CN111072213A - Zero-discharge treatment process and device for fractured rock wastewater - Google Patents
Zero-discharge treatment process and device for fractured rock wastewater Download PDFInfo
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Abstract
The invention discloses a zero-discharge treatment process and a zero-discharge treatment device for fractured rock wastewater. Treating the fracturing rock wastewater by a coagulating sedimentation treatment system, a Fenton oxidation treatment system, a softening treatment system and an ED treatment system in sequence, treating the wastewater with the concentration higher than a set value after the treatment of the ED treatment system by evaporative crystallization, and treating the wastewater with the concentration lower than the set value by a biochemical treatment system; wherein, the sludge obtained after the coagulating sedimentation treatment system, the Fenton treatment system and the softening treatment system treat the wastewater is treated in a unified way. The treated wastewater meets the recycling requirement, and the aim of zero discharge of the wastewater can be fulfilled; the purity of the evaporated and crystallized by-product is high, so that the economic income can be increased; the system has stable operation and complete online equipment, and can greatly reduce manual operation.
Description
Technical Field
The invention relates to a zero-discharge treatment process and a zero-discharge treatment device for fractured rock wastewater, and belongs to the technical field of wastewater treatment.
Background
With the increasing depletion of petroleum resources and the increasing demand of people for petroleum resources, the social energy pressure is increasing. The shale gas is unconventional natural gas and has the characteristics of cleanness, high efficiency and large reserve, global shale gas resources are abundant and widely distributed, the global shale gas resource amount is about 465.2 billion cubic meters and accounts for nearly 50% of the global unconventional gas resource amount, and with the improvement of science and technology, the technology for extracting the shale gas by people is more and more mature, and the shale gas becomes new energy gradually. The united states has entered the shale gas scale-up production phase, and shale gas assets are transacted abnormally actively, increasing production from 340 billions of cubic meters in 2007 to 950 billions of cubic meters in 2009, exceeding the annual production (830 billions of cubic meters) of regular natural gas in our country. Shale gas resources in China are abundant, but development is still in the initial stage, and the country is actively promoting the development and utilization of shale gas.
The shale gas is natural gas which is rich in organic matters, has a certain commercial biological cause, a certain commercial pyrolytic cause and a certain commercial mixed cause due to organic matter adsorption effect or cracks and matrix pores in rocks in mature dark shale or high-carbon shale. Shale gas is produced by hydraulic fracturing, which is simply a process of producing shale gas by high pressure drilling a mixture of water, sand and chemicals into the ground through a borehole to fracture the shale formation into larger and more fractures.
Generally, one shale gas well requires up to 1000 trucks of water to drill and fracture. Hydraulic fracturing recovery can produce large volumes of wastewater, and methane, heavy metals, radioactive materials, fracturing fluids, and other contaminants from gas wells can flow out through a variety of potential pathways, thereby contaminating groundwater resources. The shale gas fracturing wastewater has the characteristics of high COD, high salt content, large water amount and difficulty in treatment, the exploitation water consumption of shale gas is very large, the generated wastewater amount is also large, the water supply treatment for exploiting shale gas by hydraulic fracturing brings huge challenges, and the wastewater recovered from a shale gas well contains hydrocarbons, heavy metals, dirt and chemical salt, and is generally considered as the most difficult-to-treat industrial wastewater by the outside. Along with the large-scale application of the hydraulic fracturing method in the field of shale gas, the water treatment market scale is enlarged, and the technology for treating the fracturing rock wastewater is more and more mature.
Both for water treatment benefits and water resources, technologies for treating fracturing rock wastewater are actively being explored. The GasFrac company injects high-pressure propylene into a shale gas well to replace high-pressure water flow, so that the water production of the fractured rock wastewater is reduced from the source; treating the fracturing wastewater by ozone/biological method in combination with Wangjianggang and the like; treating the fracturing wastewater by using an electrochemical catalytic oxidation method through the Yangmen; wangshuanwu et al uses micro-electrolysis-Fenton combination method to treat the fracturing waste water. The zero discharge of the fracturing rock wastewater is realized by adopting a coagulating sedimentation method, a Fenton method, a softening method, an ED method, a biochemical method and evaporative crystallization.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the utility model provides a fracturing rock waste water zero release treatment process and device for handle fracturing rock waste water, reduce the emission of fracturing rock waste water, alleviate the pollution of fracturing rock waste water to the environment, improve water resource utilization ratio, water economy resource.
In order to solve the technical problems, the invention adopts the following technical scheme:
the zero-discharge treatment process of the fracturing rock wastewater is characterized in that the fracturing rock wastewater is sequentially treated by a coagulating sedimentation treatment system, a Fenton oxidation treatment system, a softening treatment system and an ED treatment system, the wastewater with the concentration higher than a set value obtained after the treatment of the ED treatment system is treated by evaporative crystallization, and the wastewater with the concentration lower than the set value is treated by a biochemical treatment system; wherein, the sludge obtained after the coagulating sedimentation treatment system, the Fenton treatment system and the softening treatment system treat the wastewater is treated in a unified way.
Preferably, the coagulating sedimentation treatment system adopts a coagulating sedimentation tank, the pH value of the coagulating sedimentation tank is adjusted to 8-9, flocs are generated, PAC and PAM are added to enable the flocs to form precipitates, the precipitates are discharged out of the system through a sludge discharge pump, and supernatant enters a subsequent treatment system.
More preferably, sodium hydroxide is added into the coagulating sedimentation tank to adjust the pH value.
Preferably, the Fenton oxidation treatment system adopts a Fenton oxidation tank, supernatant obtained by the coagulating sedimentation treatment system enters the Fenton oxidation tank, the pH value of the Fenton oxidation tank is adjusted to 4-5, then ferrous sulfate solution and hydrogen peroxide are added to react to generate foam, and if too much foam is generated, a defoaming agent is added; after the reaction is finished, adding sodium hydroxide to adjust the pH value to 8-9, generating flocs, adding PAC and PAM to enable the flocs to form precipitates, discharging the precipitates out of the system through a sludge discharge pump, and enabling supernatant to enter a subsequent treatment system.
More preferably, concentrated sulfuric acid with the mass concentration of 98% is added into the Fenton oxidation tank to adjust the pH value; the dosage of the ferrous sulfate is 2.5-4 g/L, and the dosage of the hydrogen peroxide is 2.5-4.5 mL/L.
Preferably, the softening treatment system adopts a softening tank, the supernatant obtained by the Fenton oxidation treatment system enters the softening tank, then sodium carbonate solution is added, after flocs are generated, PAC and PAM are added to enable the flocs to form precipitates, the precipitates are discharged out of the system through a sludge discharge pump, and the supernatant enters a subsequent treatment system.
More preferably, the adding amount of the sodium carbonate is 3-7 g/L.
More preferably, the adding amount of the PAC is 100-300 mg/L; the dosage of the PAM is 5-20 mg/L.
Preferably, the ED treatment system adopts an ED membrane, supernatant obtained by the softening treatment system passes through the ED membrane, obtained wastewater with the concentration lower than a set value, namely fresh water enters the biochemical treatment system, and effluent is subjected to biochemical treatment to meet the discharge requirement; and evaporating and crystallizing the obtained waste water with the concentration higher than a set value, namely concentrated water.
Preferably, the TDS of the concentrated water is more than 150000mg/L, and the TDS of the fresh water is less than 10000 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method adopts a coagulating sedimentation method, a Fenton method, a softening method, an ED method, a biochemical method and an evaporative crystallization method to treat the fractured rock wastewater, the treated wastewater meets the recycling requirement, and the aim of zero discharge of the wastewater can be fulfilled;
(2) the COD of the waste water is 3500mg/L, the TDS is 32000mg/L, the total hardness (calculated by calcium carbonate) is 10000mg/L, after the treatment by the process, the COD is less than 100mg/L, the total hardness (calculated by calcium carbonate) is less than 100mg/L, the TDS of the concentrated water by the ED method is more than 150000mg/L, and the TDS of the fresh water is less than 10000 mg/L;
(3) the purity of the evaporated and crystallized by-product is high, so that the economic income can be increased; (5) the system has stable operation and complete online equipment, and can greatly reduce manual operation.
Drawings
FIG. 1 is a flow chart of a zero-discharge treatment process for fractured rock wastewater provided by the invention.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
As shown in fig. 1, which is a flow chart of a zero-discharge treatment process for fractured rock wastewater provided by the present invention, the fractured rock wastewater is sequentially treated by a coagulation sedimentation treatment system, a fenton oxidation treatment system, a softening treatment system and an ED treatment system, the wastewater with the concentration higher than a set value obtained after treatment by the ED treatment system is treated by evaporation crystallization, and the wastewater with the concentration lower than the set value is treated by a biochemical treatment system; wherein, the sludge obtained after the coagulating sedimentation treatment system, the Fenton treatment system and the softening treatment system treat the wastewater is treated in a unified way.
The coagulating sedimentation treatment system adopts a coagulating sedimentation tank, and the pH value of the coagulating sedimentation tank is adjusted to 8-9; and (3) the fractured rock wastewater enters a coagulating sedimentation tank to generate flocs, PAC and PAM are sequentially added to enable the flocs to form sediment, the sediment is discharged out of the system through a sludge discharge pump, and supernatant enters a subsequent treatment system. And adding sodium hydroxide into the coagulating sedimentation tank to adjust the pH value, wherein the adding concentration of the sodium hydroxide is 40 g/L.
The Fenton oxidation treatment system adopts the Fenton oxidation pond, the supernatant that the coagulating sedimentation treatment system obtained gets into the Fenton oxidation pond, the pH value of Fenton oxidation pond is adjusted to 4-5, then ferrous sulfate solution, hydrogen peroxide solution are added in proper order, there is a large amount of foams to produce, need add the defoaming agent, after the reaction is accomplished, add sodium hydroxide and adjust pH value to 8-9, there is the floc to produce, PAC, PAM add in proper order, make the floc form the sediment, outside the discharge system through the dredge pump, the supernatant gets into in the follow-up processing system. Adding concentrated sulfuric acid with the mass concentration of 98% into the Fenton oxidation tank to adjust the pH value; the dosage of the ferrous sulfate is 3.27g/L, and the dosage of the hydrogen peroxide is 3.5 mL/L; the adding concentration of the sodium hydroxide is 40 g/L.
Softening treatment system adopts the softening tank, and the supernatant that the fenton oxidation treatment system obtained gets into softening the pond in, then adds sodium carbonate solution, has the floc to produce, adds PAC, PAM in proper order, makes the floc form the sediment, through the mud pump discharge system outside, the supernatant gets into in the follow-up processing system. The adding amount of the sodium carbonate is 5 g/L.
The ED treatment system adopts an ED membrane, supernatant obtained by the softening treatment system passes through the ED membrane, and obtained wastewater with the concentration lower than a set value, namely fresh water enters the biochemical treatment system, and effluent is subjected to biochemical treatment to meet the discharge requirement; and evaporating and crystallizing the obtained waste water with the concentration higher than a set value, namely concentrated water.
Examples
The COD of raw water of the fractured rock wastewater is 3500mg/L, the TDS is 32000mg/L, and the total hardness (calculated by calcium carbonate) is 10000 mg/L.
A zero-discharge treatment process for fractured rock wastewater comprises the following specific steps:
a coagulating sedimentation tank: lifting the wastewater to a coagulative precipitation tank by a pump, adding sodium hydroxide into the coagulative precipitation tank to adjust the pH value to 8-9, wherein the adding concentration of the sodium hydroxide is 40g/L, monitoring the pH value in real time, controlling the adding amount of the sodium hydroxide according to the pH value in the wastewater, generating a large amount of dark black flocs in the reaction process, subsequently adding PAC and PAM respectively to enable the flocs to form precipitates, discharging the precipitates out of the system by a sludge discharge pump, and feeding the supernatant into a subsequent treatment system; the adding amount of PAC and PAM is respectively 200mg/L and 15 mg/L;
a Fenton oxidation pond: pumping the supernatant of the coagulating sedimentation tank to a Fenton oxidation tank, adjusting the pH of the wastewater to 4-5 by using 98% concentrated sulfuric acid, monitoring the pH value in real time, and controlling the adding amount of the concentrated sulfuric acid according to the pH value in the wastewater; then adding ferrous sulfate solution and hydrogen peroxide, wherein the adding amount of the ferrous sulfate is 3.27g/L, and the adding amount of the hydrogen peroxide is 3.5 mL/L; the adding amount of hydrogen peroxide is controlled by the linkage of the online ORP meter and a hydrogen peroxide adding pump, so that the influence of excessive adding of hydrogen peroxide on effluent COD is avoided; in the process, a large amount of bubbles are generated, a defoaming agent is required to be added, after the reaction is finished, sodium hydroxide is added to adjust the pH value to 8-9, the pH value is monitored in real time, the adding amount of the sodium hydroxide is controlled by the pH value in the wastewater, the adding concentration of the sodium hydroxide is 40g/L, a large amount of flocs are generated, PAC and PAM are added subsequently and respectively, the flocs form precipitates, the precipitates are discharged out of a system through a sludge discharge pump, and the supernatant enters a subsequent treatment system; the adding amount of PAC and PAM is respectively 200mg/L and 15 mg/L;
a softening tank: overflowing supernatant in the Fenton oxidation tank into a softening treatment tank, adding a sodium carbonate solution into the softening treatment tank, wherein the adding amount of the sodium carbonate is 5g/L, a large amount of flocs are generated, adding PAC and PAM respectively subsequently to enable the flocs to form precipitates, discharging the precipitates out of a system through a sludge discharge pump, and feeding supernatant into a subsequent treatment system; the adding amount of PAC and PAM is respectively 200mg/L and 15 mg/L;
an ED membrane module: supernatant of the softening tank is lifted into an ED membrane module by a pump, fresh water passing through the ED membrane enters a subsequent biochemical treatment system, and effluent of biochemical treatment meets the discharge requirement; the concentrated water passing through the ED membrane enters a subsequent evaporative crystallization system;
a biochemical pool: fresh water enters a biochemical pool, and the fresh water can meet the recycling requirement after being treated by a biochemical treatment system;
evaporative crystallization device (MVR): the concentrated water enters an evaporative crystallization device for crystallization (the existing evaporative crystallization process is applicable), zero discharge of wastewater is realized, and the obtained crystals, namely the main components of byproducts are NaCl and Na2SO4。
The COD of the waste water treated by the process is less than 100mg/L, the total hardness (calculated by calcium carbonate) is less than 100mg/L, the TDS of the concentrated water is more than 150000mg/L, and the TDS of the fresh water is less than 10000 mg/L.
Claims (10)
1. The zero-discharge treatment process of the fracturing rock wastewater is characterized in that the fracturing rock wastewater is sequentially treated by a coagulating sedimentation treatment system, a Fenton oxidation treatment system, a softening treatment system and an ED treatment system, the wastewater with the concentration higher than a set value obtained after the treatment of the ED treatment system is treated by evaporative crystallization, and the wastewater with the concentration lower than the set value is treated by a biochemical treatment system; wherein, the sludge obtained after the coagulating sedimentation treatment system, the Fenton treatment system and the softening treatment system treat the wastewater is treated in a unified way.
2. The zero-emission treatment process of wastewater from fractured rocks according to claim 1, wherein the coagulating sedimentation treatment system adopts a coagulating sedimentation tank, the pH value of the coagulating sedimentation tank is adjusted to 8-9, flocs are generated, PAC and PAM are added to form precipitates of the flocs, the precipitates are discharged out of the system through a mud pump, and supernatant enters a subsequent treatment system.
3. The zero-emission treatment process of the fractured rock wastewater as claimed in claim 2, wherein sodium hydroxide is added into the coagulating sedimentation tank to adjust the pH value.
4. The zero-emission treatment process of the wastewater of the fracturing rocks according to claim 1, wherein the Fenton oxidation treatment system adopts a Fenton oxidation tank, the supernatant obtained by the coagulating sedimentation treatment system enters the Fenton oxidation tank, the pH value of the Fenton oxidation tank is adjusted to 4-5, then a ferrous sulfate solution and hydrogen peroxide are added for reaction to generate foam, and if the foam is too much, a defoaming agent is added; after the reaction is finished, adding sodium hydroxide to adjust the pH value to 8-9, generating flocs, adding PAC and PAM to enable the flocs to form precipitates, discharging the precipitates out of the system through a sludge discharge pump, and enabling supernatant to enter a subsequent treatment system.
5. The zero-emission treatment process of the wastewater of the fractured rocks according to claim 4, wherein concentrated sulfuric acid with the mass concentration of 98% is added into the Fenton oxidation pond to adjust the pH value; the dosage of the ferrous sulfate is 2.5-4 g/L, and the dosage of the hydrogen peroxide is 2.5-4.5 mL/L.
6. The zero-emission treatment process of wastewater from fractured rocks as claimed in claim 1, wherein the softening treatment system adopts a softening tank, the supernatant obtained from the Fenton oxidation treatment system enters the softening tank, then sodium carbonate solution is added, after flocs are generated, PAC and PAM are added to precipitate the flocs, the flocs are discharged out of the system through a mud pump, and the supernatant enters a subsequent treatment system.
7. The zero-emission treatment process of the fracturing rock wastewater as claimed in claim 6, wherein the addition amount of the sodium carbonate is 3-7 g/L.
8. The zero-emission treatment process of the fractured rock wastewater as claimed in claim 2, 4 or 6, wherein the addition amount of the PAC is 100-300 mg/L; the dosage of the PAM is 5-20 mg/L.
9. The zero-emission treatment process of wastewater from fractured rocks as claimed in claim 1, wherein the ED treatment system adopts an ED membrane, supernatant obtained by the softening treatment system passes through the ED membrane, and wastewater with concentration lower than a set value, namely fresh water, is obtained and enters the biochemical treatment system, and effluent is biochemically treated to meet the emission requirement; and evaporating and crystallizing the obtained waste water with the concentration higher than a set value, namely concentrated water.
10. The zero emission treatment process of wastewater from fractured rocks according to claim 1, wherein the TDS of the concentrated water is more than 150000mg/L, and the TDS of the fresh water is less than 10000 mg/L.
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Cited By (2)
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| CN115180746A (en) * | 2022-08-18 | 2022-10-14 | 延安圣洋环保有限公司 | Treatment method of high-hardness fracturing flow-back fluid |
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