Magnesium ion | |
| Concentrated water (mg/L) | 12864 | 3406 | 10425 | 0 | 0 |
| It produces water (mg/L) | 376 | 26 | 9529 | 0 | 0 |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
Depending on protection scope of the present invention.
Claims (10)
1. the wastewater zero discharge system of a kind of achievable spent acid, salkali waste, crystal salt recycling, which is characterized in that including successively connecting
The cation exchange resin system and anion connect changes resin system；The waste liquid outlet of the cation exchange resin system is connected to
Regenerating spent acid processing system, the waste liquid outlet of the anion exchange resin system are connected to regenerated alkali process system；The regeneration
The waste liquid outlet of waste acid treatment system and regenerated alkali process system is connected to waste water treatment system, the waste water treatment system
Outlet is connected to reverse osmosis membrane system, and the waste liquid outlet of the reverse osmosis membrane system is connected to strong brine nanofiltration point salt system, this is dense
Salt water nanofiltration point salt system is respectively connected to monovalent salt vapo(u)rization system and multivalent salts vapo(u)rization system.
2. the wastewater zero discharge system of achievable spent acid according to claim 1, salkali waste, crystal salt recycling, feature
Be: the outlet of the net liquid of the regenerating spent acid processing system and regenerated alkali process system is connected to boiler smoke processing system
System, recirculating cooling water system, ion exchange resin system, full factory's makeup Water System.
3. the wastewater zero discharge system of achievable spent acid according to claim 2, salkali waste, crystal salt recycling, feature
It is: the waste liquid outlet of the anion exchange resin system while is connected to the waste water treatment system, the wastewater treatment system
The entrance of system is connect with desulfurization wastewater pipeline and comprehensive wastewater pipeline.
4. the wastewater zero discharge system of achievable spent acid according to any one of claim 1-3, salkali waste, crystal salt recycling
System, it is characterised in that: further include pretreatment system and product processing system, pretreatment system setting is in the cation exchange
Before resin system, which is arranged after the monovalent salt vapo(u)rization system and multivalent salts vapo(u)rization system.
5. the wastewater zero discharge system of achievable spent acid according to claim 4, salkali waste, crystal salt recycling, feature
Be: the pretreatment system includes coagulation system, settling system, biochemistry treatment system, advanced oxidation processing system, gas
At least one of floating system, filtration system, melded system, the product processing system include reverse osmosis produced water tank system, do
Drying system and mix at least one of ash system.
6. the wastewater zero discharge system of achievable spent acid according to any one of claim 1-3, salkali waste, crystal salt recycling
System, it is characterised in that: the regenerating spent acid processing system and regenerated alkali process system include nanofiltration membrane system, electrodialysis system
One of system, diffusion dialysis system are a variety of；The waste water treatment system includes filtration system, flocculation system, clarification system
One of or it is a variety of.
7. the wastewater zero discharge system of achievable spent acid according to any one of claim 1-3, salkali waste, crystal salt recycling
System, it is characterised in that: the reverse osmosis membrane of the reverse osmosis membrane system is polyamide or poly- piperazine material；The reverse osmosis membrane is volume
Formula membrane component, flat membrane component or hollow fibre membrane component；The strong brine nanofiltration divides the nanofiltration membrane of salt system to be polyamide, is poly-
Acrylonitrile, polysulfones, polyether sulfone or poly- piperazine material, the nanofiltration membrane can be wound membrane element, flat membrane component, doughnut
Membrane component.
8. the zero emission method of wastewater of a kind of achievable spent acid, salkali waste, crystal salt recycling, which is characterized in that wanted using right
Seek wastewater zero discharge system described in 1-7, the zero emission method of wastewater the following steps are included:
S1, industrial raw water, is pre-processed by pretreatment system, which includes coagulation, precipitating, biochemistry
It is processing, advanced oxidation processing, air bearing, filtering, chemical tendering, one or more in UF membrane, by pretreated raw water into
Enter cation exchange resin system and anion changes resin system and carries out desalination or depth polishing desalting processing；
S2, the product water by anion and cation exchange resin system, which enters next stage purification system or is supplied to, uses water spot；
S3, anion and cation exchange resin system carry out resin regeneration using alkali/acid after a duty cycle terminates；
The acid regeneration waste liquid of S4, cation exchange resin system use nanofiltration membrane system, electrodialysis system and diffusion dialysis system
One of or it is a variety of separation waste liquid in impurity and recycle pure acid；The alkali regeneration liquid waste of anion exchange resin system is used and is received
One of filter membrane system, electrodialysis system and diffusion dialysis system or a variety of impurity separated in waste liquid simultaneously recycle soda ash；
S5, residual solution caused by above-mentioned nanofiltration membrane system, electrodialysis or diffusion dialysis system are useless as pH adjusting agent injection
Water treatment system；
S6, the waste water in waste water treatment system recycle pure water by reverse osmosis membrane system after pretreatment, and to salinity progress
Concentrate forms strong brine；
S7, strong brine, which enters strong brine nanofiltration point salt system, to carry out point salt and operates, and obtains the concentrated water and richness containing high price salt ion
Collect the production water of monovalence salt ion；
S8, the concentrated water and the production water carry out concentrate again again by reverse osmosis membrane system respectively, then respectively enter phase
Pure salt is prepared in the multivalent salts vapo(u)rization system and monovalent salt vapo(u)rization system answered.
9. the zero emission method of wastewater of achievable spent acid according to claim 8, salkali waste, crystal salt recycling, feature
It is: further includes purification step and/or concentrate step in S4；
The purification step is that Reusability nanofiltration membrane or resin technology carry out acid/base purifying；
The concentrate step is that Reusability reverse osmosis membrane or evaporation carry out acid/base concentrate.
10. the zero emission method of wastewater of achievable spent acid according to claim 8 or claim 9, salkali waste, crystal salt recycling,
Be characterized in that: the anion and cation exchange resin system selects the ion exchange resin of polystyrene or polyacrylic acid substrate；
The anion and cation exchange resin system is regenerated using acid or alkaline regenerative agent, the regenerative agent be hydrochloric acid, sulfuric acid, nitric acid,
Phosphoric acid, sodium hydroxide, potassium hydroxide or ammonium hydroxide.
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| CN116639769A (en) * | 2023-07-27 | 2023-08-25 | 杭州永洁达净化科技有限公司 | Method and system for recycling polished waste acid |
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