CN108117214B - Shale gas exploitation fracturing flowback waste liquid circulating tube array evaporation reduction treatment method and equipment - Google Patents
Shale gas exploitation fracturing flowback waste liquid circulating tube array evaporation reduction treatment method and equipment Download PDFInfo
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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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- C02F2001/007—Processes including a sedimentation step
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- 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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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
Abstract
A shale gas exploitation fracturing flowback waste liquid treatment method and equipment, add flocculating agent to waste liquid to coagulate preconditioning and filter-press through the filter press at first, realize the solid-liquid separation; the filtered water of the filter press is oxidized and degraded by Fenton to further oxidize and degrade refractory organics in the wastewater; adding NaOH into the wastewater after the Fenton reaction in a pipeline by adopting a static mixer to precipitate Fe in the water3+Precipitating the solution by a sedimentation tank, performing solid-liquid separation by a filter press, and filtering the filtrate by a sand filter tank; and finally, pumping the waste water filtered by the sand filter tank into a circulating tube still evaporator for evaporation concentration, and carrying out outward transportation treatment on the concentrated treated water. The sludge produced in each link is subjected to sanitary landfill. The invention has the advantages that each process section is buckled, the process is complete, and the applicability to water inlet is wide. Meanwhile, the process is simple, efficient and energy-saving, the operation cost is low, the system structure is compact, and the quantity of the waste water treated by outward transportation can be greatly reduced.
Description
Technical Field
The invention relates to the field of industrial sewage and wastewater treatment, in particular to a treatment process for reducing shale gas mining fracturing flowback waste liquid.
Background
The shale gas exploitation fracturing flowback waste liquid is special work (industrial) waste water generated in the shale gas exploitation process. The fracturing waste liquid discharged every year in shale gas exploitation in China is about 100 million tons. Has related statistics, and each shale gas production well fracturing flowback waste liquid is about 30-50 m3And d. The components are very complex and mainly contain oil,Various organic additives such as guanidine gum, formaldehyde and the like, various chemical treatment agents such as sulfate and the like, and various substances such as bacteria and the like. Therefore, the shale gas fracturing flowback waste liquid has the characteristics of high COD value, high salt content, high stability, high viscosity, strong pungent smell, difficult degradation and the like, and has great harm to the environment. After the substances enter the environment, particularly underground water and surface water environment, persistent pollution is brought to water and soil environment systems, and immeasurable loss is caused to shale gas production and long-term development. Therefore, the treatment of the fracturing flow-back waste liquid becomes one of the key environmental problems in the development process of the shale gas.
However, due to the limitations of field conditions and technical level, the treatment technology of shale gas fracturing waste liquid in China is not mature, and even some waste liquid is directly injected or discharged into the environment without treatment, which further aggravates the urgency of shale gas fracturing waste liquid treatment. At present, the commonly used fracturing waste liquid treatment process mainly comprises ' Fenton oxidation-flocculation-SBR combined treatment ', ' flocculation-oil removal-photocatalytic oxidation ', ' Fenton oxidation-flocculation reinjection treatment ', ' flocculation-oil removal-precipitation-double stage oxidation ', ' chemical destabilization-filtration-O3/H2O2-complex catalytic oxidation-deep oxidation ", etc. The combined process can realize the advantage complementation of single technology, improve the treatment effect, reduce the dosage of chemical agents, reduce the cost and the like. However, these processes focus on the treatment of suspended substances and organic substances in wastewater, and the treatment effect on salts in wastewater is not obvious. And because the salt content in the shale gas fracturing waste liquid is very high, the treatment of the salt in the waste liquid becomes a difficult problem for treating the shale gas fracturing waste liquid. And most of the treatment processes stay in the experimental research stage, the actual engineering application is less, and even if the treatment processes are applied in a few cases, the amount of externally transported reinjection water or discharged water after treatment is still large, so that the cost of externally transported reinjection water is high.
Along with increasingly severe environmental problems in China, the efficient and low-cost reduction treatment of the fracturing waste liquid generated in the shale gas exploitation process is an urgent need for the development of the fracturing waste liquid.
Disclosure of Invention
The invention aims to solve the problem of large treatment capacity of the conventional shale gas exploitation fracturing flow-back waste liquid, provides a circulating tube array evaporation reduction treatment method and equipment for the shale gas exploitation fracturing flow-back waste liquid, which have the advantages of high efficiency, simplicity and convenience in operation, convenience in movement and low treatment cost, aims at the characteristics of complex components, variability and dispersibility of the fracturing flow-back waste liquid, and mainly realizes waste liquid reduction so as to solve the problem of treatment of the fracturing flow-back waste liquid in the shale gas exploitation industry in China.
The technical scheme adopted by the invention is as follows:
a shale gas exploitation fracturing flowback waste liquid circulating tube array evaporation reduction treatment method comprises the following steps:
1. performing coagulating sedimentation pretreatment: pumping the fracturing flow-back fluid into a coagulation pretreatment tank, and adding sodium carbonate (Na) into the fracturing flow-back fluid wastewater by using a dosing machine2CO3) Performing coagulation pretreatment with aluminum polyaluminum chloride (PAC) to obtain Ca2+、Mg2+The ions form precipitates, and impurities such as turbidity, suspended matters, residual components of the fracturing fluid, crude oil and the like in the wastewater are removed. And during the coagulation pretreatment, the hydraulic retention time in the flocculation process is 15 +/-5 min. If the concentrations of organic matters, SS and other substances in the fracturing flow-back fluid are too high, and the waste liquid is colloidal, filter pressing can be carried out by a filter press to realize solid-liquid separation, and the filtered waste water is subjected to coagulating sedimentation pretreatment.
2. Fenton deep oxidation: the effluent after coagulation pretreatment is subjected to pressure filtration by a filter press to realize solid-liquid separation, the filtered wastewater automatically flows into a water inlet adjusting tank and then is pumped into a Fenton reaction tank, and H2O2In Fe3+And further deeply oxidizing and degrading the refractory organics in the wastewater by Fenton oxidation under the catalytic action of ions, wherein the reaction time is 1.25 +/-0.25 h.
3. Precipitation and filtration: the wastewater after Fenton oxidation flows into a sedimentation tank, and Fe in NaOH sedimentation water is added into the wastewater after Fenton reaction through a static mixer arranged in a pipeline in the flowing process3+Precipitating the ion and solution in a precipitation tank, performing solid-liquid separation again by a filter press, and allowing the filtrate to flow into a sand filter tank for filteringAnd (5) filtering.
4. And (3) evaporation and concentration: and pumping the waste water discharged from the sand filtering tank into a circulating tube array atmospheric evaporator for evaporation concentration, wherein the treatment process is as follows: the waste water is pumped into a spraying system in an evaporator by a circulating water pump, fully atomized waste water is uniformly sprayed into a tower through a water distributor, the atomized waste water flows through heating circulating tubes filled with high-temperature steam under the action of gravity, honeycomb fillers are filled among the heating circulating tubes to form a layer of film-shaped water flow, the heat exchange area and the heat exchange time are increased, dry air with a high break value enters the tower from the bottom under the action of a high-power fan, the air speed at the outlet of the evaporator is controlled to be 12-20m/s, the water film formed when the waste water flows through the surfaces of the fillers and high-speed flowing air are subjected to heat exchange to be rapidly vaporized into water vapor to enter a gas phase, evaporation and concentration of the waste water are realized, the air provides a part of heat required by evaporation of the waste water, the other part of heat is provided by heating of the circulating tubes, and then the air with high; the rest waste water falls back to a circulating water collecting tank at the bottom of the evaporator and is sent to a spraying system by a circulating water pump for circulating evaporation; the water drops carried in the air are blocked by the dehydrator in the tower and fall back to the surface of the heating circulation tube array for reheating and evaporating.
5. The concentrated waste water is discharged through a pipeline at the bottom of the evaporator and is transported outside for treatment. And carrying out outward transportation and sanitary landfill treatment on the sludge subjected to filter pressing.
Wherein, the PAC content in the coagulation sedimentation pretreatment stage is 28 percent to 30 percent, the hardness of the effluent is not more than 450mg/L, the pH value of the coagulation sedimentation is 9, and the hydraulic retention time of the flocculation tank is 15 +/-5 min.
In Fenton oxidation stage H2O2The mass ratio of COD/COD is 7.1, and the reaction time is 1.25 +/-0.25 h.
Filtering in a sand filter tank at the precipitation and filtration stage, wherein the hydraulic retention time is 1 +/-0.5 h, and the pH value is 9.
The invention also provides a shale gas exploitation fracturing flow-back waste liquid circulating tube array evaporation and reduction treatment device for realizing the method, which comprises a coagulation tank, a Fenton reaction tank, a filter press, a sedimentation tank, a sand filter tank, a circulating tube array atmospheric evaporator, a steam boiler, water softening equipment and a softening water tank which are sequentially communicated through a pipeline; the system also comprises a sodium carbonate and PAC dosing device connected with the coagulation tank, a hydrogen peroxide and ferric sulfate and sulfuric acid dosing device connected with the Fenton reaction tank, a sodium hydroxide dosing device connected with the static mixer, a water pump and corresponding valves arranged on pipelines.
The equipment adopts a circulating tube array atmospheric evaporator with a special structure, the circulating tube array atmospheric evaporator is of a square or round tower-shaped structure, a fan, a water collector, a water distributor, a circulating tube array heater, a packing area and a circulating water collecting tank are arranged in a tower of the evaporator, and a water suction pump is arranged outside the tower.
The fan is an axial flow type high-power fan and is arranged at the outlet of the top of the evaporator, the type and the power of the fan are determined by the required evaporation air quantity, but the power of the fan must ensure that the air speed at the outlet of the evaporator reaches 12-20 m/s.
The water distributor is arranged at the upper part of the evaporator and consists of a branch water distribution main pipe, branch pipes and nozzles which are arranged in a tree-like way, the nozzles adopt large-flow atomizing nozzles, the diameter of the water supplementing pipe and the specification of the nozzles are selected according to the designed water quantity, and the number and the arrangement mode of the nozzles are determined by the water distribution flow and the water spray flow of a single nozzle.
The water collector is arranged between the water distributor and the fan, is made of corrosion-resistant materials and is made into a wave shape.
The circulating tube array heater is arranged in a filling area in the middle of the evaporator, is made of stainless steel or copper tubes with fins, is corrosion-resistant, high-temperature-resistant and high-pressure-resistant, and is in a disc-shaped or U-shaped coil structure, so that high-flow fluid forced circulation is ensured, the circulating tube array heater is communicated with a heat source outside the tower, and the length and the number of layers of the circulating tube array are calculated according to the required heat exchange amount.
The filler in the filler area is made of high-temperature-resistant anticorrosive materials and has a honeycomb structure, and the honeycomb structure is filled between the coils of the circulating tubular heater and surrounds the circulating tubular heater.
The lower part of the evaporator is provided with an air inlet, and the bottom of the evaporator is provided with a circulating water collecting tank.
The outside of the structure is packaged by adopting an anticorrosive material to form a shell of the circulating tube array atmospheric evaporator unit.
The invention has the following characteristics:
1. the method adopts a chemical coagulation-Fenton deep oxidation-physical filter pressing combined technology as a circulating tube array evaporation concentration pretreatment step. And (3) directly performing filter pressing on the effluent after the coagulation pretreatment by using a filter press, and performing subsequent Fenton deep oxidation treatment. And precipitating the effluent after deep oxidation, and then recycling the effluent to the belt filter press for filter pressing. The process flow is simple, most organic pollutants and suspended solids in the wastewater can be effectively removed through chemical coagulation and Fenton deep oxidation treatment, solid-liquid separation is realized through filter pressing, the evaporation efficiency of the wastewater can be effectively improved, and the evaporator is prevented from scaling.
2. The invention particularly adopts the atmospheric evaporator containing the circulating tube array evaporator as evaporation concentration equipment to carry out low-temperature evaporation concentration on the wastewater after the physicochemical treatment, thereby greatly reducing the outward transportation amount of the wastewater and effectively reducing the treatment cost. The atmospheric evaporator of the present invention is structurally different from the evaporators or cooling towers commonly used in the prior art, and is also fundamentally different in principle. The common evaporator or cooling tower enters the tower through air with low break value, and after heat exchange is carried out between the air and the treated water flow with higher temperature, hot air with high break value is pumped out from the top, so as to achieve the purpose of reducing the temperature of the treated water; the air evaporator of the invention is characterized in that dry air with higher enthalpy enters the tower under the action of a high-power axial flow fan, the air transfers heat to the waste water in the tower to provide partial heat required by waste water evaporation, and then the air with low enthalpy and high humidity is pumped out by the fan, so that the evaporation capacity of the circulating waste water is improved, and the purpose of concentration is achieved. Compared with the traditional evaporator, the circulating tube array atmospheric evaporator can greatly reduce heating energy consumption. Compared with the subsequent treatment by a biological method, the method has the advantages of smaller treatment facilities, simple treatment process, reduced operation cost and wider application range of the quality of the inlet water. When the waste liquid is treated by a biological method, the waste liquid with high salt content can inhibit the growth of microorganisms and influence the treatment effect, and the problem can be avoided by adopting an evaporation concentration method. On one hand, the evaporation treatment can reduce the waste water, effectively reduce the treatment cost and greatly reduce the outward transportation amount of the waste water; on the other hand, the shale gas fracturing waste liquid is concentrated, so that the metal salts in the waste liquid can be recycled and reused in subsequent outward transportation treatment, the problem of high salt content in the shale gas fracturing waste liquid can be effectively solved, and the metal salts in the waste liquid can be recycled.
The atmospheric evaporator has several obvious structural innovations, and the specific analysis is as follows:
(1) the evaporator must adopt a high-power fan, namely, the air speed at the outlet of the evaporator is ensured to reach 12-20m/s, because the evaporator achieves the following purposes: the energy required for the evaporation of the waste water is not provided by all the heating tubes, but the heating tubes are designed to provide only a part of the heat required for the evaporation, and the other part is provided by a large amount of air with higher enthalpy which is pumped by a high-power fan. That is, in the atmospheric evaporator, a part of heat required for evaporating the waste liquid is provided by air heat transfer, and a part of heat is provided by heating of the circulating tubes. Because the liquid evaporation speed is related to the air flow rate of the liquid surface, the larger the flow speed of the water film liquid surface air is, the more favorable the evaporation speed is, therefore, the advantages of high air speed and high gas flux are utilized by the high-power fan, the air circulation is enhanced, the flow speed of the water surface air is improved, the escaped water vapor molecules are rapidly diffused, the evaporation diffusion power is maintained to be constant and is not reduced, the gas flow and the gas flow speed in the evaporator can be improved, the evaporation efficiency is improved, the heating energy consumption can be saved, the total energy consumption is greatly reduced compared with the energy consumption for providing heat required by waste water evaporation by heating the heating tube array, and the principle is an innovation of the evaporator.
(2) In order to improve the enthalpy value of air pumped by the high-power fan, the inlet air of the evaporator firstly passes through an air inlet cylinder arranged on one side of the evaporator, an air dry combustion pipe is arranged in the air inlet cylinder to heat the air entering the evaporator, the enthalpy value of the air is further improved, and the inlet air is kept dry, so that the evaporation efficiency in the evaporator is improved.
(3) The circulation tubulation of this evaporimeter arranges in the filler district, rather than separately arranging, can obtain a longer dwell time when waste water drenches into the filler district, and this time can be utilized by the circulation heating tubulation simultaneously, and the extension is to the heat time of waste water, and filler district surface area is big simultaneously, and waste water forms the heat transfer area increase behind the water film, can improve heating efficiency.
(4) This evaporimeter is to promoting the waste water that the circulation sprayed through circulating water pump, additional heating does not carry out earlier and improves evaporation efficiency, because if waste water is heated earlier, waste water temperature can be a lot of than air temperature, the heat of water can transmit the lower air of temperature, cause calorific loss, and waste water evaporation process is a heat absorption process, the evaporation that can be unfavorable for waste water appears in this kind of condition, the waste water circulation of this evaporimeter adopts circulating pump natural circulation, put into the filler district with steam heating tubulation simultaneously, can not cause the difference in temperature between air and the waste water, thereby reduce the unnecessary heat loss. In addition, the atmospheric evaporator is provided with an air inlet cylinder with an air dry burning pipe, so that the air entering the evaporator can be heated in one step, the enthalpy value of the air entering the evaporator is improved, and the heat of the air entering the evaporator is transferred to the waste water, so that the waste water can be evaporated and absorb heat.
(5) The filler of the honeycomb structure and the high-temperature-resistant anticorrosive material is adopted in the atmospheric evaporator, the service life is long, the specific surface area of the filler of the honeycomb structure is large, on one hand, the contact area between the waste water and the air can be effectively increased, the opportunity of water molecule escape is increased, on the other hand, the heat exchange area is increased, and the evaporation speed is accelerated.
3. The continuous water feeding is adopted in the operation of the invention, and the continuous operation state of the wastewater among the coagulation tank, the Fenton oxidation tank, the filter press, the sand filter tank and the evaporator is realized through the valve control, so that the delay caused by intermittent operation is avoided, and the operation efficiency is improved;
4. the invention has simple equipment, short flow and convenient maintenance, and does not need to construct a reaction tank and other buildings on site; the service life is long; the whole process flow can realize automatic control, and the personnel allocation is greatly reduced;
the treatment process is a physical and chemical combined treatment method and system for treating the shale gas fracturing flowback waste liquid by adopting a chemical coagulation-physical filter pressing-efficient evaporation concentration technology, and the method and the system can effectively solve the difficult problem of treating the fracturing flowback liquid in the shale gas exploitation process in China in economic and technical aspects.
Drawings
Fig. 1 is a schematic view of the shale gas exploitation fracturing flow-back waste liquid circulation tube array evaporation reduction treatment process.
FIG. 2 is a schematic diagram of a circulating tube array atmospheric evaporator with a specific structure of the invention.
FIG. 3 is a schematic diagram of another embodiment of the present invention of a circulating tube array atmospheric evaporator.
In the figure, 1-concrete pouring; 2-Fenton reaction tank; 3, a filter press; 4, a sedimentation tank; 5, a sand filter tank; 6-sodium hydroxide dosing device; 7-sodium carbonate and PAC dosing unit; 8-hydrogen peroxide, ferric sulfate and sulfuric acid dosing devices; 9-circulating tube array atmospheric evaporator; 10-a static mixer; 11-a water pump; 901-axial flow fan; 902-a housing; 903-water receiver; 904, a water distributor; 905-a nozzle; 906-circulating tube and tube heat exchanger; 907-a filler; 908-air intake grille; 909-flow meter; 910-circulating water pump; 911-circulation feed tank; 912-automatic water supply device; 913-a drain opening; 914-a base; 915-pressure gauge; 916, an observation window; 917-air inlet cylinder support; 918, an air inlet drum; 919-air dry-burning tube.
Detailed Description
The invention is further described in the following with reference to the accompanying drawings
Referring to the attached figure 1, the shale gas exploitation fracturing flow-back waste liquid circulating tube evaporation and reduction treatment equipment provided by the invention comprises a coagulation tank 1, a Fenton reaction tank 2, a filter press 3, a sedimentation tank 4, a sand filter tank 5, a circulating tube evaporator 9, a sodium carbonate and PAC dosing device 7 connected with the coagulation tank, a hydrogen peroxide solution, a ferric sulfate and sulfuric acid dosing device 8 connected with the Fenton reaction tank, a sodium hydroxide dosing device 6 connected with a static mixer, a static mixer 10 and a water pump 11 which are sequentially communicated through pipelines, wherein corresponding valves are arranged on the pipelines.
Referring to fig. 2, a shell 902 of the circulating tube array atmospheric evaporator 9 is a square column tower-shaped structure, an axial flow fan 901, a water collector 903, a water distributor 904, a circulating tube array heater 906, a packed bed 907 and a circulating water collecting tank 911 are arranged in the tower, and a water suction pump 910 is arranged outside the tower.
The axial flow fan 901 is arranged at the top of the evaporator and is an axial flow type high-power fan, and the power of the fan needs to ensure that the air speed at the outlet of the evaporator reaches 12-20 m/s.
The water distributor 904 is arranged on the upper part of the evaporator and consists of a branch-shaped water distribution main pipe, branch pipes and nozzles, the nozzles adopt large-flow atomizing nozzles, the diameter of the water supplementing pipe and the specification of the nozzles are selected according to the designed water quantity, and the number and the arrangement mode of the nozzles are determined by the water distribution flow and the water spray flow of a single nozzle.
The water collector 903 is installed between the water distributor 904 and the axial flow fan 901, is made of corrosion-resistant material, and is made into a wave shape.
The circulating tube array heater 906 is arranged in the middle of the evaporator, is made of high-temperature and high-pressure resistant stainless steel or copper tubes with fins for corrosion prevention, is in a U-shaped coil pipe structure in appearance, the length and the number of layers of the circulating tube array are calculated according to the required heat exchange quantity, the high-flow fluid high-pressure circulation is ensured, the circulating tube array heater is communicated with a heat source steam boiler 10 outside the tower, and the heat source is from the steam boiler.
The packed bed 907 is made of high-temperature resistant anticorrosive material and has a honeycomb structure, and the honeycomb structure is filled between the coil pipes of the circulating tubular heater. The evaporation packed bed has a wider channel, and the crystallization condition can not be achieved in the whole evaporation process, so that the packed bed can not be blocked, and the evaporation packed bed is easy to disassemble, wash and maintain daily.
The air inlet grille 908 is arranged at the lower part of the evaporator, and the circulating water collecting tank 911 is arranged at the bottom of the evaporator.
The exterior of the above structure is encapsulated by an anticorrosive material to form a shell 902 of the circulating tube array atmospheric evaporator unit.
Fig. 3 shows another construction of the circulating tube array atmospheric evaporator 9, which is based on fig. 2 and is supplemented with an air inlet stack 918 in order to increase the temperature of the air drawn into the tower. The air inlet cylinder 918 is communicated with the evaporator at the inlet of the lower part of the evaporator, the joint of the air inlet cylinder shell and the evaporator shell is sealed but can be detached, the non-joint side is sealed by an anticorrosive material, the air inlet cylinder is supported by a bracket 917, the top of the air inlet cylinder is required to be provided with an air inlet grille, and the air inlet cylinder is internally provided with an air dry burning pipe 919.
The treatment of the fracturing flow-back waste liquid mainly comprises four treatment processes:
(1) performing coagulating sedimentation pretreatment: pumping the fracturing flow-back fluid into a coagulation pretreatment tank, and adding aluminum polyaluminium chloride (PAC) and sodium carbonate (Na) into the fracturing flow-back fluid wastewater by using a dosing device 72CO3) Performing coagulation pretreatment to make Ca2+、Mg2+The ions form precipitates, and impurities such as turbidity, suspended substance fracturing fluid residual components, crude oil and the like in the wastewater are removed at the same time. The hydraulic retention time in the coagulation pretreatment flocculation process is 15 +/-5 min.
(2) Fenton oxidation: and pumping the effluent after the coagulation pretreatment into a filter press by a screw pump for filter pressing to realize solid-liquid separation, automatically flowing the filtered wastewater into a Fenton reaction tank, adding hydrogen peroxide, ferric sulfate and sulfuric acid into the Fenton reaction tank by a medicine adding device 8, and controlling the medicine feeding time and the medicine feeding amount by a valve. H2O2In Fe2+And further deeply oxidizing and degrading the refractory organics in the wastewater by Fenton oxidation under the catalytic action of ions, wherein the reaction time is 1.25 +/-0.25 h.
(3) Precipitation and filtration: the waste water after Fenton oxidation flows into a sedimentation tank 4, Fe in NaOH sedimentation water is added into the waste water after Fenton reaction through a static mixer 10 arranged in a pipeline in the flowing process3+And (4) precipitating the ions and the solution in the sedimentation tank, then carrying out solid-liquid separation again through a filter press, and enabling the filtrate to flow into a sand filter tank 5 for filtering.
(4) And (3) evaporation and concentration: and pumping the waste water out of the sand filter tank into a circulating tube array evaporator 9 for evaporation and concentration. The concentration and evaporation treatment steps of the wastewater in the circulating tube array atmospheric evaporator 9 are as follows:
when the pretreated high-salinity wastewater enters the atmospheric evaporator, the wastewater is pumped into a spraying system 905 above the circulating heating tube array 906 through a circulating water pump 910, a proper amount of fully atomized wastewater is uniformly sprayed into the tower through a water distributor 904, the atomized wastewater flows through the heating circulating tube array 906 under the action of gravity, and a layer of honeycomb filler 907 is filled between the heating circulating tube array to form a layer of film-shaped water flow, so that the heat exchange area and the heat exchange time are increased, and the heat exchange efficiency is improved. The spray wastewater is fully exchanged heat with the atmosphere and the heating circulating tubes, and then is quickly vaporized into vapor to enter a gas phase, and the vaporized vapor is taken away by the high-power fan 901, so that the evaporation and concentration of the wastewater are realized. The rest waste water falls back to a circulating water collecting tank 911 at the bottom of the evaporator and is sent to a spraying system 905 by a circulating water pump 910 for recycling. Water droplets entrained in the air are blocked by the water collector 903 and fall back into the circulating tube heater to be heated and evaporated. High-temperature steam is introduced into the circulating heating tube nest, enters the circulating tube nest from a steam inlet at the upper part of the coil, exchanges heat with spraying wastewater and air outside the circulating tube nest, is gradually condensed into liquid from gaseous state, flows out from a steam outlet at the lower part, and flows back into the softening water tank. Meanwhile, the dry air with higher temperature enters the tower from the bottom air inlet grille 908 under the action of the fan (figure 2) or enters the air inlet drum 18 (figure 3), the dry air enters the filler area of the evaporator after being heated by the air dry burning pipe 919, the waste water forms a water film to exchange heat with the air when flowing through the filler surface, the air with lower high humidity temperature is extracted from the top, part of the heat required by the evaporation of the waste liquid is provided by air heat transfer, and part of the heat is provided by the heating of the circulating tubes. The rest water of the waste liquid is dripped into the bottom circulating water collecting tank. The waste water that instils into bottom circulation header tank draws spraying system through circulating water pump resorption, gets up the hydrologic cycle, and the circulation sprays waste water, improves evaporation efficiency. In the evaporator, the ratio of the treated water amount to the circulating water amount is designed to be 1:10, and the evaporation efficiency is 50%.
Compared with the fan adopted by the common evaporator, the high-power fan adopted by the evaporator has the difference that: the fan of the common evaporator has only one drainage function, and only the steam in the tower is sucked out of the evaporator through the fan; the evaporator adopts a high-power fan, so that the gas flow and the gas flow velocity in the evaporator can be improved, the evaporation speed is related to the air flow velocity on the surface of the liquid surface, and the higher the air flow velocity is, the more the evaporation is facilitated; the evaporator is also different from the traditional evaporator in principle, the energy required by the traditional evaporator is basically provided by the heating array pipes, one part of the energy required by the evaporator is provided by the heating pipes, and the other part of the energy required by the evaporator is provided by the air with higher enthalpy, so that the heating energy consumption can be saved, and therefore, a fan with higher power is required to provide larger gas flow, but the total energy consumption is greatly reduced compared with that of the common evaporator; the power of the evaporator fan needs to be determined according to the height of the evaporator filler area and the designed evaporation capacity, the outlet air speed of the evaporator needs to be ensured to be about 12-20m/s according to actual conditions, and the outlet air speed is far greater than the outlet air speed of a common evaporator during working. In terms of energy consumption, the actually required steam amount of a common evaporator for evaporating 1kg of water is about 1.2-1.6kg, the actually required steam amount of the evaporator for evaporating 1kg of water is about 0.6-0.8kg, the total energy consumption of the evaporator is about 50-60% of that of the common evaporator, and the specific effect has certain fluctuation according to the change of the site environment temperature and humidity.
The treatment process is adopted to treat the fracturing flowback waste liquid of a shale gas exploitation well in Sichuan province, and the water quality conditions of each stage in the treatment process are shown in table 1.
TABLE 1 Water quality analysis table after treatment of fracturing flow-back fluid in each stage
COD of raw water is 565mg/L, hardness is 3710mg/L, total soluble solid is 1.52 multiplied by 104g/L, chloride 1.72X 104mg/L, design throughput of 5m3H is used as the reference value. The coagulation pretreatment and belt filter press part, the hydraulic retention time of a coagulation pool is 15min, and 3.75kg/h of polyaluminium chloride and Na are added2CO3The dosage is 18.55 kg/h. Fenton Oxidation part, FeSO4·7H2The adding amount of O is 1.25kg/H, H2O2The dosage is 3.14kg/H, H2SO4The adding amount is 0.25g/h, the adding amount of NaOH is 0.54kg/h, the oxidation reaction time is 1.25h, the retention time of an inclined plate sedimentation tank is 3h, the water quality of treated effluent is 72mg/L, the hardness is 31.32mg/L, and the total dissolved solids are 16.06 g/L. And the evaporation concentration treatment part of the circulating tube still evaporator is carried out, the ratio of the waste liquid treatment water quantity to the circulating water quantity is 1:10, and the designed evaporation capacity is 50%.
Claims (10)
1. A shale gas exploitation fracturing flowback waste liquid circulating tube array evaporation reduction treatment method is characterized in that: the processing method comprises the following steps:
(1) performing coagulating sedimentation pretreatment: pumping the fracturing flow-back fluid into a coagulation pretreatment tank, and adding sodium carbonate (Na) into the fracturing flow-back fluid wastewater2CO3) Performing coagulation pretreatment with aluminum polyaluminum chloride (PAC) to obtain Ca2+、Mg2+The ions form precipitates, and turbidity, suspended matters, residual components of the fracturing fluid and crude oil in the wastewater are removed simultaneously;
(2) fenton oxidation: the effluent after coagulation pretreatment is subjected to filter pressing by a filter press, solid-liquid separation is carried out, the filtered wastewater is pumped into a Fenton reaction tank, and H2O2In Fe2+Under the catalytic action of ions, the non-degradable organic matters in the wastewater are deeply oxidized and degraded through Fenton oxidation, and the reaction time is 1.25 +/-0.25 h;
(3) precipitation and filtration: the waste water after Fenton oxidation flows into a sedimentation tank, and NaOH is added into the waste water to precipitate Fe in the water3+Precipitating the solution, performing solid-liquid separation again by a filter press, and filtering the filtrate in a sand filter tank;
(4) and (3) evaporation and concentration: pumping the filtered waste water into a circulating tube array atmospheric evaporator for evaporation and concentration,
the waste water is pumped into a spraying system in an evaporator by a circulating water pump, fully atomized waste water is uniformly sprayed into a tower through a water distributor, the atomized waste water flows through heating circulating tubes filled with high-temperature steam under the action of gravity, honeycomb fillers are filled among the heating circulating tubes to form a layer of film-shaped water flow, the heat exchange area and the heat exchange time are increased, dry air with a high break value enters the tower from the bottom under the action of a high-power fan, the air speed at the outlet of the evaporator is controlled to be 12-20m/s, the water film formed when the waste water flows through the surfaces of the fillers and high-speed flowing air are subjected to heat exchange to be rapidly vaporized into water vapor to enter a gas phase, evaporation and concentration of the waste water are realized, the air provides a part of heat required by evaporation of the waste water, the other part of heat is provided by heating of the circulating tubes, and then the air with high; the rest waste water falls back to a circulating water collecting tank at the bottom of the evaporator and is sent to a spraying system by a circulating water pump for circulating evaporation; water drops carried in the air are blocked by a dehydrator in the tower and fall back to the surface of the heating circulating tube array for reheating and evaporation;
(5) the concentrated waste water is discharged through a pipeline at the bottom of the evaporator and is transported outside, and the sludge after filter pressing is transported outside for sanitary landfill treatment.
2. The shale gas exploitation fracturing flow-back waste liquid circulating tube array evaporation and reduction treatment method according to claim 1, characterized in that: the PAC content in the coagulation and precipitation pretreatment stage is 28-30%, the hardness of effluent is not more than 450mg/L, the pH value of the coagulation and precipitation is 9, and the hydraulic retention time of a coagulation and precipitation pretreatment tank is 15 +/-5 min.
3. The shale gas exploitation fracturing flow-back waste liquid circulating tube array evaporation and reduction treatment method according to claim 1, characterized in that: if the concentrations of organic matters, SS and other substances in the fracturing flow-back fluid are too high, so that the waste liquid is colloidal, filter pressing is firstly carried out by a filter press to realize solid-liquid separation, and the filtered waste water is subjected to coagulating sedimentation pretreatment.
4. The shale gas exploitation fracturing flow-back waste liquid circulating tube array evaporation and reduction treatment method according to claim 1, characterized in that: in Fenton oxidation stage H2O2The mass ratio of COD/COD is =7.1, and the reaction time is 1.25 +/-0.25 h.
5. The shale gas exploitation fracturing flow-back waste liquid circulating tube array evaporation and reduction treatment method of claim 1, wherein the method comprises the following steps: filtering in a sand filter tank at the precipitation and filtration stage, wherein the hydraulic retention time is 1 +/-0.5 h, and the pH value is 9.
6. The shale gas exploitation fracturing flow-back waste liquid circulating tube array evaporation and reduction treatment equipment for realizing the method of claim 1 is characterized by comprising a coagulation tank, a Fenton reaction tank, a filter press, a sedimentation tank, a sand filtration tank, a circulating tube array atmospheric evaporator, a steam boiler, water softening equipment and a softening water tank which are sequentially communicated through a pipeline; the system also comprises a sodium carbonate and PAC dosing device connected with the coagulation tank, a hydrogen peroxide and ferric sulfate and sulfuric acid dosing device connected with the Fenton reaction tank, a sodium hydroxide dosing device connected with the static mixer, a water pump and corresponding valves arranged on pipelines;
the circulating tube array atmospheric evaporator is of a square or round tower-shaped structure, an axial flow type high-power fan, a water collector, a water distributor, a circulating tube array heater, a packing area and a circulating water collecting tank are arranged in a tower of the evaporator, and a water pump is arranged outside the tower; the axial-flow type high-power fan is arranged at an outlet at the top of the evaporator, and the power of the fan needs to ensure that the air speed at the outlet of the evaporator reaches 12-20 m/s; the water distributor is arranged at the upper part of the evaporator, and the water collector is arranged between the water distributor and the axial-flow type high-power fan; the middle part of the evaporator is a filler area which is filled with high-temperature-resistant anticorrosive materials with a honeycomb structure, the circulating tube array heater is arranged in the filler area and surrounded by the filler, the circulating tube array heater is communicated with a heat source outside the tower, and the length and the number of layers of the circulating tube array are calculated according to the required heat exchange quantity; the lower part of the evaporator is provided with an air inlet, and the bottom of the evaporator is provided with a circulating water collecting tank.
7. The shale gas exploitation fracturing flow back waste liquid circulating tube array evaporation and reduction treatment equipment as claimed in claim 6, wherein: the air inlet is also connected with an air inlet cylinder, an air dry burning pipe is arranged in the air inlet cylinder, and the air inlet cylinder is hermetically connected with the air inlet of the evaporator and is of a detachable structure.
8. The shale gas exploitation fracturing flow back waste liquid circulating tube array evaporation and reduction treatment equipment as claimed in claim 7, wherein: air inlet grilles are arranged at the air inlet of the evaporator and the air inlet of the air inlet barrel.
9. The shale gas exploitation fracturing flow back waste liquid circulating tube array evaporation and reduction treatment equipment as claimed in claim 6, wherein: the water collector is made of corrosion-resistant materials and is made into a wave shape.
10. The shale gas exploitation fracturing flow back waste liquid circulating tube array evaporation and reduction treatment equipment as claimed in claim 6, wherein: the water distributor consists of a branch-shaped water distribution main pipe, branch pipes and nozzles, the nozzles adopt high-flow atomizing nozzles, and the number and the arrangement mode of the nozzles are determined by water distribution flow and water spray flow of a single nozzle; the circulating tube array heater is made of stainless steel or copper tubes with fins, is corrosion-resistant, high-temperature-resistant and high-pressure-resistant, and adopts a disc-shaped or U-shaped coil structure.
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| CN110902897A (en) * | 2019-11-27 | 2020-03-24 | 成都理工大学 | Deep treatment method for fracturing flowback fluid for shale gas exploitation |
| CN111072202B (en) * | 2019-11-28 | 2022-05-31 | 四川杰特油气工程技术服务有限公司 | Shale gas exploitation fracturing returns integration equipment of flowing back advanced treatment |
| CN111072213A (en) * | 2019-12-31 | 2020-04-28 | 上海同济建设科技股份有限公司 | Zero-discharge treatment process and device for fractured rock wastewater |
| CN112897787A (en) * | 2021-04-25 | 2021-06-04 | 重庆市涪陵页岩气环保研发与技术服务中心 | Shale gas fracturing flowback water treatment method |
| CN113233679A (en) * | 2021-05-07 | 2021-08-10 | 重庆大学 | Shale gas exploitation wastewater treatment method |
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