Water-soaked manure treatment method based on electrochemical technology

Abstract

The invention provides a blister dung treatment method based on an electrochemical technology, which comprises the following steps of: introducing blister dung into a feeding unit of an electrolysis device, separating solid impurities with larger volume under the action of a grid, enabling liquid to enter an electrolytic bath as electrolyte, generating hydrogen at a cathode through electrochemical reaction in the electrolysis process, and performing electrolysis on the blister dung to obtain the blister dung. Chlorine is generated at the anode and is collected; in the electrolysis process, salt in the water-soaked manure is decomposed in the anode reaction process, and organic pollutants are also degraded under the electrochemical oxidation effect; heavy metal ions are deposited near the cathode and are enriched on the surface of the cathode; organic substances in the electrolyzed blister dung are further oxidized or polymerized to form a water-soluble fertilizer of humic acid salts, the electrolyzed blister dung enters a separation device with a grid through a water outlet to realize solid-liquid separation, and a solid containing the water-soluble fertilizer is used as an organic fertilizer for agriculture; according to the method, the resource utilization efficiency of the blister manure is greatly improved, and the burden on the environment is reduced. And the win-win situation of environmental protection and economic benefits is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of livestock manure treatment, and in particular relates to a method for synchronously producing chlorine, hydrogen and water-soluble fertilizer from water-soaked manure. Background Art

[0002] With the rapid development of modern animal husbandry, the large amount of blister manure produced by large-scale farms has brought serious environmental problems. Blister manure contains rich pollutants such as organic matter, salt, antibiotics and heavy metals. Untreated discharge will cause great harm to the environment and human health. Existing blister manure treatment methods mainly include anaerobic fermentation, composting and chemical precipitation, but these methods have obvious limitations in treatment cycle, cost and pollutant removal efficiency, especially in the treatment of antibiotics and heavy metals, which are difficult to adapt to the needs of modern animal husbandry.

[0003] As an emerging environmental treatment method, electrochemical technology has shown significant advantages in treating organic wastewater and heavy metal wastewater. It directly converts electrical energy into chemical energy through electrode reactions, has the characteristics of no need to add chemical agents, high treatment efficiency and strong controllability, and is particularly suitable for treating wastewater containing difficult-to-degrade organic matter and heavy metals. However, electrochemical technology is currently mainly used in the field of sewage treatment and has not yet been fully applied to the treatment of blister feces. Therefore, how to combine electrochemical technology with blister feces treatment to achieve simultaneous recovery and utilization of resources is a major challenge in current research.

[0004] In addition to removing pollutants, converting organic matter in water manure into high value-added resources is also a focus of current research. Water manure is rich in humic acid substances, which can be converted into water-soluble fertilizers after treatment and have important value for agriculture. However, existing technologies often ignore the utilization of these organic substances, resulting in low resource utilization. In addition, gaseous byproducts such as hydrogen and chlorine produced during the treatment process are also a potential energy source and chemical raw material. Summary of the invention

[0005] The present invention provides a method for simultaneously producing chlorine, hydrogen and water-soluble fertilizer from blister manure based on electrochemical technology, aiming to simultaneously achieve the removal of harmful substances in blister manure, the deposition of heavy metals and the generation of water-soluble fertilizer, and the recovery of byproducts such as hydrogen and chlorine. The present invention effectively separates and transforms various components in blister manure by designing specific electrodes and electrolysis devices, thereby achieving the purposes of pollutant degradation, resource recovery and environmental protection.

[0006] The invention discloses a method for synchronously preparing chlorine, hydrogen and water-soluble fertilizer from blister manure based on electrochemical technology. The method comprises the following steps: introducing blister manure into an electrolysis device, wherein the electrolysis device comprises a shell I, wherein an electrolytic cell in the shell I is divided into a plurality of anode chambers and cathode chambers by a proton exchange membrane, wherein anodes and cathodes are alternately arranged in the alternate anode chambers and cathode chambers, wherein the top of the sealed anode chamber is connected to a chlorine storage unit through a pipeline, wherein the top of the sealed cathode chamber is connected to a hydrogen storage unit through a pipeline, wherein the anodes and cathodes are connected to positive and negative electrodes of a power source, wherein a water outlet is provided on one side of the bottom of the shell I, and a feed unit is provided on the top of the other side, wherein the feed unit comprises a shell II, wherein a feed inlet is provided on one side of the top of the shell II, and a discharge outlet is provided on one side of the bottom of the shell II, wherein the discharge outlet is connected to the shell I; wherein a grille is provided in the shell II, and after the blister manure enters the feed unit, the grille is used to make a water outlet. The solid impurities with larger volume are separated by the use of the electrolytic cell, and the liquid enters the electrolytic cell as an electrolyte. During the electrolysis process, hydrogen is generated by electrochemical reaction at the cathode, and chlorine is generated at the anode, which are collected in the hydrogen storage unit and the chlorine storage unit. During the electrolysis process, the salt in the water manure is decomposed during the anode reaction, and the organic pollutants are also degraded under the action of electrochemical oxidation. The heavy metal ions are deposited near the cathode and enriched on the cathode surface. The organic matter in the water manure after electrolysis is further oxidized or polymerized to form water-soluble fertilizers such as humates. The electrolyzed water manure enters the separation device with a grid through the water outlet to achieve solid-liquid separation. The solid containing the water-soluble fertilizer is used in agriculture as an organic fertilizer, and the liquid is discharged or reused after further treatment.

[0007] The cathode is a hydrogen evolution electrode, selected from a platinum electrode, a molybdenum electrode, a nickel electrode, and a titanium coating electrode; the anode is a chlorine evolution electrode, selected from a DSA electrode, a platinum electrode, a graphite electrode, and an iridium oxide electrode; 3-10 pairs of electrodes are arranged, and the interval between the cathode and the anode is 2-3 cm; during the electrolysis process, the electrode voltage is 1.5-3 V; The anode and cathode are installed on a detachable bracket, and the detachable bracket is arranged on the top of the shell I.

[0008] The electrolysis device of the present invention has a modular design, which is convenient for expansion and adjustment according to farms of different sizes; the proton exchange membrane is used to effectively isolate the anode and cathode chambers, so that hydrogen and chlorine can be collected separately during the electrolysis process, avoiding the safety hazards caused by gas mixing. This electrolysis device ensures the full degradation of organic pollutants in water feces and the effective deposition of heavy metals through the selection of electrode materials and the optimization of electrolysis conditions, greatly reducing the pollution risk of water feces to the environment. The humate-like water-soluble substances produced in the electrolysis process can be directly used in agricultural production as the final product to increase the soil organic matter content, improve soil structure, and increase crop yields. This technology effectively solves the problem of difficulty in degrading pollutants such as antibiotics and heavy metals in traditional water feces treatment methods, and at the same time realizes the recycling of high value-added by-products, with significant environmental and economic benefits.

[0009] In addition, the present invention further optimizes the process of treating blister manure by performing dry-wet separation on the electrolyzed blister manure, so that the solid and liquid parts can be effectively treated separately. After separation, the solid part is used as an organic fertilizer, which contains rich humus and nutrients, and can be directly applied to agricultural production, reducing the use of chemical fertilizers and improving soil fertility; the liquid part is further treated, purified to meet the emission standards or used for recycling again, avoiding secondary pollution of the environment by wastewater discharge. This dry-wet separation technology combined with electrochemical treatment technology not only improves the overall efficiency of blister manure treatment, but also realizes the maximum utilization of resources. In general, the present invention converts a variety of harmful substances in blister manure into harmless and useful substances through the innovative application of electrolysis technology, significantly reducing the environmental impact of blister manure treatment, and providing a new way for sustainable development for farms. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 It is a schematic diagram of the structure of the device of the present invention; In the figure: 1-anode; 2-cathode; 3-proton exchange membrane; 4-power supply; 5-water outlet; 6-electrolyzer; 7-hydrogen storage unit; 8-chlorine storage unit; 9-detachable bracket; 10-feed port; 11-grid. DETAILED DESCRIPTION

[0011] The present invention is further described below in conjunction with specific embodiments. The advantages and features of the present invention will become clearer as the description proceeds. However, these embodiments are merely exemplary and are intended to be used to explain the present invention, and are not to be construed as limitations on the present invention. Those skilled in the art should understand that the details and forms of the technical solutions of the present invention may be modified and replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the scope of protection of the present invention.

[0012] Example 1: Method for treating feces with water bubbles based on electrochemical technology like Figure 1 As shown, the electrolysis device used in this embodiment includes a shell I, an electrolytic cell 6 in the shell I is divided into a plurality of anode chambers and cathode chambers by a proton exchange membrane 3, an anode 1 and a cathode 2 are alternately arranged in the anode chamber and the cathode chamber through a detachable bracket 9, the top of the sealed anode chamber is connected to the chlorine storage unit 8 through a pipeline, and the top of the sealed cathode chamber is connected to the hydrogen storage unit 7 through a pipeline, the anode and the cathode are connected to the positive and negative poles of the power supply 4, a water outlet 5 is provided on one side of the bottom of the shell I, and a feed unit is provided on the top of the other side, the feed unit includes a shell II, a feed port 10 is provided on one side of the top of the shell II, and a discharge port is provided on one side of the bottom, and the discharge port is connected to the shell I; a grid 11 is provided in the shell II; the anode is a DSA electrode, the cathode is a platinum electrode, 5 pairs of electrodes are provided, the spacing between the electrodes is 3 cm, and the working voltage is set to 2.8 V to ensure the effective conduct of the electrolysis reaction, and the entire device adopts a sealed structure to prevent gas leakage or pollution during the electrolysis process.

[0013] In this embodiment, the salt content of the feces is 12 g / L, the antibiotic content is 0.06 mg / L (mainly tetracycline and sulfonamide antibiotics), copper (Cu) is 0.9 mg / L, lead (Pb) is 0.1 mg / L, and zinc (Zn) is 2.2 mg / L.

[0014] After the blister manure enters the feed unit from the feed port 10, the larger solid impurities are separated by the grid 11, and the liquid enters the electrolytic cell 6. During the electrolysis process, hydrogen is generated by electrochemical reaction at the cathode, and chlorine is generated at the anode, and they are collected in the hydrogen storage unit and the chlorine storage unit. During the electrolysis process, the salt in the blister manure is decomposed during the anode reaction, and the organic pollutants are also degraded by electrochemical oxidation. Heavy metal ions are deposited near the cathode and enriched on the cathode surface. The electrolyzed blister manure enters the separation device with the grid through the water outlet 5 to achieve solid-liquid separation. The solid containing water-soluble fertilizer is used as organic fertilizer in agriculture, and the liquid is discharged or reused after treatment.

[0015] After treatment, the salt content in the effluent water of the electrolytic cell was reduced by 97%, the residual salt content was 0.21 g / L, copper (Cu) was 0.007 mg / L, lead (Pb) was 0 mg / L, zinc (Zn) was 0.004 mg / L, and antibiotics were 0 mg / L.

[0016] Example 2: Method for treating feces with water bubbles based on electrochemical technology The device structure used in this embodiment is the same as that in embodiment 1, except that the anode is a graphite electrode and the cathode is a nickel electrode; 8 pairs of electrodes are provided, the spacing between the electrodes is 2.5 cm, and the working voltage is set to 3.2V; two grids are obliquely provided in the housing II of the feeding unit; The salt content of the feces treated in this embodiment is 8 g / L, the antibiotic content is 0.04 mg / L (mainly tetracycline and sulfonamide antibiotics), copper (Cu) is 0.5 mg / L, lead (Pb) is 0.08 mg / L, and zinc (Zn) is 0.9 mg / L.

[0017] After the blister manure enters the feed unit from the feed port 10, the larger solid impurities are separated by the grid 11, and the liquid enters the electrolytic cell 6. During the electrolysis process, hydrogen is generated by electrochemical reaction at the cathode, and chlorine is generated at the anode, and they are collected in the hydrogen storage unit and the chlorine storage unit. During the electrolysis process, the salt in the blister manure is decomposed during the anode reaction, and the organic pollutants are also degraded by electrochemical oxidation. Heavy metal ions are deposited near the cathode and enriched on the cathode surface. The electrolyzed blister manure enters the separation device with the grid through the water outlet 5 to achieve solid-liquid separation. The solid containing water-soluble fertilizer is used as organic fertilizer in agriculture, and the liquid is discharged or reused after treatment.

[0018] After treatment, the salt content in the effluent water of the electrolytic cell was 0.18 g / L, copper (Cu) 0.005 mg / L, lead (Pb) 0 mg / L, zinc (Zn) 0.002 mg / L, and antibiotics 0 mg / L.

[0019] Example 3: Method for treating feces with water bubbles based on electrochemical technology The device structure used in this embodiment is the same as that in embodiment 1, except that the anode is an iridium oxide electrode and the cathode is a molybdenum electrode; 8 pairs of electrodes are provided, the spacing between the electrodes is 2.8 cm, and the operating voltage is set to 3V; The salt content of the feces treated in this embodiment is 10 g / L, the antibiotic content is 0.05 mg / L (mainly tetracycline and sulfonamide antibiotics), copper (Cu) is 0.75 mg / L, lead (Pb) is 0.12 mg / L, and zinc (Zn) is 1.2 mg / L.

[0020] After the blister manure enters the feed unit from the feed port 10, the larger solid impurities are separated by the grid 11, and the liquid enters the electrolytic cell 6. During the electrolysis process, hydrogen is generated by electrochemical reaction at the cathode, and chlorine is generated at the anode, and they are collected in the hydrogen storage unit and the chlorine storage unit. During the electrolysis process, the salt in the blister manure is decomposed during the anode reaction, and the organic pollutants are also degraded by electrochemical oxidation. Heavy metal ions are deposited near the cathode and enriched on the cathode surface. The electrolyzed blister manure enters the separation device with the grid through the water outlet 5 to achieve solid-liquid separation. The solid containing water-soluble fertilizer is used as organic fertilizer in agriculture, and the liquid is discharged or reused after treatment.

[0021] The salt content in the effluent solution after electrolysis treatment is 0.27 g / L, copper (Cu) 0.007 mg / L, lead (Pb) 0.001 mg / L, zinc (Zn) 0.005 mg / L, and antibiotics 0 mg / L.

Claims

1. A method for treating water-foam feces based on electrochemical technology, characterized in that: The feces bubble is introduced into an electrolysis device, which comprises a shell I. The electrolysis cell in the shell I is divided into a plurality of anode chambers and cathode chambers by a proton exchange membrane (3). The anode (1) and the cathode (2) are alternately arranged in the anode chamber and the cathode chamber. The top of the sealed anode chamber is connected to the chlorine storage unit (8) through a pipeline. The top of the sealed cathode chamber is connected to the hydrogen storage unit (7) through a pipeline. The anode and the cathode are connected to the positive and negative electrodes of the power supply. A water outlet (5) is provided on one side of the bottom of the shell I, and a feed unit is provided on the top of the other side. The feed unit comprises a shell II. A water outlet (5) is provided on the top of the shell II. A feed port (10) is arranged on one side of the housing, and a discharge port is arranged on one side of the bottom, and the discharge port is communicated with the housing I. A grid (11) is arranged inside the housing II. After the water-filled feces enter the feed unit, solid impurities with larger volumes are separated under the action of the grid (11), and the liquid enters the electrolytic cell. During the electrolysis process, hydrogen is generated at the cathode through an electrochemical reaction, and chlorine is generated at the anode, and is collected in the hydrogen storage unit and the chlorine storage unit. During the electrolysis process, salt in the water-filled feces is decomposed during the anode reaction, and organic pollutants therein are also degraded under the action of electrochemical oxidation. Heavy metal ions are deposited near the cathode and are concentrated on the cathode surface. The electrolyzed water-filled feces enter a separation device with a grid through a water outlet (5) to achieve solid-liquid separation. The solid containing water-soluble fertilizer is used as organic fertilizer in agriculture, and the liquid is discharged or reused after treatment.

2. The method for treating water-foam feces based on electrochemical technology according to claim 1, characterized in that: The cathode is a hydrogen evolution electrode selected from a platinum electrode, a molybdenum electrode, a nickel electrode, and a titanium coating electrode; the anode is a chlorine evolution electrode selected from a DSA electrode, a platinum electrode, a graphite electrode, and an iridium oxide electrode.

3. The method for treating water-foam feces based on electrochemical technology according to claim 1, characterized in that: The electrodes are arranged in 3-10 pairs, and the interval between the cathode and the anode is 2-3 cm.

4. The method for treating feces with water foam based on electrochemical technology according to claim 1, characterized in that: The electrode voltage is 1.5-3V during the electrolysis process.

5. The method for treating water-foam feces based on electrochemical technology according to claim 1, characterized in that: The anode and cathode are mounted on a detachable bracket (9), and the detachable bracket is arranged on the top of the shell I.

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