WO2022142489A1 - System and method for clean energy seawater desalination and salinity gradient power generation device - Google Patents

System and method for clean energy seawater desalination and salinity gradient power generation device Download PDF

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WO2022142489A1
WO2022142489A1 PCT/CN2021/118922 CN2021118922W WO2022142489A1 WO 2022142489 A1 WO2022142489 A1 WO 2022142489A1 CN 2021118922 W CN2021118922 W CN 2021118922W WO 2022142489 A1 WO2022142489 A1 WO 2022142489A1
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seawater
power generation
module
seawater desalination
desalination
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PCT/CN2021/118922
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French (fr)
Chinese (zh)
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王倩
尹立坤
唐博进
蔺新星
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中国长江三峡集团有限公司
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Priority claimed from CN202011605331.XA external-priority patent/CN112723640A/en
Priority claimed from CN202023234022.4U external-priority patent/CN214400132U/en
Application filed by 中国长江三峡集团有限公司 filed Critical 中国长江三峡集团有限公司
Publication of WO2022142489A1 publication Critical patent/WO2022142489A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

Definitions

  • the invention relates to clean energy seawater desalination and salt difference energy power generation technology, and also relates to the treatment of waste water; in particular, it relates to a coupling of a reverse osmosis membrane seawater desalination system and a reverse electrodialysis salt difference energy power generation system using wind and solar complementary power generation .
  • distillation method thermal method
  • membrane method The technologies employed in the vast majority of operating desalination plants are Multi-Stage Flash (MSF), Multiple Effect Evaporation (MDF) and Reverse Osmosis (RO).
  • MDF Multi-Stage Flash
  • MDF Multiple Effect Evaporation
  • RO Reverse Osmosis
  • multi-stage flash evaporation and multi-effect evaporation are a kind of distillation method, both of which are energy-intensive processing methods.
  • Reverse osmosis membrane method is a kind of membrane method. Its principle is to separate seawater and freshwater by using a semi-permeable membrane that only allows solvent to pass through and does not allow solute to pass through.
  • the biggest advantage of reverse osmosis technology is energy saving. Using clean energy such as offshore wind power and solar energy as energy supply will help to greatly reduce the production cost of seawater desalination and achieve the goal of efficient and sustainable development of the water resources sector.
  • the desalination process especially reverse osmosis, produces high-salinity waste that is often injected back into the source pool, which not only reduces the long-term viability of desalination, but also threatens the marine ecosystem, creating a A potentially more costly negative externality problem. Therefore, it is a key issue to study and solve the high salinity by-products absorption and treatment technology.
  • Reverse electrodialysis technology is one of the salt difference energy generation technologies. It uses the selective permeation of ion exchange membranes to directly convert chemical energy mixed with different concentrations of salt solutions into electrical energy, which is clean, sustainable, pollution-free, and energy density. high advantage. Its application scenarios are not limited to the confluence of rivers and seas, but can also be coupled with seawater desalination devices, which can capture the salt difference energy between concentrated seawater and general seawater, so as to realize the consumption and reuse of high-salinity by-products of seawater desalination, and improve seawater production. Economical and environmentally friendly desalination, thus contributing to the sustainability of desalination.
  • the concentration of the solution has a great influence on the output power of the power generation.
  • concentration of the dilute solution is too low, although the electrochemical potential difference between the two sides of the ion membrane can be increased, it is also It will cause the resistance of the membrane stack to increase rapidly and the power density to decrease.
  • the average salinity of the world's oceans is 35 ⁇ , that is, the salt content in every kilogram of seawater is about 35 grams.
  • Its conductivity is about 30000 ⁇ S/m, which is more than a thousand times larger than that of ordinary lake water and river water, that is, the conductivity of seawater is much higher than that of ordinary fresh water.
  • seawater as a dilute solution can ensure that the resistance of the membrane group is low.
  • the desalination rate is high, up to 99%, and the actual recovery rate is generally above 75%, sometimes even 90%. Therefore, the fresh water produced by reverse osmosis membrane seawater desalination is of high purity.
  • the concentration of the obtained concentrated seawater is about 4 times that of ordinary seawater (calculated according to the recovery rate of 75%).
  • the salt difference between the two can generate electricity not only to achieve resource utilization, but also to dilute the concentrated seawater and reduce its impact on the marine environment.
  • the object of the present invention is to provide a system and method for utilizing clean energy to desalinate seawater and utilizing salinity difference energy to generate electricity to absorb high-salinity by-products of seawater desalination.
  • the reverse osmosis membrane method seawater desalination is powered by wind power and photovoltaic complementary power generation, and then the seawater desalination system is coupled with the reverse electrodialysis salt difference energy power generation system, and the salt difference energy between the seawater and the by-product of seawater desalination is used to concentrate the seawater. Consumption of high-salinity by-products of seawater desalination, and at the same time, electricity is generated to power desalination equipment or other loads.
  • the purpose of the present invention is to achieve this: a system of clean energy seawater desalination coupled with a salt difference energy power generation device, including a power supply module, the system also includes a seawater desalination module and a salt difference energy power generation module, and the seawater desalination module includes reverse osmosis device, one end of the reverse osmosis device is connected with the ultrafilter, and the other end is connected with the fresh water recovery tank and the concentrated water storage tank; the concentrated water storage tank is connected with the salt difference energy power generation module through the third pump body; the salt difference energy
  • the power generation module is mainly composed of a reverse electrodialysis device, a second pump body, a third pump body, a first three-way valve, a second three-way valve and an external load; the reverse electrodialysis device is provided with an anion exchange membrane and a cation exchange membrane Membranes, alternately arranged anion exchange membranes and cation exchange membranes form several concentrated water compartments and fresh water compartments.
  • the preparation methods of the anion exchange membrane and the cation exchange membrane are as follows: respectively, uniformly coating two kinds of ionomer resin solutions on the expanded polytetrafluoroethylene film, and waiting for the ionomer solution to slowly penetrate into the expanded polytetrafluoroethylene film. In the micropores of tetrafluoroethylene, a small amount of ionomer solution is evenly coated on the expanded polytetrafluoroethylene film, and the ionomer solution is slowly infiltrated into the micropores of expanded polytetrafluoroethylene, repeating several times.
  • the micropores of polytetrafluoroethylene are filled with the ionomer solution, and then wait for the solvent to volatilize; after the solvent is volatilized, vacuum constant temperature heat treatment is performed first, and after the heat treatment, the membrane is subjected to hot pressing treatment.
  • the concentration of the ionomer resin solution is 10-20%; after the solvent is volatilized, vacuum constant temperature heat treatment is first performed, the heat treatment temperature is 80-100 DEG C, and the heat treatment time is 8-20h; Carry out hot pressing treatment, the hot pressing temperature is 90-120 °C, on the one hand, it promotes the effective compounding of ionomer and PTFE, and on the other hand, the thickness of the film is controlled between 100-120 ⁇ m;
  • the solvent is a polar aprotonated solvent, specifically one or more of N,N-dimethylformamide, N-methylpyrrolidone or N,N-dimethylacetamide.
  • the power source of the power supply module is one or more of wind power, photovoltaic and other renewable energy sources.
  • an energy storage device is provided to ensure stable power supply, and the energy storage device is one or more of lithium batteries, nano batteries and the like.
  • the method for desalination and power generation using this system includes the following steps:
  • S1 Power supply by the power module: obtain power through one or more of the wind power generation system 1, the photovoltaic power generation system 2 or other renewable energy sources, and the obtained power is adjusted by the wind-solar hybrid controller 3, and the power part passes through the second DC/AC
  • the converter 7 supplies power to the seawater desalination module after adjustment; part of the power is stored by the energy storage device 5, and is regulated by the first DC/AC converter 6 to supply power to the seawater desalination module;
  • S21 Primary filtration: extract seawater, pass part of the seawater after precipitation, pH adjustment, sterilization, softening, etc. into the ultrafilter to further filter out the suspended solids in the seawater, and then filter the ultrafiltered seawater into the reverse osmosis device;
  • S22 reverse osmosis treatment: the seawater after ultrafiltration is passed into the reverse osmosis device and is pressurized by the first high-pressure pump to promote the desalination of seawater to obtain fresh water and concentrated seawater. into the concentrated water storage tank;
  • Salt difference energy power generation The obtained fresh water and concentrated seawater enter the salinity difference energy power generation module, using the different concentrations of seawater on both sides of the anion and cation membranes, resulting in the directional migration of anions and cations to generate potential difference power generation.
  • a concentration sensor is installed at the concentrated water outlet of the reverse electrodialysis device in the salt difference energy power generation module to detect the concentration of concentrated seawater at the outlet.
  • concentration of concentrated seawater is at a high level, adjust the three-way valve to It is recycled to the concentrated water inlet for reuse; when the concentration of concentrated seawater is low, the three-way valve is adjusted to discharge it directly into the sea; the seawater at the freshwater outlet of the reverse electrodialysis unit can be directly discharged into the sea.
  • the present invention utilizes stable clean energy to carry out reverse osmosis membrane seawater desalination, and simultaneously through reverse electrodialysis salt difference energy generation to absorb the high salinity by-products produced by seawater desalination, improve the efficiency of the entire seawater desalination process.
  • Environmentally friendly the present invention utilizes stable clean energy to carry out reverse osmosis membrane seawater desalination, and simultaneously through reverse electrodialysis salt difference energy generation to absorb the high salinity by-products produced by seawater desalination, improve the efficiency of the entire seawater desalination process.
  • the reverse osmosis membrane method seawater desalination adopted in the present invention is the most energy-saving compared to other seawater desalination methods, and compared with the most mature multi-stage flash evaporation (total energy consumption is about 10-16kWh/m3)
  • the total energy consumption of the membrane process (about 3-4kWh/m3) is about 1/4 to 1/3.
  • the present invention utilizes the salinity difference energy to generate electricity while consuming high-salinity by-products of seawater desalination, and can also generate stable electrical energy to feed seawater desalination, and the composite enhanced ion exchange membrane used can improve the output power of the entire device, While improving environmental protection, it also improves the economic benefits of the entire process.
  • the present invention utilizes a seawater desalination module for wastewater treatment, and realizes two purposes of a set of devices, which can be adjusted according to different operating conditions.
  • FIG. 1 is a schematic diagram of a clean energy seawater desalination coupled salt difference energy power generation device and system of the present invention
  • FIG. 2 is a schematic diagram of the coupled salt difference energy power generation device and system for wastewater treatment according to the present invention.
  • Wind power generation system 2. Photovoltaic power generation system, 3. Wind-solar hybrid controller, 4. DC/AC converter, 5. Energy storage device, 6. First DC/AC converter, 7. Second DC/AC converter, 8, ultrafilter, 9, first high pressure pump, 10, reverse osmosis unit, 11, fresh water outlet of reverse osmosis unit, 12, concentrated water outlet of reverse osmosis unit, 13, fresh water recovery tank, 14, Concentrated water storage tank, 15, first variable frequency pump, 16, second variable frequency pump, 17, first three-way valve, 18, second three-way valve, 19, concentration sensor, 20, concentrated water inlet, 21, fresh water inlet , 22, cathode plate, 23, cation exchange membrane, 24, anode plate, 25, anion exchange membrane, 26, fresh water chamber, 27, concentrated water chamber, 28, concentrated water outlet, 29, fresh water outlet, 30, external load, 31. Filtering device.
  • Example 1 Taking seawater desalination as an example to carry out a specific embodiment to illustrate the present invention.
  • the whole system is divided into three modules, namely power supply system module, seawater desalination module and salt difference energy power generation module.
  • the power supply system module mainly supplies energy for the seawater desalination system, which is mainly composed of a wind power generation system 1, a photovoltaic power generation system 2, an energy storage device 5, a DC/AC converter 4, a first DC/AC converter 6 and a wind-solar hybrid control. 3 components.
  • the photovoltaic power generation system 2 in the present invention generates direct current. Therefore, a DC/AC converter 4 is added to its output end, and the specific ratio is controlled by the wind-solar complementary controller 3; In order to ensure the stability of power supply, an energy storage device 5 is added for peak regulation. When the wind and solar power generation is excessive, the energy storage device can be charged, and when the power generation is insufficient, the energy storage device is used for external power supply.
  • the energy storage device can be one or more of lithium batteries, nano batteries, etc. in the electrochemical energy storage device, and its capacity is determined according to the scale of the desalination plant.
  • the seawater desalination module in the present invention mainly consists of an ultrafilter 8, a first high pressure pump 9, a reverse osmosis device 10, a fresh water outlet 11 of the reverse osmosis device, a concentrated water outlet 12 of the reverse osmosis device, a fresh water recovery tank 13 and a concentrated water storage tank 14 etc. composition.
  • One end of the reverse osmosis device 10 is connected to the ultrafilter 8 , and the other end is connected to the fresh water recovery tank 13 and the concentrated water storage tank 14 respectively;
  • the salt difference energy power generation module is mainly composed of a reverse electrodialysis device, a first variable frequency pump 15, a second variable frequency pump 16, a first three-way valve 17, a second three-way valve 18 and an external load 30, etc.; among which reverse electrodialysis
  • the device consists of a membrane group composed of anion exchange membrane 25 and cation exchange membrane 23, cathode plate 22, anode plate 24, concentrated water inlet 20, concentrated water outlet 28, fresh water inlet 21, fresh water outlet 29, concentrated water chamber 27, and fresh water chamber 26 , concentrated water flow channel, fresh water flow channel, concentration sensor 19 and so on.
  • the anion exchange membrane 23 and the cation exchange membrane 25 are arranged in the reverse electrodialysis device, and the alternately arranged anion exchange membranes 23 and cation exchange membranes 25 form several concentrated water chambers 27 and fresh water chambers 26 .
  • the concentrated seawater flows into the concentrated water channel 27 through the concentrated water inlet 20 through the second variable frequency pump 16, and the filtered seawater is driven by the first variable frequency pump 15 to flow into the fresh water channel 26 through the fresh water inlet 21 and enters the fresh water chamber 26. Due to the difference in salt concentration on both sides of the membrane, ions will migrate through the exchange membrane, resulting in a potential difference, which is output to the load 30 through the cathode plate 22 and anode plate 24; The size of the desalination plant is determined.
  • I is the current
  • R load is the external resistance
  • U is the potential energy difference
  • R stack is the membrane stack resistance
  • U is mainly related to the concentration difference of the salt solution on both sides of the membrane. It can be seen from the formula that reducing the resistance of the membrane stack can improve the output power of the reverse electrodialysis device.
  • the ohmic resistance of the reverse electrodialysis device is composed of membrane resistance, concentrated/light chamber (HC/LC) solution resistance and electrode resistance. If the non-ohmic resistance is ignored, the calculation formula of the membrane stack resistance is as follows:
  • N is the logarithm of the membrane
  • A is the membrane electrode
  • R AEM and R CEM are the anion and cation exchange membrane resistances, respectively
  • d HC , d LC are the thickness of the thick and thin chambers , respectively
  • chamber conductivity R el is the resistance generated by the electrode reaction, which can be ignored when the number of membrane pairs is large enough.
  • the preparation method of the anion exchange membrane 25 and the cation exchange membrane 23 in the present invention is to uniformly coat the two kinds of ionomer resin solutions on the expanded polytetrafluoroethylene film respectively, and wait for the ionomer solution to slowly penetrate into the expanded polytetrafluoroethylene film.
  • a small amount of ionomer solution is evenly coated on the expanded PTFE film, and the ionomer solution slowly penetrates into the micropores of expanded PTFE for several times.
  • the concentration of the ionomer resin solution is 10% to 20%
  • the selected polar aprotonated solvent is DMF
  • NMP and DMAc after the solvent volatilizes, first perform vacuum constant temperature heat treatment, the heat treatment temperature is 80-100 °C, the heat treatment time is 8-20h, the preferred heat treatment temperature is 91 °C, the heat treatment time is 13h.
  • the ionomer resin used to prepare the cation exchange membrane is sulfonated polyether ether ketone or sulfonated polyimide resin; the ionomer resin used to prepare the anion exchange membrane is quaternized polyarylene Resins such as ethers or polyarylpiperidines.
  • the film is subjected to hot pressing treatment, and the hot pressing temperature is 90-120°C, preferably 105°C; on the one hand, it promotes the effective compounding of the ionomer and PTFE, and on the other hand, the thickness of the film is controlled at 100-100°C. Between 120 ⁇ m, under the condition that the membrane has a considerable ion exchange capacity, the thickness of the membrane can be reduced, thereby reducing its resistance; by compounding with the expanded polytetrafluoroethylene skeleton, the expansion of the membrane can be suppressed and the selective permeation of the membrane can be improved.
  • the hot pressing temperature is 90-120°C, preferably 105°C; on the one hand, it promotes the effective compounding of the ionomer and PTFE, and on the other hand, the thickness of the film is controlled at 100-100°C. Between 120 ⁇ m, under the condition that the membrane has a considerable ion exchange capacity, the thickness of the membrane can be reduced, thereby reducing its resistance; by
  • the power density of the reverse osmosis device is improved; the artificially prepared sodium chloride solution is used as the test: the concentration of the concentrated water is 3-6mol/L, the concentration of the dilute solution is 0.3-0.6mol/L, and the area of the membrane is 30 ⁇ 30cm 2 -60 ⁇ 60cm 2 , resulting in a power density of about 2-6W/cm 2 .
  • the fresh water outlet 29 of the reverse electrodialysis device has a low concentration of fresh water and can be directly discharged into the ocean; the concentrated water outlet 28 flows back to the concentrated water inlet 20; by adjusting the concentrated water outlet of the reverse osmosis device and reverse electrodialysis
  • the flow control valve on the concentrated water inlet pipeline of the device is used to control the concentration of the concentrated water that passes into the reverse electrodialysis device. It is monitored by the concentration sensor 19 and discharged into the ocean when the concentration at the concentrated water outlet of the reverse electrodialysis device is low. middle. In this way, it can be ensured that the concentrated water and seawater used for generating electricity in the reverse electrodialysis device always have a relatively large concentration difference, which is beneficial to make the entire reverse electrodialysis device have a higher power density.
  • the method for desalination and power generation using this system mainly includes the following steps:
  • S1 Power supply by the power module: obtain power through one or more of the wind power generation system 1, the photovoltaic power generation system 2 or other renewable energy sources, and the obtained power is adjusted by the wind-solar hybrid controller 3, and the power part passes through the second DC/AC
  • the converter 7 supplies power to the seawater desalination module after adjustment; part of the power is stored by the energy storage device 5, and is regulated by the first DC/AC converter 6 to supply power to the seawater desalination module;
  • S21 Primary filtration: extract seawater, pass part of the seawater after precipitation, pH adjustment, sterilization, softening, etc. into the ultrafilter 8 to further filter out the suspended solids in the seawater, and then filter the ultrafiltered
  • the seawater is fed into the reverse osmosis device; in this step, the seawater removes suspended particles or substances such as algae and microorganisms in the seawater through sand filtration, flocculation sedimentation, sterilization, filtration, ultrafiltration, etc. Small pollution and blockage probability of membrane during reverse osmosis and electrodialysis, thus prolonging its service life;
  • S22 reverse osmosis treatment: the seawater part after the ultrafiltration is passed into the reverse osmosis device 10 and is pressurized by the first high-pressure pump 9 to promote the desalination of seawater, obtain fresh water and concentrated seawater, and in the fresh water recovery tank where the fresh water is introduced, the obtained The concentrated seawater is passed into the concentrated water storage tank;
  • S3 Saline difference energy power generation: The obtained fresh water and concentrated seawater enter the salinity difference energy power generation module, using the different concentrations of seawater on both sides of the anion and cation membranes, resulting in the directional migration of anions and cations to generate potential difference power generation.
  • Example 2 Taking wastewater as an example to carry out a specific embodiment to illustrate the present invention.
  • This solution is not only applicable to desalination of sea water, but also to scenarios such as waste water treatment.
  • the waste water is inorganic industrial waste water or domestic sewage
  • the concentrated water passed into the reverse electrodialysis device is waste water that passes through the filter device 31 and the reverse
  • the concentrated water obtained by the osmosis device, and the fresh water passed into the reverse electrodialysis device is one or more kinds of rainwater or river water that have been pretreated by filtration or the like.

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Abstract

A system and method for a clean energy seawater desalination and salinity gradient power generation device. The system of the present invention is mainly composed of a power supply module, a seawater desalination module, and a salinity gradient power generation module; seawater desalination is completed by using reverse osmosis technology, and power is generated by using salinity gradient power. In the present invention, stable, clean energy is used to perform seawater desalination by means of reverse osmosis, and at the same time, high-salinity by-products produced by seawater desalination are consumed by reverse electrodialysis salinity gradient power generation, which increases the environmental friendliness, reduces the energy consumption, and reduces the carbon emissions during the entire water desalination process, as well as improves the economics of seawater treatment.

Description

清洁能源海水淡化耦合盐差能发电装置的系统及方法System and method for clean energy seawater desalination coupled with salt difference energy power generation device 技术领域technical field
本发明涉及清洁能源海水淡化以及盐差能发电技术，也涉及到废水的处理；特别是涉及一种利用风光互补发电进行反渗透膜法海水淡化系统与反向电渗析盐差能发电系统的耦合。The invention relates to clean energy seawater desalination and salt difference energy power generation technology, and also relates to the treatment of waste water; in particular, it relates to a coupling of a reverse osmosis membrane seawater desalination system and a reverse electrodialysis salt difference energy power generation system using wind and solar complementary power generation .
背景技术Background technique
水资源的逐步匮乏，导致许多国家对海水淡化形成了严重的依赖。但是从成本和其对环境的影响来看，海水淡化的可持续性仍是一个问题。The gradual scarcity of water resources has led many countries to form a serious dependence on seawater desalination. But the sustainability of desalination remains an issue in terms of cost and its impact on the environment.
目前海水淡化较为成熟的技术主要分为两类：蒸馏法(热法)和膜法。绝大多数在运营的海水淡化工厂所采用的技术是多级闪蒸(MSF)、多效蒸发(MDF)和反渗透法(RO)。其中，多级闪蒸和多效蒸发都属于蒸馏法的一种，两者均为能源密集型加工方式。反渗透膜法是膜法的一种，其原理是利用只允许溶剂透过、不允许溶质透过的半透膜，将海水与淡水分隔开。反渗透技术的最大优点是节能，以海上风电、太阳能等清洁能源为能量供给，有助于大幅度降低海水淡化的生产成本，实现水资源部门的高效、可持续发展目标。At present, the more mature technologies of seawater desalination are mainly divided into two categories: distillation method (thermal method) and membrane method. The technologies employed in the vast majority of operating desalination plants are Multi-Stage Flash (MSF), Multiple Effect Evaporation (MDF) and Reverse Osmosis (RO). Among them, multi-stage flash evaporation and multi-effect evaporation are a kind of distillation method, both of which are energy-intensive processing methods. Reverse osmosis membrane method is a kind of membrane method. Its principle is to separate seawater and freshwater by using a semi-permeable membrane that only allows solvent to pass through and does not allow solute to pass through. The biggest advantage of reverse osmosis technology is energy saving. Using clean energy such as offshore wind power and solar energy as energy supply will help to greatly reduce the production cost of seawater desalination and achieve the goal of efficient and sustainable development of the water resources sector.
海水淡化过程，特别是反渗透技术，会产生高盐度的废料，这些废料往往会被注回水源池，这不仅降低了海水淡化的长期可行性，还会威胁到海洋生态系统，制造出一个潜在代价更为高昂的负外部性问题。因此，研究解决高盐度副产品的消纳和处理技术是一个关键问题。The desalination process, especially reverse osmosis, produces high-salinity waste that is often injected back into the source pool, which not only reduces the long-term viability of desalination, but also threatens the marine ecosystem, creating a A potentially more costly negative externality problem. Therefore, it is a key issue to study and solve the high salinity by-products absorption and treatment technology.
反向电渗析技术是盐差能发电技术之一，其利用离子交换膜的选择性透过，将不同浓度盐溶液混合的化学能直接转换为电能，具有清洁、可持续、无污染、能量密度高等优点。其应用场景不仅限于河海交汇处，还可以与海水淡化装置进行耦合，可以捕捉浓缩海水与一般海水之间的盐差能，从而实现海水淡化高盐度副产品的消纳和再利用，提高海水淡化的经济性和环保性，从而利于海水淡化的可持续性。Reverse electrodialysis technology is one of the salt difference energy generation technologies. It uses the selective permeation of ion exchange membranes to directly convert chemical energy mixed with different concentrations of salt solutions into electrical energy, which is clean, sustainable, pollution-free, and energy density. high advantage. Its application scenarios are not limited to the confluence of rivers and seas, but can also be coupled with seawater desalination devices, which can capture the salt difference energy between concentrated seawater and general seawater, so as to realize the consumption and reuse of high-salinity by-products of seawater desalination, and improve seawater production. Economical and environmentally friendly desalination, thus contributing to the sustainability of desalination.
在反向电渗析盐差能发电过程中，溶液的浓度对于发电的输出功率有较大影响，例如，稀溶液的浓度太低时，虽然可以增大离子膜两侧的电化学电势差，但是也会导致膜堆的电阻迅速增加，功率密度反而下降。世界大洋的平均盐度为35‰，即每千克海水中的盐含量大约为35克。其电导率约为30000μS/m，比一般的湖水、河水大千倍以上，即海水的电导率比一般的淡水高很多，以海水为稀溶液可以保证膜组的电阻较低。对于反渗透膜法海水淡化，其脱盐率较高，可达99％，实际回收率一般均在75％以上，有时甚至可以达到90％，因此，反渗透膜法海水淡化产生的淡水纯度较高；得到的浓缩海水的浓度约为普通海水的4倍(按回收率为75％计算)，该浓度的海水直接排入海洋之中会对海洋生态系统造成危害，而利用浓缩海水与普通海水之间的盐差能进行发电不仅可以实现资源利用率，同时可以起到稀释浓缩海水的作用，降低其对海洋环境的影响。In the process of reverse electrodialysis salt difference energy generation, the concentration of the solution has a great influence on the output power of the power generation. For example, when the concentration of the dilute solution is too low, although the electrochemical potential difference between the two sides of the ion membrane can be increased, it is also It will cause the resistance of the membrane stack to increase rapidly and the power density to decrease. The average salinity of the world's oceans is 35‰, that is, the salt content in every kilogram of seawater is about 35 grams. Its conductivity is about 30000μS/m, which is more than a thousand times larger than that of ordinary lake water and river water, that is, the conductivity of seawater is much higher than that of ordinary fresh water. Using seawater as a dilute solution can ensure that the resistance of the membrane group is low. For reverse osmosis membrane seawater desalination, the desalination rate is high, up to 99%, and the actual recovery rate is generally above 75%, sometimes even 90%. Therefore, the fresh water produced by reverse osmosis membrane seawater desalination is of high purity. The concentration of the obtained concentrated seawater is about 4 times that of ordinary seawater (calculated according to the recovery rate of 75%). The salt difference between the two can generate electricity not only to achieve resource utilization, but also to dilute the concentrated seawater and reduce its impact on the marine environment.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种利用清洁能源进行海水淡化并利用盐差能发电消纳 海水淡化高盐度副产品的系统及方法。通过风电、光伏互补发电为反渗透膜法海水淡化供能，然后将海水淡化系统与反向电渗析盐差能发电系统耦合，利用海水和海水淡化的副产品浓缩海水之间的盐差能，实现海水淡化高盐度副产品的消纳，同时，产生电能为海水淡化的设备或其他负载供电。The object of the present invention is to provide a system and method for utilizing clean energy to desalinate seawater and utilizing salinity difference energy to generate electricity to absorb high-salinity by-products of seawater desalination. The reverse osmosis membrane method seawater desalination is powered by wind power and photovoltaic complementary power generation, and then the seawater desalination system is coupled with the reverse electrodialysis salt difference energy power generation system, and the salt difference energy between the seawater and the by-product of seawater desalination is used to concentrate the seawater. Consumption of high-salinity by-products of seawater desalination, and at the same time, electricity is generated to power desalination equipment or other loads.
本发明的目的是这样实现的：一种清洁能源海水淡化耦合盐差能发电装置的系统，包括供电模块，系统还包括海水淡化模块和盐差能发电模块，所述的海水淡化模块包括反渗透装置，反渗透装置一端与超滤器连接，另一端分别与淡水回收箱以及浓水储罐连接；浓水储罐通过第三泵体与盐差能发电模块相连通；所述的盐差能发电模块主要由反向电渗析装置、第二泵体、第三泵体、第一三通阀和第二三通阀以及外接负载组成；反向电渗析装置内设有阴离子交换膜和阳离子交换膜，交替排列的阴离子交换膜和阳离子交换膜形成若干浓水室以及淡水室。The purpose of the present invention is to achieve this: a system of clean energy seawater desalination coupled with a salt difference energy power generation device, including a power supply module, the system also includes a seawater desalination module and a salt difference energy power generation module, and the seawater desalination module includes reverse osmosis device, one end of the reverse osmosis device is connected with the ultrafilter, and the other end is connected with the fresh water recovery tank and the concentrated water storage tank; the concentrated water storage tank is connected with the salt difference energy power generation module through the third pump body; the salt difference energy The power generation module is mainly composed of a reverse electrodialysis device, a second pump body, a third pump body, a first three-way valve, a second three-way valve and an external load; the reverse electrodialysis device is provided with an anion exchange membrane and a cation exchange membrane Membranes, alternately arranged anion exchange membranes and cation exchange membranes form several concentrated water compartments and fresh water compartments.
所述的所述阴离子交换膜以及阳离子交换膜的制备方法为：分别将两种离聚物树脂溶液均匀涂覆在膨体聚四氟乙烯薄膜上，待离聚物溶液缓慢渗入到膨体聚四氟乙烯的微孔中，再取少量离聚物溶液均匀涂覆在膨体聚四氟乙烯薄膜上，待离聚物溶液缓慢渗入到膨体聚四氟乙烯的微孔中，多次重复该操作，直至聚四氟乙烯微孔被离聚物溶液充满，然后等待溶剂挥发；待溶剂挥发完之后，先进行真空恒温热处理，热处理之后，对膜进行热压处理。The preparation methods of the anion exchange membrane and the cation exchange membrane are as follows: respectively, uniformly coating two kinds of ionomer resin solutions on the expanded polytetrafluoroethylene film, and waiting for the ionomer solution to slowly penetrate into the expanded polytetrafluoroethylene film. In the micropores of tetrafluoroethylene, a small amount of ionomer solution is evenly coated on the expanded polytetrafluoroethylene film, and the ionomer solution is slowly infiltrated into the micropores of expanded polytetrafluoroethylene, repeating several times. In this operation, the micropores of polytetrafluoroethylene are filled with the ionomer solution, and then wait for the solvent to volatilize; after the solvent is volatilized, vacuum constant temperature heat treatment is performed first, and after the heat treatment, the membrane is subjected to hot pressing treatment.
所述的离聚物树脂溶液的浓度为10-20％；，待溶剂挥发完之后，先进行真空恒温热处理，热处理温度为80-100℃，热处理的时间为8-20h；热处理之后，对膜进行热压处理，热压温度为90-120℃，一方面促进离聚物与聚四氟乙烯的有效复合，另一方面控制薄膜的厚度在100-120μm之间；The concentration of the ionomer resin solution is 10-20%; after the solvent is volatilized, vacuum constant temperature heat treatment is first performed, the heat treatment temperature is 80-100 DEG C, and the heat treatment time is 8-20h; Carry out hot pressing treatment, the hot pressing temperature is 90-120 ℃, on the one hand, it promotes the effective compounding of ionomer and PTFE, and on the other hand, the thickness of the film is controlled between 100-120 μm;
所述的溶剂为极性非质子化溶剂，具体选用N，N-二甲基甲酰胺、N-甲基吡咯烷酮或N,N-二甲基乙酰胺中的一种或几种。The solvent is a polar aprotonated solvent, specifically one or more of N,N-dimethylformamide, N-methylpyrrolidone or N,N-dimethylacetamide.
所述的供电模块电力来源为风电、光伏以及其他可再生能源中的一种或几种。The power source of the power supply module is one or more of wind power, photovoltaic and other renewable energy sources.
在供电模块中，设有储能装置，以保证供电稳定，所述的储能装置为锂电池、纳电池等中的一种或几种。In the power supply module, an energy storage device is provided to ensure stable power supply, and the energy storage device is one or more of lithium batteries, nano batteries and the like.
利用本系统进行海水淡化及发电的方法，包括以下步骤：The method for desalination and power generation using this system includes the following steps:
S1：电力模块供电：通过风力发电系统1、光伏发电系统2或其他可再生能源中的一种或几种取得电力，得到的电力通过风光互补控制器3调节后电力部分通过第二DC/AC转换器7调节后为海水淡化模块供电；部分电力由储能装置5存储，并通过第一DC/AC转换器6调节后为海水淡化模块供电；S1: Power supply by the power module: obtain power through one or more of the wind power generation system 1, the photovoltaic power generation system 2 or other renewable energy sources, and the obtained power is adjusted by the wind-solar hybrid controller 3, and the power part passes through the second DC/AC The converter 7 supplies power to the seawater desalination module after adjustment; part of the power is stored by the energy storage device 5, and is regulated by the first DC/AC converter 6 to supply power to the seawater desalination module;
S2：海水淡化：S2: Desalination:
S21：初滤：抽取海水，将经过沉淀、调pH、杀菌处理、软化等步骤处理过后的一部分海水通入超滤器中进一步过滤掉海水中的悬浮物等，然后再将超滤后的海水通入到反渗透装置中；S21: Primary filtration: extract seawater, pass part of the seawater after precipitation, pH adjustment, sterilization, softening, etc. into the ultrafilter to further filter out the suspended solids in the seawater, and then filter the ultrafiltered seawater into the reverse osmosis device;
S22：反渗透处理：超滤后的海水通入反渗透装置中并经第一高压泵加压，促进海水脱盐，得到淡水与浓缩海水，淡水通入的淡水回收箱中，得到的浓缩海水通入到浓水储罐中；S22: reverse osmosis treatment: the seawater after ultrafiltration is passed into the reverse osmosis device and is pressurized by the first high-pressure pump to promote the desalination of seawater to obtain fresh water and concentrated seawater. into the concentrated water storage tank;
S3：盐差能发电：得到的淡水及浓缩海水进入盐差能发电模块，利用阴、阳离子膜 的两侧海水的浓度不同，导致阴阳离子的定向迁移从而产生电势差发电。S3: Salt difference energy power generation: The obtained fresh water and concentrated seawater enter the salinity difference energy power generation module, using the different concentrations of seawater on both sides of the anion and cation membranes, resulting in the directional migration of anions and cations to generate potential difference power generation.
本系统中，盐差能发电模块中的反向电渗析装置浓水出口处设置有浓度传感器，用于检测出口处浓缩海水的浓度，当浓缩海水浓度在较高水平时，调节三通阀，将其循环至浓水入口处再次利用；当浓缩海水浓度较低时，调节三通阀，将其直接排入海中；反向电渗析装置淡水出口处的海水可直接排入海中。In this system, a concentration sensor is installed at the concentrated water outlet of the reverse electrodialysis device in the salt difference energy power generation module to detect the concentration of concentrated seawater at the outlet. When the concentration of concentrated seawater is at a high level, adjust the three-way valve to It is recycled to the concentrated water inlet for reuse; when the concentration of concentrated seawater is low, the three-way valve is adjusted to discharge it directly into the sea; the seawater at the freshwater outlet of the reverse electrodialysis unit can be directly discharged into the sea.
系统在处理废水中的应用。Application of the system in the treatment of wastewater.
本系统在处理工业废时，用废水替代海水进入到海水淡化模块中。When this system treats industrial waste, it replaces seawater with waste water and enters the seawater desalination module.
本发明提供的清洁能源海水淡化耦合盐差能发电装置的系统及方法具有以下有益效果：The system and method of the clean energy seawater desalination coupled salt difference energy power generation device provided by the present invention has the following beneficial effects:
1)有利用环境保护：本发明利用稳定的清洁能源进行反渗透膜法海水淡化，同时通过反向电渗析盐差能发电消纳海水淡化所产生的高盐度副产品，提高整个海水淡化过程的环保性。1) There is utilization of environmental protection: the present invention utilizes stable clean energy to carry out reverse osmosis membrane seawater desalination, and simultaneously through reverse electrodialysis salt difference energy generation to absorb the high salinity by-products produced by seawater desalination, improve the efficiency of the entire seawater desalination process. Environmentally friendly.
2)节省能源：本发明所采用反渗透膜法海水淡化相对于其他海水淡化法最节能，与目前最成熟的多级闪蒸(总能耗约为10-16kWh/m3)相比，反渗透膜法的总能耗(约为3-4kWh/m3)大概是其1/4至1/3。2) Energy saving: the reverse osmosis membrane method seawater desalination adopted in the present invention is the most energy-saving compared to other seawater desalination methods, and compared with the most mature multi-stage flash evaporation (total energy consumption is about 10-16kWh/m3) The total energy consumption of the membrane process (about 3-4kWh/m3) is about 1/4 to 1/3.
3)减少碳排放，提高经济效益：随着未来新能源装机容量的上升，以及电价的进一步下降，使用清洁能源进行海水淡化不仅可以减少碳排放，按照清洁能源电价与目前电价持平的价格(0.55元/度)计算，反渗透膜海水淡化的价格为1.65-2.2元/立方米，该价格低于目前的居民自来水价(2.8元/立方米)，有利于提高海水淡化的经济性。3) Reduce carbon emissions and improve economic benefits: With the increase in the installed capacity of new energy in the future and the further decline in electricity prices, the use of clean energy for seawater desalination can not only reduce carbon emissions, but the electricity price of clean energy is the same as the current electricity price (0.55 RMB/degree), the price of reverse osmosis membrane desalination is 1.65-2.2 yuan/cubic meter, which is lower than the current residential tap water price (2.8 yuan/cubic meter), which is conducive to improving the economy of seawater desalination.
4)输出稳定：本发明利用盐差能发电在消纳海水淡化高盐度副产品的同时还可以产生稳定电能，反哺海水淡化，而所使用的复合增强离子交换膜可以提高整个装置的输出功率，在提高环保性的同时，也提高了整个过程的经济效益。4) Stable output: the present invention utilizes the salinity difference energy to generate electricity while consuming high-salinity by-products of seawater desalination, and can also generate stable electrical energy to feed seawater desalination, and the composite enhanced ion exchange membrane used can improve the output power of the entire device, While improving environmental protection, it also improves the economic benefits of the entire process.
5)降低环境污染：本发明利用了海水淡化模块来进行废水的处理，实现了一套装置两种用途，可根据不同的使用工况进行调整。5) Reducing environmental pollution: The present invention utilizes a seawater desalination module for wastewater treatment, and realizes two purposes of a set of devices, which can be adjusted according to different operating conditions.
附图说明Description of drawings
下面结合附图和实施例对本发明作进一步说明。The present invention will be further described below with reference to the accompanying drawings and embodiments.
图1是本发明清洁能源海水淡化耦合盐差能发电装置及系统示意图；1 is a schematic diagram of a clean energy seawater desalination coupled salt difference energy power generation device and system of the present invention;
图2是本发明进行废水处理等耦合盐差能发电装置及系统示意图。FIG. 2 is a schematic diagram of the coupled salt difference energy power generation device and system for wastewater treatment according to the present invention.
图中：1、风力发电系统，2、光伏发电系统，3、风光互补控制器，4、DC/AC转换器，5、储能装置，6、第一DC/AC转换器，7、第二DC/AC转换器，8、超滤器，9、第一高压泵，10、反渗透装置，11、反渗透装置淡水出口，12、反渗透装置浓水出口，13、淡水回收箱，14、浓水储罐，15、第一变频泵，16、第二变频泵，17、第一三通阀，18、第二三通阀，19、浓度传感器，20、浓水入口，21、淡水入口，22、阴极板，23、阳离子交换膜，24、阳极板，25、阴离子交换膜，26、淡水室，27、浓水室，28、浓水出口，29、淡水出口，30、外接负载，31、过滤装置。In the figure: 1. Wind power generation system, 2. Photovoltaic power generation system, 3. Wind-solar hybrid controller, 4. DC/AC converter, 5. Energy storage device, 6. First DC/AC converter, 7. Second DC/AC converter, 8, ultrafilter, 9, first high pressure pump, 10, reverse osmosis unit, 11, fresh water outlet of reverse osmosis unit, 12, concentrated water outlet of reverse osmosis unit, 13, fresh water recovery tank, 14, Concentrated water storage tank, 15, first variable frequency pump, 16, second variable frequency pump, 17, first three-way valve, 18, second three-way valve, 19, concentration sensor, 20, concentrated water inlet, 21, fresh water inlet , 22, cathode plate, 23, cation exchange membrane, 24, anode plate, 25, anion exchange membrane, 26, fresh water chamber, 27, concentrated water chamber, 28, concentrated water outlet, 29, fresh water outlet, 30, external load, 31. Filtering device.
具体实施方式Detailed ways
实施例1：以海水淡化为例进行具体实施方案来阐述本发明。Example 1: Taking seawater desalination as an example to carry out a specific embodiment to illustrate the present invention.
整个系统分为三个模块，分别为供电系统模块、海水淡化模块以及盐差能发电模 块。The whole system is divided into three modules, namely power supply system module, seawater desalination module and salt difference energy power generation module.
其中，供电系统模块主要为海水淡化系统供能，其主要由风力发电系统1、光伏发电系统2、储能装置5、DC/AC转换器4、第一DC/AC转换器6以及风光互补控制器3组成。Among them, the power supply system module mainly supplies energy for the seawater desalination system, which is mainly composed of a wind power generation system 1, a photovoltaic power generation system 2, an energy storage device 5, a DC/AC converter 4, a first DC/AC converter 6 and a wind-solar hybrid control. 3 components.
本发明中的光伏发电系统2所产生的为直流电，因此，在其输出端加DC/AC转换器4，具体比例通过风光互补控制器3控制；由于风光资源具有一定的间歇性、波动性，为保证供电稳定性，添加储能装置5进行调峰，在风光发电过剩时可对储能装置充电，发电不足时，通过储能装置对外供电。储能装置可以是电化学储能装置中的锂电池、纳电池等中的一种或几种，其容量根据海水淡化厂的规模进行确定。The photovoltaic power generation system 2 in the present invention generates direct current. Therefore, a DC/AC converter 4 is added to its output end, and the specific ratio is controlled by the wind-solar complementary controller 3; In order to ensure the stability of power supply, an energy storage device 5 is added for peak regulation. When the wind and solar power generation is excessive, the energy storage device can be charged, and when the power generation is insufficient, the energy storage device is used for external power supply. The energy storage device can be one or more of lithium batteries, nano batteries, etc. in the electrochemical energy storage device, and its capacity is determined according to the scale of the desalination plant.
本发明中的海水淡化模块主要由超滤器8、第一高压泵9、反渗透装置10、反渗透装置淡水出口11、反渗透装置浓水出口12、淡水回收箱13以及浓水储罐14等组成。反渗透装置10一端与超滤器8连接，另一端分别与淡水回收箱13以及浓水储罐14连接；浓水储罐14通过第三泵体16与盐差能发电模块相连通。The seawater desalination module in the present invention mainly consists of an ultrafilter 8, a first high pressure pump 9, a reverse osmosis device 10, a fresh water outlet 11 of the reverse osmosis device, a concentrated water outlet 12 of the reverse osmosis device, a fresh water recovery tank 13 and a concentrated water storage tank 14 etc. composition. One end of the reverse osmosis device 10 is connected to the ultrafilter 8 , and the other end is connected to the fresh water recovery tank 13 and the concentrated water storage tank 14 respectively;
盐差能发电模块主要由反向电渗析装置、第一变频泵15、第二变频泵16、第一三通阀17、第二三通阀18以外接负载30等组成；其中反向电渗析装置由阴离子交换膜25和阳离子交换膜23组成的膜组、阴极板22、阳极板24、浓水入口20、浓水出口28、淡水入口21、淡水出口29、浓水室27、淡水室26、浓水流道以及淡水流道、浓度传感器19等组成。The salt difference energy power generation module is mainly composed of a reverse electrodialysis device, a first variable frequency pump 15, a second variable frequency pump 16, a first three-way valve 17, a second three-way valve 18 and an external load 30, etc.; among which reverse electrodialysis The device consists of a membrane group composed of anion exchange membrane 25 and cation exchange membrane 23, cathode plate 22, anode plate 24, concentrated water inlet 20, concentrated water outlet 28, fresh water inlet 21, fresh water outlet 29, concentrated water chamber 27, and fresh water chamber 26 , concentrated water flow channel, fresh water flow channel, concentration sensor 19 and so on.
阴离子交换膜23和阳离子交换膜25设置在反向电渗析装置内，交替排列的阴离子交换膜23和阳离子交换膜25形成若干浓水室27以及淡水室26。浓缩海水经第二变频泵16通过浓水入口20流入浓水流道进入浓水室27，过滤后的海水经第一变频泵15驱动通过淡水入口21流入淡水流道进入淡水室26，由于离子交换膜两侧盐浓度的差异，离子会通过交换膜发生迁移，从而产生电势差，通过阴极板22、阳极板24输出到负载30；阴离子交换膜和阳离子交换膜膜组的数量以及膜的面积大小根据海水淡化厂的规模进行确定。The anion exchange membrane 23 and the cation exchange membrane 25 are arranged in the reverse electrodialysis device, and the alternately arranged anion exchange membranes 23 and cation exchange membranes 25 form several concentrated water chambers 27 and fresh water chambers 26 . The concentrated seawater flows into the concentrated water channel 27 through the concentrated water inlet 20 through the second variable frequency pump 16, and the filtered seawater is driven by the first variable frequency pump 15 to flow into the fresh water channel 26 through the fresh water inlet 21 and enters the fresh water chamber 26. Due to the difference in salt concentration on both sides of the membrane, ions will migrate through the exchange membrane, resulting in a potential difference, which is output to the load 30 through the cathode plate 22 and anode plate 24; The size of the desalination plant is determined.
所述反向电渗析装置的输出功率，其计算公式由Kirchhoff规律得到：The output power of the reverse electrodialysis device, its calculation formula is obtained by Kirchhoff's law:
Figure PCTCN2021118922-appb-000001
Figure PCTCN2021118922-appb-000001
式中，I为电流；R load为外部电阻；U表示势能差；R stack为膜堆电阻。 In the formula, I is the current; R load is the external resistance; U is the potential energy difference; R stack is the membrane stack resistance.
其中，U主要与膜两侧盐溶液的浓度差有关，由公式可知，降低膜堆电阻可提高反向电渗析装置的输出功率。Among them, U is mainly related to the concentration difference of the salt solution on both sides of the membrane. It can be seen from the formula that reducing the resistance of the membrane stack can improve the output power of the reverse electrodialysis device.
所述反向电渗析装置的欧姆电阻是由膜电阻、浓/淡室(HC/LC)溶液电阻和电极电阻共同组成，若忽略非欧姆电阻，膜堆电阻计算公式如下：The ohmic resistance of the reverse electrodialysis device is composed of membrane resistance, concentrated/light chamber (HC/LC) solution resistance and electrode resistance. If the non-ohmic resistance is ignored, the calculation formula of the membrane stack resistance is as follows:
Figure PCTCN2021118922-appb-000002
Figure PCTCN2021118922-appb-000002
其中，N表示膜对数；A表示膜电极；R AEM、R CEM分别为阴、阳离子交换膜电阻；d HC、d LC分别表示浓、淡室厚度；κ HC、κ LC分别表示浓、淡室电导率；R el为电极反应产生的电阻，膜对数足够多时该电阻可忽略不计。 Among them, N is the logarithm of the membrane; A is the membrane electrode; R AEM and R CEM are the anion and cation exchange membrane resistances, respectively; d HC , d LC are the thickness of the thick and thin chambers , respectively; chamber conductivity; R el is the resistance generated by the electrode reaction, which can be ignored when the number of membrane pairs is large enough.
由式中可知，降低膜电阻和溶液电阻可以降低膜堆电阻，从而提高装置的输出功率。It can be seen from the formula that reducing the membrane resistance and solution resistance can reduce the membrane stack resistance, thereby increasing the output power of the device.
本发明中的阴离子交换膜25和阳离子交换膜23的制备方法为，分别将两种离聚物树脂溶液均匀涂覆在膨体聚四氟乙烯薄膜上，待离聚物溶液缓慢渗入到膨体聚四氟乙烯的 微孔中，再取少量离聚物溶液均匀涂覆在膨体聚四氟乙烯薄膜上，待离聚物溶液缓慢渗入到膨体聚四氟乙烯的微孔中，多次重复该操作，直至聚四氟乙烯微孔被离聚物溶液充满，然后等待溶剂挥发；其中，离聚物树脂溶液的浓度为10％～20％，所选极性非质子化溶剂为DMF、NMP、DMAc中的一种或几种，待溶剂挥发完之后，先进行真空恒温热处理，热处理温度为80-100℃，热处理的时间为8-20h，优先的热处理温度为91℃，热处理的时间为13h。The preparation method of the anion exchange membrane 25 and the cation exchange membrane 23 in the present invention is to uniformly coat the two kinds of ionomer resin solutions on the expanded polytetrafluoroethylene film respectively, and wait for the ionomer solution to slowly penetrate into the expanded polytetrafluoroethylene film. In the micropores of PTFE, a small amount of ionomer solution is evenly coated on the expanded PTFE film, and the ionomer solution slowly penetrates into the micropores of expanded PTFE for several times. Repeat this operation until the PTFE micropores are filled with the ionomer solution, and then wait for the solvent to volatilize; wherein, the concentration of the ionomer resin solution is 10% to 20%, and the selected polar aprotonated solvent is DMF, One or more of NMP and DMAc, after the solvent volatilizes, first perform vacuum constant temperature heat treatment, the heat treatment temperature is 80-100 ℃, the heat treatment time is 8-20h, the preferred heat treatment temperature is 91 ℃, the heat treatment time is 13h.
用于制备阳离子交换膜的离聚物树脂为磺化的聚醚醚酮类或磺化的聚酰亚胺类等树脂；用于制备阴离子交换膜的离聚物树脂为季铵化的聚芳醚类或聚芳基哌啶型等树脂。The ionomer resin used to prepare the cation exchange membrane is sulfonated polyether ether ketone or sulfonated polyimide resin; the ionomer resin used to prepare the anion exchange membrane is quaternized polyarylene Resins such as ethers or polyarylpiperidines.
热处理之后，对膜进行热压处理，热压温度为90-120℃，优选温度为105℃；一方面促进离聚物与聚四氟乙烯的有效复合，另一方面控制薄膜的厚度在100-120μm之间，在保证膜具有相当离子交换容量的条件下，降低膜的厚度，从而降低其电阻；通过与膨体聚四氟乙烯骨架的复合，可以抑制膜的膨胀，提高膜的选择透过性，从而提高反渗透装置的功率密度；以人工配制的氯化钠溶液为试验：浓水浓度为3-6mol/L，稀溶液的浓度为0.3-0.6mol/L，膜的面积为30×30cm 2-60×60cm 2，得到功率密度约为2-6W/cm 2。 After the heat treatment, the film is subjected to hot pressing treatment, and the hot pressing temperature is 90-120°C, preferably 105°C; on the one hand, it promotes the effective compounding of the ionomer and PTFE, and on the other hand, the thickness of the film is controlled at 100-100°C. Between 120μm, under the condition that the membrane has a considerable ion exchange capacity, the thickness of the membrane can be reduced, thereby reducing its resistance; by compounding with the expanded polytetrafluoroethylene skeleton, the expansion of the membrane can be suppressed and the selective permeation of the membrane can be improved. Therefore, the power density of the reverse osmosis device is improved; the artificially prepared sodium chloride solution is used as the test: the concentration of the concentrated water is 3-6mol/L, the concentration of the dilute solution is 0.3-0.6mol/L, and the area of the membrane is 30× 30cm 2 -60×60cm 2 , resulting in a power density of about 2-6W/cm 2 .
反向电渗析装置的淡水出口29排出淡水的浓度较低，可直接排入海洋中；浓水出口28水流再返回到浓水入口20处；通过调节反渗透装置浓水出口与反向电渗析装置浓水入口管道上的流量调节阀来调控通入反向电渗析装置中的浓水的浓度，经浓度传感器19监测，当反向电渗析装置浓水出口处的浓度较低时排入海洋中。如此，可以保证用于反向电渗析装置发电的浓水和海水始终保证相对较大的浓度差，利于使整个反向电渗析装置具有较高功率密度。The fresh water outlet 29 of the reverse electrodialysis device has a low concentration of fresh water and can be directly discharged into the ocean; the concentrated water outlet 28 flows back to the concentrated water inlet 20; by adjusting the concentrated water outlet of the reverse osmosis device and reverse electrodialysis The flow control valve on the concentrated water inlet pipeline of the device is used to control the concentration of the concentrated water that passes into the reverse electrodialysis device. It is monitored by the concentration sensor 19 and discharged into the ocean when the concentration at the concentrated water outlet of the reverse electrodialysis device is low. middle. In this way, it can be ensured that the concentrated water and seawater used for generating electricity in the reverse electrodialysis device always have a relatively large concentration difference, which is beneficial to make the entire reverse electrodialysis device have a higher power density.
利用本系统进行海水淡化及发电的方法，主要包括以下步骤：The method for desalination and power generation using this system mainly includes the following steps:
S1：电力模块供电：通过风力发电系统1、光伏发电系统2或其他可再生能源中的一种或几种取得电力，得到的电力通过风光互补控制器3调节后电力部分通过第二DC/AC转换器7调节后为海水淡化模块供电；部分电力由储能装置5存储，并通过第一DC/AC转换器6调节后为海水淡化模块供电；S1: Power supply by the power module: obtain power through one or more of the wind power generation system 1, the photovoltaic power generation system 2 or other renewable energy sources, and the obtained power is adjusted by the wind-solar hybrid controller 3, and the power part passes through the second DC/AC The converter 7 supplies power to the seawater desalination module after adjustment; part of the power is stored by the energy storage device 5, and is regulated by the first DC/AC converter 6 to supply power to the seawater desalination module;
S2：海水淡化：S2: Desalination:
S21：初滤：抽取海水，将经过沉淀、调pH、杀菌处理、软化等步骤处理过后的一部分海水通入超滤器8中进一步过滤掉海水中的悬浮物等，然后再将超滤后的海水通入到反渗透装置中；在本步骤中，海水通过砂滤、絮凝沉淀、杀菌、过滤、超滤等环节去除海水中的海藻、微生物等悬浮颗粒或物质，提升海水的品质，从而减小反渗透以及电渗析过程中对膜的污染以及堵塞概率，从而延长其使用寿命；S21: Primary filtration: extract seawater, pass part of the seawater after precipitation, pH adjustment, sterilization, softening, etc. into the ultrafilter 8 to further filter out the suspended solids in the seawater, and then filter the ultrafiltered The seawater is fed into the reverse osmosis device; in this step, the seawater removes suspended particles or substances such as algae and microorganisms in the seawater through sand filtration, flocculation sedimentation, sterilization, filtration, ultrafiltration, etc. Small pollution and blockage probability of membrane during reverse osmosis and electrodialysis, thus prolonging its service life;
S22：反渗透处理：超滤后的海水部分通入反渗透装置10中并经第一高压泵9加压，促进海水脱盐，得到淡水与浓缩海水，淡水通入的淡水回收箱中，得到的浓缩海水通入到浓水储罐中；S22: reverse osmosis treatment: the seawater part after the ultrafiltration is passed into the reverse osmosis device 10 and is pressurized by the first high-pressure pump 9 to promote the desalination of seawater, obtain fresh water and concentrated seawater, and in the fresh water recovery tank where the fresh water is introduced, the obtained The concentrated seawater is passed into the concentrated water storage tank;
S3：盐差能发电：得到的淡水及浓缩海水进入盐差能发电模块，利用阴、阳离子膜的两侧海水的浓度不同，导致阴阳离子的定向迁移从而产生电势差发电。S3: Saline difference energy power generation: The obtained fresh water and concentrated seawater enter the salinity difference energy power generation module, using the different concentrations of seawater on both sides of the anion and cation membranes, resulting in the directional migration of anions and cations to generate potential difference power generation.
实施例2：以废水为例进行具体实施方案来阐述本发明。本方案不仅适用于海水淡化，还适用于废水处理等场景，对于废水处理场景，废水为无机类工业废水或者生活污水，其通入反向电渗析装置的浓水为废水经过过滤装置31以及反渗透装置分离得到的浓水，通 入反向电渗析装置的淡水为经过过滤等预处理的雨水或江河水的一种或几种。Example 2: Taking wastewater as an example to carry out a specific embodiment to illustrate the present invention. This solution is not only applicable to desalination of sea water, but also to scenarios such as waste water treatment. For waste water treatment scenarios, the waste water is inorganic industrial waste water or domestic sewage, and the concentrated water passed into the reverse electrodialysis device is waste water that passes through the filter device 31 and the reverse The concentrated water obtained by the osmosis device, and the fresh water passed into the reverse electrodialysis device is one or more kinds of rainwater or river water that have been pretreated by filtration or the like.

Claims (10)

  1. 一种清洁能源海水淡化耦合盐差能发电装置的系统，包括供电模块，其特征在于：系统还包括海水淡化模块和盐差能发电模块，所述的海水淡化模块包括反渗透装置(10)，反渗透装置(10)一端与超滤器(8)连接，另一端分别与淡水回收箱(13)以及浓水储罐(14)连接；浓水储罐(14)通过第三泵体(16)与盐差能发电模块相连通；所述的盐差能发电模块主要由反向电渗析装置、第二泵体(15)、第三泵体(16)、第一三通阀(17)和第二三通阀(18)以及外接负载(30)组成；反向电渗析装置内设有阴离子交换膜(23)和阳离子交换膜(25)，交替排列的阴离子交换膜(23)和阳离子交换膜(25)形成若干浓水室(27)以及淡水室(26)。A system of clean energy seawater desalination coupled with a salt difference energy power generation device, comprising a power supply module, characterized in that the system further comprises a seawater desalination module and a salt difference energy power generation module, and the seawater desalination module includes a reverse osmosis device (10), One end of the reverse osmosis device (10) is connected with the ultrafilter (8), and the other end is connected with the fresh water recovery tank (13) and the concentrated water storage tank (14) respectively; the concentrated water storage tank (14) passes through the third pump body (16) ) is communicated with the salt difference energy power generation module; the salt difference energy power generation module is mainly composed of a reverse electrodialysis device, a second pump body (15), a third pump body (16), and a first three-way valve (17) It is composed of a second three-way valve (18) and an external load (30); an anion exchange membrane (23) and a cation exchange membrane (25) are arranged in the reverse electrodialysis device, and the anion exchange membranes (23) and cation exchange membranes (23) and cation exchange membranes (23) are arranged alternately. The exchange membrane (25) forms several concentrated water chambers (27) and fresh water chambers (26).
  2. 根据权利要求1所述的清洁能源海水淡化耦合盐差能发电装置的系统，其特征在于：所述的所述阴离子交换膜(23)以及阳离子交换膜(25)的制备方法为：分别将两种离聚物树脂溶液均匀涂覆在膨体聚四氟乙烯薄膜上，待离聚物溶液缓慢渗入到膨体聚四氟乙烯的微孔中，再取少量离聚物溶液均匀涂覆在膨体聚四氟乙烯薄膜上，待离聚物溶液缓慢渗入到膨体聚四氟乙烯的微孔中，多次重复该操作，直至聚四氟乙烯微孔被离聚物溶液充满，然后等待溶剂挥发；待溶剂挥发完之后，先进行真空恒温热处理，热处理之后，对膜进行热压处理。The system of the clean energy seawater desalination coupled salt difference energy power generation device according to claim 1, wherein the preparation method of the anion exchange membrane (23) and the cation exchange membrane (25) is as follows: The ionomer resin solution is uniformly coated on the expanded polytetrafluoroethylene film. After the ionomer solution slowly penetrates into the micropores of the expanded polytetrafluoroethylene, a small amount of the ionomer solution is evenly coated on the expanded polytetrafluoroethylene. On the bulk polytetrafluoroethylene film, the ionomer solution slowly penetrates into the micropores of the expanded polytetrafluoroethylene. Repeat this operation several times until the polytetrafluoroethylene micropores are filled with the ionomer solution, and then wait for the solvent volatilization; after the solvent is volatilized, vacuum constant temperature heat treatment is performed first, and after the heat treatment, the film is subjected to hot pressing treatment.
  3. 根据权利要求2所述的清洁能源海水淡化耦合盐差能发电装置的系统，其特征在于：所述的离聚物树脂溶液的浓度为10-20％；，待溶剂挥发完之后，先进行真空恒温热处理，热处理温度为80-100℃，热处理的时间为8-20h；热处理之后，对膜进行热压处理，热压温度为90-120℃，一方面促进离聚物与聚四氟乙烯的有效复合，另一方面控制薄膜的厚度在100-120μm之间。The system of clean energy seawater desalination coupled with a salt difference energy power generation device according to claim 2, characterized in that: the concentration of the ionomer resin solution is 10-20%; Constant temperature heat treatment, the heat treatment temperature is 80-100°C, and the heat treatment time is 8-20h; Effective compounding, on the other hand controls the thickness of the film between 100-120 μm.
  4. 根据权利要求3所述的清洁能源海水淡化耦合盐差能发电装置的系统，其特征在于：所述的溶剂为极性非质子化溶剂，具体选用N，N-二甲基甲酰胺、N-甲基吡咯烷酮或N,N-二甲基乙酰胺中的一种或几种。The system of clean energy seawater desalination coupled with a salt difference energy power generation device according to claim 3, characterized in that: the solvent is a polar aprotonated solvent, specifically N,N-dimethylformamide, N- One or more of methylpyrrolidone or N,N-dimethylacetamide.
  5. 根据权利要求1所述的清洁能源海水淡化耦合盐差能发电装置的系统，其特征在于：所述的供电模块电力来源为风电、光伏以及其他可再生能源中的一种或几种。The system of clean energy seawater desalination coupled with a salt difference energy power generation device according to claim 1, wherein the power source of the power supply module is one or more of wind power, photovoltaic and other renewable energy sources.
  6. 根据权利要求1或5所述的清洁能源海水淡化耦合盐差能发电装置的系统，其特征在于：在供电模块中，设有储能装置，以保证供电稳定，所述的储能装置为锂电池、纳电池等中的一种或几种。The system of clean energy seawater desalination coupled with a salt difference energy power generation device according to claim 1 or 5, characterized in that: in the power supply module, an energy storage device is provided to ensure stable power supply, and the energy storage device is lithium One or more of batteries, nano batteries, etc.
  7. 权利要求1-6任一权利要求所述的系统进行海水淡化及发电的方法，其特征在于：包括以下步骤：The method for desalination and power generation by the system according to any one of claims 1-6, characterized in that it comprises the following steps:
    S1：电力模块供电：通过风力发电系统(1)、光伏发电系统(2)或其他可再生能源中的一种或几种取得电力，得到的电力通过风光互补控制器(3)调节后电力部分通过第二DC/AC转换器(7)调节后为海水淡化模块供电；部分电力由储能装置(5)存储，并通过第一DC/AC转换器(6)调节后为海水淡化模块供电；S1: Power supply by the power module: obtain electricity through one or more of the wind power generation system (1), the photovoltaic power generation system (2) or other renewable energy sources, and the obtained power is adjusted by the wind-solar hybrid controller (3). Power is supplied to the seawater desalination module after being adjusted by the second DC/AC converter (7); part of the power is stored by the energy storage device (5), and is adjusted by the first DC/AC converter (6) to supply power to the seawater desalination module;
    S2：海水淡化：S2: Desalination:
    S21：初滤：抽取海水，将经过沉淀、调pH、杀菌处理、软化等步骤处理过后的一部分海水通入超滤器(8)中进一步过滤掉海水中的悬浮物等，然后再将超滤后的海水通入到反渗透装置中；S21: Primary filtration: extract seawater, pass part of the seawater after precipitation, pH adjustment, sterilization, softening, etc. into the ultrafilter (8) to further filter out the suspended solids in the seawater, and then the ultrafiltration After the seawater is passed to the reverse osmosis device;
    S22：反渗透处理：超滤后的海水通入反渗透装置(10)中并经第一高压泵(9)加压，促进海水脱盐，得到淡水与浓缩海水，淡水通入的淡水回收箱中，得到的浓缩海水通入到浓水储 罐中；S22: reverse osmosis treatment: the seawater after the ultrafiltration is passed into the reverse osmosis device (10) and is pressurized by the first high-pressure pump (9) to promote the desalination of seawater, obtain fresh water and concentrated seawater, and the fresh water is passed into the freshwater recovery tank , the obtained concentrated seawater is passed into the concentrated water storage tank;
    S3：盐差能发电：得到的淡水及浓缩海水进入盐差能发电模块，利用阴、阳离子膜的两侧海水的浓度不同，导致阴阳离子的定向迁移从而产生电势差发电。S3: Saline difference energy power generation: The obtained fresh water and concentrated seawater enter the salinity difference energy power generation module, using the different concentrations of seawater on both sides of the anion and cation membranes, resulting in the directional migration of anions and cations to generate potential difference power generation.
  8. 根据权利要求6所述的方法，其特征在于：盐差能发电模块中的反向电渗析装置浓水出口处设置有浓度传感器，用于检测出口处浓缩海水的浓度，当浓缩海水浓度在较高水平时，调节三通阀，将其循环至浓水入口处再次利用；当浓缩海水浓度较低时，调节三通阀，将其直接排入海中；反向电渗析装置淡水出口处的海水可直接排入海中。The method according to claim 6, characterized in that: a concentration sensor is arranged at the concentrated water outlet of the reverse electrodialysis device in the salinity difference energy power generation module to detect the concentration of the concentrated seawater at the outlet, and when the concentration of the concentrated seawater is higher than When the concentration is high, adjust the three-way valve to circulate it to the concentrated water inlet for reuse; when the concentration of concentrated seawater is low, adjust the three-way valve to discharge it directly into the sea; the seawater at the freshwater outlet of the reverse electrodialysis device Can be discharged directly into the sea.
  9. 权利要求1所述的系统在处理废水中的应用。Application of the system of claim 1 in the treatment of wastewater.
  10. 根据权利要求9所述的应用，其特征在于：用废水替代海水进入到海水淡化模块中。The application according to claim 9 is characterized in that: replacing seawater with waste water and entering the seawater desalination module.
PCT/CN2021/118922 2020-12-28 2021-09-17 System and method for clean energy seawater desalination and salinity gradient power generation device WO2022142489A1 (en)

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