CN111268859A - Method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine - Google Patents
Method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine Download PDFInfo
- Publication number
- CN111268859A CN111268859A CN202010071570.5A CN202010071570A CN111268859A CN 111268859 A CN111268859 A CN 111268859A CN 202010071570 A CN202010071570 A CN 202010071570A CN 111268859 A CN111268859 A CN 111268859A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- water
- reverse osmosis
- enters
- effluent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 72
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000012267 brine Substances 0.000 title claims abstract description 43
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002351 wastewater Substances 0.000 claims abstract description 70
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 238000001728 nano-filtration Methods 0.000 claims abstract description 29
- 230000001105 regulatory effect Effects 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 17
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 17
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 17
- 238000000909 electrodialysis Methods 0.000 claims abstract description 13
- 239000004576 sand Substances 0.000 claims abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 6
- 238000011010 flushing procedure Methods 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000033228 biological regulation Effects 0.000 claims description 8
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 239000013505 freshwater Substances 0.000 claims description 6
- 231100000719 pollutant Toxicity 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- -1 fluoride ions Chemical class 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000009287 sand filtration Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 230000001502 supplementing effect Effects 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000009292 forward osmosis Methods 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/20—Preparation by reacting oxides or hydroxides with alkali metal salts
-
- 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
- C02F1/44—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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to a method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine, wherein metallurgical reverse osmosis strong brine enters a regulating tank, calcium hydroxide solution and PAM are added, then anhydrous sodium carbonate is added, supernatant flows into a denitrification biological filter, methanol is added into the denitrification biological filter, and effluent of the denitrification biological filter enters a first ozone oxidation tower; the effluent of the first ozone oxidation tower enters a sand filter; then the wastewater enters an ultrafiltration device, ultrafiltration produced water enters a second-stage reverse osmosis system RO for concentration and separation, high-salt water generated by the second-stage reverse osmosis system RO is injected into chelating type ion exchange resin, and effluent enters a second ozone oxidation tower; the nanofiltration device divides the wastewater into water and concentrated water, the concentrated water is sent to a blast furnace for slag flushing or an incinerator, and the nanofiltration water is sent to a bipolar membrane electrodialysis device. The advantages are that: the process has the advantages of low energy consumption, low cost, simple equipment, easy operation and stable treatment effect.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis concentrated brine.
Background
The unit water consumption of the steel enterprises in China is still higher than the level of the advanced steel enterprises in China, so that the new water consumption per ton of steel of the steel enterprises is further reduced, the cyclic utilization rate of water of the steel enterprises is improved, and the comprehensive treatment and recycling of wastewater of the steel enterprises are enhanced, which is one of the keys for realizing sustainable development of the steel enterprises.
The reuse of wastewater is the final target of wastewater treatment, but after the wastewater is subjected to reverse osmosis treatment, most of primary pure water is obtained, and simultaneously, a large proportion of high-salinity concentrated water is also produced, the concentrated water is an inevitable product of a reverse osmosis desalination process, contains high organic matters and salt concentration, and the concentrated water content is about 25% of the reverse osmosis treatment water content. For the high-salinity concentrated water, the treatment method at the present stage is basically direct discharge, which causes a great deal of resource waste and environmental pollution.
Patent application No.: 201010283192.3, discloses a process for desalting strong brine by pervaporation technology and recovers purified water. The technology has high operation energy consumption, needs to heat the strong brine to more than 60 ℃, can only remove salt in the strong brine, and cannot effectively remove organic matters in the strong brine. Patent application No.: 200910070804.8, a forward osmosis membrane module is adopted, the seawater desalination strong brine is used as a drawing liquid, fresh water is used as a feeding liquid, part of the fresh water which permeates the seawater desalination strong brine at the permeation side of the forward osmosis membrane module and the feeding liquid side is mixed into diluted standard salt water and then is discharged out of the forward osmosis membrane module, and the rest of the feeding liquid is discharged out of the forward osmosis membrane module. The technology can only be used for treating the seawater strong brine, and is not suitable for the strong brine process in the metallurgical industry. Patent publication No. CN1030773143B discloses a strong brine zero emission treatment process of steel plant, adopts tertiary reverse osmosis process to carry out waste water concentration, then carries out evaporation crystallization. The concentration of the three-stage reverse osmosis has high operation cost, and the process does not consider the problems of organic pollution, inorganic scaling and the like of the reverse osmosis membrane. Patent publication No. CN103253820B discloses a high-efficient liquid zero release waste water treatment method and system, and although this system has the advantage that the energy consumption is low efficient, the mixed salt that obtains can't be dealt with just becomes secondary pollutant, even dangerous discarded object, consequently does not solve the problem of solid salt retrieval and utilization, still puzzles the further development of enterprise.
In conclusion, the existing strong brine treatment process of metallurgical enterprises has the defects of poor treatment effect, serious membrane pollution, low water yield of a system and overhigh process operation cost. Therefore, the development of an efficient method for resource utilization of the concentrated brine of the metallurgical enterprise can save a large amount of new water resources for the metallurgical enterprise, the adverse effect of the discharge of the concentrated brine on the environment of the surrounding water area can be reduced by greatly reducing the discharge amount of the concentrated brine, the resource utilization of the production wastewater is a new benefit growth point, and the method has important significance for realizing water saving and emission reduction of the enterprise.
Disclosure of Invention
Aiming at the reverse osmosis concentrated brine discharged by steel enterprises, the method is sequentially carried out with a sedimentation tank, a denitrification tank, an ozone oxidation tank, a sand filter, ultrafiltration, reverse osmosis, ion exchange resin, ozone oxidation, nanofiltration salt separation and bipolar membrane electrodialysis for treatment, and the concentrated solution of the comprehensive wastewater can be finally converted into acid and alkali byproducts.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis concentrated brine comprises the following steps:
1) firstly, feeding metallurgical reverse osmosis strong brine into a regulating tank, adding a calcium hydroxide solution while stirring to regulate the pH value of the wastewater to 11-12, adding 1-2ppm of PAM, and precipitating for 0.5-1.5 hours; adding anhydrous sodium carbonate, stirring for reaction for 20-30 minutes, precipitating for 1-2 hours, effectively removing total hardness and fluoride ions in raw water through precipitation, enabling supernatant to flow into a denitrification biological filter, adjusting the pH value of wastewater to 8.0-9.0, supplementing methanol into the denitrification biological filter to provide sufficient carbon source for nitrate denitrification, wherein the biological filter is filled with ceramsite filter material, and the hydraulic retention time is 7-9 hours;
2) the effluent of the denitrification biological filter enters a first ozone oxidation tower, the pH of the wastewater is controlled to be 11.0-12.0, the adding amount of ozone is 20-24mg/L, and under the strong oxidation effect of the ozone, organic matters which cannot be biodegraded in the wastewater are oxidized into micromolecular organic matters which are easy to biodegrade or are partially mineralized by the ozone;
3) the effluent of the first ozone oxidation tower enters a sand filter, fine suspended matters and particles are further removed, the quality of the effluent is enhanced, and backwash water of the biological filter and the sand filter returns to a front-end regulating tank; the pH of the effluent of sand filtration is adjusted to control the pH of the wastewater to be 6.2-6.6, then the wastewater enters an ultrafiltration device to further intercept suspended matters and colloid pollutants in the wastewater, concentrated water of the ultrafiltration device flows back to an adjusting tank to be circularly treated, ultrafiltration produced water enters a two-stage reverse osmosis system RO to be concentrated and separated to intercept most of salt and small molecular organic matters in the wastewater, the RO produced water of the two-stage reverse osmosis system enters a fresh water storage tank to be recycled, high salt water generated by the RO of the two-stage reverse osmosis system is injected into chelate ion exchange resin to adsorb residual calcium, magnesium and other metal ions in the wastewater through the exchange performance of the resin, regeneration wastewater of the ion exchange resin flows back to the adjusting tank to be circularly treated, effluent enters a second ozone oxidation tower to control the pH of the wastewater in the oxidation tank to be 11-12, and the ozone dosage to be 22-28mg/L, adjusting the pH of the effluent of the second ozone oxidation tower to 6.4-6.8, and then feeding the effluent into a nanofiltration device;
4) the nanofiltration device divides the wastewater into water and concentrated water, the nanofiltration concentrated water is sent to a blast furnace for slag flushing or an incinerator, the nanofiltration water is sent to a bipolar membrane electrodialysis device for treatment, the bipolar membrane electrodialysis device finally converts the salt in the nanofiltration water into corresponding hydrochloric acid and sodium hydroxide, and the low-concentration hydrochloric acid and sodium hydroxide can be reused for acid-base regulation in the system.
The metallurgy reverse osmosis strong brine is reverse osmosis strong brine for steel production, the pH is 7.0-8.5, the conductivity is 7.0-8.0ms/cm, the COD is 80-100mg/L, the nitrate radical is less than or equal to 90mg/L, and the fluorine ion is less than or equal to 35 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
the method is used for treating the reverse osmosis strong brine discharged by steel enterprises by a sedimentation tank, a denitrification tank, an ozone oxidation tank, a sand filter tank, ultrafiltration, reverse osmosis, ion exchange resin, ozone oxidation, nanofiltration salt separation and bipolar membrane electrodialysis in sequence, so that the recovery rate of the strong brine is more than 85 percent, the quality of recycled water is superior to the quality requirement of industrial fresh water, and the produced by-products, namely hydrochloric acid and sodium hydroxide can be recycled for regeneration of the ion exchange resin, pretreatment softening of wastewater, acidification of wastewater RO process, acid-base neutralization process and the like, thereby saving the cost of purchased acid and base and realizing resource utilization. The electric flocculation and electric adsorption technology selected in the treatment process makes full use of the characteristic of high salt content of metallurgical strong brine, and the treatment process has the advantages of low energy consumption, low cost, simple equipment, easy operation and stable treatment effect.
Drawings
FIG. 1 is a process flow diagram of a process for the simultaneous production of hydrochloric acid and sodium hydroxide using reverse osmosis concentrated brine.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1:
referring to fig. 1, the method for simultaneously preparing hydrochloric acid and sodium hydroxide by using reverse osmosis concentrated brine, wherein the metallurgy reverse osmosis concentrated brine is reverse osmosis concentrated brine produced in steel production, has the pH value of 7.0-8.5, the conductivity of 7.0-8.0ms/cm, the COD of 80-100mg/L, the nitrate radical of less than or equal to 90mg/L and the fluoride ion of less than or equal to 35mg/L, and specifically comprises the following steps:
1) the method comprises the steps of firstly feeding metallurgical reverse osmosis strong brine into a regulating tank, adding a calcium hydroxide solution while stirring to regulate the pH value of wastewater to 11, adding 1ppm PAM, precipitating for 0.5h, adding anhydrous sodium carbonate, stirring to react for 20min, precipitating for 1 h, effectively removing total hardness, fluorine and other ions in raw water through precipitation, enabling supernatant to flow into a denitrification biofilter, regulating the pH value of wastewater to 8.0, supplementing methanol into the denitrification biofilter as an additional carbon source for microbial denitrification, and controlling the hydraulic retention time of the biofilter for 7 h.
2) The effluent of the denitrification biological filter enters a first ozone oxidation tower, the pH of the wastewater is controlled to be 11.0, the ozone dosage is 20mg/L, the effluent of the first ozone oxidation tower enters a sand filter, fine suspended matters and particles are further removed, backwash water of a denitrification tank and the sand filter returns to a front end regulation tank, the pH of sand filtration effluent is regulated to control the pH of the wastewater to be 6.2, then the wastewater enters an ultrafiltration device, pollutants such as suspended matters, colloid and the like in the wastewater are further intercepted, concentrated water of the ultrafiltration device returns to the regulation tank for circulation treatment, ultrafiltration effluent enters a two-stage reverse osmosis system RO for concentration and separation, water produced by the RO system enters a new water storage tank for reuse (the conductivity is less than 80 mus/cm, the COD is less than 5mg/L, and the total hardness is less than 0.1mg/L), and the water quality is far better than the standard requirements of GB/T19923-2005-industrial water quality for regeneration and utilization of urban sewage, the total recovery rate of RO of the two-stage reverse osmosis system is 89%, high-salt water generated by the RO system is injected into chelate ion exchange resin, residual metal ions such as calcium, magnesium and the like in the wastewater are adsorbed by the exchange performance of the resin, the regeneration wastewater of the ion exchange resin flows back to the regulating reservoir for circular treatment, the effluent enters a second ozone oxidation tower, the pH of the wastewater in the oxidation tower is controlled to be 11, the ozone adding amount is 22mg/L, and the effluent of the second ozone oxidation tower enters a nanofiltration device after the pH is regulated to 6.4;
3) the nanofiltration device divides the wastewater into water and concentrated water, the nanofiltration concentrated water is sent to a blast furnace for slag flushing or an incinerator, the nanofiltration water is sent to a bipolar membrane electrodialysis device for treatment, the bipolar membrane electrodialysis device finally converts the salt in the nanofiltration water into corresponding hydrochloric acid and sodium hydroxide, the mass fraction of the hydrochloric acid is 5.82%, the mass fraction of the sodium hydroxide is 5.63%, and the recovered hydrochloric acid and sodium hydroxide can be used for regeneration of ion exchange resin, pretreatment and softening of the wastewater, acidification of wastewater RO process, acid-base neutralization process and the like, so that the cost of purchased acid-base is saved, and the resource utilization is realized.
Example 2:
referring to fig. 1, the method for simultaneously preparing hydrochloric acid and sodium hydroxide by using reverse osmosis concentrated brine, wherein the metallurgy reverse osmosis concentrated brine is reverse osmosis concentrated brine produced in steel production, has the pH value of 7.0-8.5, the conductivity of 7.0-8.0ms/cm, the COD of 80-100mg/L, the nitrate radical of less than or equal to 90mg/L and the fluoride ion of less than or equal to 35mg/L, and specifically comprises the following steps:
1) the method comprises the steps of firstly feeding metallurgical reverse osmosis strong brine into a regulating tank, adding a calcium hydroxide solution while stirring to regulate the pH value of wastewater to 11.5, adding 1.5ppm PAM, precipitating for 1.0h, adding anhydrous sodium carbonate, stirring for reacting for 25min, precipitating for 1.5h, effectively removing total hardness, fluorine and other ions in raw water through precipitation, enabling supernatant to flow into a denitrification biofilter, regulating the pH value of wastewater to 8.5, supplementing methanol into the denitrification biofilter as an additional carbon source for microbial denitrification, and controlling the hydraulic retention time of the biofilter for 8 h.
2) The effluent of the denitrification biological filter enters a first ozone oxidation tower, the pH of the wastewater is controlled to be 11.5, the ozone dosage is 22mg/L, the effluent of the first ozone oxidation tower enters a sand filter, fine suspended matters and particles are further removed, backwash water of a denitrification tank and the sand filter returns to a front end regulation tank, the pH of sand filtration effluent is regulated to control the pH of the wastewater to be 6.4, then the wastewater enters an ultrafiltration device, pollutants such as suspended matters, colloid and the like in the wastewater are further intercepted, concentrated water of the ultrafiltration device returns to the regulation tank for circulation treatment, ultrafiltration effluent enters a two-stage reverse osmosis system RO for concentration and separation, water produced by the RO system enters a new water storage tank for reuse (the conductivity is less than 80 mus/cm, the COD is less than 5mg/L, and the total hardness is less than 0.1mg/L), and the water quality is far better than the standard requirements of GB/T19923-2005-industrial water quality for regeneration and utilization of urban sewage, the total recovery rate of the two-stage reverse osmosis system is 91%, the high-salt water generated by the RO system is injected into chelate ion exchange resin, residual metal ions such as calcium, magnesium and the like in the wastewater are adsorbed by the exchange performance of the resin, the regenerated wastewater of the ion exchange resin flows back to the regulating reservoir for circular treatment, the effluent enters a second ozone oxidation tower, the pH of the wastewater in the oxidation tower is controlled to be 11.5, the ozone adding amount is 25mg/L, and the effluent of the second ozone oxidation tower enters a nanofiltration device after the pH is regulated to be 6.6;
3) the nanofiltration device divides the wastewater into water and concentrated water, the nanofiltration concentrated water is sent to a blast furnace for slag flushing or an incinerator, the nanofiltration water is sent to a bipolar membrane electrodialysis device for treatment, the bipolar membrane electrodialysis device finally converts the salt in the nanofiltration water into corresponding hydrochloric acid and sodium hydroxide, the mass fraction of the hydrochloric acid is 5.75%, the mass fraction of the sodium hydroxide is 5.52%, and the recovered hydrochloric acid and sodium hydroxide can be used for regeneration of ion exchange resin, pretreatment and softening of the wastewater, acidification of wastewater RO process, acid-base neutralization process and the like, so that the cost of purchased acid-base is saved, and the resource utilization is realized.
Example 3:
referring to fig. 1, the method for simultaneously preparing hydrochloric acid and sodium hydroxide by using reverse osmosis concentrated brine, wherein the metallurgy reverse osmosis concentrated brine is reverse osmosis concentrated brine produced in steel production, has the pH value of 7.0-8.5, the conductivity of 7.0-8.0ms/cm, the COD of 80-100mg/L, the nitrate radical of less than or equal to 90mg/L and the fluoride ion of less than or equal to 35mg/L, and specifically comprises the following steps:
1) the method comprises the steps of firstly feeding metallurgical reverse osmosis strong brine into a regulating tank, adding a calcium hydroxide solution while stirring to regulate the pH value of wastewater to 12, adding 2ppm PAM, precipitating for 1.5h, adding a certain amount of anhydrous sodium carbonate, stirring for reacting for 30min, precipitating for 2 h, effectively removing total hardness, fluorine and other ions in raw water through precipitation, feeding supernatant into a denitrification biofilter, regulating the pH value of wastewater to 9.0, supplementing methanol into the denitrification biofilter as an external carbon source for microbial denitrification, and controlling the hydraulic retention time of the biofilter for 9 h.
2) The effluent of the denitrification biological filter enters a first ozone oxidation tower, the pH of the wastewater is controlled to be 12.0, the ozone dosage is 24mg/L, the effluent of the first ozone oxidation tower enters a sand filter, fine suspended matters and particles are further removed, backwash water of the denitrification tank and the sand filter returns to a front end regulation tank, the pH of sand filtration effluent is regulated to control the pH of the wastewater to be 6.6, then the wastewater enters an ultrafiltration device, pollutants such as suspended matters, colloid and the like in the wastewater are further intercepted, concentrated water of the ultrafiltration device flows back to the regulation tank for circulation treatment, ultrafiltration product water enters a two-stage reverse osmosis system (RO) for concentration and separation, the RO system product water enters a fresh water storage tank for reuse (the electric conductivity is less than 80 mu s/cm, the COD is less than 5mg/L, and the total hardness is less than 0.1mg/L), and the water quality is far better than the standard requirements of GB/T19923-2005 urban sewage regeneration industrial water), the total recovery rate of the two-stage reverse osmosis system is 90%, the high-salt water generated by the RO system is injected into chelate ion exchange resin, residual metal ions such as calcium, magnesium and the like in the wastewater are adsorbed by the exchange performance of the resin, the regenerated wastewater of the ion exchange resin flows back to the regulating reservoir for circular treatment, the effluent enters a second ozone oxidation tower, the pH of the wastewater in the oxidation tower is controlled to be 12, the ozone adding amount is 28mg/L, and the effluent of the second ozone oxidation tower enters a nanofiltration device after the pH is regulated to 6.8;
3) nanofiltration divides the wastewater into water and concentrated water, the nanofiltration concentrated water is sent to a blast furnace for slag flushing or an incinerator, the nanofiltration water is sent to a bipolar membrane electrodialysis device for treatment, the bipolar membrane electrodialysis device finally converts the salt in the nanofiltration water into corresponding hydrochloric acid and sodium hydroxide, the mass fraction of the sodium chloride is 5.68%, the mass fraction of the sodium hydroxide is 5.47%, and the recovered hydrochloric acid and sodium hydroxide can be used for regeneration of ion exchange resin, pretreatment softening of the wastewater, acidification of wastewater RO process, acid-base neutralization process and the like, so that the cost of purchased acid-base is saved, and the resource utilization is realized.
Claims (2)
1. A method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis concentrated brine is characterized by comprising the following steps:
1) firstly, feeding metallurgical reverse osmosis strong brine into a regulating tank, adding a calcium hydroxide solution while stirring to regulate the pH value of the wastewater to 11-12, adding 1-2ppm of PAM, and precipitating for 0.5-1.5 hours; adding anhydrous sodium carbonate, stirring for reaction for 20-30 minutes, precipitating for 1-2 hours, effectively removing total hardness and fluoride ions in raw water through precipitation, enabling supernatant to flow into a denitrification biological filter, adjusting the pH value of wastewater to 8.0-9.0, supplementing methanol into the denitrification biological filter to provide sufficient carbon source for nitrate denitrification, wherein the biological filter is filled with ceramsite filter material, and the hydraulic retention time is 7-9 hours;
2) the effluent of the denitrification biological filter enters a first ozone oxidation tower, the pH of the wastewater is controlled to be 11.0-12.0, the adding amount of ozone is 20-24mg/L, and under the strong oxidation effect of the ozone, organic matters which cannot be biodegraded in the wastewater are oxidized into micromolecular organic matters which are easy to biodegrade or are partially mineralized by the ozone;
3) the effluent of the first ozone oxidation tower enters a sand filter, fine suspended matters and particles are further removed, the quality of the effluent is enhanced, and backwash water of the biological filter and the sand filter returns to a front-end regulating tank; the pH of the effluent of sand filtration is adjusted to control the pH of the wastewater to be 6.2-6.6, then the wastewater enters an ultrafiltration device to further intercept suspended matters and colloid pollutants in the wastewater, concentrated water of the ultrafiltration device flows back to an adjusting tank to be circularly treated, ultrafiltration produced water enters a two-stage reverse osmosis system RO to be concentrated and separated to intercept most of salt and small molecular organic matters in the wastewater, the RO produced water of the two-stage reverse osmosis system enters a fresh water storage tank to be recycled, high salt water generated by the RO of the two-stage reverse osmosis system is injected into chelate ion exchange resin to adsorb residual calcium, magnesium and other metal ions in the wastewater through the exchange performance of the resin, regeneration wastewater of the ion exchange resin flows back to the adjusting tank to be circularly treated, effluent enters a second ozone oxidation tower to control the pH of the wastewater in the oxidation tank to be 11-12, and the ozone dosage to be 22-28mg/L, adjusting the pH of the effluent of the second ozone oxidation tower to 6.4-6.8, and then feeding the effluent into a nanofiltration device;
4) the nanofiltration device divides the wastewater into water and concentrated water, the nanofiltration concentrated water is sent to a blast furnace for slag flushing or an incinerator, the nanofiltration water is sent to a bipolar membrane electrodialysis device for treatment, the bipolar membrane electrodialysis device finally converts the salt in the nanofiltration water into corresponding hydrochloric acid and sodium hydroxide, and the low-concentration hydrochloric acid and sodium hydroxide can be reused for acid-base regulation in the system.
2. The method as claimed in claim 1, wherein the metallurgical reverse osmosis concentrated brine is reverse osmosis concentrated brine produced from steel, pH is 7.0-8.5, conductivity is 7.0-8.0ms/cm, COD is 80-100mg/L, nitrate radical is less than or equal to 90mg/L, and fluoride ion is less than or equal to 35 mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010071570.5A CN111268859A (en) | 2020-01-21 | 2020-01-21 | Method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010071570.5A CN111268859A (en) | 2020-01-21 | 2020-01-21 | Method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111268859A true CN111268859A (en) | 2020-06-12 |
Family
ID=70994885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010071570.5A Pending CN111268859A (en) | 2020-01-21 | 2020-01-21 | Method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111268859A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045113A (en) * | 2021-03-12 | 2021-06-29 | 佛山市诚德新材料有限公司 | Waste residue drying processing system |
| CN113603302A (en) * | 2021-08-17 | 2021-11-05 | 鞍钢股份有限公司 | Coking wastewater reduction treatment method |
| CN114075018A (en) * | 2021-10-20 | 2022-02-22 | 中蓝连海设计研究院有限公司 | Recycling treatment method of epoxy propane wastewater by caustic soda saponification method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800885A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water |
| CN105800886A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment technology of high-concentration degradation-resistant salt-containing organic waste water |
| CN107640860A (en) * | 2017-10-09 | 2018-01-30 | 北京中科康仑环境科技研究院有限公司 | A kind of saliferous industrial wastewater desalination reuse technology of calcic magnesium ion, sulfate ion |
| CN107651794A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院过程工程研究所 | A kind of processing system and processing method of industrial wastewater bio-chemical effluent |
| CN108178430A (en) * | 2017-12-27 | 2018-06-19 | 天津膜天膜科技股份有限公司 | The system and method for oil refining sewerage advanced treatment and reclamation and concentrated water processing qualified discharge |
-
2020
- 2020-01-21 CN CN202010071570.5A patent/CN111268859A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800885A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment system of high-concentration degradation-resistant salt-containing organic waste water |
| CN105800886A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment technology of high-concentration degradation-resistant salt-containing organic waste water |
| CN107651794A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院过程工程研究所 | A kind of processing system and processing method of industrial wastewater bio-chemical effluent |
| CN107640860A (en) * | 2017-10-09 | 2018-01-30 | 北京中科康仑环境科技研究院有限公司 | A kind of saliferous industrial wastewater desalination reuse technology of calcic magnesium ion, sulfate ion |
| CN108178430A (en) * | 2017-12-27 | 2018-06-19 | 天津膜天膜科技股份有限公司 | The system and method for oil refining sewerage advanced treatment and reclamation and concentrated water processing qualified discharge |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045113A (en) * | 2021-03-12 | 2021-06-29 | 佛山市诚德新材料有限公司 | Waste residue drying processing system |
| CN113603302A (en) * | 2021-08-17 | 2021-11-05 | 鞍钢股份有限公司 | Coking wastewater reduction treatment method |
| CN114075018A (en) * | 2021-10-20 | 2022-02-22 | 中蓝连海设计研究院有限公司 | Recycling treatment method of epoxy propane wastewater by caustic soda saponification method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107235590B (en) | Treatment process for zero discharge and resource recycling of catalyst wastewater | |
| CN112374705B (en) | High-salinity wastewater treatment process for iron and steel enterprises | |
| CN103288309B (en) | Coal gasification wastewater zero-emission treatment method, and application thereof | |
| CN111377575B (en) | Treatment method of high-sulfate high-COD organic wastewater | |
| CN111268859A (en) | Method for simultaneously preparing hydrochloric acid and sodium hydroxide by utilizing reverse osmosis strong brine | |
| CN103771650A (en) | Method for treating coal gasification wastewater | |
| CN112479467A (en) | Graphite wastewater treatment device and use method thereof | |
| CN111233237A (en) | Method for realizing zero discharge of high-concentration brine in steel production enterprise | |
| CN111847806A (en) | Landfill leachate treatment method and process | |
| CN111233219A (en) | Treatment method for recycling strong brine of metallurgical enterprise | |
| CN111233265A (en) | Method for recycling comprehensive wastewater in steel production | |
| CN107188365B (en) | Method for advanced treatment of landfill leachate | |
| CN113415924A (en) | Reverse osmosis concentrated water treatment process for Fenton reagent oxidation enhanced adsorption | |
| CN213171875U (en) | High-salinity organic wastewater zero-discharge treatment system | |
| CN112174445A (en) | Zero-emission treatment method for high-concentration brine in metallurgical industry | |
| CN103896457A (en) | Fine chemical wastewater treatment process | |
| CN111018205A (en) | Pretreatment method of landfill leachate RO concentrated solution | |
| KR20230173997A (en) | Apparatus and Method for processing organic waste | |
| CN111018248B (en) | Treatment method of high-ammonia-nitrogen high-phosphorus-salt wastewater | |
| CN114516689A (en) | Calcium carbide method polyvinyl chloride mercury-containing wastewater treatment and recycling method and application device thereof | |
| CN114751564A (en) | Coking wastewater treatment method | |
| CN104445799A (en) | Treatment method of gold smelting plant high-salt wastewater hard to treat and containing ammonia and nitrogen | |
| CN210595643U (en) | System for zero release of power plant's whole factory waste water and resource utilization | |
| CN218435298U (en) | System for utilize reverse osmosis strong brine preparation acid-base | |
| CN113277653A (en) | Desulfurization wastewater treatment system and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200612 |
|
| RJ01 | Rejection of invention patent application after publication |