CN116573813A - System and method for treating regenerated wastewater by coupling degassing membrane with bipolar membrane - Google Patents
System and method for treating regenerated wastewater by coupling degassing membrane with bipolar membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 202
- 239000002351 wastewater Substances 0.000 title claims abstract description 193
- 238000007872 degassing Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008878 coupling Effects 0.000 title description 4
- 238000010168 coupling process Methods 0.000 title description 4
- 238000005859 coupling reaction Methods 0.000 title description 4
- 239000007788 liquid Substances 0.000 claims abstract description 108
- 238000010521 absorption reaction Methods 0.000 claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 93
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002253 acid Substances 0.000 claims abstract description 80
- 239000003513 alkali Substances 0.000 claims abstract description 76
- 238000003860 storage Methods 0.000 claims abstract description 65
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 43
- 230000008929 regeneration Effects 0.000 claims abstract description 38
- 238000011069 regeneration method Methods 0.000 claims abstract description 38
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002585 base Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 37
- 238000003795 desorption Methods 0.000 claims description 36
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 29
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 29
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 29
- 238000001223 reverse osmosis Methods 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000004576 sand Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- 238000012806 monitoring device Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000006012 monoammonium phosphate Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000005696 Diammonium phosphate Substances 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- GVJINIPSNVBILO-UHFFFAOYSA-N [Ta].[Ru].[Pt] Chemical compound [Ta].[Ru].[Pt] GVJINIPSNVBILO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 15
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012946 outsourcing Methods 0.000 description 3
- 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 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/46—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
- C02F1/4698—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electro-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
- C02F1/66—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physical Water Treatments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of wastewater treatment, in particular to a system and a method for treating regenerated wastewater by using a degassing membrane coupled bipolar membrane. Comprises a regenerated wastewater pretreatment unit, a wastewater concentration unit, a degassing membrane ammonia nitrogen removal unit, an absorption liquid regeneration and ammonia production unit and a bipolar membrane acid and alkali production unit which are connected in sequence. The degassing membrane ammonia nitrogen removal unit comprises an alkali adding water tank, a degassing membrane, an absorption liquid storage tank, an absorption liquid circulation tank and a wastewater circulation tank, wherein an outlet of the wastewater circulation tank is connected with an inlet of a degassing membrane tube side, the outlet of the degassing membrane tube side is divided into two paths, one path is connected to a reflux port of the wastewater circulation tank, and the other path is connected to the bipolar membrane acid-base making unit; the degassing membrane shell process inlet is connected with the absorption liquid circulation box outlet, the degassing membrane shell process outlet is divided into two paths, one path is connected to the absorption liquid circulation box return port, and the other path is connected with the absorption liquid regeneration and ammonia production unit; the invention realizes the recycling of ammonia resources in the wastewater and has higher economic benefit and social environmental benefit.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a system and a method for treating regenerated wastewater by using a degassing membrane coupled bipolar membrane.
Background
For large-scale thermal power plants, ammonia is generally used as an alkalizing agent to be added into a water supply system to control the pH of the water supply within a range of 9.2-9.6 in order to avoid corrosion of a thermodynamic system. Meanwhile, in order to maintain the vapor quality of the thermodynamic system, the thermal power plant is also provided with a condensate polishing system which utilizes ion exchange resin to remove corrosion products and various dissolved salt impurities in condensate formed after work is done in the steam turbine, so as to ensure the vapor quality in the thermodynamic system. Under the condition that a thermal system of a thermal power plant and a condensate water fine treatment system normally operate, the treated water quantity of the fine treatment system accounts for more than 70% of the water supply quantity of a boiler, and amino matters added into water are removed by the fine treatment system, so that the high ammonia nitrogen content in the fine treatment ion exchange resin regenerated wastewater is caused, and meanwhile, the regenerated wastewater has the characteristic of high salt content. This portion of the wastewater is usually diluted or is collected into a desulfurization system, but the diluted wastewater does not meet the increasingly strict environmental requirements, and the collection into the desulfurization system may have an adverse effect on the desulfurization system due to the extremely high chloride ion content in the regenerated wastewater.
And part of power plants treat ammonia nitrogen in the refined resin regeneration wastewater by adopting a chemical precipitation method, a break point chlorination method, a biological denitrification method, a stripping method and other methods. The chemical precipitation method and the break point chlorination method have the advantages of high medicament consumption, high cost and easiness in secondary pollution; the biological denitrification method has the advantages that the treatment process flow is long, the microbial activity is easily influenced by factors such as water quality, water temperature, toxic substances and the like, and the refined regenerated wastewater has the characteristic of large water quality fluctuation, so that the biological denitrification process parameter control difficulty is high; the stripping method has the advantages of larger power consumption, poorer economy and higher content of residual ammonia nitrogen in produced water. The ammonia nitrogen in the regenerated wastewater can be removed by a degassing membrane method, the ammonia-containing wastewater and the acid absorption liquid are separated by a hydrophobic microporous membrane, gaseous ammonia molecules in the wastewater are diffused from a wastewater phase main body to a wastewater-membrane interface, and are reacted with the acid absorption liquid through the microporous membrane to a membrane-acid absorption liquid interface, so that ammonium ions are generated and removed.
However, the problem to be considered is that after the ammonia nitrogen is removed from the refined regenerated wastewater by the method, the residual wastewater is still wastewater with high salt content, and if the wastewater is directly discharged without treatment, the wastewater can cause certain harm to water body organisms and industrial and agricultural production, so that further treatment is still needed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a system for treating the refined resin regeneration wastewater of the power plant by coupling a degassing membrane method with a bipolar membrane, so that high-purity ammonia water which can be reused for adding ammonia into the boiler feed water of the power plant is obtained, zero wastewater discharge of the refined resin regeneration system is realized, and no extra acid or alkali is needed in the power plant.
The invention realizes the aim through the following technical scheme:
a first object of the present invention is to provide a system for treating regenerated wastewater by a degassing membrane coupled bipolar membrane, comprising: the device comprises a regenerated wastewater pretreatment unit, a wastewater concentration unit, a degassing membrane ammonia nitrogen removal unit, an absorption liquid regeneration and ammonia production unit and a bipolar membrane acid and alkali production unit;
the regenerated wastewater pretreatment unit comprises a regenerated wastewater collection tank and a sand filter, wherein an outlet of the regenerated wastewater collection tank is connected to an inlet of the sand filter;
the wastewater concentration unit comprises an acid adding water tank, a cartridge filter and reverse osmosis, wherein the inlet of the acid adding water tank is connected with the outlet of the sand filter, the outlet of the acid adding water tank is connected to the inlet of the cartridge filter, and the outlet of the cartridge filter is connected to the reverse osmosis inlet;
the degassing membrane ammonia nitrogen removal unit comprises an alkali adding water tank, a degassing membrane, an absorption liquid storage tank, an absorption liquid circulation tank and a wastewater circulation tank, wherein an inlet of the alkali adding water tank is connected with a reverse osmosis concentrated water outlet; the degassing membrane shell process inlet is connected with the absorption liquid circulation box outlet, the degassing membrane shell process outlet is divided into two paths, one path is connected to the absorption liquid circulation box return port, and the other path is connected with the absorption liquid regeneration and ammonia production unit; an inlet of the absorption liquid circulation tank is connected with an outlet of the absorption liquid storage tank, and an inlet of the absorption liquid storage tank is connected with an absorption liquid regeneration and ammonia production unit;
the absorption liquid regeneration and ammonia production unit comprises a desorption tower and an ammonia water storage tank, wherein a feed liquid inlet of the desorption tower is connected with a degassing membrane shell path outlet, a lean liquid outlet of a tower kettle of the desorption tower is connected with an absorption liquid storage tank inlet, and an ammonia water outlet of a product of the desorption tower is connected with a product ammonia water storage tank inlet;
the bipolar membrane acid-base preparation unit comprises a bipolar membrane, an alkali liquor storage tank and an acid liquor storage tank; the bipolar membrane dilute brine outlet is connected with the inlet of the acid water tank of the wastewater concentration unit.
As a further improvement of the invention, an aeration device, an alkali adding port and a pH monitoring device are arranged in a regenerated wastewater collecting tank of the regenerated wastewater pretreatment unit, and the alkali adding port is connected with an outlet of an alkali liquid storage tank of the bipolar membrane acid-base preparation unit;
the acid adding water tank of the wastewater concentration unit is provided with an acid adding port and a pH monitoring device, and the acid adding port is connected with an outlet of the acid liquid storage tank;
the reverse osmosis low-salt-content produced water outlet of the wastewater concentration unit is connected to a circulating cooling water system and a desulfurization system of the power plant.
As a further improvement of the invention, the alkali adding water tank of the degassing membrane ammonia nitrogen removal unit is provided with an alkali adding port and a pH monitoring device, and the alkali adding port is connected with an outlet of an alkali liquid storage tank of the bipolar membrane acid-base making unit.
As a further improvement of the invention, the degassing membrane of the degassing membrane ammonia nitrogen removal unit adopts a shell-and-tube membrane component prepared from a hollow fiber microporous hydrophobic membrane, and the material of the shell-and-tube membrane component is a high polymer nonpolar material, including polypropylene, polyethylene, polytetrafluoroethylene or polyvinylidene chloride.
As a further improvement of the invention, the electrode of the bipolar membrane acid-base making unit adopts a titanium-based tantalum-platinum-ruthenium-coated acid-base corrosion-resistant electrode, the anion exchange membrane adopts a perfluoro-grafted acid-base-resistant cathode membrane, the cation exchange membrane adopts a modified hardness-resistant alkali-resistant anode membrane, and the bipolar membrane adopts a modified hardness-resistant bipolar membrane.
As a further improvement of the invention, a bivalent separation device is additionally arranged between the acid adding water tank and the security filter; the multivalent salt solution outlet of a divalent separating device enters a collecting device and is used for a desulfurization system.
A method for treating a system for treating regenerated wastewater by using a degassing membrane coupled bipolar membrane, comprising the following steps:
collecting and storing the fine-treated regenerated wastewater of a power plant in a regenerated wastewater collecting tank, uniformly mixing the regenerated wastewater of negative and positive resins, regulating the pH of the wastewater to 10-10.5, filtering out suspended matters of waste large particles by using a sand filter, conveying the wastewater to an acid adding water tank, regulating the pH of the wastewater to 6-8 by using an acid liquor prepared by using a bipolar membrane, filtering out the suspended matters by using a security filter, conveying to reverse osmosis for concentration, and obtaining concentrated water with the salt content of 10-18% and conveying to an alkali adding water tank;
adjusting the pH value of the concentrated water to be more than 11.5, then sending the concentrated water to a wastewater circulation tank, carrying out circulation treatment on the deaeration membrane tube side, and sending the treated produced water to a salt chamber of a bipolar membrane device for treatment; the degassing membrane shell side utilizes the absorption liquid to absorb free ammonia in the wastewater of the degassing membrane tube side;
and (3) conveying the obtained diammonium phosphate rich solution to the middle and upper parts of a desorption tower, heating the tower bottom of the desorption tower by adopting a reboiler, enabling the diammonium phosphate rich solution to be in countercurrent contact with water vapor generated by the reboiler for mass transfer and heat transfer, condensing a gas phase obtained at the top of the desorption tower, conveying the condensed gas phase to an ammonia water storage tank, obtaining monoammonium phosphate lean solution at the tower bottom of the desorption tower, temporarily storing the monoammonium phosphate lean solution in an absorption solution storage tank, and conveying the absorption solution storage tank for recycling.
As an optional embodiment, the degassing membrane of the ammonia nitrogen removal unit of the degassing membrane adopts monoammonium phosphate with the mass fraction of 20% -30% as the absorption liquid;
when ammonium dihydrogen phosphate is used as an absorption liquid to remove ammonia in the refined resin regenerated wastewater, the absorption liquid passes through a shell pass and the refined resin regenerated wastewater passes through a tube pass, and the flow direction of the absorption liquid is opposite to that of the wastewater.
As an alternative embodiment, a plate tower or a packing tower is adopted as a desorption tower of the absorption liquid regeneration and ammonia production unit, 145-200 ℃ steam is adopted as a tower kettle reboiler heat source, and the operation pressure is 0.1-1.2 MPa (A).
As an alternative embodiment, the bipolar membrane of the bipolar membrane acid-base making unit adopts a three-compartment structure, and the three compartments are respectively circulated independently; when the system is operated for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L is introduced into the acid chamber, and sodium hydroxide with the concentration of 0.05-0.2 mol/L is introduced into the alkali chamber;
when the system starts to operate for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L and sodium hydroxide with the concentration of 0.05-0.2 mol/L are introduced into an acid chamber of the bipolar membrane, the acid chamber is circularly operated to enable the mass fraction of acid liquor to reach 5-8% and stored in an acid liquor storage tank, the mass fraction of alkali liquor in the alkali chamber reaches 5-8% and stored in the alkali liquor storage tank, the salt content of the wastewater in the salt chamber is reduced to 0.5-2%, and the wastewater is recovered to a reverse osmosis inlet for concentration treatment.
Compared with the prior art, the invention has the following advantages:
the invention comprises a regenerated wastewater pretreatment unit, a wastewater concentration unit, a degassing membrane ammonia nitrogen removal unit, an absorption liquid regeneration and ammonia production unit and a bipolar membrane acid and alkali production unit which are connected in sequence. The method comprises the steps of utilizing a degassing membrane coupled with a bipolar membrane to treat the fine-treated resin regeneration wastewater of a power plant, separating ammonia in the wastewater and preparing ammonia water which can be reused for adding ammonia into boiler feed water, recycling ammonia resources in the wastewater, preparing acid liquor and alkali liquor which can be reused for resin regeneration by utilizing the bipolar membrane, and enabling the power plant to be free from outsourcing acid and alkali, thereby realizing zero emission of the fine-treated resin regeneration wastewater, ensuring safe and reliable overall operation performance and having higher economic benefit and social environment benefit. Removing ammonia nitrogen in the resin regeneration wastewater by using a degassing membrane to obtain high-purity ammonia water which can be reused for adding ammonia into boiler feed water of a power plant, and further treating the resin regeneration wastewater from which the ammonia nitrogen is removed by using a bipolar membrane to obtain acid liquor and alkali liquor which can be reused for resin regeneration, thereby realizing zero discharge of wastewater of a fine treatment resin regeneration system.
Drawings
The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way. In addition, the shapes, proportional sizes, and the like of the respective components in the drawings are merely illustrative for aiding in understanding the present invention, and are not particularly limited. In the drawings:
FIG. 1 is a block diagram of the process flow of embodiment 1 of the present invention;
FIG. 2 is a schematic flow chart of an apparatus according to embodiment 1 of the present invention;
FIG. 3 is a block diagram of the process flow of embodiment 2 of the present invention;
fig. 4 is a schematic flow chart of the apparatus in embodiment 2 of the present invention.
Detailed Description
It will be understood that when an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a system for treating regenerated wastewater by coupling a degassing membrane with a bipolar membrane, which specifically comprises a regenerated wastewater pretreatment unit, a wastewater concentration unit, a degassing membrane ammonia nitrogen removal unit, an absorption liquid regeneration and ammonia production unit and a bipolar membrane acid and alkali production unit, wherein the system is shown in fig. 1 to 4.
The regenerated wastewater pretreatment unit comprises a regenerated wastewater collection tank, a sand filter and other devices, wherein the regenerated wastewater collection tank is used for collecting refined resin regenerated wastewater of a power plant, the outlet of the regenerated wastewater collection tank is connected to the inlet of the sand filter, and the outlet of the sand filter is connected to the wastewater concentration unit.
The wastewater concentration unit comprises an acid adding water tank, a cartridge filter, a reverse osmosis device and the like, wherein an inlet of the acid adding water tank is connected with an outlet of a sand filter of the fine treatment and regeneration wastewater pretreatment unit, an outlet of the acid adding water tank is connected to an inlet of the cartridge filter, an outlet of the cartridge filter is connected to a reverse osmosis inlet, and an outlet of the reverse osmosis concentrated water is connected to a degassing membrane ammonia nitrogen removal unit.
The degassing membrane ammonia nitrogen removal unit comprises an alkali adding water tank, a degassing membrane, an absorption liquid storage tank, an absorption liquid circulation tank, a wastewater circulation tank and other devices, wherein an inlet of the alkali adding water tank is connected with a reverse osmosis concentrated water outlet of the wastewater concentration unit, an outlet of the alkali adding water tank is connected with an inlet of the wastewater circulation tank, an outlet of the wastewater circulation tank is connected with a tube side inlet of the degassing membrane, the tube side outlet of the degassing membrane is divided into two paths, one path is connected to a reflux port of the wastewater circulation tank, and the other path is connected to the bipolar membrane acid-base making unit; the degassing membrane shell process inlet is connected with the absorption liquid circulation box outlet, the degassing membrane shell process outlet is divided into two paths, one path is connected to the absorption liquid circulation box return port, and the other path is connected with the absorption liquid regeneration and ammonia production unit; the inlet of the absorption liquid circulation tank is connected with the outlet of the absorption liquid storage tank, and the inlet of the absorption liquid storage tank is connected with the absorption liquid regeneration and ammonia production unit.
The absorption liquid regeneration and ammonia production unit comprises a desorption tower, an ammonia water storage tank and the like, wherein a material liquid inlet of the desorption tower is connected with a degassing membrane shell outlet of the degassing membrane ammonia nitrogen removal unit, a lean liquid outlet of a tower kettle of the desorption tower is connected with an absorption liquid storage tank inlet of the degassing membrane ammonia nitrogen removal unit, and an ammonia water outlet of a product of the desorption tower is connected with an ammonia water storage tank inlet of the product.
The bipolar membrane acid-base preparation unit comprises a bipolar membrane, an alkali liquor storage tank and an acid liquor storage tank. The bipolar membrane feed liquid inlet is connected with the degassing membrane tube side outlet of the degassing membrane ammonia nitrogen removal unit, the bipolar membrane alkali production port is connected with the alkali liquor storage tank inlet, the bipolar membrane acid production port is connected with the acid liquor storage tank inlet, and the bipolar membrane dilute brine outlet is connected with the acid water tank inlet of the wastewater concentration unit.
The invention comprises a regenerated wastewater pretreatment unit, a wastewater concentration unit, a degassing membrane ammonia nitrogen removal unit, an absorption liquid regeneration and ammonia production unit and a bipolar membrane acid and alkali production unit which are connected in sequence. According to the invention, the degassing membrane is utilized to separate ammonia in the refined resin regenerated wastewater of the power plant and prepare ammonia water, so that the recycling of ammonia resources in the wastewater is realized, the bipolar membrane is utilized to prepare acid and alkali, the power plant does not need to purchase acid and alkali externally, the zero emission of the refined resin regenerated wastewater is realized, and the method has higher economic benefit and social environmental benefit.
Preferably, an aeration device, an alkali adding port and a pH monitoring device are arranged in the regenerated wastewater collecting tank of the regenerated wastewater pretreatment unit, the aeration device is used for uniformly mixing the refined resin regenerated wastewater, sufficient oxygen is blown into the aeration device to convert ferrous ions in the wastewater into ferric ions, the alkali adding port is connected with an outlet of an alkali liquid storage tank of the bipolar membrane acid-base preparation unit, and the pH of the wastewater in the regenerated wastewater collecting tank is adjusted to 10-10.5 by using alkali liquid prepared by the bipolar membrane, so that the stability of iron oxide is ensured.
Preferably, an acid adding water tank of the wastewater concentration unit is provided with an acid adding port and a pH monitoring device, the acid adding port is connected with an outlet of the acid liquid storage tank, and the pH of reverse osmosis inflow water is adjusted to 6-8 by using acid prepared by a bipolar membrane.
Preferably, the reverse osmosis low-salt-content produced water of the wastewater concentration unit can be reused in a circulating cooling water system, a desulfurization system and the like of a power plant.
Preferably, the degassing membrane ammonia nitrogen removal unit alkali adding water tank is provided with an alkali adding port and a pH monitoring device, the alkali adding port is connected with an alkali liquor storage tank outlet of the bipolar membrane acid-base preparation unit, and the pH of the concentrated regenerated wastewater is adjusted to be more than 11.5 by using alkali prepared by the bipolar membrane, so that ammonia in the water exists in a free ammonia form.
Preferably, the degassing membrane of the degassing membrane ammonia nitrogen removal unit adopts a shell-and-tube membrane component prepared from a hollow fiber microporous hydrophobic membrane, and the material of the shell-and-tube membrane component is a high polymer nonpolar material comprising polypropylene, polyethylene, polytetrafluoroethylene, polyvinylidene chloride and the like.
The invention also provides a treatment method of the system for treating the regenerated wastewater by using the degassing membrane coupled bipolar membrane, which comprises the following steps:
collecting and storing the fine-treated regenerated wastewater of a power plant in a regenerated wastewater collecting tank, uniformly mixing the regenerated wastewater of negative and positive resins, regulating the pH of the wastewater to 10-10.5, filtering out suspended matters of waste large particles by using a sand filter, conveying the wastewater to an acid adding water tank, regulating the pH of the wastewater to 6-8 by using an acid liquor prepared by using a bipolar membrane, filtering out the suspended matters by using a security filter, conveying to reverse osmosis for concentration, and obtaining concentrated water with the salt content of 10-18% and conveying to an alkali adding water tank;
adjusting the pH value of the concentrated water to be more than 11.5, then sending the concentrated water to a wastewater circulation tank, carrying out circulation treatment on the deaeration membrane tube side, and sending the treated produced water to a salt chamber of a bipolar membrane device for treatment; the degassing membrane shell side utilizes the absorption liquid to absorb free ammonia in the wastewater of the degassing membrane tube side;
and (3) conveying the obtained diammonium phosphate rich solution to the middle and upper parts of a desorption tower, heating the tower bottom of the desorption tower by adopting a reboiler, enabling the diammonium phosphate rich solution to be in countercurrent contact with water vapor generated by the reboiler for mass transfer and heat transfer, condensing a gas phase obtained at the top of the desorption tower, conveying the condensed gas phase to an ammonia water storage tank, obtaining monoammonium phosphate lean solution at the tower bottom of the desorption tower, temporarily storing the monoammonium phosphate lean solution in an absorption solution storage tank, and conveying the absorption solution storage tank for recycling.
Preferably, when ammonia in the refined regenerated wastewater is removed by the degassing membrane of the ammonia nitrogen removal unit, ammonium dihydrogen phosphate with the mass fraction of 20% -30% is selected as an absorption liquid, 60% -95% of the ammonium dihydrogen phosphate content in the absorption liquid is converted into ammonium dihydrogen phosphate in the actual absorption process, and the percentage of the ammonium dihydrogen phosphate in the absorption liquid converted into the ammonium dihydrogen phosphate is the conversion degree. The greater the degree of conversion (i.e., the greater the amount of monoammonium phosphate converted to diammonium phosphate), the greater the amount of ammonia absorbed, however, since the degree of conversion is limited by the reaction equilibrium and phase equilibrium, the absorption mass transfer rate decreases after the degree of conversion is increased, and thus the increase in the degree of conversion is detrimental to the absorption capacity of the solution, while too low a degree of conversion will result in waste of the absorption liquid, leading to an increase in the running cost and energy consumption, and therefore it is important to select an appropriate degree of conversion. In the embodiment of the invention, the conversion degree of phosphoric acid is 60% -95%, and the balance of enhancing the absorption effect and reducing the energy consumption is realized.
Preferably, when ammonium dihydrogen phosphate is used as an absorption liquid to remove ammonia in the refined resin regenerated wastewater, the absorption liquid passes through a shell pass and the refined resin regenerated wastewater passes through a tube pass, and the flow direction of the absorption liquid is opposite to that of the wastewater, so that the absorption efficiency is improved.
Preferably, a plate tower or a packing tower is adopted as a desorption tower of the absorption liquid regeneration and ammonia production unit, 145-200 ℃ steam is adopted as a tower kettle reboiler heat source, and the operation pressure is 0.1-1.2 MPa (A).
Preferably, the electrode of the bipolar membrane acid-base making unit adopts a titanium-based tantalum-platinum-ruthenium-coated acid-base corrosion-resistant electrode, the anion exchange membrane adopts a perfluoro-grafted acid-base-resistant cathode membrane, the cation exchange membrane adopts a modified hardness-resistant alkali-resistant anode membrane, and the bipolar membrane adopts a modified hardness-resistant bipolar membrane.
Preferably, the bipolar membrane of the bipolar membrane acid-base making unit adopts a three-compartment structure, and the three compartments are respectively and independently circulated. The refined resin regenerated wastewater after ammonia nitrogen removal by the degassing membrane enters a salt chamber of the bipolar membrane, and when the system is operated for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L is introduced into an acid chamber, and sodium hydroxide with the concentration of 0.05-0.2 mol/L is introduced into an alkali chamber.
Optionally, part of thermal power plants mix the resin regenerated wastewater of the fine treatment resin regenerated wastewater and the resin regenerated wastewater of the desalted water preparation system together for treatment, and the mixed wastewater contains divalent cations such as calcium, magnesium and the like, so that serious scaling problems can occur when the wastewater is treated by utilizing a bipolar membrane.
In order that the objects, technical solutions and advantages of the present invention may be more clearly understood, various embodiments of the present invention will be described below with reference to the accompanying drawings, and the present invention will be further described in detail. The described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, shall fall within the scope of the invention.
Example 1
The first embodiment of the invention relates to a device for treating fine treatment resin regeneration wastewater of a power plant by using a degassing membrane coupled with a bipolar membrane. The main body of the embodiment comprises a regenerated wastewater collecting tank, a sand filter, an acid adding water tank, a cartridge filter, reverse osmosis, an alkali adding water tank, a wastewater circulating tank, a degassing membrane, a desorption tower, an absorption liquid storage tank, an absorption liquid circulating tank, an ammonia water storage tank, a bipolar membrane, an acid liquid storage tank and an alkali liquid storage tank, wherein the connection modes of the parts are shown in the figure 2.
The operation flow of the device for treating the fine treatment resin regeneration wastewater of the power plant is as follows:
collecting and storing the fine-treated regenerated wastewater of a power plant in a regenerated wastewater collecting tank, uniformly mixing the regenerated wastewater of negative and positive resins by an aeration device in the regenerated wastewater collecting tank, regulating the pH of the wastewater to 10-10.5 by using an alkali liquor prepared by a bipolar membrane, ensuring the stability of iron oxides in the wastewater, filtering large-particle suspended matters such as the iron oxides in the wastewater by using a sand filter, conveying the wastewater to an acid water tank, regulating the pH of the wastewater to 6-8 by using an acid liquor prepared by using the bipolar membrane, filtering the residual suspended matters in the wastewater by using a security filter, conveying to reverse osmosis for concentration, obtaining concentrated water with the salt content of 10-18%, conveying to an alkali adding water tank, regulating the pH of the concentrated water to above 11.5 by using the bipolar membrane, ensuring that ammonia in the concentrated water exists in a free ammonia form, conveying the pH-regulated concentrated water to a wastewater circulation tank, carrying out circulation treatment on a degassing membrane tube side, and conveying the treated produced water to a salt chamber of the bipolar membrane device for treatment. The degassing membrane shell side uses ammonium dihydrogen phosphate with the mass fraction of 20% -30% as an absorption liquid, the circulation is carried out on the shell side of the degassing membrane, free ammonia in waste water in the tube side of the degassing membrane is absorbed, the circulation flow direction of the absorption liquid is opposite to the circulation flow direction of the waste water, 60% -95% of the ammonium dihydrogen phosphate content in the absorption liquid is converted into ammonium dihydrogen phosphate in the actual absorption process, the obtained ammonium dihydrogen phosphate rich liquid is conveyed to the middle upper part of a desorption tower, a reboiler is adopted for heating at the tower bottom of the desorption tower, a heat source of the reboiler adopts steam with the temperature of 145-200 ℃, the operation pressure is 0.1-1.2 MPa (A), the ammonium dihydrogen phosphate rich liquid is in countercurrent contact with steam generated by the reboiler for carrying out mass transfer, ammonia water with the mass fraction of 5-18% is obtained after the gas phase obtained at the top of the desorption tower is condensed and conveyed to an ammonia water storage tank, the ammonium dihydrogen phosphate lean liquid is obtained at the tower bottom of the desorption tower, and is temporarily stored to an absorption liquid storage tank, and then the ammonium phosphate rich liquid is conveyed to the absorption liquid circulation tank for cyclic utilization. When the system starts to operate for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L and sodium hydroxide with the concentration of 0.05-0.2 mol/L are introduced into an acid chamber of the bipolar membrane, the acid chamber is circularly operated to enable the mass fraction of acid liquor to reach 5-8% and stored in an acid liquor storage tank, the mass fraction of alkali liquor in the alkali chamber reaches 5-8% and stored in the alkali liquor storage tank, the salt content of the wastewater in the salt chamber is reduced to 0.5-2%, and the wastewater is recovered to a reverse osmosis inlet for concentration treatment.
The method can realize zero emission of the fine treatment resin regenerated wastewater of the power plant, and can prepare ammonia water with the mass fraction of 5-18% and acid-base with the mass fraction of 5-8%, and the power plant does not need outsourcing of the acid-base, so that the method has higher economic benefit and social environment benefit.
Example two
The second embodiment of the invention designs a device for treating resin regeneration wastewater of a power plant by using a degassing membrane coupled bipolar membrane. The difference between this embodiment and the first embodiment is that: the wastewater to be treated in this embodiment includes resin regeneration wastewater of a demineralized water preparation system of a power plant in addition to fine treatment resin regeneration wastewater of the power plant, and the wastewater contains higher divalent cations such as calcium and magnesium, if the wastewater is directly treated by using a bipolar membrane, serious scaling problems can occur, so that a divalent separation device is additionally arranged behind an acid adding water tank of a wastewater concentration unit in this embodiment. The process flow diagram of the embodiment is shown in figure 3, the main body comprises a regenerated wastewater collecting tank, a sand filter, an acid adding water tank, a binary separation device, a cartridge filter, reverse osmosis, an alkali adding water tank, a wastewater circulation tank, a degassing membrane, a desorption tower, an absorption liquid storage tank, an absorption liquid circulation tank, an ammonia water storage tank, a bipolar membrane, an acid liquid storage tank and an alkali liquid storage tank, and the connection modes of the parts are shown in figure 4.
The operation flow of treating the resin regeneration wastewater of the power plant by using the device of the embodiment is as follows:
collecting and storing the fine-treated regenerated wastewater of a power plant in a regenerated wastewater collecting tank, uniformly mixing the regenerated wastewater of negative and positive resins by an aeration device in the regenerated wastewater collecting tank, preparing alkali liquor by using a bipolar membrane to adjust the pH of the wastewater to 10-10.5, ensuring the stability of iron oxides in the wastewater, filtering large-particle suspended matters such as the iron oxides in the wastewater by using a sand filter, conveying the wastewater to an acid water tank, preparing acid liquor by using the bipolar membrane to adjust the pH of the wastewater to 6-8, separating calcium ions, magnesium ions and the like in the wastewater by using a binary separation device, conveying the obtained monovalent salt solution to a security filter, filtering the residual suspended matters, conveying the obtained monovalent salt solution to reverse osmosis for concentration, obtaining concentrated water with the salt content of 10-18%, conveying the concentrated water to an alkali adding water tank, preparing the alkali liquor by using the bipolar membrane to adjust the pH of the concentrated water to above 11.5, ensuring that ammonia in the ammonia exists in a free ammonia form, conveying the concentrated water after the pH adjustment to a wastewater circulation tank, carrying out circulation treatment in a bipolar membrane tube side, and conveying the treated produced water to a salt chamber of the bipolar membrane device for treatment. The degassing membrane shell side uses ammonium dihydrogen phosphate with the mass fraction of 20% -30% as an absorption liquid, the circulation is carried out on the shell side of the degassing membrane, free ammonia in waste water in the tube side of the degassing membrane is absorbed, the circulation flow direction of the absorption liquid is opposite to the circulation flow direction of the waste water, 60% -95% of the ammonium dihydrogen phosphate content in the absorption liquid is converted into ammonium dihydrogen phosphate in the actual absorption process, the obtained ammonium dihydrogen phosphate rich liquid is conveyed to the middle upper part of a desorption tower, a reboiler is adopted for heating at the tower bottom of the desorption tower, a heat source of the reboiler adopts steam with the temperature of 145-200 ℃, the operation pressure is 0.1-1.2 MPa (A), the ammonium dihydrogen phosphate rich liquid is in countercurrent contact with steam generated by the reboiler for carrying out mass transfer, ammonia water with the mass fraction of 5-18% is obtained after the gas phase obtained at the top of the desorption tower is condensed and conveyed to an ammonia water storage tank, the ammonium dihydrogen phosphate lean liquid is obtained at the tower bottom of the desorption tower, and is temporarily stored to an absorption liquid storage tank, and then the ammonium phosphate rich liquid is conveyed to the absorption liquid circulation tank for cyclic utilization. When the system starts to operate for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L and sodium hydroxide with the concentration of 0.05-0.2 mol/L are introduced into an acid chamber of the bipolar membrane, the acid chamber is circularly operated to enable the mass fraction of acid liquor to reach 5-8% and stored in an acid liquor storage tank, the mass fraction of alkali liquor in the alkali chamber reaches 5-8% and stored in the alkali liquor storage tank, the salt content of the wastewater in the salt chamber is reduced to 0.5-2%, and the wastewater is recovered to a reverse osmosis inlet for concentration treatment.
The method can realize zero emission of the fine treatment resin regenerated wastewater of the power plant, and can prepare ammonia water with the mass fraction of 5-18% and acid-base with the mass fraction of 5-8%, and the power plant does not need outsourcing of the acid-base, so that the method has higher economic benefit and social environment benefit.
The device elements in the above embodiments are conventional device elements unless otherwise specified, and the structural arrangement, operation or control modes in the embodiments are conventional arrangement, operation or control modes in the art unless otherwise specified.
Finally, it is noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and that other modifications and equivalents thereof by those skilled in the art should be included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A system for degassing membrane-coupled bipolar membrane treatment of regenerated wastewater, comprising:
a regeneration wastewater pretreatment unit comprising a regeneration wastewater collection tank and a sand filter, wherein the outlet of the regeneration wastewater collection tank is connected to the inlet of the sand filter;
the wastewater concentration unit comprises an acid adding water tank, a cartridge filter and reverse osmosis, wherein the inlet of the acid adding water tank is connected with the outlet of the sand filter, the outlet of the acid adding water tank is connected to the inlet of the cartridge filter, and the outlet of the cartridge filter is connected to the reverse osmosis inlet;
the degassing membrane ammonia nitrogen removal unit comprises an alkali adding water tank, a degassing membrane, an absorption liquid storage tank, an absorption liquid circulation tank and a wastewater circulation tank, wherein an inlet of the alkali adding water tank is connected with a reverse osmosis concentrated water outlet; the degassing membrane shell process inlet is connected with the absorption liquid circulation box outlet, the degassing membrane shell process outlet is divided into two paths, one path is connected to the absorption liquid circulation box return port, and the other path is connected with the absorption liquid regeneration and ammonia production unit; an inlet of the absorption liquid circulation tank is connected with an outlet of the absorption liquid storage tank, and an inlet of the absorption liquid storage tank is connected with an absorption liquid regeneration and ammonia production unit;
the absorption liquid regeneration and ammonia production unit comprises a desorption tower and an ammonia water storage tank, wherein a feed liquid inlet of the desorption tower is connected with a degassing membrane shell path outlet, a lean liquid outlet of a tower kettle of the desorption tower is connected with an absorption liquid storage tank inlet, and an ammonia water outlet of a product of the desorption tower is connected with a product ammonia water storage tank inlet;
the bipolar membrane acid-base preparation unit comprises a bipolar membrane, an alkali liquor storage tank and an acid liquor storage tank; the bipolar membrane dilute brine outlet is connected with the inlet of the acid water tank of the wastewater concentration unit.
2. The system for treating the regenerated wastewater by the degassing membrane coupled bipolar membrane according to claim 1, wherein an aeration device, an alkali adding port and a pH monitoring device are arranged in a regenerated wastewater collecting tank of the regenerated wastewater pretreatment unit, and the alkali adding port is connected with an alkali storage tank outlet of the bipolar membrane acid-base making unit;
the acid adding water tank of the wastewater concentration unit is provided with an acid adding port and a pH monitoring device, and the acid adding port is connected with an outlet of the acid liquid storage tank;
the reverse osmosis low-salt-content produced water outlet of the wastewater concentration unit is connected to a circulating cooling water system and a desulfurization system of the power plant.
3. The system for treating regenerated wastewater by using the degassing membrane coupled bipolar membrane according to claim 1, wherein an alkali adding water tank of the ammonia nitrogen removal unit of the degassing membrane is provided with an alkali adding port and a pH monitoring device, and the alkali adding port is connected with an outlet of an alkali liquid storage tank of the acid-base making unit of the bipolar membrane.
4. The system for treating regenerated wastewater by using the degassing membrane coupled with the bipolar membrane according to claim 1, wherein the degassing membrane of the ammonia nitrogen removal unit of the degassing membrane adopts a shell-and-tube membrane component made of a hollow fiber microporous hydrophobic membrane, and the material of the shell-and-tube membrane component is a high polymer nonpolar material comprising polypropylene, polyethylene, polytetrafluoroethylene or polyvinylidene chloride.
5. The system for treating regenerated wastewater by using a degassing membrane coupled bipolar membrane according to claim 1, wherein the electrode of the bipolar membrane acid-base making unit adopts a titanium-based tantalum-platinum-ruthenium-coated acid-base corrosion-resistant electrode, the anion exchange membrane adopts a perfluoro-grafted acid-base-resistant cathode membrane, the cation exchange membrane adopts a modified hardness-base-resistant anode membrane, and the bipolar membrane adopts a modified hardness-resistant bipolar membrane.
6. The system for treating regenerated waste water by using degassing membrane coupled bipolar membrane according to claim 1, wherein a divalent separation device is arranged between the acid adding water tank and the cartridge filter; the multivalent salt solution outlet of a divalent separating device enters a collecting device and is used for a desulfurization system.
7. A method of treating a system for treating regenerated wastewater by a degassing membrane coupled bipolar membrane as claimed in any one of claims 1 to 6, comprising the steps of:
collecting and storing the fine-treated regenerated wastewater of a power plant in a regenerated wastewater collecting tank, uniformly mixing the regenerated wastewater of negative and positive resins, regulating the pH of the wastewater to 10-10.5, filtering out suspended matters of waste large particles by using a sand filter, conveying the wastewater to an acid adding water tank, regulating the pH of the wastewater to 6-8 by using an acid liquor prepared by using a bipolar membrane, filtering out the suspended matters by using a security filter, conveying to reverse osmosis for concentration, and obtaining concentrated water with the salt content of 10-18% and conveying to an alkali adding water tank;
adjusting the pH value of the concentrated water to be more than 11.5, then sending the concentrated water to a wastewater circulation tank, carrying out circulation treatment on the deaeration membrane tube side, and sending the treated produced water to a salt chamber of a bipolar membrane device for treatment; the degassing membrane shell side utilizes the absorption liquid to absorb free ammonia in the wastewater of the degassing membrane tube side;
and (3) conveying the obtained diammonium phosphate rich solution to the middle and upper parts of a desorption tower, heating the tower bottom of the desorption tower by adopting a reboiler, enabling the diammonium phosphate rich solution to be in countercurrent contact with water vapor generated by the reboiler for mass transfer and heat transfer, condensing a gas phase obtained at the top of the desorption tower, conveying the condensed gas phase to an ammonia water storage tank, obtaining monoammonium phosphate lean solution at the tower bottom of the desorption tower, temporarily storing the monoammonium phosphate lean solution in an absorption solution storage tank, and conveying the absorption solution storage tank for recycling.
8. The treatment method of the system for treating regenerated wastewater by using the degassing membrane coupled with the bipolar membrane, which is characterized in that the degassing membrane of the degassing membrane ammonia nitrogen removal unit adopts ammonium dihydrogen phosphate with the mass fraction of 20-30% as an absorption liquid;
when ammonium dihydrogen phosphate is used as an absorption liquid to remove ammonia in the refined resin regenerated wastewater, the absorption liquid passes through a shell pass and the refined resin regenerated wastewater passes through a tube pass, and the flow direction of the absorption liquid is opposite to that of the wastewater.
9. The system for treating regenerated wastewater by using a degassing membrane coupled bipolar membrane according to claim 7, wherein a plate tower or a packed tower is adopted as a desorber of the absorption liquid regeneration and ammonia production unit, 145-200 ℃ steam is adopted as a tower kettle reboiler heat source, and the operation pressure is 0.1-1.2 MPa (A).
10. The system for treating regenerated wastewater by using a degassing membrane coupled bipolar membrane according to claim 7, wherein the bipolar membrane of the bipolar membrane acid-base making unit adopts a three-compartment structure, and the three compartments are respectively and independently circulated; when the system is operated for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L is introduced into the acid chamber, and sodium hydroxide with the concentration of 0.05-0.2 mol/L is introduced into the alkali chamber;
when the system starts to operate for the first time, sulfuric acid with the concentration of 0.05-0.2 mol/L and sodium hydroxide with the concentration of 0.05-0.2 mol/L are introduced into an acid chamber of the bipolar membrane, the acid chamber is circularly operated to enable the mass fraction of acid liquor to reach 5-8% and stored in an acid liquor storage tank, the mass fraction of alkali liquor in the alkali chamber reaches 5-8% and stored in the alkali liquor storage tank, the salt content of the wastewater in the salt chamber is reduced to 0.5-2%, and the wastewater is recovered to a reverse osmosis inlet for concentration treatment.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117865420A (en) * | 2024-03-11 | 2024-04-12 | 中天合创能源有限责任公司 | Equipment and method for treating ammonia nitrogen in sewage of coal chemical gasification process by membrane technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117865420A (en) * | 2024-03-11 | 2024-04-12 | 中天合创能源有限责任公司 | Equipment and method for treating ammonia nitrogen in sewage of coal chemical gasification process by membrane technology |
| CN117865420B (en) * | 2024-03-11 | 2024-05-10 | 中天合创能源有限责任公司 | Equipment and method for treating ammonia nitrogen in sewage of coal chemical gasification process by membrane technology |
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