CN212247228U - Contain salt waste water recycling apparatus based on electrolysis hydrogen manufacturing technique - Google Patents
Contain salt waste water recycling apparatus based on electrolysis hydrogen manufacturing technique Download PDFInfo
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Abstract
The utility model relates to a contain salt waste water recovery and recycle device based on electrolysis hydrogen manufacturing technique, the device contain the COD detection device of electrolysis trough, hydrogen aftertreatment device and peripheral hardware, and this electrolysis trough has the diaphragm that removes COD electrode group, hydrogen manufacturing electrode group and keep apart anode chamber and cathode chamber, and the electrolysis trough is equipped with and contains salt waste water entry and electrolyte export, and this hydrogen aftertreatment device connects in the cathode chamber of electrolysis trough. Adopt the utility model discloses the device carries out the resourceful recycle to containing salt waste water, reducible its destruction to ecological environment obtains usable hydrogen and sodium hypochlorite solution simultaneously.
Description
Technical Field
The utility model belongs to the technical field of clean energy preparation, a utilize electrolysis water technology hydrogen manufacturing technology is related to, especially relate to an utilize electrolysis to contain device of salt waste water hydrogen manufacturing while by-product sodium hypochlorite.
Background
In recent years, as fossil energy and other primary energy resources are being developed, hydrogen energy has been gaining favor because of its characteristics of cleanliness, high efficiency, and abundant sources. The hydrogen can be produced by using fossil energy such as coal, petroleum and the like, and can also be produced by using electrolyzed water. The raw material for hydrogen production by water electrolysis is generally saline wastewater, only electric energy is consumed in the production process, waste is hardly generated, and the method is an environment-friendly hydrogen production technology.
Salt-containing wastewater is produced by numerous industries and cannot be discharged directly into natural water bodies due to the continuous deterioration of the ecological environment and the gradual strictness of national environmental policies. The treatment and the consumption of the salt-containing wastewater are always difficult, and particularly the treatment cost of the high-salt wastewater with the salt content of more than 10000mg/L is very high.
The invention patent (patent publication No. CN 107098527A) discloses a method for resource utilization of desulfurization waste water. Comprises the following steps: filtering the wastewater, pretreating, electrochemically removing COD, concentrating the salt-containing wastewater, electrolyzing and the like to obtain products such as alkali, ferric chloride, water and the like. However, the method has complex flow, reagents such as acid and alkali are required to be added in the flow to adjust the pH, chemicals are consumed, and the obtained product has low value.
SUMMERY OF THE UTILITY MODEL
To the above-mentioned problem that exists among the prior art, the utility model aims at providing a contain salt waste water recovery and recycle device and technology based on electrolysis hydrogen manufacturing technique promptly, aims at optimizing the utilization ratio that contains salt waste water, reduces the use of chemical agent.
The technical means adopted by the utility model are as follows.
A contains salt waste water recovery and recycle device based on electrolysis hydrogen manufacturing technique contains: electrolytic cell, hydrogen aftertreatment device and the peripheral hardware COD detection device, this electrolytic cell have remove COD electrode group, hydrogen manufacturing electrode group and keep apart the diaphragm of anode chamber and cathode chamber, the electrolytic cell is equipped with and contains salt waste water entry and electrolyte export, hydrogen aftertreatment device connect in the cathode chamber of electrolytic cell.
Wherein the hydrogen post-treatment device comprises hydrogen cooling, drying and purifying equipment.
The anode of the COD removing electrode group is a titanium-based metal oxide electrode, and the cathode of the COD removing electrode group is a carbon material; the anode of the hydrogen production electrode group is a titanium-based metal oxide electrode, and the cathode of the hydrogen production electrode group is a nickel-based material; the diaphragm of the electrolytic cell is a polyphenylene sulfide fiber membrane.
The device also includes: the buffer tank is arranged in front of a salt-containing wastewater inlet of the electrolytic cell, and the hydrogen storage equipment is connected to an outlet of the hydrogen post-treatment device.
The device also comprises a reaction tank, and the reaction tank is connected with the anode chamber of the electrolytic tank and the electrolyte outlet.
Based on the utility model discloses contain salt waste water recycling apparatus's technology based on electrolysis hydrogen manufacturing technique mainly does: sampling the salt-containing wastewater, detecting by COD, discharging into an electrolytic cell, and starting a COD removing electrode group when the COD of the salt-containing wastewater is more than or equal to 10 mg/L; starting a hydrogen production electrode group and closing a COD removal electrode group until the COD of the salt-containing wastewater is lower than 10 mg/L; the cathode chamber and the anode chamber of the electrolytic cell are isolated by arranging a diaphragm, and the salt-containing wastewater is electrolyzed by the hydrogen production electrode group to generate chlorine in the anode chamber of the electrolytic cell and hydrogen in the cathode chamber of the electrolytic cell; and the generated hydrogen is treated by the hydrogen post-treatment device and then discharged into the hydrogen storage equipment.
The initial salt content of the salt-containing wastewater is more than or equal to 10000mg/L, the pH value is 5-11, the suspended matters are less than or equal to 0.5mg/L, the COD is less than or equal to 500 mg/L, and Cl is contained in the salt-containing wastewater-、Na+、Ka+The total content of (A) is more than 9000mg/L, and the total content of other ions is less than or equal to 1000 mg/L.
When the salt content of the electrolyte after electrolysis in the electrolytic cell is more than or equal to 80000mg/L, stopping electrolysis of the hydrogen production electrode group, and sampling again to detect the COD of the electrolyte; if the COD is more than or equal to 10mg/L, the COD removing electrode group is started again to reduce the COD of the electrolyte; if the COD of the electrolyte is lower than 10mg/L, discharging the electrolyte into a reaction tank; chlorine generated in the anode chamber of the electrolytic cell is discharged into the reaction tank, and the chlorine reacts with electrolyte in the reaction tank to generate sodium hypochlorite solution.
And controlling the potential of the anode of the electrolytic cell by a direct current stabilized voltage power supply to keep the anode at a chlorine evolution potential.
The hydrogen post-processing device comprises a hydrogen post-processing device and a hydrogen post-processing device, wherein the hydrogen post-processing device comprises the following steps: cooling, drying and purifying, wherein the cooling process enables the gas temperature to be lower than 35 ℃, the drying process enables the gas dew point to be lower than-70 ℃, and the purifying process enables the gas oxygen content to be lower than 1 ppm.
The utility model discloses produced beneficial effect as follows.
(1) The salt content of the salt-containing wastewater is high, the conductivity is high, the electrolysis is facilitated, any chemical agent is hardly consumed for preparing hydrogen by electrolyzing the salt-containing wastewater, and the method is green and environment-friendly and accords with the concept of sustainable development.
(2) The utility model discloses set up in the electrolysis trough and removed COD electrode group, when reducing to contain COD content in the salt waste water and reach and reduce its pollution degree, the electric conductivity of waste water also improves along with COD's reduction, does benefit to going on of electrolysis hydrogen manufacturing process.
(3) When the hydrogen is produced by electrolyzing the salt-containing wastewater, the pH value of the salt-containing wastewater is increased, and the by-product chlorine reacts with the electrolyzed alkaline wastewater to generate a sodium hypochlorite solution with the disinfection and sterilization effects, so that the resource utilization rate of the wastewater is maximized.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of the salt-containing wastewater recycling device based on the electrolytic hydrogen production technology.
FIG. 2 is a schematic structural diagram of an embodiment of an electrolytic cell in the salt-containing wastewater recycling device based on the electrolytic hydrogen production technology.
Detailed Description
Referring to fig. 1, the present invention is a schematic structural diagram of an embodiment of a device for recycling salt-containing wastewater based on an electrolytic hydrogen production technology. In this embodiment, the apparatus mainly comprises an electrolytic cell 1, a hydrogen gas post-treatment apparatus 2, a reaction tank 3, and an external COD detection apparatus (not shown). Wherein, electrolysis trough 1 is equipped with and contains salt waste water entry and electrolyte export, and hydrogen aftertreatment device 2 is connected in electrolysis trough 1's cathode chamber, and reaction tank 3 is connected in electrolysis trough 1's anode chamber and electrolyte export, and the COD detection device of peripheral hardware mainly used contains the COD detection of salt waste water in the whole technological process.
As shown in the figure, still can set up buffer tank 14 before the salt waste water entry of electrolysis trough 1, the industry contains salt waste water promptly before getting into electrolysis trough 1, can also discharge into buffer tank 14 earlier, both can conveniently sample its COD to containing salt waste water, can play the effect of buffer storage again.
In addition, the hydrogen post-treatment device 2 in the present embodiment may include a hydrogen cooling device, a hydrogen drying device, and a hydrogen purification device. Meanwhile, a hydrogen storage device 21 can be arranged at the outlet of the hydrogen post-treatment device 2, and the treated hydrogen can be directly discharged into the hydrogen storage device 21 (such as a hydrogen storage tank) for standby.
Referring to fig. 2, the electrolytic cell 1 of the present embodiment is provided with a group of COD removing electrode sets 11, a group of hydrogen producing electrode sets 12, and a diaphragm 13 separating the anode chamber and the cathode chamber. Preferably, the anode of the electrode group 11 except COD adopts titanium-based metal oxide electrode, and the cathode adopts carbon material; the anode of the hydrogen production electrode group 12 adopts a titanium-based metal oxide electrode, and the cathode adopts a nickel-based material; the diaphragm 13 of the electrolytic cell adopts a polyphenylene sulfide fiber membrane. Of course, the number of the COD removing electrode groups and the hydrogen producing electrode groups of the electrolytic cell in the device of the utility model, and the materials adopted by each electrode group and the diaphragm are not limited to the above.
The process flow of the saline wastewater recycling device based on the electrolytic hydrogen production technology based on the embodiment can be as follows:
the salt-containing wastewater is firstly discharged into a buffer water tank 14, and is detected by a COD detection device after being sampled in the buffer water tank 4; then discharging the salt-containing wastewater into the electrolytic cell 1, and when the COD of the salt-containing wastewater is more than or equal to 10mg/L, starting the COD removing electrode group 11, and stopping the hydrogen production electrode group 12; starting the hydrogen production electrode group 12 and closing the COD removal electrode group 11 until the COD of the salt-containing wastewater is lower than 10 mg/L;
the cathode chamber and the anode chamber of the electrolytic cell 1 are isolated by a diaphragm 13, and the salt-containing wastewater is electrolyzed by the hydrogen production electrode group 12 to generate chlorine in the anode chamber of the electrolytic cell 1 and generate hydrogen in the cathode chamber of the electrolytic cell 1; the generated hydrogen is processed by a hydrogen post-processing device 2, and the processing process comprises the following steps: cooling, drying and purifying, wherein preferably, the cooling process can ensure that the gas temperature is lower than 35 ℃, the drying process can ensure that the gas dew point is lower than-70 ℃, and the purifying process can ensure that the oxygen content of the gas is lower than 1 ppm; after the post-treatment is completed, the hydrogen can be directly discharged into the hydrogen storage device 21 for later use;
when the salt content of the electrolyte after electrolysis in the electrolytic cell 1 is more than or equal to 80000mg/L, stopping the electrolysis of the hydrogen production electrode group 12, and sampling again to detect the COD of the electrolyte; if the COD is more than or equal to 10mg/L, the COD removing electrode group 11 is started again to reduce the COD of the electrolyte; if the COD is lower than 10mg/L, discharging the electrolyte into the reaction tank 3; chlorine generated in the anode chamber of the electrolytic cell 1 is discharged into the reaction tank 3, and the chlorine can fully react with the electrolyte in the reaction tank 3 to generate sodium hypochlorite solution which can be used as a disinfectant.
In the process, the potential of the anode of the electrolytic cell 1 can be controlled by the direct current stabilized voltage power supply to be always kept at a chlorine evolution potential, so that the anode of the electrolytic cell 1 is ensured to only generate chlorine gas, and other gases are not generated. The chlorine evolution potential can be determined by tests: the anode potential of the cell was varied and the potential at which the chlorine production reached a maximum was identified as the chlorine evolution potential.
Furthermore, the utility model discloses a device and technology are applicable in the salt waste water of trades such as chemical industry, printing and dyeing, papermaking, pharmacy, and this technology requires as follows to the originated parameter of each item that contains salt waste water:
the salt content is 10000mg/L or more, for example 10000, 20000, 30000mg/L and the like, preferably 50000 mg/L;
the pH is 5-11, for example, 5, 6, 7, etc., preferably 9;
the suspended matter is 0.5mg/L or less, for example, 0.5, 0.4, 0.3, 0.2mg/L, etc., preferably 0.1 mg/L;
COD is 500 mg/L or less, for example, 500 mg/L, 400 mg/L, 300 mg/L, etc., preferably less than 10 mg/L;
cl in salt-containing wastewater-、Na+、Ka+The total content of (B) is more than 9000mg/L, and the total content of other ions is not more than 1000mg/L, for example, 1000, 900, 800mg/L, preferably 100 mg/L.
Claims (5)
1. The utility model provides a contain salt waste water recovery and recycle device based on electrolysis hydrogen manufacturing technique which characterized in that contains:
the electrolytic cell comprises an electrolytic cell (1), wherein the electrolytic cell (1) is provided with a COD removing electrode group (11), a hydrogen production electrode group (12) and a diaphragm (13) for separating an anode chamber and a cathode chamber, and the electrolytic cell (1) is provided with a salt-containing wastewater inlet and an electrolyte outlet;
a hydrogen gas post-treatment device (2), the hydrogen gas post-treatment device (2) being connected to the cathode chamber of the electrolytic cell (1);
a COD detection device arranged outside.
2. The brine wastewater recycling device based on the hydrogen production by electrolysis as claimed in claim 1, wherein the hydrogen post-treatment device (2) comprises hydrogen cooling, drying and purifying equipment.
3. The brine wastewater recycling device based on the hydrogen production by electrolysis technology as claimed in claim 1, wherein the anode of the COD removing electrode group (11) is a titanium-based metal oxide electrode, and the cathode is a carbon material; the anode of the hydrogen production electrode group (12) is a titanium-based metal oxide electrode, and the cathode is a nickel-based material; the diaphragm of the electrolytic cell (1) is a polyphenylene sulfide fiber membrane.
4. The device for recycling the saline wastewater based on the electrolytic hydrogen production technology according to any one of claims 1 to 3, further comprising: a buffer water tank (14) arranged in front of a salt-containing wastewater inlet of the electrolytic bath (1) and a hydrogen storage device (21) connected to an outlet of the hydrogen post-treatment device (2).
5. The device for recycling the brine waste based on the hydrogen production technology through electrolysis as claimed in any one of claims 1 to 3, further comprising a reaction tank (3), wherein the reaction tank (3) is connected with the anode chamber and the electrolyte outlet of the electrolytic cell (1).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636073A (en) * | 2020-06-24 | 2020-09-08 | 中国电力工程顾问集团华北电力设计院有限公司 | Device and process for recycling salt-containing wastewater |
| CN114000163A (en) * | 2021-11-30 | 2022-02-01 | 中国华能集团清洁能源技术研究院有限公司 | A kind of salty wastewater electrolysis hydrogen production system and its working method |
| CN115491708A (en) * | 2022-09-28 | 2022-12-20 | 西南石油大学 | Electrode for electrolytic hydrogen production of salt-containing wastewater and preparation method and application thereof |
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2020
- 2020-06-24 CN CN202021192182.4U patent/CN212247228U/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636073A (en) * | 2020-06-24 | 2020-09-08 | 中国电力工程顾问集团华北电力设计院有限公司 | Device and process for recycling salt-containing wastewater |
| CN114000163A (en) * | 2021-11-30 | 2022-02-01 | 中国华能集团清洁能源技术研究院有限公司 | A kind of salty wastewater electrolysis hydrogen production system and its working method |
| CN114000163B (en) * | 2021-11-30 | 2024-05-28 | 中国华能集团清洁能源技术研究院有限公司 | Salt-containing wastewater electrolytic hydrogen production system and working method thereof |
| CN115491708A (en) * | 2022-09-28 | 2022-12-20 | 西南石油大学 | Electrode for electrolytic hydrogen production of salt-containing wastewater and preparation method and application thereof |
| CN115491708B (en) * | 2022-09-28 | 2023-04-28 | 西南石油大学 | Electrode for electrolytic hydrogen production of salt-containing wastewater and preparation method and application thereof |
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