CN110713290A - High-salt-content evaporation mother liquor recycling treatment system and method - Google Patents
High-salt-content evaporation mother liquor recycling treatment system and method Download PDFInfo
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- CN110713290A CN110713290A CN201810771003.3A CN201810771003A CN110713290A CN 110713290 A CN110713290 A CN 110713290A CN 201810771003 A CN201810771003 A CN 201810771003A CN 110713290 A CN110713290 A CN 110713290A
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 114
- 238000001704 evaporation Methods 0.000 title claims abstract description 79
- 230000008020 evaporation Effects 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 86
- 239000007789 gas Substances 0.000 claims abstract description 81
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000746 purification Methods 0.000 claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- 238000005273 aeration Methods 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000005540 biological transmission Effects 0.000 claims abstract description 17
- 239000012495 reaction gas Substances 0.000 claims abstract description 16
- 238000005070 sampling Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 46
- 230000001590 oxidative effect Effects 0.000 claims description 36
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical class [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 39
- 239000000460 chlorine Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000010413 mother solution Substances 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a recycling treatment system and method for high-salt-content evaporation mother liquor, belonging to the technical field of wastewater treatment and comprising an electrolysis device, a neutralization reaction device and an adsorption purification device; the electrolysis device comprises a reaction box body with a liquid inlet pipe, a liquid outlet pipe and a sampling pipe, wherein a positive plate and a negative plate are arranged in the reaction box body, and a reaction gas outlet is arranged at the top of the reaction box body; the neutralization reaction device comprises a reaction barrel, a liquid inlet pipe, a liquid outlet pipe, a chemical feeding port and an exhaust port are arranged on the reaction barrel, an aeration pipe with an aeration head at the bottom is arranged in the middle of the reaction barrel, the adsorption purification device comprises an activated carbon column wrapped by a shell, an air inlet pipe is arranged at the bottom of the shell, and a discharge pipe is arranged at the top of the shell; the reaction gas outlet of the electrolysis device is connected with the inlet of the aeration pipe of the neutralization reaction device through a gas transmission pipeline with an air extractor, and the exhaust port of the neutralization reaction device is connected with the gas inlet pipeline of the adsorption purification device through a gas transmission pipeline.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a high-salt-content evaporation mother liquor recycling treatment system and method.
Background
During the development of petroleum and natural gas, a great amount of high-salt-content gas production wastewater, fracturing wastewater, drilling wastewater and the like can be generated. The salt content of the wastewater can reach 10000-150000 mg/L, the COD can reach 2000-50000 mg/L, the ammonia nitrogen can reach 50-200 mg/L, the concentration of other pollutants is higher, and the water quality is quite complex.
Most of oil and gas fields are treated by reinjection, but the reinjection difficulty is quite large in areas with very dense stratums. At present, chemical oxidation and other methods are mostly adopted for treatment, but with the increase of environmental management intensity, measures are adopted to limit the discharge concentration of substances such as chloride ions in the discharged sewage in many places, and if the discharge concentration of chloride ions is limited to be below 300mg/L in some regions, desalination measures are required. The existing wastewater desalination process mainly comprises evaporation, reverse osmosis, electrodialysis and the like.
The low-temperature multi-effect evaporation is one of the better desalination technologies at present, compared with the desalination technologies such as membrane treatment and the like, the low-temperature multi-effect evaporation has the advantages that the quality of evaporated condensate water is better, less residual mother liquor is left, salt obtained by evaporation crystallization can be fully utilized as a product, and the like, and the evaporated condensate water can be recycled in priority because inorganic salts such as chloride ions and various pollutants in the wastewater are removed. However, the total water amount of the evaporation mother liquor is still about 5-10%, most organic matters in the waste water and part of inorganic ions such as calcium, magnesium and the like are remained in the mother liquor in the evaporation process, so that the mother liquor cannot directly return to a system for continuous evaporation, other directions are difficult to find, and the application of the evaporation desalination technology is severely restricted. The treatment problem of the mother liquor is always a great problem of the waste water evaporation treatment process.
However, in the prior art, as the chinese patent publication with publication number CN107585938A entitled "system and method for recycling denitration catalyst regeneration wastewater for catalyst recovery process", a system and method for recycling denitration catalyst regeneration wastewater for catalyst recovery process are disclosed, the system includes a coagulation sedimentation tank, a reverse osmosis concentration unit, a concentrated brine tank, a sodium sulfate electrolysis unit, and an evaporation crystallization unit; the invention also provides a method for treating denitration catalyst regeneration wastewater and recovering acid and alkali by using the system; according to the characteristics of the wastewater, the invention designs a link of recycling acid liquor and alkali liquor, on one hand, the generation amount of the wastewater is reduced, on the other hand, the recycled acid liquor and alkali liquor can be used for a denitration catalyst recycling process, the use amount of a medicament is reduced, and the effective combination of the catalyst regeneration and recycling process is realized.
Disclosure of Invention
The invention aims to provide a system and a method for recycling evaporation mother liquor wastewater with high salt content generated in the evaporation treatment process of wastewater generated in the gas field development process.
The purpose of the invention is realized by the following technical scheme:
high salt evaporation mother liquor resourceful treatment system that contains, its characterized in that: comprises an electrolysis device, a neutralization reaction device and an adsorption purification device;
the electrolysis device comprises a reaction box body with a liquid inlet pipe, a liquid outlet pipe and a sampling pipe, wherein a positive plate and a negative plate are arranged in the reaction box body, and a reaction gas outlet is arranged at the top of the reaction box body;
the neutralization reaction device comprises a reaction barrel, a liquid inlet pipe, a liquid outlet pipe, a dosing port and an exhaust port are arranged on the reaction barrel, and an aeration pipe with an aeration head at the bottom is arranged in the middle of the reaction barrel;
the adsorption and purification device comprises an activated carbon column wrapped by a shell, the bottom of the shell is provided with an air inlet pipe, and the top of the shell is provided with a discharge pipe;
the reaction gas outlet of the electrolysis device is connected with the inlet of the aeration pipe of the neutralization reaction device through a gas transmission pipeline with an air extractor, and the exhaust port of the neutralization reaction device is connected with the gas inlet pipeline of the adsorption purification device through a gas transmission pipeline.
And the top in the reaction box body of the electrolysis device is provided with a pickling spray device, and the pickling spray device comprises a plurality of acid liquor spray heads with outlets facing the positive plate and the negative plate.
The gas transmission pipeline between the reaction gas outlet of the electrolysis device and the inlet of the aeration pipe of the neutralization reaction device comprises a vertical pipe arranged at the reaction gas outlet of the electrolysis device, the outlet of the vertical pipe is provided with a bent pipeline with a fan-shaped gas collecting cover, and the bent pipeline is connected into the inlet of the aeration pipe of the neutralization reaction device; the air pump is arranged on the bent pipeline.
And a PH detector is also arranged in the neutralization reaction device.
And a plurality of air outlet holes are formed in the tube body of the air inlet tube.
The resource treatment method of the evaporation mother liquor with high salt content is characterized by comprising the following steps:
an electrolysis step, namely feeding the pretreated high-salt-content evaporation mother liquor into an electrolysis device through a liquid inlet pipe of the electrolysis device for electrolysis to generate HCL and Cl2Acid gas and saturated sodium hypochlorite liquid, wherein the saturated sodium hypochlorite liquid flows out through the liquid outlet pipe to be used as an oxidant for pretreating organic matters in mother liquor, and HCL and Cl generated by electrolysis2Acid gas is sucked into the neutralization reaction device through an exhaust port;
a neutralization step of generating HCl and Cl through the electrolysis step2The acid gas enters a reaction barrel of the neutralization reaction device along an aeration pipe of the neutralization reaction device and is released by an aeration head, and the released HCL and Cl2The acid gas and the alkali liquor in the reaction barrel are subjected to neutralization reaction, and the gas generated by the neutralization reaction flows into the adsorption purification device through the exhaust port;
and an adsorption purification step, wherein gas generated after the neutralization reaction step enters an air inlet pipe of the adsorption purification device along an air conveying pipeline, is released by the air inlet pipe from bottom to top and passes through an activated carbon column of the adsorption purification device to be adsorbed and purified, and finally the gas subjected to adsorption purification is discharged by a discharge pipe of the adsorption purification device.
And in the electrolysis step, spraying acidic liquid to the positive plate and the negative plate of the electrolysis device by an acid washing and spraying device to wash off attachments.
In the electrolysis step, the high-salt-content evaporation mother liquor in the electrolysis device is sampled through a sampling pipe of the electrolysis device to determine whether a saturated sodium hypochlorite solution is generated in the electrolysis process, and the acid gas generated by electrolysis is extracted through a gas transmission pipeline with an air extractor and is transmitted to a neutralization reaction device.
In the neutralization reaction step, a pH detector on the neutralization reaction device is used for monitoring the pH value of the alkaline liquid in the neutralization reaction device in real time, and the alkaline liquid is supplemented through a medicine adding port so as to keep the pH value of the liquid in the neutralization reaction device alkaline.
The beneficial effects of this technical scheme are as follows:
according to the high-salt-content evaporation mother liquor recycling treatment system provided by the invention, the high-salt-content mother liquor which is difficult to treat is electrolyzed, the organic matter in the mother liquor is degraded by using the high-oxidability hypochlorous acid generated by electrolysis, the mother liquor still contains saturated hypochlorous acid after the organic matter is removed, the mother liquor has strong oxidability, the mother liquor is introduced into the wastewater to be evaporated, the organic pollutant in the wastewater is removed by using the oxidability of the mother liquor, and the generation amount of the evaporation mother liquor can be greatly reduced after the concentration of the pollutant is reduced; and after the absorption liquid is saturated, the absorption liquid is introduced into the wastewater to be evaporated to oxidize organic pollutants in the wastewater.
The system enables the treated mother liquor to be doped into the pretreatment of the feed liquid before evaporation, on one hand, oxidizing pretreatment is carried out on the quasi-evaporation wastewater by using oxidizing substances generated after the mother liquor treatment, organic matters in the quasi-evaporation wastewater are removed, and the resource utilization of the mother liquor is realized; on the other hand, residual organic matters in the mother liquor are oxidized by the generated oxides through electrolytic treatment, so that the treated mother liquor can return to an evaporation system for continuous evaporation. And finally, only evaporating condensed water and salt are left in the evaporated material, and the evaporated condensed water and the salt can be comprehensively utilized, so that the aim of zero emission is fulfilled, and the generation of secondary pollution is avoided.
Furthermore, the generated acid gas is collected by adopting a bent pipeline with a fan-shaped gas collecting cover, so that the acid gas is prevented from leaking outwards, and the mother liquor in the electrolysis device is prevented from being directly sucked out due to too large suction force; an acid washing spraying device is arranged at the upper part of an electrode plate in the electrolysis device, and acid liquor can be adopted to spray and soak the electrode plate after the electrode plate is scaled so as to play a role in cleaning scales on the electrode plate; the bottom of the electrolysis device is provided with an aeration device, and chlorine gas generated by electrolysis is blown into the acid gas neutralization device by the aeration device to be absorbed, so that sodium hypochlorite solution with oxidizability is generated and is recycled; the acid gas attaches together the device, and the aeration pipe afterbody adopts the aeration dish can effectively reduce the bubble volume, makes acid gas can absorb with the contact of absorption liquid bigger area.
The method for recycling the high-salt-content evaporation mother liquor comprises the steps of firstly, electrolyzing the high-salt-content mother liquor by adopting an electrolysis technology, wherein oxidizing substances such as saturated sodium hypochlorite and the like are generated by electrolyzing the high-salt-content mother liquor, and the oxidizing substances such as sodium hypochlorite and the like with strong oxidizing property can oxidize organic matters in the mother liquor; because the electrolysis continuously generates the sodium hypochlorite solution, the electrolyzed mother solution finally contains oxidizing substances such as saturated sodium hypochlorite and the like, and the electrolyzed mother solution containing the oxidizing substances such as the saturated sodium hypochlorite and the like can be used as an oxidizing agent for the oxidation pretreatment of the waste water before evaporation, thereby reducing the generation rate of the mother solution from the source. Chlorine and hydrogen chloride gases which are not dissolved in the mother liquor in the high-salt-content mother liquor are electrolyzed and absorbed by alkali liquor, and after the alkali liquor is absorbed for a period of time, the absorption liquid mainly generates a saturated sodium hypochlorite solution which can also be used as an oxidant for treating the wastewater to be evaporated, so that the high-salt-content evaporation mother liquor is finally recycled. The harmful gas which is not completely absorbed is discharged after being absorbed by the active carbon, so that the discharged gas is harmless.
Compared with the prior mother liquor treatment technology, the method adopts the technology of electrolysis, generation of oxidizing substances, oxidation pretreatment of a water sample (mother liquor with oxidizing property) and entering of an evaporation system, realizes resource utilization of the mother liquor, and reduces the harm to the environment; the existing chemical method treatment needs to consume a large amount of chemical agents, residual agents easily enter the environment, adverse effects are caused to the environment, and the salt quality can be influenced, after the method is adopted, the high-salt-content mother liquor can be effectively recycled, other agents are not additionally introduced, adverse effects are not caused to the later-stage salt quality, the problem of mother liquor outlet is solved, and the method is a technical support for effectively applying a low-temperature multi-effect evaporation technology; compared with reinjection, the method has the advantages that the high-salt-content mother liquor is electrolyzed to generate oxidizing substances, the oxidizing substances are used in the pretreatment process, the mother liquor is recycled, the discharge to the environment is avoided, the re-evaporation treatment of a mother liquor return evaporation system is realized, and the technology is environment-friendly.
Drawings
The foregoing and following detailed description of the invention will be apparent when read in conjunction with the following drawings, in which:
FIG. 1 is a schematic structural view of a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of the internal composition of a preferred embodiment of the present invention;
in the figure:
1. an electrolysis device; 1.1, a liquid inlet pipe; 1.2, a liquid outlet pipe; 1.3, sampling tube; 1.4, a positive plate; 1.5, negative pole pieces; 2. a neutralization reaction device; 2.1, an aeration pipe; 2.2, an aeration head; 2.3, adding a medicine port; 2.4, a PH detector; 3. an adsorption purification device; 3.1, a discharge pipe; 3.2, an active carbon column; 3.3, an air inlet pipe; 4. a gas transmission pipeline; 4.1, vertical pipes; 4.2, a fan-shaped air collecting cover; 4.3, bending the pipeline; 5. an air extractor.
Detailed Description
The technical solutions for achieving the objects of the present invention are further illustrated by the following specific examples, and it should be noted that the technical solutions claimed in the present invention include, but are not limited to, the following examples.
Example 1
As one of the most basic embodiments of the system of the present invention, as shown in fig. 1 and 2, this example discloses a recycling treatment system for high salt-containing evaporation mother liquor, which comprises an electrolysis device 1, a neutralization reaction device 2 and an adsorption purification device 3; the electrolysis device 1 comprises a reaction box body with a liquid inlet pipe 1.1, a liquid outlet pipe 1.2 and a sampling pipe 1.3, wherein a positive plate 1.4 and a negative plate 1.5 are arranged in the reaction box body, and a reaction gas outlet is arranged at the top of the reaction box body; the neutralization reaction device 2 comprises a reaction barrel, a liquid inlet pipe 1.1, a liquid outlet pipe 1.2, a chemical adding port 2.3 and an exhaust port are arranged on the reaction barrel, and an aeration pipe 2.1 with an aeration head 2.2 at the bottom is arranged in the middle of the reaction barrel; the adsorption and purification device 3 comprises an activated carbon column 3.2 wrapped by a shell, an air inlet pipe 3.3 is arranged at the bottom of the shell, and a discharge pipe 3.1 is arranged at the top of the shell; the reaction gas outlet of the electrolysis device 1 is connected with the inlet of the aeration pipe 2.1 of the neutralization reaction device 2 through a gas transmission pipeline 4 with an air extractor 5, and the exhaust port of the neutralization reaction device 2 is connected with the gas inlet pipe 3.3 of the adsorption purification device 3 through the gas transmission pipeline 4.
According to the high-salt evaporation mother liquor recycling treatment system, high-salt mother liquor which is difficult to treat is electrolyzed, high-oxidability hypochlorous acid generated by electrolysis is used for degrading organic matters in the mother liquor, the mother liquor still contains saturated hypochlorous acid after the organic matters are removed, the mother liquor has strong oxidability, the mother liquor is introduced into waste water to be evaporated, organic pollutants in the waste water are removed by utilizing the oxidability of the mother liquor, and the generation amount of the evaporation mother liquor can be greatly reduced after the concentration of the pollutants is reduced; and after the absorption liquid is saturated, the absorption liquid is introduced into the wastewater to be evaporated to oxidize organic pollutants in the wastewater.
The system enables the treated mother liquor to be doped into the pretreatment of the feed liquid before evaporation, on one hand, oxidizing pretreatment is carried out on the quasi-evaporation wastewater by using oxidizing substances generated after the mother liquor treatment, organic matters in the quasi-evaporation wastewater are removed, and the resource utilization of the mother liquor is realized; on the other hand, residual organic matters in the mother liquor are oxidized by the generated oxides through electrolytic treatment, so that the treated mother liquor can return to an evaporation system for continuous evaporation. And finally, only evaporating condensed water and salt are left in the evaporated material, and the evaporated condensed water and the salt can be comprehensively utilized, so that the aim of zero emission is fulfilled, and the generation of secondary pollution is avoided.
Example 2
As a preferred embodiment of the system of the present invention, as shown in fig. 1 and 2, this example discloses a recycling treatment system for high salt-containing evaporation mother liquor, comprising an electrolysis device 1, a neutralization reaction device 2 and an adsorption purification device 3; the electrolytic device 1 comprises a reaction box body with a liquid inlet pipe 1.1, a liquid outlet pipe 1.2 and a sampling pipe 1.3, a positive plate 1.4 and a negative plate 1.5 are arranged in the reaction box body, the top in the reaction box body of the electrolytic device 1 is provided with an acid washing spray device, the acid washing spray device comprises a plurality of acid liquor spray heads with outlets facing the positive plate 1.4 and the negative plate 1.5, and the top of the reaction box body is provided with a reaction gas outlet; the neutralization reaction device 2 comprises a reaction barrel, a liquid inlet pipe 1.1, a liquid outlet pipe 1.2, a chemical adding port 2.3 and an exhaust port are arranged on the reaction barrel, an aeration pipe 2.1 with an aeration head 2.2 at the bottom is arranged in the middle of the reaction barrel, and a PH detector 2.4 is also arranged in the neutralization reaction device 2; the adsorption and purification device 3 comprises an activated carbon column 3.2 wrapped by a shell, an air inlet pipe 3.3 is arranged at the bottom of the shell, a plurality of air outlet holes are formed in the pipe body of the air inlet pipe 3.3, and a discharge pipe 3.1 is arranged at the top of the shell; the reaction gas outlet of the electrolysis device 1 is connected with the inlet of the aeration pipe 2.1 of the neutralization reaction device 2 through a gas transmission pipeline 4 with an air extractor 5, and the exhaust port of the neutralization reaction device 2 is connected with the gas inlet pipe 3.3 of the adsorption purification device 3 through the gas transmission pipeline 4.
Moreover, as shown in fig. 2, the gas transmission pipeline 4 between the reaction gas outlet of the electrolysis device 1 and the inlet of the aeration pipe 2.1 of the neutralization reaction device 2 comprises a vertical pipe 4.1 arranged at the reaction gas outlet of the electrolysis device 1, a bent pipeline 4.3 with a fan-shaped gas collecting cover 4.2 is arranged on the outlet of the vertical pipe 4.1, and the bent pipeline 4.3 is connected into the inlet of the aeration pipe 2.1 of the neutralization reaction device 2; the air pump 5 is arranged on the bent pipeline 4.3.
According to the high-salt evaporation mother liquor recycling treatment system, high-salt mother liquor which is difficult to treat is electrolyzed, high-oxidability hypochlorous acid generated by electrolysis is used for degrading organic matters in the mother liquor, the mother liquor still contains saturated hypochlorous acid after the organic matters are removed, the mother liquor has strong oxidability, the mother liquor is introduced into waste water to be evaporated, organic pollutants in the waste water are removed by utilizing the oxidability of the mother liquor, and the generation amount of the evaporation mother liquor can be greatly reduced after the concentration of the pollutants is reduced; and after the absorption liquid is saturated, the absorption liquid is introduced into the wastewater to be evaporated to oxidize organic pollutants in the wastewater.
The system enables the treated mother liquor to be doped into the pretreatment of the feed liquid before evaporation, on one hand, oxidizing pretreatment is carried out on the quasi-evaporation wastewater by using oxidizing substances generated after the mother liquor treatment, organic matters in the quasi-evaporation wastewater are removed, and the resource utilization of the mother liquor is realized; on the other hand, residual organic matters in the mother liquor are oxidized by the generated oxides through electrolytic treatment, so that the treated mother liquor can return to an evaporation system for continuous evaporation. And finally, only evaporating condensed water and salt are left in the evaporated material, and the evaporated condensed water and the salt can be comprehensively utilized, so that the aim of zero emission is fulfilled, and the generation of secondary pollution is avoided.
The generated acid gas is collected by adopting a bent pipeline 4.3 with a fan-shaped gas collecting cover 4.2, which is beneficial to avoiding the leakage of the acid gas and simultaneously avoiding the direct suction of the mother liquor in the electrolysis device 1 due to too large suction force; an acid washing spraying device is arranged at the upper part of the electrode plate in the electrolysis device 1, and acid liquor can be adopted to spray and soak the electrode plate after the electrode plate is scaled so as to play a role in cleaning scales on the electrode plate; the bottom of the electrolysis device 1 is provided with an aeration device, chlorine gas generated by electrolysis is blown into the acid gas neutralization device by the aeration device to be absorbed, and sodium hypochlorite solution with oxidizability is generated for resource utilization; the acid gas attaches together the device, and the aeration pipe afterbody adopts the aeration dish can effectively reduce the bubble volume, makes acid gas can absorb with the contact of absorption liquid bigger area.
Example 3
As a most basic embodiment of the method of the present invention, as shown in fig. 1 and 2, the present example discloses a method for recycling evaporation mother liquor with high salt content, comprising the following steps:
an electrolysis step, namely sending the pretreated high-salt-content evaporation mother liquor into an electrolysis device 1 through a liquid inlet pipe 1.1 of the electrolysis device 1 for electrolysis to generate HCL and Cl2Acid gas and saturated sodium hypochlorite liquid, wherein the saturated sodium hypochlorite liquid flows out through the liquid outlet pipe 1.2 to be used as an oxidant for pretreating organic matters in mother liquor, and HCL and Cl generated by electrolysis2Acid gas is sucked into the neutralization reaction device 2 through an exhaust port;
a neutralization step of generating HCl and Cl through the electrolysis step2The acid gas enters the reaction barrel of the neutralization reaction device 2 along the aeration pipe 2.1 of the neutralization reaction device 2 and is released by the aeration head 2.2, and the released HCL and Cl2The acid gas and the alkali liquor in the reaction barrel are subjected to neutralization reaction, and the gas generated by the neutralization reaction flows into the adsorption purification device 3 through the exhaust port;
and an adsorption purification step, wherein gas generated after the neutralization reaction step enters an air inlet pipe 3.3 of the adsorption purification device 3 along an air delivery pipeline 4, is released from bottom to top by the air inlet pipe 3.3 and passes through an activated carbon column 3.2 of the adsorption purification device 3 to be adsorbed and purified, and finally, the gas subjected to adsorption purification is discharged from a discharge pipe 3.1 of the adsorption purification device 3.
The method for recycling the high-salt-content evaporation mother liquor comprises the steps of firstly, electrolyzing the high-salt-content mother liquor by adopting an electrolysis technology, wherein oxidizing substances such as saturated sodium hypochlorite and the like are generated by electrolyzing the high-salt-content mother liquor, and the oxidizing substances such as sodium hypochlorite and the like with strong oxidizing property can oxidize organic matters in the mother liquor; because the electrolysis continuously generates the sodium hypochlorite solution, the electrolyzed mother solution finally contains oxidizing substances such as saturated sodium hypochlorite and the like, and the electrolyzed mother solution containing the oxidizing substances such as the saturated sodium hypochlorite and the like can be used as an oxidizing agent for the oxidation pretreatment of the waste water before evaporation, thereby reducing the generation rate of the mother solution from the source. Chlorine and hydrogen chloride gases which are not dissolved in the mother liquor in the high-salt-content mother liquor are electrolyzed and absorbed by alkali liquor, and after the alkali liquor is absorbed for a period of time, the absorption liquid mainly generates a saturated sodium hypochlorite solution which can also be used as an oxidant for treating the wastewater to be evaporated, so that the high-salt-content evaporation mother liquor is finally recycled. The harmful gas which is not completely absorbed is discharged after being absorbed by the active carbon, so that the discharged gas is harmless.
Example 4
As a most basic embodiment of the method of the present invention, as shown in fig. 1 and 2, the present example discloses a method for recycling evaporation mother liquor with high salt content, comprising the following steps:
an electrolysis step, namely sending the pretreated high-salt-content evaporation mother liquor into an electrolysis device 1 through a liquid inlet pipe 1.1 of the electrolysis device 1 for electrolysis to generate HCL and Cl2Acid gas and saturated sodium hypochlorite liquid, wherein the saturated sodium hypochlorite liquid flows out through the liquid outlet pipe 1.2 to be used as an oxidant for pretreating organic matters in mother liquor, and HCL and Cl generated by electrolysis2Acid gas is sucked into the neutralization reaction device 2 through an exhaust port; spraying acidic liquid to the positive plate 1.4 and the negative plate 1.5 of the electrolysis device 1 by an acid washing and spraying device to wash off attachments; sampling the high-salt-content evaporation mother liquor in the electrolysis device 1 through a sampling pipe 1.3 of the electrolysis device 1 to determine whether a saturated sodium hypochlorite solution is generated in the electrolysis process, and extracting and conveying the acid gas generated by electrolysis to the neutralization reaction device 2 through a gas transmission pipeline 4 with an air extractor 5;
a neutralization step of generating HCl and Cl through the electrolysis step2The acid gas enters the reaction barrel of the neutralization reaction device 2 along the aeration pipe 2.1 of the neutralization reaction device 2 and is released by the aeration head 2.2, and the released HCL and Cl2The acid gas and the alkali liquor in the reaction barrel are subjected to neutralization reaction, and the gas generated by the neutralization reaction flows into the adsorption purification device 3 through the exhaust port; the method also comprises the steps of monitoring the pH value of the alkaline liquid in the neutralization reaction device 2 in real time through a pH detector 2.4 on the neutralization reaction device 2, and supplementing the alkaline liquid through a medicine adding port 2.3 to keep the pH value of the liquid in the reaction device alkaline
And an adsorption purification step, wherein gas generated after the neutralization reaction step enters an air inlet pipe 3.3 of the adsorption purification device 3 along an air delivery pipeline 4, is released from bottom to top by the air inlet pipe 3.3 and passes through an activated carbon column 3.2 of the adsorption purification device 3 to be adsorbed and purified, and finally, the gas subjected to adsorption purification is discharged from a discharge pipe 3.1 of the adsorption purification device 3.
The method for recycling the high-salt-content evaporation mother liquor comprises the steps of firstly, electrolyzing the high-salt-content mother liquor by adopting an electrolysis technology, wherein oxidizing substances such as saturated sodium hypochlorite and the like are generated by electrolyzing the high-salt-content mother liquor, and the oxidizing substances such as sodium hypochlorite and the like with strong oxidizing property can oxidize organic matters in the mother liquor; because the electrolysis continuously generates the sodium hypochlorite solution, the electrolyzed mother solution finally contains oxidizing substances such as saturated sodium hypochlorite and the like, and the electrolyzed mother solution containing the oxidizing substances such as the saturated sodium hypochlorite and the like can be used as an oxidizing agent for the oxidation pretreatment of the waste water before evaporation, thereby reducing the generation rate of the mother solution from the source. Chlorine and hydrogen chloride gases which are not dissolved in the mother liquor in the high-salt-content mother liquor are electrolyzed and absorbed by alkali liquor, and after the alkali liquor is absorbed for a period of time, the absorption liquid mainly generates a saturated sodium hypochlorite solution which can also be used as an oxidant for treating the wastewater to be evaporated, so that the high-salt-content evaporation mother liquor is finally recycled. The harmful gas which is not completely absorbed is discharged after being absorbed by the active carbon, so that the discharged gas is harmless.
Compared with the prior mother liquor treatment technology, the method adopts the technology of electrolysis, generation of oxidizing substances, oxidation pretreatment of a water sample (mother liquor with oxidizing property) and entering of an evaporation system, realizes resource utilization of the mother liquor, and reduces the harm to the environment; the existing chemical method treatment needs to consume a large amount of chemical agents, residual agents easily enter the environment, adverse effects are caused to the environment, and the salt quality can be influenced, after the method is adopted, the high-salt-content mother liquor can be effectively recycled, other agents are not additionally introduced, adverse effects are not caused to the later-stage salt quality, the problem of mother liquor outlet is solved, and the method is a technical support for effectively applying a low-temperature multi-effect evaporation technology; compared with reinjection, the method has the advantages that the high-salt-content mother liquor is electrolyzed to generate oxidizing substances, the oxidizing substances are used in the pretreatment process, the mother liquor is recycled, the discharge to the environment is avoided, the re-evaporation treatment of a mother liquor return evaporation system is realized, and the technology is environment-friendly.
Claims (9)
1. High salt evaporation mother liquor resourceful treatment system that contains, its characterized in that: comprises an electrolysis device (1), a neutralization reaction device (2) and an adsorption purification device (3);
the electrolysis device (1) comprises a reaction box body with a liquid inlet pipe (1.1), a liquid outlet pipe (1.2) and a sampling pipe (1.3), wherein a positive plate (1.4) and a negative plate (1.5) are arranged in the reaction box body, and a reaction gas outlet is arranged at the top of the reaction box body;
the neutralization reaction device (2) comprises a reaction barrel, a liquid inlet pipe (1.1), a liquid outlet pipe (1.2), a chemical feeding port (2.3) and an exhaust port are arranged on the reaction barrel, and an aeration pipe (2.1) with an aeration head (2.2) at the bottom is arranged in the middle of the reaction barrel;
the adsorption purification device (3) comprises an activated carbon column (3.2) wrapped by a shell, an air inlet pipe (3.3) is arranged at the bottom of the shell, and a discharge pipe (3.1) is arranged at the top of the shell;
the reaction gas outlet of the electrolysis device (1) is connected with the inlet of the aeration pipe (2.1) of the neutralization reaction device (2) through a gas transmission pipeline (4) with an air pump (5), and the exhaust port of the neutralization reaction device (2) is connected with the gas inlet pipe (3.3) of the adsorption purification device (3) through the gas transmission pipeline (4).
2. The high salt-containing evaporation mother liquor recycling treatment system according to claim 1, characterized in that: and the top in the reaction box body of the electrolysis device (1) is provided with a pickling spray device, and the pickling spray device comprises a plurality of acid liquor spray heads with outlets facing the positive plate (1.4) and the negative plate (1.5).
3. The high salt-containing evaporation mother liquor recycling treatment system according to claim 1, characterized in that: the gas transmission pipeline (4) between the reaction gas outlet of the electrolysis device (1) and the inlet of the aeration pipe (2.1) of the neutralization reaction device (2) comprises a vertical pipe (4.1) arranged at the reaction gas outlet of the electrolysis device (1), the outlet of the vertical pipe (4.1) is provided with a bent pipeline (4.3) with a fan-shaped gas collecting cover (4.2), and the bent pipeline (4.3) is connected into the inlet of the aeration pipe (2.1) of the neutralization reaction device (2); the air pump (5) is arranged on the bent pipeline (4.3).
4. The high-salt-content evaporation mother liquor recycling treatment system as claimed in claim 1 or 3, characterized in that: and a PH detector (2.4) is also arranged in the neutralization reaction device (2).
5. The high-salt-content evaporation mother liquor recycling treatment system as claimed in claim 1 or 3, characterized in that: and a plurality of air outlet holes are formed in the tube body of the air inlet tube (3.3).
6. The resource treatment method of the evaporation mother liquor with high salt content is characterized by comprising the following steps:
an electrolysis step, namely feeding the pretreated high-salt-content evaporation mother liquor into an electrolysis device (1) through a liquid inlet pipe (1.1) of the electrolysis device (1) for electrolysis to generate HCL and Cl2Acid gas and saturated sodium hypochlorite liquid, wherein the saturated sodium hypochlorite liquid flows out through a liquid outlet pipe (1.2) to be used as an oxidant for pretreating organic matters in mother liquor, and HCL and Cl generated by electrolysis2Acid gas is sucked into the neutralization reaction device (2) through an exhaust port;
a neutralization step of generating HCl and Cl through the electrolysis step2The acid gas enters a reaction barrel of the neutralization reaction device (2) along an aeration pipe (2.1) of the neutralization reaction device (2) and is released by an aeration head (2.2), and HCL and Cl released by the acid gas2The acid gas and the alkali liquor in the reaction barrel are subjected to neutralization reaction, and the gas generated by the neutralization reaction flows into the adsorption purification device (3) through the exhaust port;
and an adsorption purification step, wherein gas generated after the neutralization reaction step enters an air inlet pipe (3.3) of the adsorption purification device (3) along an air delivery pipeline (4), is released by the air inlet pipe (3.3) and passes through an activated carbon column (3.2) of the adsorption purification device (3) from bottom to top for adsorption purification, and finally, the gas subjected to adsorption purification is discharged by a discharge pipe (3.1) of the adsorption purification device (3).
7. The resource treatment method of the evaporation mother liquor with high salt content as claimed in claim 6, characterized in that: and in the electrolysis step, acid liquid is sprayed to the positive plate (1.4) and the negative plate (1.5) of the electrolysis device (1) through an acid washing spraying device to wash off attachments.
8. The resource treatment method of the evaporation mother liquor with high salt content as claimed in claim 6, characterized in that: in the electrolysis step, the high-salinity evaporation mother liquor in the electrolysis device (1) is sampled through a sampling pipe (1.3) of the electrolysis device (1) to determine whether a saturated sodium hypochlorite solution is generated in the electrolysis process, and acid gas generated by electrolysis is extracted through a gas transmission pipeline (4) with an air extractor (5) and is transmitted to a neutralization reaction device (2).
9. The resource treatment method of the evaporation mother liquor with high salt content as claimed in claim 6, characterized in that: in the neutralization reaction step, the pH value of alkaline liquid in the neutralization reaction device (2) is monitored in real time through a pH detector (2.4) on the neutralization reaction device (2), and alkaline liquid is supplemented through a medicine adding port (2.3) to keep the pH value of liquid in the reaction device alkaline.
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