CN107285505A - A kind of oil gas field wastewater with high concentration of sulfide reduces standard discharge method - Google Patents
A kind of oil gas field wastewater with high concentration of sulfide reduces standard discharge method Download PDFInfo
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- CN107285505A CN107285505A CN201610219488.6A CN201610219488A CN107285505A CN 107285505 A CN107285505 A CN 107285505A CN 201610219488 A CN201610219488 A CN 201610219488A CN 107285505 A CN107285505 A CN 107285505A
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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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- 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
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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
- C02F1/44—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
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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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Abstract
Standard discharge method is reduced the present invention relates to a kind of oil gas field wastewater with high concentration of sulfide.This method uses negative pressure desulfurization+chemical catalytic oxidation+flocculating setting+organic membrane filter+catalytic ozonation+high pressure reverse osmosis technology, the purpose of sulfide in oil gas field wastewater with high concentration of sulfide, suspension, organic matter, chloride and oily deep removal can be achieved, high pressure reverse osmosis concentrated water sulfur content, suspension content and the oil content finally given meets oil gas field re-injection water quality standard, and high pressure reverse osmosis produced water meets qualified discharge standard.
Description
Technical field
The present invention relates to field of industrial waste water treatment, specifically a kind of oil gas field wastewater with high concentration of sulfide
Reduce standard discharge method.Espespecially using negative pressure desulfurization+chemical catalytic oxidation+flocculating setting+
The high sulfur-bearing of organic membrane filter+catalytic ozonation+high pressure reverse osmosis technology processing oil gas field gives up
Water reduces standard discharge method.
Background technology
With socio-economic development and the continuous improvement of living standards of the people, to demand for energy day
Increasingly big, exploitation of oil-gas field amount increases year by year.In the exploitation of oil gas field, particularly in gas field
The middle and later periods of exploitation, because stratum water can invade gas reservoir along tomography and structural fracture, into shaft bottom,
Increase gas reservoir energy loss, well head pressure reduction, band outlet capacity is deteriorated, and causes the gas well underproduction
Or water logging stops production, to maintain the steady production of natural gas, water drainage-gas recovery technology is carried out in gas field energetically,
So that the aquifer yield of gas well increases sharply, many gas wells are forced to close because extracted waste water can not be handled
Well, have impact on normal gas production production.
Oil gas field extracted waste water to oil gas field production while problem is caused, caused society
Problem also appears undoubtedly, huge pressure, especially mining area of southwest China is caused to natural environment high
The a large amount of extracted waste waters produced in Oil ＆ gas field in sulfur recovery process, this strand of waste water contains a large amount of vulcanizations
Hydrogen and sulfide, belong to sulfur-containing waste water.If cannot effectively handle, environment can not only be produced
Raw severe contamination, can also produce heavy corrosion to waterline, there is severe compromise.
For the processing of oil gas field extracted waste water, mainly have at present reinjection into reservoir, comprehensive utilization and
Handle three kinds of modes of standard discharge.For existing handling process, presently mainly fitted
Re-injection after degree processing, is rarely reported in terms of standard discharge.According to the reinjection standard that China is existing,
For oil gas field wastewater with high concentration of sulfide, main processing target be water removal in hydrogen sulfide,
Sulfide and suspension.
The content of the invention
For defect present in prior art, it is an object of the invention to provide a kind of oil gas field
Wastewater with high concentration of sulfide reduces standard discharge method, using negative pressure desulfurization+chemical catalytic oxidation+flocculation
Sedimentation+organic membrane filter+catalytic ozonation+high pressure reverse osmosis technology, can effectively remove waste water
In sulfide, suspension, organic matter, chloride and oil, solve oil gas field wastewater with high concentration of sulfide
In re-injection process the problem of sulfur content, suspension content and too high oil content, effectively reduce useless
Water re-injection amount, realizes the standard discharge of oil gas field wastewater with high concentration of sulfide.
To achieve the above objectives, the present invention is adopted the technical scheme that：
A kind of oil gas field wastewater with high concentration of sulfide reduces standard discharge method, it is characterised in that：Including
Following steps：Using the sulfide in oil gas field wastewater with high concentration of sulfide in acid condition waste water with sulphur
Change the characteristic that hydrogen form is present, the first step, using negative pressure desulfurization technology by the major part in waste water
Hydrogen sulfide stripping comes out centralized burning；Second step, is taken off negative pressure using chemical catalytic oxidation technology
Remaining Oxidation of Hydrogen Sulfide in sulphur water outlet；3rd step, it is heavy that catalytic oxidation desulfurization water outlet carries out flocculation
Drop；4th step, flocculating setting water outlet enters organic membrane filter unit and carries out organic membrane filter；The
Five steps, organic membrane filter water outlet carries out catalytic ozonation processing；6th step, ozone catalytic oxygen
Dissolve water and carry out separation concentration into high pressure reverse osmosis units；High pressure reverse osmosis concentrated water carries out re-injection
Processing, high pressure reverse osmosis produced water qualified discharge.
On the basis of above-mentioned technical proposal, following steps are specifically included：
Step 1, wastewater with high concentration of sulfide is after first time pH regulations, into negative pressure desulfurization unit
Carry out desulfurization；The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal；
Step 2, negative pressure desulfurization water outlet is after second of pH regulation, into chemical catalysis oxygen
Change unit and carry out treating technology desulfurization；
Step 3, catalytic oxidation desulfurization water outlet is heavy into flocculation after third time pH regulations
Drop unit and carry out flocculating setting；Outward transport processing is concentrated after flocculating setting slag class is cured；
Step 4, flocculating setting water outlet enters organic membrane filter unit progress organic membrane filter；
Step 5, organic membrane filter water outlet enters ozone catalytic oxidation unit progress ozone catalytic oxygen
Change is handled；
Step 6, catalytic ozonation water outlet enters the progress separation concentration of high pressure reverse osmosis units；
High pressure reverse osmosis concentrated water carries out reinjection technology, high pressure reverse osmosis produced water qualified discharge.
On the basis of above-mentioned technical proposal, the main water quality of the oil gas field wastewater with high concentration of sulfide is special
Levy for：2000~20000mg/L of sulfide, 10000~50000mg/L of total dissolved solid,
500~5000mg/L of suspension, 0~100mg/L of oil content, total hardness (CaCO3Meter)
1000~1600mg/L, Na+5000~15000mg/L, Cl-6000~20000mg/L,
SO4 2-800~1500mg/L of 1000~2000mg/L, COD.
On the basis of above-mentioned technical proposal, through step 1~6 processing after the high sulfur-bearing of oil gas field
Waste water, high pressure reverse osmosis concentrated water sulfur content<0.5mg/L, oil content ＜ 5mg/L, suspension ＜
1mg/L, meets oil gas field re-injection water quality standard, reverse osmosis produced water COD ＜ 100mg/L, Cl-
＜ 300mg/L, meet discharge standard.
On the basis of above-mentioned technical proposal, the negative pressure desulfurization unit sets circulating pump to be given up
Water circulation, reflux ratio is 2~5:1.
On the basis of above-mentioned technical proposal, in step 1, first time pH regulations tune used
Section agent is one kind in hydrochloric acid, sulfuric acid or nitric acid；
Wastewater with high concentration of sulfide is after first time pH regulations, and pH scopes are 4~6.
On the basis of above-mentioned technical proposal, in step 2, second of pH regulation tune used
Section agent is one kind in hydrochloric acid, sulfuric acid or nitric acid；
Negative pressure desulfurization water outlet is after second of pH regulation, and pH scopes are 3~4.
On the basis of above-mentioned technical proposal, in step 3, third time pH regulations tune used
Section agent is sodium hydroxide；
Catalytic oxidation desulfurization water outlet is after third time pH regulations, and pH scopes are 8~9.
On the basis of above-mentioned technical proposal, in step 1, the waste water of negative pressure desulfurization unit is stopped
Time is 20~30min；
The inflow temperature of negative pressure desulfurization unit is 35~45 DEG C, and operation negative pressure is
- 0.04~-0.07MPa.
On the basis of above-mentioned technical proposal, in step 2, the treating technology desulfurization is
It is sulfate ion by sulphion catalysis oxidation；
The oxidant of the chemical catalytic oxidation unit is hydrogen peroxide, and catalyst is ferrous sulfate；
Oxidizer is 100~300mg/L, and catalyst amount is 40~120mg/L.
On the basis of above-mentioned technical proposal, in step 3, the flocculation aid of flocculating setting unit is
Anion-polyacrylamide, molecular weight 5,000,000~8,000,000；
The flocculation aid consumption of flocculating setting unit is 2-5mg/L；
The flocculating setting time is 10~20min.
On the basis of above-mentioned technical proposal, in step 4, the filtering shape of organic membrane filter unit
Formula filters for Ge Er；
The membrane material of organic membrane filter unit is polytetrafluoroethylene (PTFE), 0.1~0.25 μm of membrane aperture；
The membrane flux of organic membrane filter unit is controlled in 300~500L/m2·h。
On the basis of above-mentioned technical proposal, in step 5, the ozone catalytic oxidation unit
Service condition is：Inlet flow-patterm 6~9,15~45 DEG C of inflow temperature is 1~3h of the residence time, smelly
10~50mg/L of oxygen concentration.
On the basis of above-mentioned technical proposal, in step 6, the high pressure reverse osmosis units are used
Disc tube reverse osmosis (dt-ro) membrane module, membrane module form is that multiple disc-type diaphragms are connected on a center
Disc-type film post is constituted on pipe；
The service condition of high pressure reverse osmosis units is：Operating pressure is 9~12MPa, inlet flow-patterm
6~9,15~45 DEG C of inflow temperature.
Oil gas field wastewater with high concentration of sulfide of the present invention reduces standard discharge method, de- using negative pressure
Sulphur+chemical catalytic oxidation+flocculating setting+organic membrane filter+catalytic ozonation+high pressure reverse osmosis
Saturating technology, can effectively remove sulfide, suspension, organic matter, chloride and the oil in waste water,
Solve sulfur content, suspension content and oil content mistake in oil gas field wastewater with high concentration of sulfide re-injection process
High the problem of, and waste water reinjection amount is effectively reduced, realize the up to standard outer of oil gas field wastewater with high concentration of sulfide
Row.
Brief description of the drawings
The present invention has drawings described below：
The process chart of Fig. 1 present invention.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing.
As shown in figure 1, oil gas field wastewater with high concentration of sulfide of the present invention reduces standard discharge side
Method, using the sulfide in oil gas field wastewater with high concentration of sulfide in acid condition waste water with hydrogen sulfide shape
The characteristic that formula is present, the first step, using negative pressure desulfurization technology by most of hydrogen sulfide in waste water
Removing comes out centralized burning；Second step, using chemical catalytic oxidation technology by negative pressure desulfurization water outlet
In remaining Oxidation of Hydrogen Sulfide；3rd step, catalytic oxidation desulfurization water outlet carries out flocculating setting；The
Four steps, flocculating setting water outlet enters organic membrane filter unit and carries out organic membrane filter；5th step,
Organic membrane filter water outlet carries out catalytic ozonation processing；6th step, catalytic ozonation water outlet
Separation concentration is carried out into high pressure reverse osmosis units；High pressure reverse osmosis concentrated water carries out reinjection technology,
High pressure reverse osmosis produced water qualified discharge.
Specifically include following steps：
Step 1, oil gas field wastewater with high concentration of sulfide is de- into negative pressure after first time pH regulations
Sulphur unit carries out desulfurization；The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal；
Step 2, negative pressure desulfurization water outlet is after second of pH regulation, into chemical catalysis oxygen
Change unit and carry out treating technology desulfurization；
Step 3, catalytic oxidation desulfurization water outlet is heavy into flocculation after third time pH regulations
Drop unit and carry out flocculating setting；Outward transport processing is concentrated after flocculating setting slag class is cured；
Step 4, flocculating setting water outlet enters organic membrane filter unit progress organic membrane filter；
Step 5, organic membrane filter water outlet enters ozone catalytic oxidation unit progress ozone catalytic oxygen
Change is handled；
Step 6, catalytic ozonation water outlet enters the progress separation concentration of high pressure reverse osmosis units,
High pressure reverse osmosis concentrated water carries out reinjection technology, high pressure reverse osmosis produced water qualified discharge.
On the basis of above-mentioned technical proposal, (oil gas field is high for wastewater with high concentration of sulfide described in step 1
Sulfur-containing waste water) main water quality characteristic be：2000~20000mg/L of sulfide, total dissolubility
10000~50000mg/L of solid, 500~5000mg/L of suspension, 0~100mg/L of oil content,
Total hardness (CaCO3Meter) 1000~1600mg/L, Na+5000~15000mg/L, Cl-
6000~20000mg/L, SO4 2-800~1500mg/L of 1000~2000mg/L, COD.
On the basis of above-mentioned technical proposal, through step 1~6 processing after the high sulfur-bearing of oil gas field
Waste water, high pressure reverse osmosis concentrated water sulfur content<0.5mg/L, oil content ＜ 5mg/L, suspension ＜
1mg/L, meets oil gas field re-injection water quality standard, high pressure reverse osmosis produced water COD ＜ 100mg/L,
Cl-＜ 300mg/L, meet discharge standard.
On the basis of above-mentioned technical proposal, the negative pressure desulfurization unit sets circulating pump to be given up
Water circulation, reflux ratio is 2~5:1.
On the basis of above-mentioned technical proposal, in step 1, first time pH regulations tune used
Section agent is one kind in hydrochloric acid, sulfuric acid or nitric acid；
Wastewater with high concentration of sulfide is after first time pH regulations, and pH scopes are 4~6.
On the basis of above-mentioned technical proposal, in step 2, second of pH regulation tune used
Section agent is one kind in hydrochloric acid, sulfuric acid or nitric acid；
Negative pressure desulfurization water outlet is after second of pH regulation, and pH scopes are 3~4.
On the basis of above-mentioned technical proposal, in step 3, third time pH regulations tune used
Section agent is sodium hydroxide；
Catalytic oxidation desulfurization water outlet is after third time pH regulations, and pH scopes are 8~9.
On the basis of above-mentioned technical proposal, in step 1, the waste water of negative pressure desulfurization unit is stopped
Time is 20~30min；
The inflow temperature of negative pressure desulfurization unit is 35~45 DEG C, and operation negative pressure is
- 0.04~-0.07MPa.
On the basis of above-mentioned technical proposal, in step 2, the treating technology desulfurization is
It is sulfate ion by sulphion catalysis oxidation；
The oxidant of the chemical catalytic oxidation unit is hydrogen peroxide, and catalyst is ferrous sulfate；
Oxidizer is 100~300mg/L, and catalyst amount is 40~120mg/L.
On the basis of above-mentioned technical proposal, in step 3, the flocculation aid of flocculating setting unit is
Anion-polyacrylamide, molecular weight 5,000,000~8,000,000；
The flocculation aid consumption of flocculating setting unit is 2-5mg/L；
The flocculating setting time is 10~20min.
On the basis of above-mentioned technical proposal, in step 4, the filtering shape of organic membrane filter unit
Formula filters for Ge Er；
The membrane material of organic membrane filter unit is polytetrafluoroethylene (PTFE), 0.1~0.25 μm of membrane aperture；
The membrane flux of organic membrane filter unit is controlled in 300~500L/m2·h。
On the basis of above-mentioned technical proposal, in step 5, the ozone catalytic oxidation unit
Service condition is：Inlet flow-patterm 6~9,15~45 DEG C of inflow temperature is 1~3h of the residence time, smelly
10~50mg/L of oxygen concentration.
On the basis of above-mentioned technical proposal, in step 6, the high pressure reverse osmosis units are used
Disc tube reverse osmosis (dt-ro) membrane module, membrane module form is that multiple disc-type diaphragms are connected on a center
Disc-type film post is constituted on pipe；
The service condition of high pressure reverse osmosis units is：Operating pressure is 9~12MPa, inlet flow-patterm
6~9,15~45 DEG C of inflow temperature.
The essential distinction of the present invention and prior art are：Technology for prior art lacks
Fall into, present invention use negative pressure desulfurization+chemical catalytic oxidation+flocculating setting+organic membrane filter+smelly
Oxygen catalysis oxidation+high pressure reverse osmosis technology processing oil gas field wastewater with high concentration of sulfide.By using the skill
Art, realizes the efficient, quick, inexpensive of oil gas field wastewater with high concentration of sulfide and reduces at standard discharge
Reason.Compared to the prior art, technical equipment of the present invention is simple, operation maintenance is easy,
Strong environmental adaptability, desulfuration efficiency are high, skid processing, operating cost can be achieved drops significantly
Low, Technical Economy is good.For oil gas field wastewater with high concentration of sulfide, it is of the present invention reduce it is up to standard
Outer row's treatment technology is more economical, reasonable, feasible.Its advantage is：
1st, present invention use negative pressure desulfurization technical finesse oil gas field wastewater with high concentration of sulfide, and stripping,
Stripping Desulfuration technology is compared, and technical equipment of the present invention is simple, automaticity is high, fortune
Row safeguards that easy, strong environmental adaptability, floor space are few, and desulfuration efficiency is high, sled can be achieved
Dressization processing, operating cost are substantially reduced, and the negative pressure desulfurization technology that the present invention is used is especially suitable
Wastewater with high concentration of sulfide processing in place and auxiliary facility imperfection area；
2nd, negative pressure desulfurization unit of the invention carries out waste water circulation by using circulating pump, accelerates
Hydrogen sulfide in wastewater with high concentration of sulfide overflows, and shortens waste water desulfurization time, improves desulfurized effect；
3rd, negative pressure desulfurization unit of the invention is by the matching between negative pressure and wastewater pH,
While reducing waste water desulphurization cost, the hydrogen sulfide eliminated in waste water of maximal efficiency；
4th, colloid of the chemical catalytic oxidation unit due to generating molysite in the present invention, therefore nothing
Flocculant need to be added, only need to add a small amount of flocculation aid achieves that flocculating setting；
5th, the efficient coupling of the invention by negative pressure desulfurization technology and chemical catalytic oxidation technology,
On the basis of most of sulphion during waste water is removed using negative pressure desulfurization technology, useization again
Learn catalytic oxidation technologies depth and remove a small amount of sulphion remained in waste water so that the sulphur in waste water
Ion concentration is preferably minimized, and reduces simple reagent consumption and waste residue using needed for chemical oxidation
Amount, operating cost is substantially reduced；
6th, the present invention handles the advantage of high suspended matter content waste water using gore film, by using
Ge Er organic membrane filters, solve the filtration problem of the high oil gas field waste water of suspension content, gram
The limitation of organic film process oil gas field high suspended matter content waste water is taken；
7th, the present invention handles the oil gas field waste water of high suspended matter content by using gore film, keeps away
Exempt from the high flow rate operational mode using other forms membrane filtration, reduce operating cost, and
Membrane flux is high, and the cycle of operation is long；
8th, the present invention removes the organic matter in waste water using catalytic ozonation, extends follow-up
The cleaning frequency of membranous system, it is ensured that the operation steady in a long-term of follow-up membranous system；
9th, the present invention uses high pressure counter-infiltration, realizes the depth concentration of oil gas field hc effluent,
The re-injection amount of oil gas field waste water is reduced to greatest extent；
10th, reducing at standard discharge using method progress oil gas field wastewater with high concentration of sulfide of the invention
Reason, solve the problems, such as oil gas field high oil-containing wastewater reduces standard discharge.
It is some specific embodiments below.
Embodiment 1
The main water quality characteristic of oil gas field wastewater with high concentration of sulfide is：Sulfide 2000mg/L, always
Soluble solid 10000mg/L, suspension 500mg/L, oil content 0mg/L are total hard
Spend (CaCO3Meter) 1000mg/L, Na+5000mg/L, Cl-6000mg/L, SO4 2-1000
Mg/L, COD 800mg/L.
Process step is as follows：
The first step, wastewater with high concentration of sulfide adjusts the pH to 6 of waste water using sulfuric acid for the first time, afterwards
Desulfurization is carried out into negative pressure desulfurization unit, the operating condition of negative pressure desulfurization is：Inflow temperature
35 DEG C, negative pressure -0.04MPa, retention time of sewage 20min are run, the reflux ratio of circulating pump is
5:1；
Second step, negative pressure desulfurization water outlet adjusts the pH to 3 of waste water using sulfuric acid for the second time, it
Enter chemical catalytic oxidation unit afterwards and carry out treating technology desulfurization, oxidant is dioxygen
Water, consumption is 100mg/L, and catalyst is ferrous sulfate, and consumption is 40mg/L；
3rd step, catalytic oxidation desulfurization water outlet adjusts the pH of waste water using sodium hydroxide third time
To 8, flocculating setting unit is entered afterwards and carries out flocculating setting, flocculation aid is anionic poly- third
Acrylamide, molecular weight 5,000,000, flocculation aid consumption is 2mg/L, and the flocculating setting time is
10min；
4th step, flocculating setting unit water outlet enters organic membrane filter unit and carries out Ge Er mistakes
Filter, organic film material is polytetrafluoroethylene (PTFE), and membrane aperture is 0.1 μm, the control of gore film flux
In 500L/m2·h.Under the constant flux, in the running of continuous 15 days, micro-filtration
Operating pressure the 0.09MPa in later stage is risen to by initial 0.04MPa；
5th step, organic membrane filter water outlet enters ozone catalytic oxidation unit and carries out ozone catalytic oxygen
Change is handled, and service condition is：Inlet flow-patterm 6,15 DEG C of inflow temperature, residence time 1.5h,
Ozone concentration 10mg/L；
6th step, catalytic ozonation water outlet enters the progress separation of high pressure reverse osmosis units and is concentrated to give
To reverse osmosis produced water and reverse osmosis concentrated water, service condition is：Operating pressure is 9MPa, water inlet
PH 6,15 DEG C of inflow temperature；
On this condition, the rate of recovery more than 80% of high pressure counter-infiltration.
Oil gas field wastewater with high concentration of sulfide after above-mentioned steps are handled, high pressure reverse osmosis concentrated water sulphur contains
Amount<0.5mg/L, oil content ＜ 5mg/L, suspension ＜ 1mg/L, meet oil gas field reinjected water
Standard, high pressure reverse osmosis produced water COD ＜ 100mg/L, Cl-＜ 300mg/L, meet discharge mark
It is accurate.
The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal, flocculating setting slag class
Outward transport processing is concentrated after cured.
Embodiment 2
The main water quality characteristic of oil gas field wastewater with high concentration of sulfide is：Sulfide 5000mg/L, always
Soluble solid 20000mg/L, suspension 1500mg/L, oil content 30mg/L, always
Hardness (CaCO3Meter) 1100mg/L, Na+8000mg/L, Cl-9000mg/L,
SO4 2-1300mg/L, COD 1000mg/L.
Process step is as follows：
The first step, wastewater with high concentration of sulfide adjusts the pH to 4.5 of waste water using hydrochloric acid for the first time, it
Enter negative pressure desulfurization unit afterwards and carry out desulfurization, the operating condition of negative pressure desulfurization is：Inflow temperature
40 DEG C, negative pressure -0.05MPa, retention time of sewage 25min are run, the reflux ratio of circulating pump is
4:1；
Second step, negative pressure desulfurization water outlet adjusts the pH of waste water using hydrochloric acid to 3.3 for the second time,
Enter chemical catalytic oxidation unit afterwards and carry out treating technology desulfurization, oxidant is dioxygen
Water, consumption is 100mg/L, and catalyst is ferrous sulfate, and consumption is 40mg/L；
3rd step, catalytic oxidation desulfurization water outlet adjusts the pH of waste water using sodium hydroxide third time
To 8.3, flocculating setting unit is entered afterwards and carries out flocculating setting, flocculation aid is poly- for anionic
Acrylamide, molecular weight 6,000,000, flocculation aid consumption is 2mg/L, and the flocculating setting time is
10min；
4th step, flocculating setting unit water outlet enters organic membrane filter unit and carries out Ge Er mistakes
Filter, organic film material is polytetrafluoroethylene (PTFE), and membrane aperture is 0.15 μm, the control of gore film flux
In 450L/m2·h.Under the constant flux, in the running of continuous 15 days, micro-filtration
Operating pressure the 0.11MPa in later stage is risen to by initial 0.04MPa；
5th step, organic membrane filter water outlet enters ozone catalytic oxidation unit and carries out ozone catalytic oxygen
Change is handled, and service condition is：Inlet flow-patterm 7,25 DEG C of inflow temperature is residence time 1h, smelly
Oxygen concentration 30mg/L；
6th step, catalytic ozonation water outlet enters the progress separation of high pressure reverse osmosis units and is concentrated to give
To reverse osmosis produced water and reverse osmosis concentrated water, service condition is：Operating pressure is 10MPa, water inlet
PH 7,25 DEG C of inflow temperature；
On this condition, the rate of recovery more than 70% of high pressure counter-infiltration.
Oil gas field wastewater with high concentration of sulfide after above-mentioned steps are handled, high pressure reverse osmosis concentrated water sulphur contains
Amount<0.5mg/L, oil content ＜ 5mg/L, suspension ＜ 1mg/L, meet oil gas field reinjected water
Standard, high pressure reverse osmosis produced water COD ＜ 100mg/L, Cl-＜ 300mg/L, meet discharge mark
It is accurate.
The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal, flocculating setting slag class
Outward transport processing is concentrated after cured.
Embodiment 3
The main water quality characteristic of oil gas field wastewater with high concentration of sulfide is：Sulfide 10000mg/L, always
Soluble solid 30000mg/L, suspension 3000mg/L, oil content 50mg/L are total hard
Spend (CaCO3Meter) 1200mg/L, Na+10000mg/L, Cl-11000mg/L, SO4 2-1400
Mg/L, COD 1200mg/L.
Process step is as follows：
The first step, wastewater with high concentration of sulfide adjusts the pH to 5 of waste water using nitric acid for the first time, afterwards
Desulfurization is carried out into negative pressure desulfurization unit, the operating condition of negative pressure desulfurization is：Inflow temperature
45 DEG C, negative pressure -0.06MPa, retention time of sewage 30min are run, the reflux ratio of circulating pump is
3:1；
Second step, negative pressure desulfurization water outlet adjusts the pH of waste water using nitric acid to 3.5 for the second time,
Enter chemical catalytic oxidation unit afterwards and carry out treating technology desulfurization, oxidant is dioxygen
Water, consumption is 200mg/L, and catalyst is ferrous sulfate, and consumption is 80mg/L；
3rd step, catalytic oxidation desulfurization water outlet adjusts the pH of waste water using sodium hydroxide third time
To 8.5, flocculating setting unit is entered afterwards and carries out flocculating setting, flocculation aid is poly- for anionic
Acrylamide, molecular weight 7,000,000, flocculation aid consumption is 3mg/L, and the flocculating setting time is
20min；
4th step, flocculating setting unit water outlet enters organic membrane filter unit and carries out Ge Er mistakes
Filter, organic film material is polytetrafluoroethylene (PTFE), and membrane aperture is 0.2 μm, the control of gore film flux
In 400L/m2·h.Under the constant flux, in the running of continuous 15 days, micro-filtration
Operating pressure the 0.12MPa in later stage is risen to by initial 0.05MPa；
5th step, organic membrane filter water outlet enters ozone catalytic oxidation unit and carries out ozone catalytic oxygen
Change is handled, and service condition is：Inlet flow-patterm 7,35 DEG C of inflow temperature is residence time 2h, smelly
Oxygen concentration 40mg/L；
6th step, catalytic ozonation water outlet enters the progress separation of high pressure reverse osmosis units and is concentrated to give
To reverse osmosis produced water and reverse osmosis concentrated water, service condition is：Operating pressure is 11MPa, water inlet
PH 7,35 DEG C of inflow temperature；
On this condition, the rate of recovery more than 60% of high pressure counter-infiltration.
Oil gas field wastewater with high concentration of sulfide after above-mentioned steps are handled, high pressure reverse osmosis concentrated water sulphur contains
Amount<0.5mg/L, oil content ＜ 5mg/L, suspension ＜ 1mg/L, meet oil gas field reinjected water
Standard, high pressure reverse osmosis produced water COD ＜ 100mg/L, Cl-＜ 300mg/L, meet discharge mark
It is accurate.
The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal, flocculating setting slag class
Outward transport processing is concentrated after cured.
Embodiment 4
The main water quality characteristic of oil gas field wastewater with high concentration of sulfide is：Sulfide 20000mg/L, always
Soluble solid 50000mg/L, suspension 5000mg/L, oil content 80mg/L are total hard
Spend (CaCO3Meter) 1600mg/L, Na+15000mg/L, Cl-20000mg/L, SO4 2-2000
Mg/L, COD 1500mg/L.
Process step is as follows：
The first step, wastewater with high concentration of sulfide adjusts the pH to 5.5 of waste water using hydrochloric acid for the first time, it
Enter negative pressure desulfurization unit afterwards and carry out desulfurization, the operating condition of negative pressure desulfurization is：Inflow temperature
45 DEG C, negative pressure -0.07MPa, retention time of sewage 30min are run, the reflux ratio of circulating pump is
2:1；
Second step, negative pressure desulfurization water outlet adjusts the pH to 4 of waste water using hydrochloric acid for the second time, it
Enter chemical catalytic oxidation unit afterwards and carry out treating technology desulfurization, oxidant is dioxygen
Water, consumption is 300mg/L, and catalyst is ferrous sulfate, and consumption is 120mg/L；
3rd step, catalytic oxidation desulfurization water outlet adjusts the pH of waste water using sodium hydroxide third time
To 9, flocculating setting unit is entered afterwards and carries out flocculating setting, flocculation aid is anionic poly- third
Acrylamide, molecular weight 8,000,000, flocculation aid consumption is 5mg/L, and the flocculating setting time is
20min；
4th step, flocculating setting unit water outlet enters organic membrane filter unit and carries out Ge Er mistakes
Filter, organic film material is polytetrafluoroethylene (PTFE), and membrane aperture is 0.2 μm, the control of gore film flux
In 350L/m2·h.Under the constant flux, in the running of continuous 15 days, micro-filtration
Operating pressure the 0.12MPa in later stage is risen to by initial 0.04MPa；
5th step, organic membrane filter water outlet enters ozone catalytic oxidation unit and carries out ozone catalytic oxygen
Change is handled, and service condition is：Inlet flow-patterm 8,40 DEG C of inflow temperature is residence time 3h, smelly
Oxygen concentration 40mg/L；
6th step, catalytic ozonation water outlet enters the progress separation of high pressure reverse osmosis units and is concentrated to give
To reverse osmosis produced water and reverse osmosis concentrated water, service condition is：Operating pressure is 11MPa, water inlet
PH 8,40 DEG C of inflow temperature；
On this condition, the rate of recovery more than 40% of high pressure counter-infiltration.
Oil gas field wastewater with high concentration of sulfide after above-mentioned steps are handled, high pressure reverse osmosis concentrated water sulphur contains
Amount<0.5mg/L, oil content ＜ 5mg/L, suspension ＜ 1mg/L, meet oil gas field reinjected water
Standard, high pressure reverse osmosis produced water COD ＜ 100mg/L, Cl-＜ 300mg/L, meet discharge mark
It is accurate.
The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal, flocculating setting slag class
Outward transport processing is concentrated after cured.
Embodiment 5
The main water quality characteristic of oil gas field wastewater with high concentration of sulfide is：Sulfide 20000mg/L, always
Soluble solid 50000mg/L, suspension 5000mg/L, oil content 100mg/L, always
Hardness (CaCO3Meter) 1600mg/L, Na+15000mg/L, Cl-20000mg/L, SO4 2-
2000mg/L, COD 1500mg/L.
Process step is as follows：
The first step, wastewater with high concentration of sulfide adjusts the pH to 4 of waste water using hydrochloric acid for the first time, afterwards
Desulfurization is carried out into negative pressure desulfurization unit, the operating condition of negative pressure desulfurization is：Inflow temperature
45 DEG C, negative pressure -0.07MPa, retention time of sewage 30min are run, the reflux ratio of circulating pump is
3:1；
Second step, negative pressure desulfurization water outlet adjusts the pH to 4 of waste water using hydrochloric acid for the second time, it
Enter chemical catalytic oxidation unit afterwards and carry out treating technology desulfurization, oxidant is dioxygen
Water, consumption is 200mg/L, and catalyst is ferrous sulfate, and consumption is 80mg/L；
3rd step, catalytic oxidation desulfurization water outlet adjusts the pH of waste water using sodium hydroxide third time
To 8.6, flocculating setting unit is entered afterwards and carries out flocculating setting, flocculation aid is poly- for anionic
Acrylamide, molecular weight 8,000,000, flocculation aid consumption is 5mg/L, and the flocculating setting time is
20min；
4th step, flocculating setting unit water outlet enters organic membrane filter unit and carries out Ge Er mistakes
Filter, organic film material is polytetrafluoroethylene (PTFE), and membrane aperture is 0.25 μm, the control of gore film flux
In 300L/m2·h.Under the constant flux, in the running of continuous 15 days, micro-filtration
Operating pressure the 0.11MPa in later stage is risen to by initial 0.03MPa；
5th step, organic membrane filter water outlet enters to be advanced into ozone catalytic oxidation unit ozone catalytic oxygen
Change is handled, and service condition is：Inlet flow-patterm 9,45 DEG C of inflow temperature is residence time 3h, smelly
Oxygen concentration 50mg/L；
6th step, catalytic ozonation water outlet enters the progress separation of high pressure reverse osmosis units and is concentrated to give
To reverse osmosis produced water and reverse osmosis concentrated water, service condition is：Operating pressure is 12MPa, water inlet
PH 9,45 DEG C of inflow temperature；
On this condition, the rate of recovery more than 40% of high pressure counter-infiltration.
Oil gas field wastewater with high concentration of sulfide after above-mentioned steps are handled, high pressure reverse osmosis concentrated water sulphur contains
Amount<0.5mg/L, oil content ＜ 5mg/L, suspension ＜ 1mg/L, meet oil gas field reinjected water
Standard, high pressure reverse osmosis produced water COD ＜ 100mg/L, Cl-＜ 300mg/L, meet discharge mark
It is accurate.
The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal, flocculating setting slag class
Outward transport processing is concentrated after cured.
The preferable possible embodiments of the present invention are the foregoing is only, not thereby limit to the present invention's
The scope of the claims, therefore the equivalence changes that every utilization description of the invention and accompanying drawing content are made,
It is contained in protection scope of the present invention.
The content not being described in detail in this specification belongs to known in professional and technical personnel in the field
Prior art.
Claims (13)
1. a kind of oil gas field wastewater with high concentration of sulfide reduces standard discharge method, it is characterised in that：
Comprise the following steps：
The first step, collection is come out using negative pressure desulfurization technology by most of hydrogen sulfide stripping in waste water
It is middle to burn；
Second step, using chemical catalytic oxidation technology by the remaining hydrogen sulfide in negative pressure desulfurization water outlet
Oxidation；
3rd step, catalytic oxidation desulfurization water outlet carries out flocculating setting；
4th step, flocculating setting water outlet enters organic membrane filter unit and carries out organic membrane filter；
5th step, organic membrane filter water outlet carries out catalytic ozonation processing；
6th step, catalytic ozonation water outlet enters high pressure reverse osmosis units and carries out separation concentration；
High pressure reverse osmosis concentrated water carries out re-injection, high pressure reverse osmosis produced water qualified discharge.
2. oil gas field wastewater with high concentration of sulfide as claimed in claim 1 reduces standard discharge method,
It is characterized in that：The oil gas field wastewater with high concentration of sulfide reduce standard discharge method specifically include with
Lower step：
Step 1, wastewater with high concentration of sulfide is after first time pH regulations, into negative pressure desulfurization unit
Carry out desulfurization；The hydrogen sulfide produced after negative pressure desulfurization, which is collected, carries out burning disposal；
Step 2, negative pressure desulfurization water outlet is after second of pH regulation, into chemical catalysis oxygen
Change unit and carry out treating technology desulfurization；
Step 3, catalytic oxidation desulfurization water outlet is heavy into flocculation after third time pH regulations
Drop unit and carry out flocculating setting；Outward transport processing is concentrated after flocculating setting slag class is cured；
Step 4, flocculating setting water outlet enters organic membrane filter unit progress organic membrane filter；
Step 5, organic membrane filter water outlet enters ozone catalytic oxidation unit progress ozone catalytic oxygen
Change is handled；
Step 6, catalytic ozonation water outlet enters the progress separation concentration of high pressure reverse osmosis units；
High pressure reverse osmosis concentrated water carries out reinjection technology, high pressure reverse osmosis produced water qualified discharge.
3. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：
Through step 1~the 6 oil gas field wastewater with high concentration of sulfide after processing, high pressure reverse osmosis concentrated water sulphur contains
Amount<0.5mg/L, oil content ＜ 5mg/L, suspension ＜ 1mg/L, meet oil gas field reinjected water
Standard；High pressure reverse osmosis produced water COD ＜ 100mg/L, Cl-＜ 300mg/L, meet discharge mark
It is accurate.
4. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：The negative pressure desulfurization unit sets circulating pump to carry out waste water circulation, and reflux ratio is
2~5:1.
5. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 1, first time pH regulations conditioning agent used is hydrochloric acid, sulfuric acid
Or one kind in nitric acid；
Wastewater with high concentration of sulfide is after first time pH regulations, and pH scopes are 4~6.
6. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 2, second of pH regulations conditioning agent used is hydrochloric acid, sulfuric acid
Or one kind in nitric acid；
Negative pressure desulfurization water outlet is after second of pH regulation, and pH scopes are 3~4.
7. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 3, third time pH regulations conditioning agent used is sodium hydroxide；
Catalytic oxidation desulfurization water outlet is after third time pH regulations, and pH scopes are 8~9.
8. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 1, the retention time of sewage of negative pressure desulfurization unit is 20~30min；
The inflow temperature of negative pressure desulfurization unit is 35~45 DEG C, and operation negative pressure is
- 0.04~-0.07MPa.
9. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 2, the treating technology desulfurization is by sulphion catalysis oxidation
For sulfate ion；
The oxidant of the chemical catalytic oxidation unit is hydrogen peroxide, and catalyst is ferrous sulfate；
Oxidizer is 100~300mg/L, and catalyst amount is 40~120mg/L.
10. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 3, the flocculation aid of flocculating setting unit is anionic polyacrylamide
Amine, molecular weight 5,000,000~8,000,000；
The flocculation aid consumption of flocculating setting unit is 2-5mg/L；
The flocculating setting time is 10~20min.
11. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 4, the filtered version of organic membrane filter unit filters for Ge Er；
The membrane material of organic membrane filter unit is polytetrafluoroethylene (PTFE), 0.1~0.25 μm of membrane aperture；
The membrane flux of organic membrane filter unit is controlled in 300~500L/m2·h。
12. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 5, the service condition of the ozone catalytic oxidation unit is：Water inlet
PH 6~9,15~45 DEG C of inflow temperature, 1~3h of residence time, 10~50mg/L of ozone concentration.
13. oil gas field wastewater with high concentration of sulfide as claimed in claim 2 reduces standard discharge method,
It is characterized in that：In step 6, the high pressure reverse osmosis units use disc tube reverse osmosis (dt-ro) film group
Part, membrane module form is that multiple disc-type diaphragms are connected on composition disc-type film on a central tube
Post；
The service condition of high pressure reverse osmosis units is：Operating pressure is 9~12MPa, inlet flow-patterm
6~9,15~45 DEG C of inflow temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115974211A (en) * | 2023-01-05 | 2023-04-18 | 中煤科工西安研究院(集团)有限公司 | High-salinity mine water zero-discharge purification and deep-layer reinjection synergistic system and process |
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| US20120055875A1 (en) * | 2010-09-02 | 2012-03-08 | General Electric Company | Method to treat produced waters from thermally induced heavy crude oil production (tar sands) |
| CN103880202A (en) * | 2012-12-12 | 2014-06-25 | 王炜 | Rejection processing technology for gas production wastewater in sulfur acid containing gas field |
| CN203807199U (en) * | 2014-01-26 | 2014-09-03 | 山东洁通环保设备有限公司 | Device for removing hydrogen sulfide by vacuum membrane method |
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