CN111592176A - Comprehensive treatment method and system for oil-gas wastewater and oil sludge - Google Patents
Comprehensive treatment method and system for oil-gas wastewater and oil sludge Download PDFInfo
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- CN111592176A CN111592176A CN202010366564.2A CN202010366564A CN111592176A CN 111592176 A CN111592176 A CN 111592176A CN 202010366564 A CN202010366564 A CN 202010366564A CN 111592176 A CN111592176 A CN 111592176A
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
- C02F11/145—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances using calcium compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- 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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- 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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- 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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- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
The invention discloses a comprehensive treatment method of oil-gas wastewater and oil sludge, which comprises the following steps: s100, carrying out pretreatment operations of air flotation oil removal, coagulation/flocculation precipitation and filtration on the oil gas wastewater to obtain effluent and scum, and concentrating the effluent to obtain high-salinity concentrated water and fresh water with low-salinity and high-organic matters, wherein the high-salinity concentrated water is recycled, and the fresh water with low-salinity and high-organic matters enters the step S300 for treatment; s200, adding a demulsifier and/or a gel breaker into the oil sludge for demulsification reaction, performing solid-liquid separation on the oil sludge through flotation and filter pressing, further separating oil and water from the obtained oil-water mixture, and treating the water in the step S300; s300, mixing the fresh water with low salinity and high organic matters in the step S100 with the water in the step S200, and performing microbial degradation, ultrafiltration and reverse osmosis on the mixture to obtain the recycled water reaching the standard. The invention also discloses a comprehensive treatment system for the oil-gas wastewater and the oil sludge.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a comprehensive treatment method and a comprehensive treatment system for oil-gas wastewater and oil sludge.
Background
The oil gas waste water refers to industrial waste water which is generated along with the drilling operation in the process of oil and natural gas exploitation. The oil gas wastewater has the characteristics of high organic matter content, high chromaticity, large content of inorganic salt substances, a plurality of suspended matters, heavy metals, mineral oil and the like, and can greatly damage the ecological environment if not treated or not treated properly. Meanwhile, the oil gas wastewater has very complex components due to different chemical additives adopted in the environments of petroleum and natural gas, development depth, exploitation technology and exploitation. Particularly, when the chlorine ions in the oil and gas wastewater exceed 10000mg/L, the high-concentration organic pollutants and the high-concentration chlorine ions are interwoven together, and interfere with each other, are restricted with each other and influence each other, so that the difficulty of wastewater treatment is greatly increased. In addition, during the oil exploitation, transportation and refining processes, oil sludge waste is generated, including surface oil spill, ground oil sludge, tank bottom oil sludge, oil refinery oil-containing sludge and the like. The oil contained in the oil sludge is various in nature and complex in type, so that the treatment of the oil sludge is very difficult.
The traditional oil gas wastewater treatment method mainly comprises the following steps: (1) and (4) storing the waste liquid pool: storing the oil gas wastewater in a waste liquid pool, drying in a natural evaporation mode, and finally directly burying. The treatment method not only consumes long time, but also the pollutants such as oil, heavy metals, aldehyde, phenol and the like can still be leached from the landfill sludge block, and serious secondary pollution exists. (2) Reinjection: and collecting the oil gas wastewater, filtering, precipitating, and injecting back to the ground surface. The method has the disadvantages of large transportation cost, high cost and serious water resource waste. For the treatment of the oil sludge waste, methods such as direct landfill, solidification landfill, solvent extraction, direct incineration and the like are mainly adopted, and although a certain centralized treatment effect can be achieved, most of the methods are temporary solution and permanent solution, and recycling and cleaning cannot be achieved. And the existing treatment method and system based on oil gas wastewater and oil sludge are independent systems, and need to be treated independently, so that the method and system not only wastes time and labor, but also has large scale of treatment system, and causes waste and unreasonable distribution of manpower and energy.
Disclosure of Invention
Therefore, there is a need for a comprehensive treatment method and system for oil-gas wastewater and oil sludge, which realizes common treatment and effective combination of oil-gas wastewater and oil sludge, can generate a mutual promotion effect, improves the treatment capacity of oil-gas wastewater, improves the treatment capacity of oil sludge waste, saves manpower, and improves the resource utilization rate.
The invention provides a comprehensive treatment method of oil-gas wastewater and oil sludge, which comprises the following steps:
s100, carrying out pretreatment operations of air flotation oil removal, coagulation/flocculation precipitation and filtration on the oil gas wastewater to obtain effluent and scum, and concentrating the effluent to obtain high-salinity concentrated water and fresh water with low-salinity and high-organic matters, wherein the high-salinity concentrated water is recycled, and the fresh water with low-salinity and high-organic matters enters the step S300 for treatment;
s200, adding a demulsifier and/or a gel breaker into the oil sludge for demulsification reaction, performing solid-liquid separation on the oil sludge through flotation and filter pressing, further separating oil and water from the obtained oil-water mixture, and treating the water in the step S300;
s300, mixing the fresh water with low salinity and high organic matters in the step S100 with the water in the step S200, and performing microbial degradation, ultrafiltration and reverse osmosis on the mixture to obtain the recycled water reaching the standard.
In one embodiment, in step S200, the amount of the demulsifier or the gel breaker added is 1 to 8 per mill of the total mass of the oil sludge, the pH value of the demulsification reaction is 7, and the reaction time is 20 to 30 min.
In one embodiment, in step S300, the method of the microbial degradation treatment is any one of MBR, AAO, SBR, oxidation ditch, MBBR, and bio-contact oxidation.
In one embodiment, in step S300, in the step of microbial degradation treatment, the microorganism is a self-cultured microorganism or the self-cultured microorganism and an external microbial agent, and the culture conditions of the self-cultured microorganism are as follows: intermittent cyclic aeration is adopted, the pH is controlled to be 6.5-8.5, the dissolved oxygen is controlled to be 2.0-4.0 mg/L, the water temperature is 15-25 ℃, and the inoculated microbial agent is one or more of petroleum degrading bacteria, COD degrading bacteria, ammonia nitrogen degrading bacteria and total nitrogen degrading bacteria.
In one embodiment, the addition amount of the microbial agent is 0.1-0.5% of the total water amount in the microbial degradation.
In one embodiment, step S300 further includes dewatering the sludge after the microbial degradation, returning the supernatant, and recycling the dewatered sludge.
In one embodiment, the method further comprises a step S400 of dehydrating the sludge coagulated/flocculated and precipitated in the step S100, and performing solid waste treatment on the dehydrated sludge and the sludge obtained after the solid-liquid separation of the oil sludge in the step S200.
In one embodiment, the method further includes step S500, and the scum obtained in step S100 and the oil obtained in step S200 cooperate to recover oil.
In one embodiment, in step S300, the concentrated ultrafiltration water SS obtained after the ultrafiltration step is less than or equal to 0.2mg/L, and the turbidity is less than or equal to 0.2 NTU.
The invention further provides a comprehensive treatment system for oil-gas wastewater and oil sludge, which comprises a pretreatment system, a concentration system, an oil sludge treatment system and a cooperative purification system,
the pretreatment system comprises an air floatation oil removal unit, a coagulation/flocculation precipitation unit and a filtration unit which are connected in sequence;
the concentration system is used for concentrating the pretreated effluent to obtain high-salinity concentrated water and fresh water with low salinity and high organic matters;
the oil sludge treatment system comprises a solid-liquid separation unit and an oil-water separation unit which are sequentially connected and is used for extracting oil in the oil sludge;
the cooperative purification system comprises a biochemical degradation unit, an ultrafiltration unit and a reverse osmosis unit which are connected in sequence;
the biochemical degradation unit is respectively connected with the oil-water separation unit and the concentration system and is used for mixing the water separated by the oil-water separation unit with the fresh water of the low-salinity high-organic matter and carrying out microbial degradation treatment on the mixture.
In one embodiment, the air flotation oil removal unit is any one of a pressurized dissolved air flotation unit, a cavitation air flotation unit, an induced air flotation unit and a micro-nano air flotation unit.
In one embodiment, the coagulation/flocculation precipitation unit comprises a hardness-removing silicon-removing tank, a coagulation tank, a flocculation tank and a precipitation tank which are connected in sequence.
In one embodiment, the filtration unit comprises one or more of a V-bank filter, a D-bank filter, sand filtration, multi-media filter, self-cleaning filter, ultrafiltration.
In one embodiment, the concentration system comprises an evaporative concentration unit and/or an electrodialysis concentration unit.
In one embodiment, the integrated oil-gas wastewater and oil sludge treatment system further comprises a zero-emission system, and the zero-emission system is connected with the concentration system and is used for recovering inorganic salts from the high-salinity concentrated water obtained after the concentration by the concentration system.
In one embodiment, the biochemical degradation unit comprises a microbial culture device and a microbial degradation device, and the microbial degradation device is any one of MBR, AAO, SBR, oxidation ditch and biological contact oxidation treatment device.
In one embodiment, the comprehensive treatment system for oil-gas wastewater and oil sludge further includes an oil recovery system, and the oil recovery system is connected to the air flotation oil removal unit and the oil-water separation unit, respectively, and is configured to cooperatively recover scum discharged by the air flotation oil removal unit and oil obtained by the oil-water separation unit.
The invention has the beneficial effects that:
1. at present, no reasonable, economic and feasible resource utilization method exists for the wastewater and the oil sludge generated in the process of exploiting the oil-gas field. The invention can carry out comprehensive cooperative treatment on the two wastes and fully recover the available resources in the two wastes at the same time, for example, the recovered water meets the standard of 'supplement water of an open circulating cooling water system' specified in 'urban sewage comprehensive utilization industrial water quality' (GB19923-2005), thereby realizing the reutilization and resource utilization of water, recovering oil content and salinity, and realizing the resource recovery and utilization while integrally treating the wastes.
2. The traditional oil sludge treatment method has the problems of incomplete treatment, complex treatment process, high-temperature energy consumption and the like. According to the invention, chemical dosing is adopted, solid-liquid separation is matched with oil-water separation, the separation of solid and liquid in the oil sludge is realized under the conditions of normal temperature and normal pressure, and the oil content in the oil sludge is kept on the liquid side as far as possible, so that a good foundation is provided for subsequent oil content recovery.
3. According to the invention, the condensed water discharged from the concentration system is mixed with the wastewater discharged from the oil-water separator, so that the organic matters in the condensed water and the organic matters in the wastewater are subjected to a cross-linking reaction, the types of the organic matters are increased, the overall treatment effect of the microbial degradation system is improved, the wastewater generated by oil-water separation is purified, and then the recovery of the standard-reaching reuse water is realized by matching ultrafiltration and reverse osmosis.
Drawings
FIG. 1 is a schematic flow chart of a comprehensive treatment method of oil and gas wastewater and oil sludge according to an embodiment of the invention;
fig. 2 is a schematic composition diagram of an oil-gas wastewater and oil sludge comprehensive treatment system in an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Unless otherwise specified, the technical means used in the present invention are conventional means well known to those skilled in the art, and the reagents used are commercially available.
In the present invention, "TDS" is the total amount of dissolved solids, and "SS" is the suspended solids concentration.
The comprehensive treatment method and system for oil-gas wastewater and oil sludge of the invention are described in detail below. In the steps of the comprehensive treatment method for oil-gas wastewater and oil sludge, the labels S100, S200, S300 and the like are only used for distinguishing different steps, and do not have the limiting function of numerical sequence. The steps do not have a sequence, can be operated simultaneously under the condition of not influencing the technical effect, and generally operate according to the logic sequence known in the field.
The embodiment of the invention provides a comprehensive treatment method of oil-gas wastewater and oil sludge, which comprises the following steps:
s100, carrying out pretreatment operations of air flotation oil removal, coagulation/flocculation precipitation and filtration on the oil gas wastewater to obtain effluent and scum, and concentrating the effluent to obtain high-salinity concentrated water and fresh water with low-salinity and high-organic matters, wherein the high-salinity concentrated water is recycled, and the fresh water with low-salinity and high-organic matters enters the step S300 for treatment;
s200, adding a demulsifier and/or a gel breaker into the oil sludge for demulsification reaction, performing solid-liquid separation on the oil sludge through flotation and filter pressing, further separating oil and water from the obtained oil-water mixture, and treating the water in the step S300;
s300, mixing the fresh water with low salinity and high organic matters in the step S100 with the water in the step S200, and performing microbial degradation, ultrafiltration and reverse osmosis on the mixture to obtain the recycled water reaching the standard.
The comprehensive treatment method of the oil gas wastewater and the oil sludge can comprehensively and cooperatively treat the two wastes, and simultaneously fully recover available resources in the two wastes, for example, the recovered water meets the standard of 'supplement water of an open circulating cooling water system' specified in 'urban sewage comprehensive utilization industrial water quality' (GB19923-2005), so that the reutilization and resource utilization of water, the oil content recovery and the salt recovery are realized, and the resource recovery and utilization are realized while the waste treatment is integrally realized.
The content of petroleum in the oil gas wastewater is 100-500 mg/L, the oil gas wastewater mainly exists in a suspended state, and part of the oil gas wastewater is in an emulsified state; the content of organic matters (COD) is between 800 and 3000mg/L, and the wastewater also contains cyclic aromatic hydrocarbon derivatives; the suspended matter content is high, but the particle size is small, the SS is 300-2000 mg/L, and the particle size is 1-100 mu m; the mineralization degree is high, the main components are chloride ions, calcium ions and a small amount of other ions, such as sulfide, iron ions, aluminum ions, boron ions and the like, and the concentration of the chloride ions is up to thousands of mg/L to tens of thousands of mg/L.
The air floatation oil removal is a technology that air is introduced and micro bubbles are generated in water, so that floating oil, dispersed oil or suspended particles in water in sewage are attached to bubbles and float to the water surface along with the bubbles and are recovered. The air flotation oil removal can be any one of pressurization dissolved air flotation, cavitation air flotation, induced air flotation and micro-nano air flotation.
The scum is a mixture collected after the oil is removed by the air flotation, and comprises oil content, partial organic matters and suspended matters in the oil-gas wastewater.
The coagulating/flocculating settling step may comprise: s112, adding a hardness remover and a silicon remover to enable hardness ions and silicon dioxide particles in the oil gas wastewater to form large-particle-size precipitates;
s114, adding a coagulant to coagulate the precipitate to obtain precipitate flocs;
s116, adding a flocculating agent to further grow the precipitated flocs to form alum flocs;
s118, settling the formed alum flocs and other suspended matters.
In step S112, the hardness removing agent is sodium carbonate and sodium hydroxide, and hardness ions (such as calcium ions and magnesium ions) and carbonate ions are reacted under the condition that the pH is greater than 10.5, so as to generate calcium carbonate or magnesium carbonate precipitate. The silicon dioxide reacts with the silicon removing agent to generate sodium silicate precipitate. The reaction time is 5min to 30min, so as to achieve the best effect of removing hardness and silicon.
The coagulant in step S114 includes one or more of ferric trichloride, polymeric ferric chloride, and polymeric aluminum chloride, preferably ferric trichloride. Through the coagulation effect of the coagulant, the precipitate after the hardness and silicon removal is destabilized and condensed, and a precipitate floc is formed gradually. In one embodiment, the addition amount of the coagulant is 60g/m3～120g/m3The action time is 1-5 min.
The flocculant in the step S116 is an organic flocculant including propyleneOne or more of amide, styrene sulfonate, lignosulfonate, acrylic acid and methacrylic acid. In one embodiment, the flocculant is added in an amount of 150g/m3～300g/m3The action time is 10 min-30 min.
The settling time in step S118 is 1 to 2 hours. The step can settle the formed alum floc and other suspended matters, and obtain sludge and relatively clear effluent through the settling effect (namely, the solid-liquid precipitation principle is used for separating solid and water in the oil-gas wastewater). The step can ensure that suspended matters influencing the operation of the concentration step in the effluent are reduced as much as possible, and is convenient for subsequent filtration.
The filtration step is preferably precise filtration, and the turbidity of the oil gas wastewater can be less than or equal to 1NTU through the precise filtration.
Further, the outlet water after the precise filtration can also comprise a step of removing alkalinity, and the step can be implemented by adopting a carbon remover. Specifically, the carbon remover converts carbonate and bicarbonate in the oil gas wastewater into CO under acidic conditions2And water, CO2The alkalinity is removed by blowing in a gas form.
The oil gas wastewater is pretreated to obtain the following components in the effluent: the total hardness is less than or equal to 200mg/L, the bicarbonate radical is less than or equal to 100mg/L, the silicon dioxide is less than or equal to 5mg/L, the SS is less than or equal to 3mg/L, the turbidity is less than or equal to 10NTU, and the oil content is less than or equal to 1 mg/L.
The concentration treatment may be evaporative concentration and/or electrodialysis concentration. The mass volume concentration percentage of the concentrated high-salinity concentrated water is 15-25%.
The temperature of the evaporation concentration is 75-102 ℃.
The operation conditions during the electrodialysis concentration are as follows: the water recovery rate is 60-90 percent, the linear velocity of the oil gas wastewater entering the pipeline opening is 50-200 mm/s, and the operating pressure is 0.5kg/cm2～3.0kg/cm2The operation voltage is 100V-250V, and the current is 1A-3A.
The high-salinity concentrated water comprises inorganic salts such as sodium chloride, calcium chloride and sulfide, and can be respectively recovered after zero discharge treatment according to subsequent applications and the mass concentration of each inorganic salt. The specific method of the zero emission treatment is the same as in the following patent documents and literatures: ZL201410796519.5, ZL201410796518.0, ZL201610072785.2 or ZL 201610072782.9.
And concentrating the pretreated effluent to obtain high-salinity concentrated water and fresh water containing no inorganic salt, namely the low-salinity high-organic matter, wherein the fresh water contains a large amount of organic matters and a plurality of microorganisms.
In step S200, the main components of the oil sludge are a mixture of water, mud, oil and other impurities, the particles are fine and are flocculent, the density difference is small (the densities of the oil and the water are close), the water content is 40 wt% -90 wt%, and the oil content is 20 wt% -50 wt%.
The gel breaker can be one or more of sodium hypochlorite, hydrogen peroxide and polyaluminium chloride.
The demulsifier can be quicklime and/or polyether demulsifier.
In one embodiment, the addition amount of the demulsifier or the gel breaker accounts for 1-8 per mill of the total mass of the oil sludge, the pH value of the demulsification reaction is 7, and the reaction time is 20-30 min.
The oil sludge is subjected to solid-liquid separation to obtain sludge (solid component) and an oil-water mixture (liquid component).
The water content of the produced mud is less than or equal to 30 percent, and the oil content is less than or equal to 2 percent.
Further, the comprehensive treatment method of oil-gas wastewater and oil sludge further comprises the step S400: and (3) dehydrating the sludge subjected to coagulation/flocculation precipitation in the pretreatment step of S100, and performing solid waste treatment on the dehydrated sludge and the sludge obtained by solid-liquid separation of the oil sludge.
The comprehensive treatment method of the oil-gas wastewater and the oil sludge further comprises the step S500: and (4) oil separated from the oil-water mixture is recovered together with scum obtained by air floatation oil removal in the pretreatment step of the step S100.
The microbial degradation treatment method in step S300 is any one of MBR, AAO, SBR, oxidation ditch, MBBR, and bio-contact oxidation.
The microorganisms in the microbial degradation process can be self-cultured by utilizing the fresh water with low salinity and high organic matters and the microorganisms contained in the water separated from the oil-water mixture to obtain the self-cultured microorganisms.
In one embodiment, the culture conditions for the self-culturing microorganism are: intermittent cyclic aeration is adopted, the pH is controlled to be 6.5-8.5, the dissolved oxygen is controlled to be 2.0-4.0 mg/L, and the water temperature is controlled to be 15-25 ℃.
Furthermore, microbial agents can be inoculated to further improve the degradation efficiency. The inoculated microbial agent is one or more of petroleum degrading bacteria, COD degrading bacteria, ammonia nitrogen degrading bacteria and total nitrogen degrading bacteria. Preferably, the inoculated microbial agent is two or more microbial agents, wherein one microbial agent is a petroleum degrading bacterium.
The addition amount of the inoculated microbial inoculum is 0.1-0.5 per mill of the total water amount in the microbial degradation.
When the inoculated microbial agents are two or more than two microbial agents, and one microbial agent is a petroleum degrading bacterium, the mass ratio of the petroleum degrading bacterium to the other microbial agents is (0.4-1): 1.
Furthermore, the sludge obtained after the microbial degradation is further dehydrated, the dehydrated sludge can be recycled, and the supernatant liquid flows back and further enters the circulating treatment of the microbial degradation. The sludge can be used as soil for municipal and greening planting, and realizes reutilization and no solid waste discharge.
The ultrafiltration aims at separating macromolecules and micromolecules, solvent (water) and micromolecule solute which are smaller than the pore diameter of the ultrafiltration membrane permeate the membrane to form purified liquid (filtered liquid), and solute groups which are larger than the pore diameter of the membrane are intercepted and discharged along with water flow to form ultrafiltration concentrated water. The ultrafiltration concentrate is further subjected to the reverse osmosis step.
In one embodiment, the ultrafiltration membrane has a pore size of 20A°～1000A°。
In one embodiment, the ultrafiltration concentrated water obtained after the ultrafiltration step has SS less than or equal to 0.2mg/L and turbidity less than or equal to 0.2NTU, so that the reverse osmosis step can be better performed.
The reverse osmosis step can intercept various inorganic ions, colloidal substances and macromolecular solutes in the water, thereby obtaining the qualified reuse water.
The standard-reaching reuse water meets the standard of 'supplement water of an open circulating cooling water system' specified in 'urban sewage comprehensive utilization industrial water quality' (GB 19923-2005).
Referring to fig. 1, an embodiment of the present invention further provides an integrated oil-gas wastewater and oil sludge treatment system, which includes a pretreatment system 100, a concentration system 200, an oil sludge treatment system 300, and a cooperative purification system 400,
the pretreatment system 100 comprises an air flotation oil removal unit 110, a coagulation/flocculation precipitation unit 120 and a filtering unit 130;
the concentration system 200 is configured to concentrate the effluent to obtain high-salinity concentrated water and low-salinity high-organic fresh water;
the oil sludge treatment system 300 comprises a solid-liquid separation unit 310 and an oil-water separation unit 320 which are connected in sequence and used for extracting oil in the oil sludge;
the cooperative purification system 400 comprises a biochemical degradation unit 410, an ultrafiltration unit 420 and a reverse osmosis unit 430 which are connected in sequence,
the biochemical degradation unit 410 is connected to the oil-water separation unit 320 and the concentration system 200, and is configured to mix the water separated by the oil-water separation unit with the fresh water of the low-salinity high-organic matter, and perform a microbial degradation process on the mixture.
The air floatation oil removal unit 110 may be any one of a pressurized dissolved air floatation unit, a cavitation floatation unit, an induced floatation unit, and a micro-nano floatation unit.
In one embodiment, the coagulation/flocculation unit 120 includes a de-hardening desilication tank, a coagulation tank, a flocculation tank, and a sedimentation tank, which are connected in sequence. The hardness-removing and silicon-removing tank, the coagulation tank, the flocculation tank and the sedimentation tank are all conventional sewage treatment devices in the field.
Further, a dosing device and a pH measuring device are further disposed in the coagulation/flocculation unit 120, so that dosing can be performed in real time, and the pH in water can be detected in real time.
The filtering unit 130 may be one or more of a V-type filter, a D-type filter, sand filtration, a multi-media filter, a self-cleaning filter, and ultrafiltration.
In one embodiment, the pretreatment system 100 further comprises a carbon remover connected after the filtering unit 130 for removing alkalinity of the oil and gas wastewater.
The concentration system 200 includes an evaporative concentration unit and/or an electrodialysis concentration unit.
In an embodiment, the integrated oil and gas wastewater and sludge treatment system further comprises a zero emission system 500. The zero-discharge system 500 is connected to the concentration system 200, and is configured to perform inorganic salt recovery on the high-salinity concentrated water obtained after the concentration system 200 is concentrated. The zero emission system 500 is the same as in the following patent documents and literature: ZL201410796519.5, ZL201410796518.0, ZL201610072785.2 or ZL 201610072782.9.
As a specific embodiment, the solid-liquid separation unit 310 is a high-efficiency solid-liquid separator.
In one embodiment, the oil-water separation unit 320 is an industrial oil-water separator.
The biochemical degradation unit 410 includes a microbial culture device 412 and a microbial degradation device 414.
The microbial degradation device 414 may be any one of MBR, AAO, SBR, oxidation ditch, and bio-contact oxidation device.
In one embodiment, the ultrafiltration unit 420 comprises an ultrafiltration membrane having a membrane pore size of 20A ° to 1000A °.
In an embodiment, the integrated oil and gas wastewater and sludge treatment system further comprises an oil recovery system 600. The oil recovery system 600 is connected to the air flotation oil removal unit 110 and the oil-water separation unit 320, and is configured to cooperatively recover the scum discharged by the air flotation oil removal unit 110 and the oil component obtained by the oil-water separation unit 320.
As a specific embodiment, the oil recovery system 600 is a distillation apparatus and/or a solvent extraction apparatus.
In an embodiment, the oil-gas wastewater recycling treatment system further includes a homogeneous uniform-amount adjusting tank 800. The homogeneous uniform regulating reservoir 800 is arranged in front of the pretreatment system 100 and is used for ensuring that the oil-gas wastewater in the system is not influenced by the front-end production process to cause fluctuation of water inflow and fluctuation of water quality in different time periods, so that the content of each substance in the oil-gas wastewater tends to be stable, the change of the water quality, the water quantity and the water temperature of the oil-gas wastewater is balanced and regulated, surplus is stored, and shortage is supplemented, so that the oil-gas wastewater entering the pretreatment system 100 is uniformly fed.
In one embodiment, a return pipeline is connected between the reverse osmosis unit 430 and the homogeneous volume-equalizing regulating reservoir 800, and is used for returning the residual wastewater after reverse osmosis interception to the oil-gas wastewater and oil sludge comprehensive treatment system.
Further, the coagulation/flocculation unit 120 is further connected to a sludge dewatering system 700, and the sludge dewatering system 700 is used for dewatering sludge.
Further, the biochemical degradation unit 410 is also connected with a sludge dewatering system 700.
The following describes in detail the specific implementation of the method and system for comprehensively treating oil-gas wastewater and oil sludge in the present application, by taking the oil-gas wastewater and oil sludge produced by a certain project as an example.
Example 1
Preliminary detection has been carried out to oil gas waste water before handling, and this oil gas waste water quality of water index is as follows: water quantity: 500m3TDS (total dissolved solids): 87100mg/L, COD: 2660mg/L, Ca2+：19300mg/L，Mg2+：1310mg/L，Cl-：66100mg/L，SO4 2-：＜8mg/L，NO3-：＜0.1mg/L，HCO3 -：170.9mg/L，SiO2: 75.72mg/L, pH: 5.88, chroma: 256-fold, turbidity: 700 ℃ and the oil content of 70.6 mg/kg. The oil sludge is tank bottom oil sludge, and has an oil content of 20 wt% and a water content of 40 wt%.
(1) The oil gas wastewater is conveyed to a homogenizing and quantity-equalizing regulating tank 800, enters a pretreatment system 100 after being regulated by the homogenizing and quantity-equalizing regulating tank, and sequentially passes through an air flotation oil removal unit 110, a coagulation/flocculation precipitation unit 120, a filtering unit 130 and a carbon remover. The effluent of the pretreated oil gas wastewater contains the following components: the total hardness is less than or equal to 200mg/L, the bicarbonate radical is less than or equal to 100mg/L, the silicon dioxide is less than or equal to 5mg/L, the turbidity is less than or equal to 1NTU, and the oil content is less than or equal to 1 mg/L.
(2) And (2) further feeding the effluent of the oil-gas wastewater in the step (1) into a concentration system 200 for electrodialysis concentration to obtain electrodialysis concentrated water with the mass volume concentration percentage of 25% of sodium chloride and electrodialysis fresh water containing organic matters, recovering the electrodialysis concentrated water after zero discharge treatment, and feeding the electrodialysis fresh water into the step (3) for treatment. The operation conditions during the electrodialysis concentration are as follows: the water recovery rate is 80 percent, the linear velocity of the oil gas wastewater entering the pipeline opening is 150mm/s, and the operating pressure is 2.5kg/cm2The operating voltage is 250V and the current is 2A.
(3) 100kg of oil sludge is placed in a solid-liquid separation unit 310 (a high-efficiency solid-liquid separator) for solid-liquid separation, 0.2kg of sodium hypochlorite and 0.6kg of quicklime are added for demulsification reaction, the pH value is adjusted to 7, and the reaction time is 20 min. The effluent water after solid-liquid separation enters an oil-water separation unit 320, and the discharged sludge and the sludge generated by the coagulation/flocculation precipitation unit 120 are subjected to solid waste treatment together. The oil-water separation unit 320 (industrial oil-water separator) separates oil and moisture, the oil enters the oil recovery system 600, and the moisture enters the biochemical degradation unit 410. The oil recovery rate was 95%.
(4) The electrodialytic fresh water in the step (2) and the water from the oil-water separation unit 320 in the step (3) are in a range of 4m3And/h, entering the biochemical degradation unit 410, fully mixing, and then entering the microbial culture device 412 for microbial culture under the following culture conditions: intermittent cyclic aeration is adopted, the pH is controlled to be 8.0, the dissolved oxygen is controlled to be 4.0mg/L, and the water temperature is controlled to be 25 ℃. And adding 0.8kg of biochemical degradation complex bacteria (Shandong Biwofeng ecological environment limited, the complex bacteria comprises three bacteria of COD degradation bacteria, ammonia nitrogen degradation bacteria and total nitrogen degradation bacteria) and 0.8kg of BDB-n biodegradation bacteria (produced by Nanyang Donghua engineering science and technology limited), and further adding into the mixtureMicrobial degradation was carried out with a residence time of 24 hours.
(5) And (4) mixing the water obtained after the oil-water separation unit treatment in the step (3) and the produced water obtained by the microbial degradation device 414 in the step (4), and then feeding the mixture into an ultrafiltration unit 420. The ultrafiltration unit adopts immersed ultrafiltration, and the operating pressure is 0.25 MPa. After ultrafiltration treatment, the SDI in the produced water is less than or equal to 1, the turbidity is less than or equal to 0.2NTU, and the SS is less than 0.2 mg/L.
(6) The produced water after the ultrafiltration interception filtration enters the reverse osmosis unit 430. The operating pressure of the reverse osmosis system is 20Mpa, and after desalination and concentration by the reverse osmosis system, the final effluent water is the standard of ' make-up water of an open circulating cooling water system ' specified in urban sewage comprehensive utilization industrial water quality ' (GB19923-2005), and most salt ions and organic matters are intercepted in the reverse osmosis concentrated water and returned to the regulating reservoir.
In the embodiment, the recycled water reaching the standard is produced, and the standard of 'supplementing water of an open circulating cooling water system' specified in 'urban sewage comprehensive utilization industrial water quality' (GB19923-2005) is met. And high-content sodium chloride concentrated water is produced, oil content is recovered, and the oil-gas wastewater and oil sludge are subjected to cooperative resource utilization and high utilization rate.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (17)
1. A comprehensive treatment method of oil gas wastewater and oil sludge is characterized by comprising the following steps:
s100, carrying out pretreatment operations of air flotation oil removal, coagulation/flocculation precipitation and filtration on the oil gas wastewater to obtain effluent and scum, and concentrating the effluent to obtain high-salinity concentrated water and fresh water with low-salinity and high-organic matters, wherein the high-salinity concentrated water is recycled, and the fresh water with low-salinity and high-organic matters enters the step S300 for treatment;
s200, adding a demulsifier and/or a gel breaker into the oil sludge for demulsification reaction, performing solid-liquid separation on the oil sludge through flotation and filter pressing, further separating oil and water from the obtained oil-water mixture, and treating the water in the step S300;
s300, mixing the fresh water with low salinity and high organic matters in the step S100 with the water in the step S200, and performing microbial degradation, ultrafiltration and reverse osmosis on the mixture to obtain the recycled water reaching the standard.
2. The comprehensive treatment method of oil and gas wastewater and oil sludge according to claim 1, wherein in step S200, the addition amount of the demulsifier or the gel breaker is 1-8 per mill of the total mass of the oil sludge, the pH value of the demulsification reaction is 7, and the reaction time is 20-30 min.
3. The integrated oil and gas wastewater and oil sludge treatment method according to claim 1, wherein in the step S300, the microbial degradation treatment method is any one of MBR, AAO, SBR, oxidation ditch, MBBR and biological contact oxidation.
4. The integrated treatment method for oil and gas wastewater and oil sludge according to claim 1, wherein in the step S300, the microorganism is a self-cultured microorganism or the self-cultured microorganism and an external microbial agent, and the culture conditions of the self-cultured microorganism are as follows: intermittent cyclic aeration is adopted, the pH is controlled to be 6.5-8.5, the dissolved oxygen is controlled to be 2.0-4.0 mg/L, the water temperature is 15-25 ℃, and the inoculated microbial agent is one or more of petroleum degrading bacteria, COD degrading bacteria, ammonia nitrogen degrading bacteria and total nitrogen degrading bacteria.
5. The comprehensive oil and gas wastewater and oil sludge treatment method according to claim 1, wherein the addition amount of the microbial agent is 0.1-0.5 per mill of the total water amount in the microbial degradation.
6. The integrated oil and gas wastewater and oil sludge treatment method according to claim 1, wherein the step S300 further comprises the steps of dehydrating the sludge after the microbial degradation, refluxing the obtained supernatant, and recycling the dehydrated sludge.
7. The integrated treatment method for oil and gas wastewater and oil sludge according to claim 1, further comprising a step S400 of dehydrating the sludge coagulated/flocculated and precipitated in the step S100, wherein the dehydrated sludge and the sludge obtained after the solid-liquid separation of the oil sludge in the step S200 are subjected to solid waste treatment.
8. The integrated oil-gas wastewater and sludge treatment method according to claim 1, further comprising a step S500 of recovering oil from the dross obtained in the step S100 and the oil obtained in the step S200 in cooperation.
9. The integrated oil and gas wastewater and oil sludge treatment method according to claim 1, wherein in step S300, the concentrated ultrafiltration water SS obtained after the ultrafiltration step is less than or equal to 0.2mg/L, and the turbidity is less than or equal to NTU (nitrilotris) and less than or equal to 0.2.
10. A comprehensive treatment system for oil-gas wastewater and oil sludge is characterized by comprising a pretreatment system, a concentration system, an oil sludge treatment system and a cooperative purification system,
the pretreatment system comprises an air floatation oil removal unit, a coagulation/flocculation precipitation unit and a filtration unit which are connected in sequence;
the concentration system is used for concentrating the pretreated effluent to obtain high-salinity concentrated water and fresh water with low salinity and high organic matters;
the oil sludge treatment system comprises a solid-liquid separation unit and an oil-water separation unit which are sequentially connected and is used for extracting oil in the oil sludge;
the cooperative purification system comprises a biochemical degradation unit, an ultrafiltration unit and a reverse osmosis unit which are connected in sequence;
the biochemical degradation unit is respectively connected with the oil-water separation unit and the concentration system and is used for mixing the water separated by the oil-water separation unit with the fresh water of the low-salinity high-organic matter and carrying out microbial degradation treatment on the mixture.
11. The comprehensive oil and gas wastewater and oil sludge treatment system according to claim 10, wherein the air floatation oil removal unit is any one of a pressurized dissolved air floatation unit, a cavitation floatation unit, an induced floatation unit and a micro-nano floatation unit.
12. The integrated oil and gas wastewater and sludge treatment system according to claim 10, wherein the coagulation/flocculation precipitation unit comprises a de-hardening desilication tank, a coagulation tank, a flocculation tank and a sedimentation tank which are connected in sequence.
13. The integrated oil and gas wastewater and sludge treatment system according to claim 10, wherein the filtration unit comprises one or more of a V-type filter, a D-type filter, sand filtration, multi-media filter, self-cleaning filter, and ultrafiltration.
14. The integrated oil and gas wastewater and sludge treatment system according to claim 10, wherein the concentration system comprises an evaporative concentration unit and/or an electrodialysis concentration unit.
15. The integrated oil and gas wastewater and oil sludge treatment system according to claim 10, further comprising a zero-emission system, wherein the zero-emission system is connected with the concentration system and is used for recovering inorganic salts from the high-salinity concentrated water obtained after the concentration by the concentration system.
16. The integrated oil and gas wastewater and sludge treatment system according to claim 10, wherein the biochemical degradation unit comprises a microbial cultivation device and a microbial degradation device, and the microbial degradation device is any one of MBR, AAO, SBR, oxidation ditch and biological contact oxidation treatment device.
17. The comprehensive oil-gas wastewater and oil sludge treatment system according to claim 10, further comprising an oil recovery system, wherein the oil recovery system is respectively connected to the air-flotation oil removal unit and the oil-water separation unit, and is configured to cooperatively recover scum discharged by the air-flotation oil removal unit and oil obtained by the oil-water separation unit.
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