CN110563223A - process method for treating difficultly degraded COD (chemical oxygen demand) in produced water of high-sulfur-content gas field - Google Patents
process method for treating difficultly degraded COD (chemical oxygen demand) in produced water of high-sulfur-content gas field Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000007789 gas Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 title abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 11
- 239000001301 oxygen Substances 0.000 title abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 56
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 230000003647 oxidation Effects 0.000 claims abstract description 49
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 238000001471 micro-filtration Methods 0.000 claims abstract description 26
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 26
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 20
- 238000005273 aeration Methods 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 2
- ARYKTOJCZLAFIS-UHFFFAOYSA-N hydrogen peroxide;ozone Chemical compound OO.[O-][O+]=O ARYKTOJCZLAFIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012629 purifying agent Substances 0.000 description 5
- 238000011001 backwashing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- -1 hydroxyl radicals Chemical class 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000003672 gas field water Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 229940105847 calamine Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
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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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
- 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
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- 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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- Water Supply & Treatment (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The invention belongs to the technical field of oil and gas field ground engineering, and particularly relates to a process for removing nondegradable COD (chemical oxygen demand) in produced water of a high-sulfur-content gas field. Aiming at the situation that the difficultly degraded COD component in the produced water of the high-sulfur-content gas field and the pretreated inflow water COD are generally 1000mg/L and are difficultly degraded COD, in order to realize the resource recycling of the produced water of the high-sulfur-content gas field, the process suitable for removing the difficultly degraded COD in the produced water of the high-sulfur-content gas field is provided, and the treatment process of 'Fenton oxidation + ozone ultraviolet catalytic oxidation + micro/ultrafiltration membrane + reverse osmosis membrane' is adopted to degrade and remove the difficultly degraded COD, volatile phenol and other organic components in the produced water of the high-sulfur-content gas field. The process is used for treating the gas field produced water under the condition that the COD (chemical oxygen demand) of the gas field produced water is less than or equal to 1000mg/L, and the qualified effluent COD is less than or equal to 50 mg/L.
Description
Technical Field
The invention belongs to the technical field of oil and gas field ground engineering, and particularly relates to a process method for removing nondegradable COD (chemical oxygen demand) in produced water of a high-sulfur-content gas field.
Background
At present, the developed and put-into-operation high-sulfur gas fields in China mainly comprise a plain gas field and a Yuan-Ba gas field. The COD component in the gas field water is complicated and has more difficultly-degraded components due to the fact that the high-sulfur gas field produced water produced in the gas field production process comes from different stratums and is mixed with the corrosion inhibitor added in the gas field production process in the conveying process, and the COD component in the high-sulfur gas field water is analyzed through GC-MS (gas chromatography-Mass spectrometer), which is specifically shown in Table 1.
table 1: COD main component of gas field produced water
From the COD component situation, the main component is aromatic compounds, and the B/C of the produced water of the gas field is only about 0.1, so that the overall biodegradability of the produced water is poor.
In the prior art, a high-grade oxidation mode is generally adopted for difficultly degraded COD, and at present, the high-grade oxidation modes mainly comprise the following modes, and each application range is as follows.
(1) Fenton oxidation
Fenton oxidation is the oxidation of ferrous ions (Fe)2+) As catalyst, hydrogen peroxide (H)2O2) A method for treating wastewater by chemical oxidation. The system composed of ferrous ions and hydrogen peroxide, also called Fenton's reagent, can generate hydroxyl radicals with strong oxidizing property, and generate organic radicals with refractory organics in aqueous solution to destroy the structure, and finally oxidize and decompose. The Fenton oxidation method has no strict limitation on the COD of the inlet water, but has the defect of large cement production because the Fenton agent dosage is large under the condition of high COD.
(2) Catalytic oxidation with ozone
ozone is a strong oxidant and is commonly used in wastewater treatment to remove organic matter. The ozone catalytic oxidation is to utilize ozone to generate hydroxyl radical-OH under the action of a catalyst, wherein the hydroxyl radical has stronger oxidizing capability than ozone molecules, has no selectivity in reaction, and can quickly oxidize and decompose a large amount of organic pollutants in sewage. The catalysis mode can be ultraviolet light catalysis oxidation, ultrasonic wave catalysis oxidation, solid catalyst catalysis oxidation and the like. In any case, the catalytic oxidation is performed in order to increase the amount of hydroxyl radicals generated by ozone. Ozone catalytic oxidation belongs to a high-grade oxidation technology, and is generally used for removing difficultly degraded COD (chemical oxygen demand), and the COD of inlet water is generally less than 200 mg/L.
At present, the high-sulfur gas field (plain gas field, Yuan-Ba gas field) exploited in China is mainly distributed in Sichuan areas. The area has high population density and poor reinjection capacity of the reinjection well, most importantly, along with the coming of more strict environmental protection policies of the state, the concept that the green water Qingshan is the Jinshan Yinshan is continuously deep into the mind, and the existing treatment reinjection mode of the produced water of the high-sulfur-content gas field is no longer suitable for the environmental protection requirements under the existing national conditions. Based on the reasons, in order to ensure stable production of the gas field and stable gas utilization of the Chuan gas to downstream users, an energy-saving and environment-friendly treatment process for the produced water of the high-sulfur-content gas field is urgently needed to realize resource recycling of the produced water of the gas field. The most important point for recycling is the control of effluent COD. The COD of the gas field produced water generally fluctuates within the range of 2000-12000 mg/L, the COD can be reduced to about 1000mg/L after pretreatment such as desulfurization, evaporation or primary blow-off oxidation and the like is carried out on the gas field produced water by the front end, and the part of COD is difficultly degraded COD, so that a process is urgently needed to remove the part of COD for meeting the requirement of water quality reuse. (COD < 50mg/L)
Disclosure of Invention
The invention aims to provide a process scheme suitable for removing refractory COD in the produced water of a high-sulfur-containing gas field aiming at the condition that refractory COD components exist in the produced water of the high-sulfur-containing gas field, and the pretreated inlet water is generally 1000mg/L and is refractory COD, so as to ensure the realization of resource recycling of the produced water of the high-sulfur-containing gas field.
in order to achieve the purpose, the technical scheme of the invention is that a whole set of brand-new treatment process is adopted, and the treatment process specifically comprises the treatment process steps of Fenton oxidation, ozone ultraviolet light catalytic oxidation, micro/ultrafiltration membrane and reverse osmosis membrane, and the like, and the degradation and removal of organic components such as difficultly-degraded COD (chemical oxygen demand) and volatile phenol in the produced water of the high-sulfur-containing gas field are realized.
the invention provides a treatment process for nondegradable COD (chemical oxygen demand) in produced water of a high-sulfur-content gas field, which comprises the following specific steps of:
The first step is as follows: the pretreated high-sulfur-content gas field produced water firstly enters a Fenton reaction device for oxidation reaction;
the second step is that: carrying out ozone ultraviolet light catalytic oxidation treatment on the produced water subjected to the first step of treatment;
The third step: the produced water treated in the second step enters a micro/ultrafiltration membrane for filtration treatment;
The fourth step: and (4) treating the produced water treated in the third step by using a reverse osmosis membrane to obtain the qualified produced water after treatment.
Furthermore, the Fenton oxidation process is adopted in the first step of the invention, wherein the Fenton oxidation reaction device comprises a pH value adjusting area, a reaction area, a degassing area, a precipitation area, a mixing fan, a high-efficiency anti-blocking aeration pipeline, a dosing system and the like. Wherein the pH value adjusting area mainly controls the pH value of inlet water, and is generally controlled between 2 and 4. The reaction zone is mainly added with a Fenton reaction reagent, the dosage of the reagent is related to the concentration of COD (chemical oxygen demand) of inlet water, generally, the mass ratio of hydrogen peroxide to COD is 2: 1-6: 1, and the hydrogen peroxide to Fe2+The mass ratio of (A) to (B) is in the range of 5:1 to 15: 1. The Fenton reaction time is 2-4 h. The COD of the effluent of the Fenton reaction is generally controlled to be 150 mg/L-200 mg/L. The mixing form of the medicaments in the reaction process can adopt an aeration mixing form.
furthermore, the second step of the invention adopts an ozone ultraviolet light catalytic oxidation treatment process, and the main equipment of the process comprises an ozone hydrogen peroxide solution pressure reaction tank, an ozone generator, an ultraviolet lamp tube, an ozone diffusion system and the like. The adding concentration range of ozone is generally 100 mg/L-500 mg/L, the adding amount of hydrogen peroxide is 20-50 mg/L, and the ultraviolet light intensity range is generally 100-3000 mJ/cm in the whole reaction process2. The reaction time of the ozone ultraviolet light catalytic oxidation is 1-3 h. The COD of the treated effluent is generally controlled between 80mg/L and 100 mg/L.
furthermore, a micro/ultrafiltration membrane is adopted in the third step of the invention, wherein the micro/ultrafiltration membrane preferably adopts an inorganic membrane, and the material of the inorganic membrane can be selected from a ceramic membrane, an inorganic carbon membrane and the like. Organic membranes can be used in the case of effluent oxidation-reduction potentials less than 200 in the front-end treatment process. The inorganic film has the advantages of pollution resistance, strong oxidation resistance and the like. The operating pressure of the micro/ultrafiltration membrane is generally 0.02 MPa-0.2 MPa, the water yield is more than or equal to 80 percent, and the cross-flow filtration mode is adopted as much as possible.
The principle of the invention is detailed as follows:
As shown in the attached figure 1, the main equipment for removing the nondegradable COD in the produced water of the high-sulfur gas field comprises:
(1) The Fenton advanced oxidation device mainly plays a role in degrading organic matters which are difficult to degrade in water through the strong oxidation of hydroxyl radicals. The device comprises a pH value adjusting and medicament mixing area, a reaction area, a degassing area, a flocculation settling area, a matched mixing fan, a high-efficiency anti-blocking aeration pipeline and a medicament adding system; wherein the pH value adjusting area is mainly used for controlling the pH value of the Fenton reaction to be 2-4. The main function of the reagent mixing zone is to mix the reaction reagents hydrogen peroxide and ferrous salt, and the reaction zone mainly carries out Fenton reaction. The degassing area is mainly used for adjusting the pH value back to 6-9 and removing unreacted hydrogen peroxide. The main function of the settling zone is to remove ferric hydroxide in the water by adding a water purifying agent.
(2) Ozone ultraviolet light catalytic oxidation device, the device main function is through ultraviolet light catalytic action, arouses ozone and hydrogen peroxide solution to produce hydroxyl free radical, further reduces aquatic COD. The device comprises a buffer water tank, a pressure reaction tank, an ozone generator, an ozone diffusion device, an ultraviolet light tube and the like. And (3) the Fenton effluent enters a buffer water tank and is lifted by a pump to enter a pressure reaction tank, an ultraviolet light tube is arranged in the pressure reaction tank, hydrogen peroxide and ozone are added into the reaction tank, the ozone is uniformly dispersed into the reaction tank through an ozone diffusion system, and catalytic oxidation reaction is carried out under the irradiation of ultraviolet light emitted by the ultraviolet light tube.
(3) The micro/ultrafiltration membrane system mainly has the functions of removing suspended matters in water and iron mud generated by reaction at the front section and providing water quality guarantee for the rear section reverse osmosis membrane system. The system typically includes an intermediate buffer tank, booster pump, micro/ultrafiltration membrane, circulation pump, etc.
(4) The reverse osmosis membrane system, the device main function is the COD of further getting rid of aquatic, provides the water quality assurance for anterior segment processing apparatus. The system generally includes a surge tank, a booster pump, a high pressure pump, a reverse osmosis membrane, and the like.
the treatment process method for removing the nondegradable COD in the produced water of the high-sulfur-content gas field comprises the following specific operation flows:
Firstly, pretreated gas field produced water enters a Fenton oxidation device, after the pH value of the device is adjusted to a proper interval, a medicament is added into a medicament mixing area, the adding amount is determined according to the COD value of the incoming water, and the medicament mixing mode of the medicament mixing area adopts an aeration mixing mode. And the produced water after the reaction enters a degassing area of the Fenton reaction device, and a pH regulator is added at the degassing area. The degassed produced water enters a settling zone, and a water purifying agent is added into the zone firstly and then enters a settling tank. The COD of the effluent of the Fenton reaction is generally controlled to be 150 mg/L-200 mg/L.
And then, the produced water passing through the Fenton reaction device enters an ozone ultraviolet light catalytic oxidation treatment device. The produced water firstly enters a buffer water tank, is lifted by a lifting pump to enter a pressure reaction tank, hydrogen peroxide and ozone are added into the tank, and an ultraviolet light lamp tube is started at the same time. The reaction time of the ozone ultraviolet light catalytic oxidation is 1-3 h. The COD of the treated effluent is generally controlled between 80mg/L and 100 mg/L. Ozone tail gas enters a tail gas damage system.
And the produced water passing through the ozone ultraviolet light catalytic oxidation system continuously enters an intermediate buffer water tank of a micro/ultrafiltration membrane system, is lifted by a booster pump to pass through a micro/ultrafiltration membrane, and finally enters a reverse osmosis system. The micro/ultrafiltration membrane system is provided with automatic backwashing.
And finally, the produced water passing through the micro/ultrafiltration membrane system enters an intermediate water tank of the reverse osmosis system, is lifted by a lifting pump and a high-pressure pump and then enters the reverse osmosis membrane system, and the produced water passing through the reverse osmosis membrane finally enters a finished product water tank. The reverse osmosis concentrated water is used as the water for back washing of the front end micro/ultra-filtration membrane.
The invention has the following advantages:
(1) In the first step, the Fenton reaction in the Fenton advanced oxidation device is completed in the high-efficiency anti-blocking aeration system, so that the mixing reaction can be ensured to be very uniform, and meanwhile, the dosage of the medicament can be reduced because the aeration system is not easy to block;
(2) Because the ozone ultraviolet light catalytic oxidation device is adopted to continue to process the produced water after the first step is finished in the second step, the COD in the water can be further degraded, so that the dosage of Fenton reaction agents can be reduced, the yield of the iron mud can be ensured, and the water production cost in the whole process scheme can be reduced.
(3) in the third step, a micro/ultrafiltration membrane system is adopted, and an inorganic carbon membrane is preferably selected as the membrane, so that the pollution resistance and the oxidation resistance are strong, and the next reverse osmosis membrane system can be guaranteed;
(4) And in the fourth step, because a reverse osmosis system is adopted, COD, BOD, conductivity and the like in the produced water can be further controlled, and the quality of the produced water is ensured.
(5) the process has the advantages of short operation system flow, short reaction time, small occupied area and small overall investment.
aiming at the characteristics of the components of the COD which are difficult to degrade in the produced water of the high-sulfur-content gas field, the invention adopts a complete treatment process comprising Fenton oxidation, ozone ultraviolet light catalytic oxidation, micro/ultrafiltration membrane and reverse osmosis membrane, so that the removal of the COD which is difficult to degrade in the produced water of the high-sulfur-content gas field can be effectively realized, and the COD of the produced water is less than or equal to 50mg/L under the condition that the CODcr of the inlet water is less than or equal to 1000 mg/L. Meanwhile, the degradation and removal of volatile phenol and other organic components in the produced water can be realized
Drawings
Fig. 1 is a schematic block diagram of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Example 1:
A treatment process for difficultly degraded COD in produced water of a high-sulfur-content gas field comprises the following specific steps:
The first step is as follows: performing Fenton oxidation treatment on the produced water of the high-sulfur-content gas field;
The second step is that: carrying out ozone ultraviolet light catalytic oxidation treatment on the produced water subjected to the first step of treatment;
The third step: subjecting the produced water treated in the second step to micro/ultrafiltration membrane treatment;
The fourth step: and (4) performing reverse osmosis membrane treatment on the produced water subjected to the third step of treatment to obtain qualified produced water after treatment.
Specifically, as shown in fig. 1, the main devices adopted in this embodiment include: a Fenton advanced oxidation device, an ozone ultraviolet light catalytic oxidation device, a micro/ultrafiltration membrane system and a reverse osmosis system.
The specific operation process steps are as follows:
The pretreated gas field produced water firstly enters a Fenton oxidation device, the pH value is adjusted to be 2-4 in a pH value adjusting area of the Fenton reaction device, hydrogen peroxide and ferrous salt are added in a medicament mixing area, wherein the adding amount of the medicament is determined according to the COD value of the incoming water, the mass ratio of the hydrogen peroxide to the COD is generally 2: 1-6: 1, and the mass ratio of the hydrogen peroxide to the Fe is2+The mass ratio of the components is 5: 1-15: 1, and the medicament mixing mode in the medicament mixing area adopts an aeration mixing mode. The effluent of the agent mixing zone enters a reaction zone, and an aeration mixing device is arranged at the bottom of the reaction zone to carry out a complete mixing reaction on the produced water entering the reaction zone. The reaction time of the reaction zone is generally 2 to 4 hours. And (3) the produced water after the reaction enters a degassing area of the Fenton reaction device, a pH value regulator is added at the degassing area, the pH value is adjusted back to 6-9, and the produced water is also subjected to reaction in an aeration mixing mode in the area. And (3) the degassed produced water enters a settling zone, a water purifying agent is added into the zone at first, and then the water purifying agent enters a settling tank, wherein a mechanical stirring mode is adopted when the water purifying agent is added. The COD of the effluent treated in the step is generally controlled to be 150 mg/L-200 mg/L.
The effluent of the Fenton reaction device enters an ozone ultraviolet light catalytic oxidation treatment device, the produced water firstly enters a pressure reaction tank, hydrogen peroxide and ozone are added into the pressure reaction tank, and an ultraviolet light lamp tube is opened at the same time. Wherein the adding concentration range of the ozone is generally 100 mg/L-500 mg/L, the adding amount range of the hydrogen peroxide is 20-50 mg/L, and an ozone diffusion system is adopted for adding the ozone. The ultraviolet light intensity range is generally 100-3000 mJ/cm2. The reaction time of the ozone ultraviolet light catalytic oxidation is controlled to be 2.5 h. The COD of the effluent treated in the step is generally controlled to be 80 mg/L-100 mg/L.
The outlet water of the ozone ultraviolet light catalytic oxidation system enters a middle buffer water tank of a micro/ultrafiltration membrane system, and is lifted by a booster pump to sequentially pass through a filter and a micro/ultrafiltration membrane. And finally, the effluent enters a reverse osmosis system. The micro/ultrafiltration membrane system is provided with automatic backwashing, generally runs for about 1h, and then is backwashed for 45 s.
and the outlet water of the micro/ultrafiltration membrane system enters an intermediate water tank of the reverse osmosis system, is lifted by a lift pump and a high-pressure pump and then enters the reverse osmosis membrane system, and the reverse osmosis concentrated water is used as backwashing water of the front-end micro/ultrafiltration membrane. The water yield of the final reverse osmosis system is generally about 80%.
the produced water obtained after the treatment of the steps is a qualified finished product and finally enters a subsequent finished product water tank.
the produced water after the final treatment in this embodiment can meet the water quality index of the circulating cooling water make-up water of the purification plant, specifically, examination index for water saving and emission reduction and control index for recycled water quality of refinery corporation Q/SH 0104-2007.
The specific water quality index of the produced water treated in this example is detailed in the water quality test report table of table 2.
Table 2:
| Serial number | Item | quality index of make-up water in purification plant |
| 1 | pH value | 6.96 |
| 2 | Ammonia nitrogen (mg/L) | 0.90 |
| 3 | CODcr(mg/L) | ≤50 |
| 4 | suspended substance (mg/L) | ≤30.0 |
| 5 | turbidity (NTU) | ≤10.0 |
| 6 | Sulfide (mg/L) | ≤0.1 |
| 7 | Petroleum hydrocarbon (mg/L) | ≤2.0 |
| 8 | Chloride ion (mg/L) | ≤200.0 |
| 9 | Sulfate ion (mg/L) | ≤300.0 |
| 10 | Total iron (mg/L) | ≤0.5 |
| 11 | Conductivity (μ S/cm) | ≤1200 |
| 12 | Water temperature (. degree.C.) | ≤30 |
| 13 | BOD5(mg/L) | ≤10 |
| 14 | Volatile phenol (mg/L) | ≤0.5 |
| 15 | Calamine/Total alkali (mg/L) | 50～300 |
| 16 | Chemical oxygen demand (mg/L) | 13.9 |
| 17 | five-day biochemical oxygen demand (mg/L) | 4.4 |
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A treatment process for difficultly degraded COD in produced water of a high-sulfur-content gas field is characterized by comprising the following steps of:
The first step is as follows: carrying out oxidation reaction treatment on the pretreated high-sulfur-content gas field produced water through a Fenton reaction device;
The second step is that: carrying out catalytic oxidation treatment on the produced water subjected to the first-step treatment by an ozone ultraviolet catalytic oxidation device;
The third step: filtering the produced water treated in the second step by a micro/ultrafiltration membrane system;
The fourth step: and (4) treating the produced water treated in the third step by a reverse osmosis membrane system to obtain the qualified produced water after treatment.
2. The treatment process according to claim 1, wherein the Fenton oxidation reaction device adopted in the first step consists of a pH value adjusting area, a reaction area, a degassing area, a precipitation area, a mixing fan, a high-efficiency anti-blocking aeration pipeline and a dosing system.
3. The treatment process according to claim 1, wherein in the Fenton oxidation treatment process adopted in the first step, the pH value of inlet water is controlled to be 2-4, the mass ratio of hydrogen peroxide to COD in a dosing system is controlled to be 2: 1-6: 1, and the mass ratio of hydrogen peroxide to Fe in the dosing system is controlled to be 2: 1-6: 12+The mass ratio of (A) to (B) is 5: 1-15: 1, and the Fenton reaction time is 2-4 h.
4. The treatment process according to claim 1, wherein the ozone ultraviolet catalytic oxidation device used in the second step comprises an ozone hydrogen peroxide solution pressure reaction tank, an ozone generator, an ultraviolet lamp tube and an ozone diffusion system.
5. The treatment process according to claim 1, wherein in the ozone ultraviolet light catalytic oxidation reaction process of the second step, the adding concentration of ozone is controlled to be 100 mg/L-500 mg/L, the adding amount of hydrogen peroxide is controlled to be 20 mg/L-50 mg/L, and the ultraviolet light intensity is controlled to be 100 mJ/cm-3000 mJ/cm2the catalytic oxidation reaction time is 1-3 h.
6. The process according to claim 1, wherein the micro/ultrafiltration membrane system used in the third step comprises an intermediate buffer water tank, a booster pump, a micro/ultrafiltration membrane and a circulating pump, and the micro/ultrafiltration membrane system is an inorganic membrane or an organic membrane.
7. The process of claim 1, wherein the reverse osmosis membrane system unit in the fourth step comprises a surge tank, a booster pump, a high pressure pump and a reverse osmosis membrane.
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| CN113121048A (en) * | 2019-12-30 | 2021-07-16 | 湖北金汉江精制棉有限公司 | Refined cotton wastewater treatment and recycling process |
| CN116040785A (en) * | 2023-03-01 | 2023-05-02 | 中国石油化工股份有限公司 | Device and method for treating sulfur-containing organic wastewater |
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