CN108083567A - A kind of sulfur-containing gas exploit sewage water treatment method - Google Patents
A kind of sulfur-containing gas exploit sewage water treatment method Download PDFInfo
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- CN108083567A CN108083567A CN201711367860.9A CN201711367860A CN108083567A CN 108083567 A CN108083567 A CN 108083567A CN 201711367860 A CN201711367860 A CN 201711367860A CN 108083567 A CN108083567 A CN 108083567A
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- water
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- 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
-
- 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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
Abstract
The invention discloses a kind of sulfur-containing gas to exploit sewage water treatment method, comprises the following steps：After being pre-processed from the sulfur-containing gas of raw water tank exploitation sewage, film concentration is carried out into high-pressure membrane upgrading unit, obtains concentrate and permeate, concentration is evaporated to gained concentrate, obtain condensed water, mother liquor, salt slurry, after gained salt slurry centrifugal dehydration, drying product salt；The condensed water of gained removes organic matter and ammonia nitrogen in MBR, then carries out film concentration into low-pressure membrane upgrading unit together with the permeate of gained, obtains concentrated water and fresh water；The concentrated water returns to high-pressure membrane upgrading unit and is further processed, and fresh water reuse is as natural gas extraction industrial water；The mother liquor of gained carries out light electrolysis catalysis oxidation, is then back to raw water tank.Ammonia-nitrogen content is less than 10mg/L in the fresh water of gained after low pressure concentration of the present invention, can realize the zero-emission of natural gas extraction sewage as the supplement water in natural gas purification or production process.
Description
Technical field
The present invention relates to the sewage treatment field in green technology, especially a kind of natural gas extraction sewage disposal technology.
Background technology
Natural gas is a kind of cleaning, efficient, cheap gaseous energy and industrial chemicals, and purposes is very extensive, very much
Field can replace oil and coal resources.The underground storage of natural gas is quite abundant, is the following strategic energy that can be relied on for a long time
One of source.At present, global natural gas exploration and development technology, extensive storaging and transport technology and downstream application technology have developed rapidly, and add
Oil, the finiteness of coal resources contradicted with demand high growth, the high standards of natural environment is with using oil coal
The high pollution of charcoal resource contradicts so that the strategic position of natural gas and effect are more and more significant.
Natural gas extraction sewage, that is, gas water be the water flooding taken out of in gas production process with natural gas from gas well and collection,
The condensation water that unstripped gas is generated by pressure change by separator in gas production process, mainly contains inorganic salts, organic matter, ammonia nitrogen etc..
Due to subterranean oil gas reservoir and rock stratum long-term co-existence, natural gas field water generally all dissolves in or has been mixed into bulk petroleum class, solvable
The components such as property salt, suspended matter.In addition, it often needs to add in the chemistry such as foam discharging agent, corrosion inhibiter, antisludging agent during gas production and collection are defeated
Auxiliary agent so that gas field recovered water composition is more complicated and changeful, and it is organic to show petroleum content height, volatility
The features such as object content is high, suspension content is high and salinity is high.For sulfur Gas Fields, in gas water also containing hydrogen sulfide,
The toxic and harmful gas such as orgainc sulfur compounds, carbon monoxide belong to high-concentration hardly-degradable sulfur-bearing brine waste.
In the prior art, it is mainly the sulfur Gas Fields of " pretreatment+multiple-effect evaporation " for the processing of natural gas extraction sewage
Desalination process, but this technical costs is high, the solid waste generated in processing procedure such as sludge, mother liquor etc. are not dealt with；And
The difficult degradations chemical assistants such as foam discharging agent, corrosion inhibiter, antisludging agent in exploitation sewage are not processed, environment will be polluted after discharge.
The content of the invention
The technical problems to be solved by the invention are to provide the sulfur-containing gas that a kind of waste resource utilizes, realizes zero-emission
Exploit the processing method of sewage.
The technical solution adopted by the present invention to solve the technical problems is：A kind of sulfur-containing gas exploit sewage disposal side
Method comprises the following steps：
(1) will be exploited from the sulfur-containing gas of raw water tank after sewage pre-processed, into high-pressure membrane upgrading unit into
Row film concentrates, and obtains concentrate and permeate, the pressure of the high-pressure membrane upgrading unit is 5.5-6.5MPa；
(2) evaporation element is entered to gained concentrate and is evaporated concentration, obtain condensed water, mother liquor, salt slurry, by gained salt slurry
After centrifugal dehydration, drying product salt；
(3) condensed water obtained by step (2) is removed into organic matter and ammonia nitrogen, then the transmission obtained by with step (1) in MBR
Liquid carries out film concentration into low-pressure membrane upgrading unit together, obtains concentrated water and fresh water, the pressure of the low-pressure membrane upgrading unit is
0.2-0.3MPa；The concentrated water returns to high-pressure membrane upgrading unit and is further processed, and fresh water reuse is produced as natural gas extraction and used
Water；
(4) mother liquor obtained by step (2) is subjected to light electrolysis catalysis oxidation 2-3h, is then back to raw water tank.
Further, DTRO films or RO films can be selected in the high-pressure membrane upgrading unit.
Further, the low-pressure membrane upgrading unit selects RO films.
Further, sodium chloride content >=98% in product salt obtained by step (2), magnesium ion, calcium ion content≤
1.2%.
Further, the pH value of mother liquor is 3-4 during step (4) light electrolysis catalysis oxidation.
Further, step (4) light electrolysis catalysis oxidation selects the iron carbon integration micro-electrolysis materials of ZY -101.
Further, the pretreatment is to add in sodium hydroxide and sodium carbonate, reaction in sulfur-containing gas exploit sewage
Filtering and impurity removing afterwards.
Mother liquor is commonly called as bittern, is that remaining saturation after precipitation or crystal is isolated in chemical precipitation or crystallization process is molten
Liquid.
MBR is also known as membrane bioreactor (Membrane Bio-Reactor), be one kind by activated sludge process and UF membrane
The new water technology that technology is combined.
DTRO films (disc tube reverse osmosis (dt-ro) film) are a kind of reverse osmosis forms, are the films for being specifically used to processing high-concentration sewage
Component, core technology are dish tubular membrane film columns.Reverse osmosis membrane and waterpower flow guiding disc are stacked together, use center pull rod
It is fixed with end plate, then inserts in pressure jacket, just form a film column.
RO films, reverse osmosis also known as reverse osmosis, one kind isolate the UF membrane of solvent using pressure differential as motive force from solution
Operation.Because the direction of it and naturally osmotic is on the contrary, therefore claim reverse osmosis.According to the different osmotic of various materials, so that it may so that
With the reverse osmosis pressure more than osmotic pressure, i.e. hyperfiltration, achieve the purpose that separation, extraction, purifying and concentration.
The beneficial effects of the invention are as follows：A kind of processing method of sulfur-containing gas exploitation sewage of the present invention, passes through high pressure
Concentration, evaporation, film process, low pressure concentration and light electrolysis catalysis oxidation synergistic effect, effectively recycled the salt in sewage
Product, wherein sodium chloride content are up to more than 98%；Volatile organism in evaporating concentration process sewage enters with condensed water
Membrane bioreactor is further processed, and is then rested on without volatile organism in evaporation mother liquor, and micro- electricity is carried out to evaporation mother liquor
Catalysis oxidation is solved, makes in evaporation mother liquor COD removal rates up to more than 60%, returns again to raw water tank with sulphur natural gas extraction sewage together
Processing；Ammonia-nitrogen content is less than 10mg/L in the fresh water of gained after low pressure concentration, can be as in natural gas purification or production process
Water is supplemented, realizes the zero-emission of natural gas extraction sewage；The present invention has applied widely, high treating effect and stabilization, behaviour
Make easy, reusing sewage rate height, operating cost has saved more than 50% compared with multiple-effect evaporation processing system.
Description of the drawings
Fig. 1 is a kind of process flow chart of sulfur-containing gas exploitation sewage water treatment method of the present invention.
Specific embodiment
The present invention is further described with reference to the accompanying drawings and examples.
The experiment that the present invention is carried out：
1st, sulfur-containing gas sewage concentration：
Pretreated sulfur-containing gas sewage is taken, into DTRO systems, control system pressure after high-pressure pump pressurizes
6MPa collects concentrate and permeate respectively, sample presentation analysis detection.It will transmit through liquid and enter the further desalination of low pressure RO systems,
RO fresh water and concentrated water are collected respectively, sample presentation analysis detection.The results are shown in Table 1:
1 film of table concentrates experimental data
| Cl-(g/l) | COD(g/ml) | Ammonia nitrogen (g/ml) | |
| Pretreating sewage | 16.89 | 66 | 36.35 |
| Permeate | 0.614 | 12 | 6.6 |
| Concentrate | 36.78 | 132 | 72.7 |
| RO fresh water | 0.016 | 2 | 1 |
| RO concentrated waters | 2.408 | 43 | 23.8 |
As it can be seen from table 1 sulfur-containing gas sewage, after DTRO concentrations, ammonia nitrogen, COD and salt are enriched in concentration
In liquid, COD and ammonia nitrogen can reach recycle water standard in permeate, but chlorion is exceeded, and DTRO concentrates take off again through low pressure RO
After salt, fresh water can reach recycle water standard.After two-stage film process, COD, ammonia nitrogen and the effective of salt in sewage can be divided
From most COD, ammonia nitrogen and salt are trapped in concentrated water, so as to fulfill the concentration of sewage.
2nd, evaporation analysis salt：
The concentrate after DTRO concentrations is collected, is pumped into vaporising device and carries out concentration analysis salt, fed in evaporation, take out and steam
It feels cold condensate, mother liquor, salt slurry, measures respectively, sampling detection.After salt slurry centrifugal dehydration, drying product salt, after drying
Product salt censorship analysis.The results are shown in Table 2:
2 product salt experimental data of table
As can be seen from Table 2, evaporation gained product salt sodium chloride content is 98.26%, has reached refining industrial salt two level
Standard requirement.
3rd, evaporative condenser water process：
By evaporation condensed water using MBR (membrane bioreactor) come organics removal and ammonia nitrogen, using sewage treatment plant
Sludge is tamed, and gradually increases the ratio of evaporation condensed water, and microorganism is made gradually to adapt to new environmental condition, microbial acclimation
After finishing, evaporation condensed water is continuously added to, periodically sampling detection MBR system water outlet, and by MBR effluent collections.By MBR water outlets into
Enter low pressure RO units (control pressure 0.25MPa) further to purify, mainly separate ammonia nitrogen, RO fresh water and concentrated water are collected respectively,
Sample presentation analysis detection.The results are shown in Table 3,
3 evaporation condensed water advanced treating experimental data of table
Evaporation condensed water COD and ammonia nitrogen after MBR is handled are greatly lowered, and COD can reach recycle-water and emission request, but
Ammonia nitrogen is influenced by removal rate, fails to reach standard requirement.MBR is again after low pressure RO purifications, and COD and ammonia nitrogen are further in fresh water
It reduces, ammonia-nitrogen content is 3.1mg/l in fresh water, can be used as the supplement water in natural gas purification or production process.
A kind of sulfur-containing gas exploit sewage water treatment method, comprise the following steps：
(1) will be exploited from the sulfur-containing gas of raw water tank after sewage pre-processed, into high-pressure membrane upgrading unit into
Row film concentrates, and obtains concentrate and permeate, the pressure of the high-pressure membrane upgrading unit is 5.5-6.5MPa；The high-pressure membrane concentration
DTRO films or RO films can be selected in unit.
(2) evaporation element is entered to gained concentrate and is evaporated concentration, obtain condensed water, mother liquor, salt slurry, by gained salt slurry
After centrifugal dehydration, drying product salt；Sodium chloride content >=98% in product salt obtained by step (2), magnesium ion, calcium ion contain
Amount≤1.2%.Product salt after saturated brine washs flotation meets the requirement of refining industrial salt top grade product standard.
(3) condensed water obtained by step (2) is removed into organic matter and ammonia nitrogen, then the transmission obtained by with step (1) in MBR
Liquid carries out film concentration into low-pressure membrane upgrading unit together, obtains the concentrated water containing ammonia nitrogen in high density and organic matter and removes organic matter
With the fresh water of ammonia nitrogen, the pressure of the low-pressure membrane upgrading unit is 0.2-0.3MPa；The concentrated water returns to high-pressure membrane upgrading unit
It is further processed, fresh water reuse is as natural gas extraction industrial water；
(4) mother liquor obtained by step (2) is subjected to light electrolysis catalysis oxidation 2-3h, is then back to raw water tank.Light electrolysis is urged
The pH value of mother liquor is 3-4 when changing oxidation.After mother liquor reacts 2-3h under conditions of through pH value for 3-4, COD removal rates reach 60%
More than, Mother liquor COD is handled close to the COD of natural gas extraction sewage, therefore returns to raw water tank to destroy the processing of system
Balance, i.e., will not cause system fluctuation and influence treatment effect, be dropped if difficult to foam discharging agent, corrosion inhibiter, antisludging agent in mother liquor etc.
Solution chemical assistant will would seriously pollute the environment without processing directly discharge, be carried out subsequently if evaporation mother liquor is introduced directly into raw water tank
Processing so that the organic matter enrichment of difficult degradation in system seriously affects the treatment effect of processing system, and then influences recycle-water
Quality.
4 embodiment 1-3 sulfur-containing gas of table exploit the water quality index of sewage
Embodiment 1：
As shown in Figure 1, exploiting sewage as raw water using main component sulfur-containing gas as shown in table 4, NaOH is added in
And Na2CO3The solid wastes such as deliming, magnesium are gone, adjust pH to 11.23, enter DTRO systems with high-pressure pump control pressure 6MPa pressurizations,
DTRO permeate enters back into the further desalination of low pressure RO systems, and the collection of DTRO concentrates is spare, is pumped into 500L vaporising devices
The DTRO concentrates of 400L, vacuum evaporation, 45 DEG C of boiling point of control or more, collect condensed water, when concentration material liquid volume concentration
For 90L when, 90L concentrations feed liquid is transferred to 100L vaporising devices and continues vacuum evaporation, control 45 DEG C of boiling point or more, concentration is straight
To salt crystallization is precipitated, salt slurry is dehydrated into obtain product salt.It is 3 to evaporate mother liquor to adjust pH value, anti-using light electrolysis catalysis oxidation
More than 2h is answered, after removing most of organic matter, returns to sewage raw water tank.Evaporation condensed water enters MBR removal COD and ammonia nitrogen.MBR
Water outlet is into low pressure RO upgrading units, control pressure 0.2MPa, further removes COD and ammonia nitrogen, low pressure RO upgrading units it is light
Water water quality parameter and product salt parameter are as shown in table 5, and concentrated water backs into high pressure DTRO upgrading units and is further processed.
Embodiment 2：
As shown in Figure 1, exploiting sewage as raw water using main component sulfur-containing gas as shown in table 4, NaOH is added in
And Na2CO3The solid wastes such as deliming, magnesium are gone, adjust pH to 11.35, enter DTRO systems with high-pressure pump control pressure 6MPa pressurizations,
DTRO permeate enters back into the further desalination of low pressure RO systems, and the collection of DTRO concentrates is spare, is pumped into 500L vaporising devices
350LDTRO concentrates, vacuum evaporation, 85 DEG C of boiling point of control or more, collect condensed water, when concentration material liquid volume concentration is
During 90L, 90L concentrations feed liquid is transferred to 100L vaporising devices and continues vacuum evaporation, control 85 DEG C of boiling point or more, concentration until
Salt crystallization is precipitated, salt slurry is dehydrated.It is 4 to evaporate mother liquor to adjust pH value, using more than light electrolysis catalytic oxidation 2h, is gone
After most of organic matter, sewage raw water tank is returned.Evaporation condensed water enters MBR removal COD and ammonia nitrogen.MBR water outlets are into low pressure
RO systems, control pressure 0.2MPa further remove COD and ammonia nitrogen, the fresh water water quality parameter and salt of low pressure RO upgrading units
Product parameters are as shown in table 5, and concentrated water backs into high pressure DTRO upgrading units and is further processed.
Embodiment 3：
As shown in Figure 1, exploiting sewage as raw water using main component sulfur-containing gas as shown in table 4, NaOH is added in
And Na2CO3The solid wastes such as deliming, magnesium are gone, adjust pH to 11.23, enter DTRO systems with high-pressure pump control pressure 7MPa pressurizations,
DTRO permeate enters back into the further desalination of low pressure RO systems, and the collection of DTRO concentrates is spare, is pumped into 500L vaporising devices
350LDTRO concentrates, vacuum evaporation, 45 DEG C of boiling point of control or more, collect condensed water, when concentration material liquid volume concentration is
During 90L, 90L concentrations feed liquid is transferred to 100L vaporising devices and continues vacuum evaporation, control 45 DEG C of boiling point or more, concentration until
Salt crystallization is precipitated, salt slurry is dehydrated into obtain product salt.It is 3 to evaporate mother liquor to adjust pH value, using light electrolysis catalytic oxidation
More than 2h after removing most of organic matter, returns to sewage raw water tank.Evaporation condensed water enters MBR removal COD and ammonia nitrogen.MBR goes out
Water further removes COD and ammonia nitrogen, the fresh water water quality of low pressure RO upgrading units into low pressure RO systems, control pressure 0.2MPa
Parameter and product salt parameter are as shown in table 5, and concentrated water backs into high pressure DTRO upgrading units and is further processed.
5 embodiment 1-3 sulfur-containing gas of table exploitation sewage treated ingredient
Claims (7)
1. a kind of sulfur-containing gas exploit sewage water treatment method, it is characterised in that：Comprise the following steps：
(1) after being pre-processed from the sulfur-containing gas of raw water tank exploitation sewage, film is carried out into high-pressure membrane upgrading unit
Concentration obtains concentrate and permeate, and the pressure of the high-pressure membrane upgrading unit is 5.5-6.5MPa；
(2) evaporation element is entered to gained concentrate and is evaporated concentration, obtain condensed water, mother liquor, salt slurry, gained salt slurry is centrifuged
After dehydration, drying product salt；
(3) condensed water obtained by step (2) is removed into organic matter and ammonia nitrogen, then the permeate one obtained by with step (1) in MBR
It rises into low-pressure membrane upgrading unit and carries out film concentration, obtain concentrated water and fresh water, the pressure of the low-pressure membrane upgrading unit is 0.2-
0.3MPa；The concentrated water returns to high-pressure membrane upgrading unit and is further processed, and fresh water reuse is as natural gas extraction industrial water；
(4) mother liquor obtained by step (2) is subjected to light electrolysis catalysis oxidation 2-3h, is then back to raw water tank.
2. a kind of sulfur-containing gas exploitation sewage water treatment method according to claim 1, it is characterised in that：The high-pressure membrane
DTRO films or RO films can be selected in upgrading unit.
3. a kind of sulfur-containing gas exploitation sewage water treatment method according to claim 1, it is characterised in that：The low-pressure membrane
Upgrading unit selects RO films.
4. a kind of sulfur-containing gas exploitation sewage water treatment method according to claim 1, it is characterised in that：Step (2) institute
Obtain sodium chloride content >=98% in product salt, magnesium ion, calcium ion content≤1.2%.
5. a kind of sulfur-containing gas exploitation sewage water treatment method according to claim 1, it is characterised in that：Step (4) is micro-
The pH value of mother liquor is 3-4 during catalytic and oxidative electrolysis technology.
6. a kind of sulfur-containing gas exploitation sewage water treatment method according to claim 1 or 5, it is characterised in that：Step (4)
Light electrolysis catalysis oxidation selects the iron carbon integration micro-electrolysis materials of ZY -101.
7. a kind of sulfur-containing gas exploitation sewage water treatment method according to claim 1, it is characterised in that：The pretreatment
To add in sodium hydroxide and sodium carbonate, filtering and impurity removing after reaction in sulfur-containing gas exploitation sewage.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110028201A (en) * | 2019-05-08 | 2019-07-19 | 杭州齐创环境工程有限公司 | A kind of waste emulsified mixture resource utilization processing system and technique |
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| CN205856230U (en) * | 2016-06-12 | 2017-01-04 | 双良节能系统股份有限公司 | A kind of system reclaiming sodium chloride from high slat-containing wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014164255A1 (en) * | 2013-03-13 | 2014-10-09 | Massachusetts Institute Of Technology | Multi-stage membrane distillation process |
| CN204224377U (en) * | 2014-11-19 | 2015-03-25 | 大连善水德环保科技有限公司 | Desulphurization denitration high-salt wastewater reclamation set |
| CN104891723A (en) * | 2015-05-25 | 2015-09-09 | 自贡市轻工业设计研究院有限责任公司 | Treatment method of high-salt content, high-ammonia nitrogen content and high-COD (Chemical Oxygen Demand) gas field water |
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| CN110028201A (en) * | 2019-05-08 | 2019-07-19 | 杭州齐创环境工程有限公司 | A kind of waste emulsified mixture resource utilization processing system and technique |
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