CN110548548A - Double-chamber ion exchanger in-situ regeneration process, device and water treatment system - Google Patents
Double-chamber ion exchanger in-situ regeneration process, device and water treatment system Download PDFInfo
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- CN110548548A CN110548548A CN201910967649.3A CN201910967649A CN110548548A CN 110548548 A CN110548548 A CN 110548548A CN 201910967649 A CN201910967649 A CN 201910967649A CN 110548548 A CN110548548 A CN 110548548A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 230000008929 regeneration Effects 0.000 title claims abstract description 44
- 238000011069 regeneration method Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 123
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 108
- 239000003513 alkali Substances 0.000 claims abstract description 105
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 230000001172 regenerating effect Effects 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 99
- 239000000243 solution Substances 0.000 claims description 99
- 239000012528 membrane Substances 0.000 claims description 95
- 239000007788 liquid Substances 0.000 claims description 45
- 150000001450 anions Chemical class 0.000 claims description 24
- 239000002699 waste material Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010612 desalination reaction Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 4
- 239000002585 base Substances 0.000 abstract description 22
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000006004 Quartz sand Substances 0.000 description 6
- 238000011033 desalting Methods 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 4
- 238000011001 backwashing Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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 description 1
- 230000009471 action Effects 0.000 description 1
- -1 cation ion Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000004706 scrotum Anatomy 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- 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
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
the invention belongs to the field of ion exchange water treatment, and particularly relates to a double-chamber ion exchanger in-situ regeneration process, a double-chamber ion exchanger in-situ regeneration device and a double-chamber ion exchanger in-situ regeneration water treatment system, which solve the problems that strong acid and strong base corrode equipment, influence human health, cause environmental pollution, and the transportation and purchase cost of the strong acid and the strong base at the early stage is high when the regeneration process of the double-chamber ion exchanger is carried out in the prior art. The regeneration process mainly comprises the following steps: 1. preparing a dilute acid solution and a dilute alkali solution with the concentration of 6-11%: 2. lower concentration Hcl and NaOH solutions were prepared: 3. and (4) regenerating the resin.
Description
Technical Field
the invention belongs to the field of ion exchange water treatment, and particularly relates to a double-chamber ion exchanger in-situ regeneration process, a double-chamber ion exchanger in-situ regeneration device and a water treatment system.
background
In water treatment in various industrial fields of electric power, chemical industry, metallurgy and light textile, the preparation of pure water mainly adopts the modes of ion exchange resin or reverse osmosis physics and the like to remove cations and anions contained in water to required contents, and the technology for removing salts dissolved in water is started from the last 50 th century, but because the technological base of China is poor at that time, the ion exchange technology of America, Japan and Germany is mostly adopted to carry out water treatment.
Since the two-chamber ion exchanger was successfully developed in our country in the last 80 th century, our country also has an advanced water treatment facility which is self-innovated, and the facility has a unique self-cleaning function, i.e. when the resin is regenerated, one or two backwashing operations are not needed as in other processes.
since the back washing operation is eliminated, 5% of the water consumption is saved and 11% of the resin loss is saved. The saving of 5% of tap water means that no further treatment of 5% of the waste water is required. Since the used self-service water will eventually become waste water. Compared with other desalted water treatment processes, the method has the advantages of minimum self-water consumption, resin loss and operation procedures, highest running flow rate, and lowest investment cost and running cost.
however, the resin failure problem exists after the double-chamber ion exchanger operates for a period of time, and the current method for solving the resin failure problem is to regenerate the resin by using a strong acid (Hcl) solution and a strong base (NaOH) solution;
however, this solution has certain problems:
1. the strong acid (HCl) solution and the strong base (NaOH) solution belong to dangerous transport products, and can be transported to the site by special protective vehicles after being examined and approved by relevant departments during purchase, and are stored in an acid-base storage tank, so that the purchase of the strong acid and the strong base can be seen, the procedure is complex, the transportation cost is high, and the transportation risk is high.
2. The strong acid (HCl) solution and the strong base (NaOH) solution have high concentrations, so that the strong acid (HCl) solution and the strong base (NaOH) solution can corrode human bodies and equipment, and particularly, the strong acid (HCl) solution can volatilize HCl gas when in use, so that the health of the human bodies and the pollution to the environment are influenced.
Disclosure of Invention
The invention provides a regeneration process of a double-chamber ion exchanger, aiming at solving the problems that strong acid and strong base can corrode equipment, influence human health and cause environmental pollution when the regeneration process of the double-chamber ion exchanger is carried out in the prior art, and the transportation and purchase cost of the strong acid and the strong base at the early stage is high.
at the same time, a set of double-chamber ion exchanger regenerating device with simple and reasonable structure and a set of water treatment system are designed.
in order to solve the existing problems, the invention provides a specific technical scheme that:
the invention provides a double-chamber ion exchanger in-situ regeneration process, which comprises the following steps:
preparing a dilute acid solution and a dilute alkali solution with the concentration of 6-11 percent:
Continuously supplying a NaCl feed liquid to the bipolar membrane electrodialyzer; separating 6-11% HCl solution and NaOH solution by using a bipolar membrane electrodialyzer;
Step [ 1.2 ] respectively conveying the HCl solution and the NaOH solution to a dilute acid tank and a dilute alkali tank through pipelines;
step [ 2 ] preparing a lower concentration of HCl solution and NaOH solution:
conveying the HCl solution with the concentration of 6-11% in the dilute acid tank to an acid metering box and an acid ejector in sequence through a pipeline for secondary dilution to obtain the HCl solution with lower concentration;
Meanwhile, conveying the 6-11% NaOH solution in the dilute alkali tank to an alkali metering box and an alkali ejector in sequence through a pipeline for secondary dilution to obtain a lower-concentration NaOH solution;
step [ 3 ] resin regeneration:
the lower-concentration Hcl solution obtained in the step 2 enters the bottom of the positive double-chamber ion exchanger through a pipeline, and positive resin layers in the lower chamber and the upper chamber of the positive double-chamber ion exchanger are sequentially regenerated from bottom to top;
and (3) allowing the NaOH solution with lower concentration obtained in the step (2) to enter the bottom of the anion double-chamber ion exchanger through a pipeline, and sequentially regenerating the negative resin layers in the lower chamber and the upper chamber of the anion double-chamber ion exchanger from bottom to top.
Further, the concentration of the lower-concentration HCl solution is 2.6-3.1%; the concentration of the lower-concentration NaOH solution is 1.9-2.2%.
Further, in the step (3), both the HCl solution with a concentration of 2.6-3.1% and the NaOH solution with a concentration of 1.9-2.2% are injected into the positive double-chamber ion exchanger and the negative double-chamber ion exchanger at a speed of 4-5 m/h.
Further, when the acid resin layer and the alkaline resin layer are regenerated synchronously, the method also comprises the step (4);
Step [ 4 ]: the waste HCl solution and the waste NaOH solution of the positive double-chamber ion exchanger and the negative double-chamber ion exchanger are neutralized and then discharged.
further, the method also comprises the step of storing the lower-concentration HCl solution and NaOH solution obtained in the step (1) before the step (2).
based on the above description of the regeneration process of the dual-chamber ion exchanger, a specific regeneration device for implementing the process is now introduced:
A double-chamber ion exchanger in-situ regeneration device comprises a bipolar membrane electrodialyzer, a feed liquid tank, a feed liquid pump, a dilute acid tank, a dilute acid pump, a dilute alkali tank, a dilute alkali pump, an electrode water tank, an electrode water pump, an acid concentration adjusting unit and an alkali concentration adjusting unit;
The bipolar membrane electrodialyzer comprises a feed liquid chamber, an electrode water chamber, a dilute acid chamber and a dilute alkali chamber;
the inlets and outlets of all the feed liquid chambers are respectively communicated with the feed liquid tank and the feed liquid pump through pipelines, so that a feed liquid circulation loop is formed;
the inlets and outlets of all the polar water chambers are respectively communicated with the polar water tank and the polar water pump through pipelines, so that a polar water circulation loop is formed;
the inlets and outlets of all the dilute acid chambers are respectively communicated with a dilute acid tank and a dilute acid pump through pipelines, so that a dilute acid circulation loop is formed;
Inlets and outlets of all the dilute alkali chambers are respectively communicated with the dilute alkali tank and the dilute alkali pump through pipelines, so that a dilute alkali circulation loop is formed;
The acid concentration adjusting unit is used for adjusting the concentration of the dilute acid solution in the dilute acid tank and providing the dilute acid solution to the positive double-chamber ion exchanger through a pipeline;
The alkali concentration adjusting unit is used for adjusting the concentration of the dilute alkali solution in the dilute alkali tank and supplying the dilute alkali solution to the anion double-chamber ion exchanger through a pipeline.
further, the acid concentration adjusting unit comprises an acid metering tank, an acid ejector and a first water pump;
the dilute acid tank is communicated with a liquid inlet of the acid metering box through a pipeline, and a liquid outlet of the acid metering box is communicated with the bottom of the positive double-chamber ion exchanger through the acid ejector; the first water pump injects external water into the acid ejector through a pipeline;
The alkali concentration adjusting unit comprises an alkali metering tank, an alkali ejector and a second water pump;
The dilute alkali tank is communicated with a liquid inlet of the alkali metering box through a pipeline, and a liquid outlet of the alkali metering box is communicated with the bottom of the anion dual-chamber ion exchanger through the alkali ejector; the second water pump injects external water into the alkali sprayer through a pipe.
Further, the above bipolar membrane electrodialyzer comprises an anode plate, a cathode plate, a membrane stack and a clamping device; the anode plate and the cathode plate are respectively connected with the positive pole and the negative pole of an external direct current power supply; the membrane stack is arranged between the anode plate and the cathode plate;
The membrane stack comprises a plurality of negative membranes, a plurality of positive membranes and a plurality of bipolar membranes; sorting by adopting a mode that a negative membrane, a positive membrane and a bipolar membrane alternately appear; each membrane is separated by a clapboard;
the clamping device connects the anode plate, the cathode plate and the membrane stack into a whole;
An anode water chamber is formed between the most front cathode film and the anode electrode plate; a cathode water chamber is formed between the anode film at the rearmost end and the cathode electrode plate;
A feed liquid chamber is formed between the negative film and the positive film;
A dilute alkali chamber is formed between the anode membrane and the bipolar membrane;
a dilute acid chamber is formed between the bipolar membrane and the scrotum;
further, the anode plate is a titanium-coated ruthenium or titanium-coated platinum plate, and the cathode plate is a ruthenium dioxide or stainless steel plate.
the invention also provides a water treatment system based on the regeneration device, which comprises the regeneration device and desalting equipment; the desalting equipment comprises an anode double-chamber ion exchanger and an anion double-chamber ion exchanger;
The bottom of the positive double-chamber ion exchanger is communicated with an outlet of an acid concentration adjusting unit in the device through a pipeline; the bottom of the anion double-chamber ion exchanger is communicated with an outlet of an alkali concentration adjusting unit in the device through a pipeline;
the water outlet of the positive double-chamber ion exchanger is communicated with the water inlet of the negative double-chamber ion exchanger through a pipeline.
the invention has the advantages that:
1. The invention adopts dilute acid solution and dilute alkali solution which are prepared in situ by Nacl feed liquid through a bipolar membrane electrodialyzer, and utilizes an acid concentration regulating unit and an alkali concentration regulating unit to carry out secondary dilution on the dilute acid solution and the dilute alkali solution respectively to generate regenerated acid-alkali solution, thereby avoiding the danger caused by carrying out regeneration of a double-chamber ion exchanger by purchasing and transporting strong acid and alkali solutions outside places, avoiding the problems of environmental pollution, equipment corrosion and influence on human health caused by volatile Hcl gas, and having good economical efficiency compared with the prior purchased acid-alkali solution.
2. the bipolar membrane electrodialyzer is especially suitable for remote areas where acid and alkali transportation is more difficult and coastal areas where seawater is desalinated, and can bring more environmental protection, economic and social benefits due to the application of the areas. For example, the seawater desalination work is carried out, firstly, the pH of the reverse osmosis inlet water is regulated, the dilute HCl produced by the process can be used as acid for regulating the pH, and in addition, the waste concentrated seawater discharged in the desalting process of the reverse osmosis can be used as a resource and used as raw material salt solution of the process. For other processes adopting reverse osmosis pre-desalination, the pH can be adjusted by using the dilute Hcl prepared by the process, and the problems caused by using the concentrated Hcl can be avoided.
3. The cation-anion double-chamber ion exchanger can be designed for synchronous regeneration, and can simultaneously perform acid-base neutralization on waste acid and waste alkali discharged during cation-anion bed regeneration, thereby not only saving the acid-base neutralization cost, but also preventing environmental pollution.
drawings
FIG. 1 is a schematic diagram of a dual-chamber ion exchanger in-situ regeneration apparatus.
the reference numbers are as follows:
1-liquid feed tank, 2-liquid feed pump, 3-dilute acid tank, 4-dilute acid pump, 5-dilute alkali tank, 6-dilute alkali pump, 7-pole water tank, 8-pole water pump, 9-bipolar membrane electrodialyzer, 10-acid concentration regulating unit, 11-alkali concentration regulating unit, 12-anode plate, 13-cathode plate, 14-cathode membrane, 15-anode membrane, 16-bipolar membrane, 17-anode water chamber, 18-cathode water chamber, 19-liquid feed chamber, 20-dilute alkali chamber, 21-dilute acid chamber, 22-acid metering tank, 23-acid ejector, 24-first water pump, 25-anode double-chamber ion exchanger, 26-alkali metering tank, 27-alkali ejector, 28-second water pump, 29-anion double-chamber ion exchanger, 30-a first cylinder, 31-a water inlet device, 32-a weak acid resin layer, 33-a porous plate, 34-a strong acid resin layer, 35-a quartz sand cushion layer, 36-a second cylinder, 37-a weak base resin layer and 38-a strong base resin layer.
A1-1 grade negative membrane, B1-1 grade positive membrane, C1-bipolar membrane, A2-2 grade negative membrane, B2-2 grade positive membrane, C2-2 grade bipolar membrane, A3-3 grade negative membrane, B3-3 grade positive membrane, C3-3 grade bipolar membrane, AN-N grade negative membrane and BN-N grade positive membrane.
Detailed Description
the following describes embodiments of the present invention with reference to the drawings.
the following optimization data were obtained by the inventors through a number of experiments: the concentration of Hcl used by the regenerated double-chamber ion exchanger is 2.6-3.1%, and the concentration of NaOH used by the regenerated double-chamber ion exchanger is 1.9-2.2%, so that resin can be regenerated, and the deposition of colloidal silica generated during regeneration of the double-chamber ion exchanger can be prevented.
Based on the optimized data, the regeneration process of the double-chamber ion exchanger is provided, and the specific execution steps are as follows:
Step 1: preparing a dilute acid solution and a dilute alkali solution with the concentration of 6-11%;
Step 1.1: continuously supplying a NaCl feed liquid to the bipolar membrane electrodialyzer; separating 6-11% HCl solution and NaOH solution by using a bipolar membrane electrodialyzer;
Step 1.2: conveying the Hcl solution and the NaOH solution to a dilute acid tank and a dilute alkali tank respectively through pipelines;
it should be noted that, when preparing acid and alkali, the selected raw material liquid is only NaCl, but not Na 2 SO 4, if Na 2 SO 4 is used, the strong acid produced is H 2 SO 4, but not Hcl, the positive double-chamber ion exchanger regenerated by H 2 SO 4 is easy to generate CaSO 4 sediment, if CaSO 4 is deposited in the resin layer, the advantages of self-cleaning function and the like of the positive double-chamber ion exchanger do not exist, and harm is brought.
step 2: lower concentration Hcl and NaOH solutions were prepared: in the process, the effect of the lower-concentration Hcl solution and the NaOH solution is the best in the range of 2.6-3.1% of the Hcl solution and 1.9-2.2% of the NaOH solution respectively;
conveying the Hcl solution with the concentration of 6-11% in the dilute acid tank to an acid metering box and an acid ejector in sequence through a pipeline for secondary dilution to obtain the Hcl solution with the concentration of 2.6-3.1%;
meanwhile, conveying the 6-11% HCl solution in the dilute alkali tank to an alkali metering box and an alkali ejector in sequence through a pipeline for secondary dilution to obtain a 1.9-2.2% NaOH solution;
And step 3: regenerating the resin;
the lower-concentration Hcl solution (2.6-3.1%) enters from the bottom of the positive double-chamber ion exchanger at a speed of 4-5 m/h, and the positive resin layers in the lower chamber and the upper chamber of the positive double-chamber ion exchanger are sequentially regenerated from bottom to top;
NaOH solution (1.9-2.2%) with lower concentration enters from the bottom of the anion dual-chamber ion exchanger at the speed of 4-5 m/h, and the negative resin layers in the lower chamber and the upper chamber of the anion dual-chamber ion exchanger are regenerated from bottom to top in sequence.
in addition, the above-mentioned technological process has still carried out reasonable treatment to the waste liquid after regenerating, step 4: when the positive resin layer and the negative resin layer are synchronously regenerated, the waste HCl solution and the waste NaOH solution of the positive double-chamber ion exchanger and the negative double-chamber ion exchanger can be neutralized and then discharged.
in the actual production process, before the step [ 2 ] is executed, the HCl solution and the NaOH solution with the concentration of 6-11% obtained in the step [ 1 ] can be stored for later direct use, and production does not need to be carried out in a time-consuming manner.
based on the description of the process, the invention also provides a double-chamber ion exchanger regeneration device for realizing the process; as shown in fig. 1, the regeneration device comprises a feed liquid tank 1, a feed liquid pump 2, a dilute acid tank 3, a dilute acid pump 4, a dilute alkali tank 5, a dilute alkali pump 6, a polar water tank 7, a polar water pump 8, a bipolar membrane electrodialyzer 9, an acid concentration adjusting unit 10, an alkali concentration adjusting unit 11 and a plurality of pipelines (not shown in the figure);
wherein, the specific structure of the bipolar membrane electrodialyzer 9 is as follows:
the bipolar membrane electrodialyzer 9 comprises three parts, namely a membrane stack, a polar region and a clamping device;
The polar region comprises an anode plate 12 and a cathode plate 13, wherein the anode plate 12 and the cathode plate 13 are respectively connected with the positive pole and the negative pole of an external direct current power supply; the anode electrode plate 12 is typically a titanium-ruthenium-or titanium-platinum-coated plate, and the cathode electrode plate 13 is typically a ruthenium dioxide or stainless steel plate.
the film stack is arranged between the anode electrode plate 12 and the cathode electrode plate 13, which is the sum of the film pairs between the anode electrode plate 12 and the cathode electrode plate 13; the number of membrane pairs used in bipolar membrane electrodialysers is generally less than 180 pairs.
The membrane stack comprises a plurality of negative membranes 14, a plurality of positive membranes 15 and a plurality of bipolar membranes 16; sequencing by adopting a mode that a negative membrane 14, a positive membrane 15 and a bipolar membrane 16 alternately appear; each membrane is separated by a clapboard; the specific assembly of the pole region and the film stack provided in this example is shown in fig. 1, and the arrangement order is: level 1 is: the positive electrode plate 12, the grade 1 negative membrane A1, the grade 1 positive membrane B1 and the grade 1 bipolar membrane C1, the grade 2 is: grade 2 scrotal membrane A2, grade 2 anodal membrane B2 and grade 2 bipolar membrane C2, grade 3 is: a 3-grade negative membrane A3, a 3-grade positive membrane B3 and a 3-grade bipolar membrane C3, wherein the Nth grade of … … is AN N-grade negative membrane AN, AN N-grade positive membrane BN and a negative electrode plate 13;
wherein, an anode water chamber 17 is formed between the grade 1 cathode film A1 and the anode electrode plate 12; a cathode water chamber 18 is formed between the N-grade anode film BN and the cathode electrode plate 13; a feed liquid chamber 19 is formed between each stage of the negative film 14 and the positive film 15; a dilute alkali chamber 20 is formed between each level of anode membrane 15 and bipolar membrane 16; a dilute acid chamber 21 is formed between the upper bipolar membrane 16 and the lower vaginal membrane 14.
The operation system is provided with 4 circulation loops of feed liquid, polar water, dilute acid and dilute alkali;
inlets and outlets of all feed liquid chambers 19 in the bipolar membrane electrodialyzer 9 are respectively communicated with the feed liquid tank 1 and the feed liquid pump 2 through pipelines, so that a feed liquid circulation loop is formed;
an inlet and an outlet of an electrode water chamber 18 in the bipolar membrane electrodialyzer 9 are respectively communicated with an electrode water tank 7 and an electrode water pump 8 through pipelines, so that an electrode water circulation loop is formed;
Inlets and outlets of all dilute acid chambers 21 in the bipolar membrane electrodialyzer 9 are respectively communicated with the dilute acid tank 3 and the dilute acid pump 4 through pipelines, so that a dilute acid circulation loop is formed;
inlets and outlets of all dilute alkali chambers 20 in the bipolar membrane electrodialyzer 9 are respectively communicated with the dilute alkali tank 5 and the dilute alkali pump 6 through pipelines, so that a dilute alkali circulation loop is formed;
the acid concentration adjusting unit 10 is used for adjusting the concentration of the dilute acid solution in the dilute acid tank 3 and providing the dilute acid solution to the dual-chamber ion exchanger 25 through a pipeline; the specific structure of the acid concentration regulating unit here is: comprises an acid metering tank 22, an acid ejector 23 and a first water pump 24;
the dilute acid tank 3 is communicated with a liquid inlet of the acid metering box 22 through a pipeline, and a liquid outlet of the acid metering box 22 is communicated with the bottom of an external double-chamber cation ion exchanger 25 through the acid ejector 23; the first water pump 24 injects external water into the acid injector 23 through a pipe;
the alkali concentration adjusting unit 11 is used for adjusting the concentration of the dilute alkali solution in the dilute alkali tank 5 and providing the dilute alkali solution to the anion double-chamber ion exchanger 29 through a pipeline; the specific structure of the alkali concentration adjusting unit is as follows: comprises an alkali metering tank 26, an alkali injector 27 and a second water pump 28;
The dilute alkali tank 5 is communicated with a liquid inlet of the alkali metering tank 26 through a pipeline, and a liquid outlet of the alkali metering tank 26 is communicated with the bottom of the anion dual-chamber ion exchanger 29 through the alkali ejector 27; the second water pump 28 injects external water into the alkali injector 27 through a pipe.
compared with the conventional electrolyzed water, the bipolar membrane electrodialyzer has the advantages that the water dissociation speed can be improved by 5 million times under the action of a bipolar membrane electric field, and the energy consumption can be greatly reduced. It is estimated that the acid and alkali cost consumed by 300MW thermal power plant is about 250 ten thousand yuan per year, and if the bipolar membrane electrodialyzer is used for preparing dilute acid and dilute alkali, the operating cost per year can be reduced to about 130 ten thousand yuan.
Based on the regeneration device, the invention also provides a water treatment system,
the system comprises the regeneration device and the desalting equipment; the desalting equipment comprises an anode double-chamber ion exchanger 25 and an anion double-chamber ion exchanger 29;
the bottom of the positive double-chamber ion exchanger 25 is communicated with the acid ejector 23 in the regeneration device through a pipeline; the bottom of the anion dual-chamber ion exchanger 29 is communicated with the alkali ejector 27 in the regeneration device through a pipeline;
The water outlet of the positive double-chamber ion exchanger 25 is communicated with the water inlet of the negative double-chamber ion exchanger 29 through a pipeline.
specifically, the double-chamber ion exchanger comprises a first cylinder 30, and a water inlet device 31, a weak acid or strong acid resin layer 32, a porous plate 33, a strong acid resin layer 34 and a quartz sand cushion 35 which are sequentially arranged in the first cylinder 30 from top to bottom; the anion dual-chamber ion exchanger 29 comprises a second cylinder 36 and a water inlet device 31, a weak base or strong base resin layer 37, a porous plate 33, a strong base resin layer 38 and a quartz sand cushion layer 35 which are sequentially arranged in the second cylinder 36 from top to bottom. (the structure is a simple introduction in the prior art and is not described in too much detail).
The water treatment system integrates the functions of producing pure water, producing regenerated acid-base solution on site and regenerating resin. The specific working process is as follows:
1. preparing pure water: raw water enters a water inlet device 31 of a first cylinder 30 (namely enters the cation double-chamber ion exchanger) to start water distribution, the required water flow rate is adjusted, the water flow passes through a weak acid or strong acid resin layer 32 of an upper chamber, a porous plate 33 and a strong acid resin layer 34 of a lower chamber from top to bottom, and a quartz sand cushion 35 flows to the anion double-chamber ion exchanger 29 through a water outlet.
Then the pure water is produced after passing through a water inlet device 31 of a second cylinder 36 (namely entering the anion double-chamber ion exchanger), a weak base or strong base resin layer 37, a porous plate 33, a lower strong base resin layer 38 and a quartz sand cushion layer 35, and a resin regeneration process in the cation double-chamber ion exchanger and the anion double-chamber ion exchanger is carried out by using a starting regeneration device until the effluent water is close to the superscale;
2. regeneration: starting the regeneration device, so that the dilute alkali pump 6, the polar water tank 7, the polar water pump 8, the bipolar membrane electrodialyzer 9, the acid metering tank 22, the acid ejector 23, the first water pump 24, the alkali metering tank 26, the alkali ejector 27 and the second water pump 28 start to work; the produced HCl solution with the concentration of 2.6-3.1% and NaOH solution with the concentration of 1.9-2.2% are used as regeneration solutions and respectively enter a first cylinder 30 (namely, an ion exchanger with an anode double chamber) and a second cylinder 36 (namely, an ion exchanger with an anion double chamber) at the speed of 4-5 m/h, so that a weak acid or strong acid resin layer 32, a strong acid resin layer 34, a weak alkali or strong alkali resin layer 37 and a strong alkali resin layer 38 in the first cylinder 30 and the second cylinder 36 are respectively regenerated, and when the amount of the entering regeneration solution reaches the requirement, the regeneration device stops working;
3. and (3) replacement: supplying pure water from the bottoms of the positive double-chamber ion exchanger 25 and the negative double-chamber ion exchanger 29 at the flow rate of 4-5 m/h, respectively, cleaning resin layers in the positive double-chamber ion exchanger 25 and the negative double-chamber ion exchanger 29, and stopping supplying the pure water after the specified index requirements are met;
4. washing in a normal way: raw water respectively enters the positive double-chamber ion exchanger 25 and the negative double-chamber ion exchanger 29, and is positively washed after passing through the upper chamber resin layer, the porous plate, the lower chamber resin layer and the quartz sand cushion layer from top to bottom, and when the quality of the effluent reaches the standard (the conductivity of primary desalted effluent is less than 5 mu S/cm, and the conductivity of secondary desalted effluent is less than 0.1-0.2 mu S/cm), the positive double-chamber ion exchanger and the negative double-chamber ion exchanger are reserved or put into operation.
based on the water treatment, a two-stage desalting mixed bed water treatment process can be omitted, and an advanced double-chamber ion exchanger is used, so that multiple defects caused by the operation of a mixed bed can be overcome due to the use of the process.
the process has the comprehensive advantages that the double-chamber ion exchanger has the advantages of minimum operation procedures, highest operation flow rate (up to 40 m/h), no backwashing operation, lowest water consumption (< 5%), 11% resin loss saving, and lowest operation cost and investment cost, which are the operation technical indexes with international leading level.
Claims (10)
1. a process for regenerating a dual-chamber ion exchanger in situ, comprising: the method comprises the following steps:
preparing a dilute acid solution and a dilute alkali solution with the concentration of 6-11 percent:
Continuously supplying a NaCl feed liquid to the bipolar membrane electrodialyzer; separating 6-11% HCl solution and NaOH solution by using a bipolar membrane electrodialyzer;
Step [ 1.2 ] respectively conveying the HCl solution and the NaOH solution to a dilute acid tank and a dilute alkali tank through pipelines;
Step [ 2 ] preparing a lower concentration of HCl solution and NaOH solution:
Conveying the HCl solution with the concentration of 6-11% in the dilute acid tank to an acid metering box and an acid ejector in sequence through a pipeline for secondary dilution to obtain the HCl solution with lower concentration;
meanwhile, conveying the 6-11% NaOH solution in the dilute alkali tank to an alkali metering box and an alkali ejector in sequence through a pipeline for secondary dilution to obtain a lower-concentration NaOH solution;
step [ 3 ] resin regeneration:
The lower-concentration Hcl solution obtained in the step 2 enters the bottom of the positive double-chamber ion exchanger through a pipeline, and positive resin layers in the lower chamber and the upper chamber of the positive double-chamber ion exchanger are sequentially regenerated from bottom to top;
And (3) allowing the NaOH solution with lower concentration obtained in the step (2) to enter the bottom of the anion double-chamber ion exchanger through a pipeline, and sequentially regenerating the negative resin layers in the lower chamber and the upper chamber of the anion double-chamber ion exchanger from bottom to top.
2. the dual chamber ion exchanger in-situ regeneration process of claim 1, wherein: the concentration of the lower-concentration HCl solution is 2.6-3.1%; the concentration of the lower-concentration NaOH solution is 1.9-2.2%.
3. The dual chamber ion exchanger in-situ regeneration process of claim 2, wherein: in the step (3), both the HCl solution with the concentration of 2.6-3.1% and the NaOH solution with the concentration of 1.9-2.2% are respectively injected into the positive double-chamber ion exchanger and the negative double-chamber ion exchanger at the speed of 4-5 m/h.
4. the dual chamber ion exchanger in-situ regeneration process of claim 3, wherein: when the positive resin layer and the negative resin layer are synchronously regenerated, the method also comprises the step (4);
Step [ 4 ]: the waste HCl solution and the waste NaOH solution of the positive double-chamber ion exchanger and the negative double-chamber ion exchanger are neutralized and then discharged.
5. The dual chamber ion exchanger in-situ regeneration process of claim 3, wherein: before the step (2), a step of storing the HCl solution and the NaOH solution with the concentration of 6-11% obtained in the step (1) is also included.
6. An in-situ regeneration device of a double-chamber ion exchanger, which is characterized in that: comprises a bipolar membrane electrodialyzer (9), a feed liquid tank (1), a feed liquid pump (2), a dilute acid tank (3), a dilute acid pump (4), a dilute alkali tank (5), a dilute alkali pump (6), an electrode water tank (7), an electrode water pump (8), an acid concentration adjusting unit (10) and an alkali concentration adjusting unit (11);
The bipolar membrane electrodialyzer (9) comprises a feed liquid chamber (19), a polar water chamber, a dilute acid chamber (21) and a dilute alkali chamber (20);
inlets and outlets of all the feed liquid chambers (19) are respectively communicated with the feed liquid tank (1) and the feed liquid pump (2) through pipelines, so that a feed liquid circulation loop is formed;
the inlets and outlets of all the polar water chambers are respectively communicated with a polar water tank (7) and a polar water pump (8) through pipelines, so that a polar water circulation loop is formed;
inlets and outlets of all the dilute acid chambers (21) are respectively communicated with the dilute acid tank (3) and the dilute acid pump (4) through pipelines, so that a dilute acid circulation loop is formed;
inlets and outlets of all the dilute alkali chambers (20) are respectively communicated with the dilute alkali tank (5) and the dilute alkali pump (6) through pipelines, so that a dilute alkali circulation loop is formed;
the acid concentration adjusting unit (10) is used for adjusting the concentration of the dilute acid solution in the dilute acid tank (3) and providing the dilute acid solution to the positive double-chamber ion exchanger through a pipeline;
the alkali concentration adjusting unit (11) is used for adjusting the concentration of the dilute alkali solution in the dilute alkali tank (5) and providing the dilute alkali solution to the anion dual-chamber ion exchanger through a pipeline.
7. the apparatus of claim 6, wherein:
The acid concentration adjusting unit (10) comprises an acid metering tank (22), an acid ejector (23) and a first water pump (24);
the dilute acid tank (3) is communicated with a liquid inlet of the acid metering tank (22) through a pipeline, and a liquid outlet of the acid metering tank (22) is communicated with the bottom of the positive double-chamber ion exchanger (25) through the acid ejector (23); a first water pump (24) injects external water into the acid ejector (23) through a pipe;
The alkali concentration adjusting unit (11) comprises an alkali metering tank (26), an alkali ejector (27) and a second water pump (28);
The dilute alkali tank (5) is communicated with a liquid inlet of the alkali metering tank (26) through a pipeline, and a liquid outlet of the alkali metering tank (26) is communicated with the bottom of the anion dual-chamber ion exchanger (29) through the alkali ejector (27); a second water pump (28) injects external water into the alkali injector (27) through a pipe.
8. the apparatus of claim 7, wherein:
the bipolar membrane electrodialyzer (9) comprises an anode plate (12), a cathode plate (13), a membrane stack and a clamping device; the anode plate (12) and the cathode plate (13) are respectively connected with the positive pole and the negative pole of an external direct current power supply; the membrane stack is arranged between the anode plate (12) and the cathode plate (13);
The membrane stack comprises a plurality of negative membranes (14), a plurality of positive membranes (15) and a plurality of bipolar membranes (16); sorting by adopting a mode that a negative membrane (14), a positive membrane (15) and a bipolar membrane (16) alternately appear; each membrane is separated by a clapboard;
The clamping device connects the anode electrode, the cathode electrode plate (13) and the membrane stack into a whole;
an anode water chamber (17) is formed between the frontmost cathode film (14) and the anode electrode plate (12); a cathode water chamber (18) is formed between the anode film (15) at the rearmost end and the cathode electrode plate (13);
a feed liquid chamber (19) is formed between the negative film (14) and the positive film (15);
A dilute alkali chamber (20) is formed between the anode membrane (15) and the bipolar membrane (16);
a dilute acid chamber (21) is formed between the bipolar membrane (16) and the cathode membrane (14).
9. the apparatus of claim 8, wherein: the anode plate is a titanium-coated ruthenium or titanium-coated platinum plate, and the cathode plate is a ruthenium dioxide or stainless steel plate.
10. a water treatment system characterized by: comprising desalination means and regeneration means according to claim 6 or 7 or 8 or 9;
the desalination equipment comprises an anode double-chamber ion exchanger (25) and an anion double-chamber ion exchanger (29);
The bottom of the positive double-chamber ion exchanger (25) is communicated with the outlet of the acid concentration regulating unit (10) in the device through a pipeline; the bottom of the anion double-chamber ion exchanger (29) is communicated with the outlet of the alkali concentration adjusting unit (11) in the device through a pipeline;
the water outlet of the positive double-chamber ion exchanger (25) is communicated with the water inlet of the negative double-chamber ion exchanger (29) through a pipeline.
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| CN110790343A (en) * | 2019-11-15 | 2020-02-14 | 师宗煤焦化工有限公司 | Mixed bed regeneration method for water conservation and emission reduction |
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