CN111925040B - Method for co-production of hydrogen by electrochemical treatment of high-salinity wastewater - Google Patents
Method for co-production of hydrogen by electrochemical treatment of high-salinity wastewater Download PDFInfo
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- CN111925040B CN111925040B CN202010764991.6A CN202010764991A CN111925040B CN 111925040 B CN111925040 B CN 111925040B CN 202010764991 A CN202010764991 A CN 202010764991A CN 111925040 B CN111925040 B CN 111925040B
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
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Abstract
The invention discloses a method for co-producing hydrogen by electrochemically treating high-salinity wastewater, which comprises the steps of heating the high-salinity wastewater to 35-85 ℃, adding copper tailings and iron tailings, and stirring for 3-7 hours; filtering the treated mixed solution to separate a solid phase from a liquid phase; adding the separated liquid phase into an electrochemical reactor, electrifying for 2-5 h, collecting hydrogen at the cathode of the electrochemical reactor, and filtering the liquid in the electrochemical reactor after the treatment is finished, so that the liquid can be discharged for use; the method has the characteristics of low cost, high efficiency, strong universality, good treatment effect and the like, fully utilizes the copper tailings and the iron tailings while treating the high-salinity wastewater, and can stably produce hydrogen at low voltage; therefore, the resource utilization of wastes is realized at lower cost, the treatment of wastes with processes of wastes against one another is realized, and the corresponding economic benefit is obtained while the sewage is treated.
Description
Technical Field
The invention belongs to the technical field of high-salinity wastewater treatment, and particularly relates to a method for treating high-salinity wastewater and co-producing new energy by using an electrochemical method.
Background
The current crisis of land fresh water resources seriously restricts the sustainable development of social economy, and the recycling of water resources is highly emphasized. With the vigorous development of the industry in China, the problem of effective treatment of industrial wastewater is more and more serious, and a large amount of high SO is generated every year in the industries of coal chemical industry, petrochemical industry, electric power, metallurgy and the like 4 2- 、NO 3- 、Cl - 、Mg 2+ 、Ca 2+ 、Na + Saline wastewater with plasma concentration. The treatment of high-salinity wastewater is a worldwide problem, the amount of wastewater generated in China is more than 3 billion cubic meters every year, the wastewater accounts for more than 5 percent of the total wastewater generation amount, the wastewater is still increased at a rate of 2 percent every year at present, and most of the wastewater is not reasonably treated, so that huge pressure is brought to the ecological environment.
While the industry is developing rapidly, the mining industry is also developing rapidly as an important support for the development of the industry, but with the increase of mining speed in recent decades, the ore grade is significantly reduced, resulting in the increase of complexity of mining operation and the continuous increase of the amount of tailings. The continuous and irreparable effects caused by sewage, polluted air, degraded soil, damage of animals and plants and other mining operations of mining facilities may increase the risk of mine development, which brings new complex challenges to the sustainable development of the mining industry; how to effectively treat a series of tailings generated in the mining process becomes an important problem in the mining industry.
The traditional energy industry has gradually begun to fail to address the environmental, energy and feedstock challenges faced by modern society, and hydrogen is considered to be the most important candidate in 21 st century technological innovation, economic expansion and global advancement. Currently, over 5,000 million tons of hydrogen are produced annually, with the consumption increasing at a rate of about 6% annually. However, at present, 96% of hydrogen is still derived from hydrocarbon resources such as natural gas, petroleum and coal. A large amount of carbon dioxide (greenhouse gas) is released into the atmosphere, destroying the ecological environment. In the long term, hydrogen production from non-renewable hydrocarbon sources is not a sustainable way, and hydrogen must be produced by clean processes that use renewable resources and avoid carbon dioxide emissions altogether.
Chinese patent CN106006800A discloses a method and a device for evaporation concentration of high-salinity wastewater, which can reduce energy input in the subsequent treatment process to a certain extent by using circulating cooling water of a condenser to perform heat exchange heating on the high-salinity wastewater, but the essence of the method still lies in that the evaporation technology is used to treat the high-salinity wastewater, and the high-salinity wastewater cannot be treated more effectively. Chinese patent CN108751480A discloses a "method and system for treating industrial high-salt wastewater" by first pretreating high-salt wastewater, then separating the high-salt wastewater into high-salt permeate water and low-salt permeate water using a reverse osmosis membrane, which cannot avoid the problem of membrane contamination and does not really treat the high-salt wastewater by simply pretreating the high-salt wastewater. Chinese patent CN105621771A discloses a "zero discharge method of high-salinity wastewater" to treat high-salinity wastewater through a series of operations of ultrafiltration, resin adsorption, reverse osmosis and evaporative crystallization, which is tedious in process and very high in treatment cost, and most of the steps adopt a membrane filtration mode, so that it is obviously impossible to treat a large amount of high-salinity wastewater on a large scale.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides the method for electrochemically treating the high-salinity wastewater, which has a better treatment effect and can co-produce hydrogen simultaneously.
The method comprises the following steps:
(1) Heating the high-salinity wastewater to a certain temperature, adding the copper tailings and the iron tailings, and maintaining stirring for a period of time;
the mass ratio of the copper tailings to the high-salinity wastewater is 1 (3.5-7);
the mass ratio of the iron tailings to the high-salinity wastewater is 1 (3-6);
heating the high-salinity wastewater to 35-85 ℃ and stirring for 3-7 h;
(2) Filtering the treated mixed solution to separate a solid phase from a liquid phase;
(3) Adding the liquid phase separated in the step (2) into an electrochemical reactor, electrifying for a certain time, collecting hydrogen at a cathode in the electrochemical reactor, and after the treatment is finished, filtering the liquid in the electrochemical reactor, and then discharging for use;
the electrified voltage is 5-12V, and the electrification treatment is carried out for 2-5 h.
The electrochemical reactor is a reactor which is divided into two chambers by an anion exchange membrane, the anode is one of an iron electrode, an aluminum electrode, a graphite electrode and a platinum electrode, and the cathode is one of the iron electrode, the aluminum electrode, the graphite electrode and the platinum electrode.
The invention has the advantages that: the method has the advantages that the mining waste tailings are used for realizing the pretreatment of the high-salt wastewater, other wastes are not generated while the wastes are treated by the wastes, simultaneously, the iron-copper primary battery is formed under the combined action of elements leached from the tailings so as to decompose and remove related components in the polluted water body, finally, the pretreated water body is further treated in an electrochemical mode, hydrogen is obtained, the wastes are efficiently treated, certain economic benefits are obtained while the wastes are treated, the characteristics of the related wastes are fully utilized, the economy is developed while the environment is treated, the whole reaction process is simple, convenient, efficient and easy to popularize, and a new thought and a new method are provided for the high-salt wastewater treatment in future.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited to the above-mentioned descriptions.
Example 1:
(1) 500g of high-salinity wastewater from a certain mineral plant in Yunnan is taken and put into a beaker, the salt concentration of the high-salinity wastewater is 15900mg/l, the temperature of the high-salinity wastewater is raised to 50 ℃ by utilizing a water bath kettle, 90g of copper tailings and 100g of iron tailings are added, and the operation is carried out for 5 hours under the conditions of magnetic stirring and constant temperature of 50 ℃;
(2) Filtering the treated mixed solution by using qualitative filter paper to separate a solid phase from a liquid phase;
(3) Adding the liquid phase separated in the step (2) into a 100mL electrochemical reactor (the electrochemical reactor is a reactor which is divided into two chambers by an anion exchange membrane), using a 2cm multiplied by 2cm iron electrode as an anode and a 2cm multiplied by 2cm platinum mesh electrode as a cathode, operating at 6V voltage for 4h, and collecting hydrogen at the cathode;
(4) After the reaction is finished, filtering the liquid in the electrochemical reactor, and then discharging for use;
the removal rate of related salt components is 67.8 percent through the detection of a salinity meter, and the hydrogen production is 0.78L/h in the reaction process; experiments show that the method has good treatment effect, can produce hydrogen simultaneously, and can achieve the aim of treating high-salinity wastewater without other reagents.
Example 2:
(1) Taking 5kg of high-salinity wastewater from a certain mineral plant in Yunnan, putting the high-salinity wastewater into a beaker, raising the salt concentration of the high-salinity wastewater to 25600mg/l by using a quick heater, and then operating 1.25kg of copper tailings and 0.91kg of iron tailings for 7h under the conditions of magnetic stirring and constant temperature of 40 ℃;
(2) Carrying out solid-phase and liquid-phase separation on the treated mixed solution;
(3) Adding the liquid phase separated in the step (2) into an electrochemical reactor (the electrochemical reactor is a reactor separated into two chambers by an anion exchange membrane), using an aluminum electrode of 50cm multiplied by 45cm as an anode and a graphite electrode of 50cm multiplied by 45cm as a cathode, operating for 5 hours at a voltage of 10V, and collecting hydrogen at the cathode;
(4) After the reaction is finished, filtering the liquid in the electrochemical reactor, and then discharging for use;
the removal rate of related salt components is 74.3 percent through the detection of a salinity meter, and the hydrogen production is 0.55L/h in the reaction process.
Example 3:
(1) 10kg of high-salinity wastewater from a certain mineral plant in Yunnan is taken and put into a container, the salt concentration of the high-salinity wastewater is 8000mg/l, after the temperature of the high-salinity wastewater is raised to 80 ℃ by utilizing a quick heater, 1.54kg of copper tailings and 3.3kg of iron tailings are stirred by magnetic force and run for 3 hours under the constant temperature condition of 80 ℃;
(2) Carrying out solid-phase and liquid-phase separation on the treated mixed solution;
(3) Adding the liquid phase separated in the step (2) into an electrochemical reactor (the electrochemical reactor is a reactor which is divided into two chambers by an anion exchange membrane), using an iron electrode as an anode and a graphite electrode as a cathode, operating for 10 hours at 8V voltage, and collecting hydrogen at the cathode;
(4) After the reaction is finished, filtering the liquid in the electrochemical reactor, and then discharging for use;
the removal rate of related salt components is 79.6 percent through the detection of a salinity meter, and the hydrogen production is 0.66L/h in the reaction process.
The foregoing are preferred embodiments of the present invention, and it should be noted that those skilled in the art can make appropriate changes and modifications without departing from the present invention, and such changes and modifications should also fall within the scope of the present invention.
Claims (3)
1. A method for co-producing hydrogen by electrochemically treating high-salinity wastewater is characterized by comprising the following steps: the specific steps are as follows,
(1) Heating the high-salinity wastewater to 35-85 ℃, adding the copper tailings and the iron tailings, and stirring for 3-7 hours;
(2) Filtering the treated mixed solution to separate a solid phase from a liquid phase;
(3) Adding the liquid phase separated in the step (2) into an electrochemical reactor, electrifying for 2-5 h, collecting hydrogen at the cathode in the electrochemical reactor, and filtering the liquid in the electrochemical reactor after the treatment is finished, so that the liquid can be discharged for use;
the electrochemical reactor is a reactor which is divided into two chambers by an anion exchange membrane, the anode is one of an iron electrode, an aluminum electrode, a graphite electrode and a platinum electrode, the cathode is one of the iron electrode, the aluminum electrode, the graphite electrode and the platinum electrode, and the electrifying voltage is 5-12V.
2. The method for the electrochemical treatment of high-salinity wastewater with the co-production of hydrogen according to claim 1, characterized in that: the mass ratio of the copper tailings to the high-salinity wastewater is 1 (3.5-7).
3. The method for the electrochemical treatment of high-salinity wastewater with the co-production of hydrogen according to claim 1, characterized in that: the mass ratio of the iron tailings to the high-salinity wastewater is 1 (3-6).
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