CN108341551B - Treatment method of liquefied gas alkali residue waste liquid - Google Patents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
The invention belongs to the technical field of wastewater treatment, and discloses a method for treating liquefied gas alkali residue waste liquid. The main process of the invention adopts a micro-electrolysis reactor and a high-efficiency bioreactor. The method comprises the following steps: a) pumping the liquefied gas caustic sludge wastewater into an oil separation tank; b) starting a micro-electrolysis reactor provided with an electrode plate, and introducing the pretreated wastewater into the micro-electrolysis reactor for treatment under the action of electrochemistry to obtain treated wastewater; c) diluting the electrolyzed effluent to the salinity of about 20000mg/L, and then adjusting the pH of the wastewater to 10-11 by using phosphoric acid; d) and (3) pumping the neutralized waste alkaline residues into a biochemical reactor, and performing biochemical treatment by high-efficiency halotolerant bacteria to obtain treated wastewater. The invention provides an efficient and energy-saving alkali residue wastewater treatment method, the whole treatment process is carried out at normal temperature and normal pressure, the process is simple, and integrated equipment is realized. The method provided by the invention reduces the COD of the liquefied gas caustic sludge wastewater to 1000 mg/L.
Description
Technical Field
The invention relates to a method for treating caustic sludge waste liquid, in particular to a method for treating caustic sludge waste liquid generated in the refining process of liquefied gas.
Background
Liquefied gas needs to be desulfurized in the refining process, and generally coking liquefied gas needs to be subjected to two processes of amine elution of hydrogen sulfide and alkali elution of mercaptan. The alkaline washing waste liquid contains free alkali, neutral oil and naphthenic acid with different concentrations, also contains a large amount of sodium sulfide, mercaptan, thioether, miscellaneous phenol and other substances, has the characteristics of deep color, stink smell and strong corrosivity, and is listed in the national records of dangerous goods (the number is HW 35).
At present, the refinery adopts more alkali washing waste liquid treatment methods including concentrated sulfuric acid neutralization, refinery acid wastewater neutralization, high-temperature wet oxidation, calcination for recovering caustic soda or sodium bicarbonate and the like, and also has a unit for professional recovery of alkali slag, and the treatment cost is about 2000 yuan/ton and 5000 yuan/ton. Therefore, the manpower and cost for the liquefied gas caustic sludge treatment are considerable each year. In addition, conventional treatment methods for treating the caustic sludge include an incineration method, a catalytic oxidation method, a wet oxidation method and the like, and the engineering application is limited to a certain extent due to potential adverse factors such as secondary pollution, high equipment investment, high operating cost, large occupied area and the like.
Disclosure of Invention
The invention aims to provide a treatment method for treating liquefied gas caustic sludge waste liquid, which makes up for the defects of the prior art.
The technical scheme of the invention is as follows:
a treatment method of liquefied gas alkali residue waste liquid comprises the following steps:
a) introducing the liquefied gas alkaline residue wastewater into an oil separation tank, wherein the light oil floats upwards and the heavy oil sinks under the action of gravity; removing floating light oil and sinking heavy oil to obtain liquefied gas alkaline residue wastewater after oil removal; wherein, the hydraulic retention time of the liquefied gas alkali residue wastewater in the oil removal tank is 3-4 h, and the descending speed is 0.5-0.8 mm/s;
b) starting a micro-electrolysis reactor (ME) provided with an electrode plate, and introducing the deoiled liquefied gas caustic sludge wastewater into the micro-electrolysis reactor for treatment under the action of electrochemistry to obtain treated wastewater;
the voltage between the effective polar plates in the operating process of the micro-electrolysis reactor is 0.3-1V/cm;
the electrode plates are completely filled with functional materials, the functional materials comprise activated carbon and quartz sand, and the volume ratio of the activated carbon to the quartz sand is 1:1-1: 2;
the hydraulic retention time of the deoiled liquefied gas caustic sludge wastewater in the micro-electrolysis reactor is 4-6 h;
c) diluting the wastewater treated in the step b) to 20000mg/L by using nutrient salt, and adjusting pH to 10-11;
the nutrient salt contains nutrient substances of carbon, nitrogen and phosphorus, and the ratio of carbon, nitrogen and phosphorus is not less than 100:5: 1;
the acid used for adjusting the pH is hydrochloric acid or phosphoric acid;
d) introducing the wastewater adjusted in the step c) into a biochemical reactor, and performing biochemical treatment of halotolerant bacteria to obtain treated wastewater;
the biochemical reactor comprises an anaerobic reactor and an aerobic reactor; introducing the adjusted wastewater in the step c) into an anaerobic reactor, wherein the hydraulic retention time of the anaerobic reactor is 7d, the microorganisms of the anaerobic reactor are halotolerant bacteria, and the added biological sludge amount is 4-6 kg/m3(ii) a The effluent of the anaerobic reactor is introduced into an aerobic reactor, the hydraulic retention time of the aerobic reactor is 4 d, and the amount of the added biological mud is 2-3 kg/m3(ii) a The aerobic reactors are at least two-stage connected in series, the pH of the waste water in the last stage aerobic reactor is controlled at 7-8, the temperature is 25-30 ℃, the dissolved oxygen is controlled at 2-4mg/L, and the alkalinity of the outlet water is CaCO3More than 150 mg/L;
the water quality of the effluent after the liquefied gas caustic sludge wastewater treatment reaches: COD is less than 1000mg/L, pH is 6-9, and the sewage directly enters a sewage treatment plant in a chemical industrial park for continuous treatment.
The anaerobic reactor adopts an anaerobic VTBR reactor. The aerobic reactor adopts an aerobic VTBR reactor.
And part of the effluent of the aerobic VTBR flows back to the anaerobic VTBR.
The invention has the beneficial effects that: the main process of the invention adopts a micro-electrolysis reactor (ME) and a bioreactor (VTBR), which is called MEBR processing technology for short. The operation of the invention is carried out under normal pressure and normal temperature, the process is simple, and the operation cost is lower; the reactors are all closed tank bodies, so that secondary odor pollution can not be caused, and anaerobic gas is thoroughly oxidized in an aerobic process; the microbial bioreactor VTBR does not produce sludge and does not produce secondary pollution; the whole equipment is compact, the occupied area is small, and integrated skid-mounted equipment can be realized.
Detailed Description
Example 1
A treatment method of liquefied gas alkali residue waste liquid comprises the following steps:
a) introducing the liquefied gas alkaline residue wastewater into an oil separation tank, wherein the light oil floats upwards and the heavy oil sinks under the action of gravity; removing floating light oil and sinking heavy oil to obtain liquefied gas alkaline residue wastewater after oil removal; wherein the hydraulic retention time of the liquefied gas alkali residue wastewater in the oil removal tank is 3 h, and the descending speed is 0.5 mm/s;
b) starting a micro-electrolysis reactor (ME) provided with an electrode plate, and introducing the deoiled liquefied gas caustic sludge wastewater into the micro-electrolysis reactor for treatment under the action of electrochemistry to obtain treated wastewater;
the voltage between effective polar plates in the operating process of the micro-electrolysis reactor is 0.3V;
the electrode plates are completely filled with functional materials, the functional materials comprise activated carbon and quartz sand, and the volume ratio of the activated carbon to the quartz sand is 1: 1;
the hydraulic retention time of the deoiled liquefied gas caustic sludge wastewater in the micro-electrolysis reactor is 4 h;
c) diluting the wastewater treated in the step b) to 20000mg/L by using nutrient salt, and adjusting pH to 10;
the nutrient salt contains nutrient substances of carbon, nitrogen and phosphorus, and the ratio of carbon, nitrogen and phosphorus is not less than 100:5: 1;
the acid used for adjusting the pH is hydrochloric acid or phosphoric acid;
d) introducing the wastewater adjusted in the step c) into a biochemical reactor, and performing biochemical treatment of halotolerant bacteria to obtain treated wastewater;
the biochemical reactor comprises an anaerobic reactor and an aerobic reactor; introducing the adjusted wastewater in the step c) into an anaerobic reactor, wherein the hydraulic retention time of the anaerobic reactor is 7d, the microorganisms of the anaerobic reactor are halotolerant bacteria, and the added biological sludge amount is 4 kg/m3(ii) a The effluent of the anaerobic reactor is introduced into an aerobic reactor, the hydraulic retention time of the aerobic reactor is 4 d, and the amount of added biological mud is 2 kg/m3(ii) a The aerobic reactors are at least two-stage series connection, the pH value of the waste water in the last stage aerobic reactor is controlled at 7, the temperature is 25 ℃, the dissolved oxygen is controlled at 2mg/L, and the alkalinity of the outlet water is CaCO3More than 150 mg/L;
the water quality of the effluent after the liquefied gas caustic sludge wastewater treatment reaches: COD is less than 1000mg/L, pH is 6, and the sewage treatment plant directly goes on to continue processing in the chemical industry park.
The anaerobic reactor adopts an anaerobic VTBR reactor. The aerobic reactor adopts an aerobic VTBR reactor.
And part of the effluent of the aerobic VTBR flows back to the anaerobic VTBR.
Example 2
A treatment method of liquefied gas alkali residue waste liquid comprises the following steps:
a) introducing the liquefied gas alkaline residue wastewater into an oil separation tank, wherein the light oil floats upwards and the heavy oil sinks under the action of gravity; removing floating light oil and sinking heavy oil to obtain liquefied gas alkaline residue wastewater after oil removal; wherein the hydraulic retention time of the liquefied gas alkali residue wastewater in the oil removal tank is 4 h, and the descending speed is 0.8 mm/s;
b) starting a micro-electrolysis reactor (ME) provided with an electrode plate, and introducing the deoiled liquefied gas caustic sludge wastewater into the micro-electrolysis reactor for treatment under the action of electrochemistry to obtain treated wastewater;
the voltage between effective polar plates in the operating process of the micro-electrolysis reactor is 1V;
the electrode plates are completely filled with functional materials, the functional materials comprise activated carbon and quartz sand, and the volume ratio of the activated carbon to the quartz sand is 1: 2;
the hydraulic retention time of the deoiled liquefied gas caustic sludge wastewater in the micro-electrolysis reactor is 6 h;
c) diluting the wastewater treated in the step b) to 20000mg/L by using nutrient salt, and adjusting the pH to 11;
the nutrient salt contains nutrient substances of carbon, nitrogen and phosphorus, and the ratio of carbon, nitrogen and phosphorus is not less than 100:5: 1;
the acid used for adjusting the pH is hydrochloric acid or phosphoric acid;
d) introducing the wastewater adjusted in the step c) into a biochemical reactor, and performing biochemical treatment of halotolerant bacteria to obtain treated wastewater;
the biochemical reactor comprises an anaerobic reactorA reactor and an aerobic reactor; introducing the adjusted wastewater in the step c) into an anaerobic reactor, wherein the hydraulic retention time of the anaerobic reactor is 7d, the microorganisms of the anaerobic reactor are halotolerant bacteria, and the added biological sludge amount is 6 kg/m3(ii) a The effluent of the anaerobic reactor is introduced into an aerobic reactor, the hydraulic retention time of the aerobic reactor is 4 d, and the amount of the added biological mud is 3 kg/m3(ii) a The aerobic reactors are at least two-stage series connection, the pH value of the waste water in the last stage aerobic reactor is controlled at 8, the temperature is 30 ℃, the dissolved oxygen is controlled at 4mg/L, and the alkalinity of the outlet water is CaCO3More than 150 mg/L;
the water quality of the effluent after the liquefied gas caustic sludge wastewater treatment reaches: COD is less than 1000mg/L, pH is 9, directly go on to the sewage treatment plant in the chemical industry park and continue processing.
The anaerobic reactor adopts an anaerobic VTBR reactor. The aerobic reactor adopts an aerobic VTBR reactor.
And part of the effluent of the aerobic VTBR flows back to the anaerobic VTBR.
Claims (3)
1. The method for treating the liquefied gas alkali residue waste liquid is characterized by comprising the following steps of:
a) introducing the liquefied gas alkaline residue wastewater into an oil separation tank, wherein the light oil floats upwards and the heavy oil sinks under the action of gravity; removing floating light oil and sinking heavy oil to obtain liquefied gas alkaline residue wastewater after oil removal; wherein, the hydraulic retention time of the liquefied gas alkali residue wastewater in the oil removal tank is 3-4 h, and the descending speed is 0.5-0.8 mm/s;
b) starting a micro-electrolysis reactor provided with an electrode plate, and introducing the deoiled liquefied gas caustic sludge wastewater into the micro-electrolysis reactor for treatment under the action of electrochemistry to obtain treated wastewater;
the voltage between the effective polar plates in the operating process of the micro-electrolysis reactor is 0.3-1V;
the electrode plates are completely filled with functional materials, the functional materials comprise activated carbon and quartz sand, and the volume ratio of the activated carbon to the quartz sand is 1:1-1: 2;
the hydraulic retention time of the deoiled liquefied gas caustic sludge wastewater in the micro-electrolysis reactor is 4-6 h;
c) diluting the wastewater treated in the step b) to 20000mg/L by using nutrient salt, and adjusting pH to 10-11;
the nutrient salt contains nutrient substances of carbon, nitrogen and phosphorus, and the ratio of carbon, nitrogen and phosphorus is not less than 100:5: 1;
the acid used for adjusting the pH is hydrochloric acid or phosphoric acid;
d) introducing the wastewater adjusted in the step c) into a biochemical reactor, and performing biochemical treatment of halotolerant bacteria to obtain treated wastewater;
the biochemical reactor comprises an anaerobic reactor and an aerobic reactor; introducing the adjusted wastewater in the step c) into an anaerobic reactor, wherein the hydraulic retention time of the anaerobic reactor is 7d, the microorganisms of the anaerobic reactor are halotolerant bacteria, and the added biological sludge amount is 4-6 kg/m3(ii) a The effluent of the anaerobic reactor is introduced into an aerobic reactor, the hydraulic retention time of the aerobic reactor is 4 d, and the amount of the added biological mud is 2-3 kg/m3(ii) a The aerobic reactors are at least two-stage connected in series, the pH of the waste water in the last stage aerobic reactor is controlled at 7-8, the temperature is 25-30 ℃, the dissolved oxygen is controlled at 2-4mg/L, and the alkalinity of the outlet water is CaCO3More than 150 mg/L;
the water quality of the effluent after the liquefied gas caustic sludge wastewater treatment reaches: COD is less than 1000mg/L, pH is 6-9, and the sewage directly enters a sewage treatment plant in a chemical industrial park for continuous treatment.
2. The method for treating liquefied gas alkali residue waste liquid according to claim 1, wherein the anaerobic reactor is an anaerobic VTBR reactor, and the aerobic reactor is an aerobic VTBR reactor.
3. The method for treating the alkali residue liquid in the liquefied gas as claimed in claim 2, wherein a part of the effluent of the aerobic VTBR reactor is returned to the anaerobic VTBR reactor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172739A (en) * | 2007-11-16 | 2008-05-07 | 天津莱特化工有限公司 | Alkaline residue processing method |
| CN205635275U (en) * | 2016-05-17 | 2016-10-12 | 大连佳尔沃水处理工程技术有限公司 | High -efficient sewage treatment unit of integration |
| CN206538318U (en) * | 2017-03-17 | 2017-10-03 | 大连理工大学环境工程设计研究院有限公司 | A kind of device for handling the high organic wastewater of industrial high salt |
| CN206538321U (en) * | 2017-03-17 | 2017-10-03 | 大连理工大学环境工程设计研究院有限公司 | A kind of light electrolysis biological einforcement method handles Utilization Techniqueof Water Alkali of Oil Refining device |
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- 2018-02-28 CN CN201810167970.9A patent/CN108341551B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172739A (en) * | 2007-11-16 | 2008-05-07 | 天津莱特化工有限公司 | Alkaline residue processing method |
| CN205635275U (en) * | 2016-05-17 | 2016-10-12 | 大连佳尔沃水处理工程技术有限公司 | High -efficient sewage treatment unit of integration |
| CN206538318U (en) * | 2017-03-17 | 2017-10-03 | 大连理工大学环境工程设计研究院有限公司 | A kind of device for handling the high organic wastewater of industrial high salt |
| CN206538321U (en) * | 2017-03-17 | 2017-10-03 | 大连理工大学环境工程设计研究院有限公司 | A kind of light electrolysis biological einforcement method handles Utilization Techniqueof Water Alkali of Oil Refining device |
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