CN114180736A - Shale gas wastewater internal recycling treatment method based on adsorption and membrane technology - Google Patents

Shale gas wastewater internal recycling treatment method based on adsorption and membrane technology Download PDF

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CN114180736A
CN114180736A CN202111418129.0A CN202111418129A CN114180736A CN 114180736 A CN114180736 A CN 114180736A CN 202111418129 A CN202111418129 A CN 202111418129A CN 114180736 A CN114180736 A CN 114180736A
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shale gas
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adsorbent
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CN114180736B (en
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刘百仓
刘元慧
陈忱
刘石
何启平
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Sichuan University
Hainan Litree Purifying Technology Co Ltd
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Hainan Litree Purifying Technology Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28047—Gels
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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    • 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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    • C02F2101/30—Organic compounds
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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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Abstract

The invention relates to a shale gas wastewater internal recycling treatment method based on adsorption and membrane technologies, which sequentially comprises the following steps: (1) performing adsorption treatment, namely adding an aerogel powder adsorbent into the shale gas wastewater, adsorbing under stirring, standing, or filling an aerogel particle adsorbent into an adsorption bed reactor, and then passing the shale gas wastewater through the adsorption bed reactor in a continuous water inlet and continuous water outlet operation mode to mainly remove soluble organic pollutants and suspended pollutants; (2) performing ultrafiltration treatment, namely removing residual suspended pollutants and powder adsorbents in supernate obtained by adsorption treatment of the aerogel powder adsorbents, or removing residual suspended pollutants and soluble organic pollutants in effluent of an adsorption bed reactor; (3) and (4) nanofiltration treatment, namely removing divalent cations in the ultrafiltration water. The method can realize the internal recycling of the shale gas wastewater in the shale gas exploitation process, simplify the treatment process of the shale gas wastewater, relieve the membrane pollution in the treatment process and reduce the treatment cost.

Description

Shale gas wastewater internal recycling treatment method based on adsorption and membrane technology
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and relates to a shale gas wastewater recycling treatment method.
Background
With the proposal of national energy transformation targets, shale gas is receiving more and more attention and developing rapidly as one of clean energy. According to the shale gas development plan (2016-. Shale gas production relies heavily on hydraulic fracturing and horizontal drilling techniques, but the application of these techniques presents serious water environmental pollution problems. By 2030, 5-7.3 million cubic meters of shale gas wastewater is expected to be generated in China, and meanwhile, the demand of the shale gas exploitation on fresh water is further increased. Therefore, if the shale gas wastewater is treated to meet the requirement of exploitation and reuse of shale gas, the pollution of the shale gas wastewater to the environment can be solved, and the requirement of exploitation of a large amount of water by the shale gas can be met.
In order to ensure that the prepared fracturing fluid has better fracturing performance so as to obtain higher gas yield during shale gas fracturing exploitation, the shale gas wastewater needs to be treated to a certain extent so as to meet the requirement of internal recycling. Suspended contaminants in shale gas wastewater are the first material to be removed because it affects the viscosity of the fracturing fluid and thus reduces the fracturing efficiency. In addition, divalent cations and organic contaminants in shale gas wastewater can form scale and adversely affect the effective materials in the fracturing fluid, thereby affecting fracturing efficiency and reducing gas production rates. In addition, soluble organic pollution and divalent ions in the shale gas wastewater can cause membrane pollution and membrane scaling in the treatment process, seriously affect the wastewater treatment efficiency and increase the wastewater treatment cost. Therefore, most suspended pollutants should be removed during the treatment of the shale gas wastewater, and the content of organic pollutants and divalent cations should be reduced as much as possible so as to reduce the adverse effect on the membrane process and the shale gas exploitation during the internal recycling during the treatment.
The Chinese patent with publication number CN106800345A develops a shale gas wastewater treatment method, which mainly removes suspended pollutants and organic pollutants in shale gas wastewater by adopting oil removal, Fenton oxidation, coagulating sedimentation, artificial infiltration and filtration processes, and the treated effluent can be used for exploiting the shale gas wastewater by a fracturing technology. However, the method has a long process flow, and the Fenton oxidation technology may cause incomplete mineralization of organic matters and even cause secondary pollution, thereby generating unknown risks to the environment. In addition, the process does not involve divalent ion removal, which may result in decreased performance of the fracturing fluid during reuse and decreased gas production efficiency during shale gas production.
Disclosure of Invention
The invention aims to provide an internal recycling treatment method of shale gas wastewater based on adsorption and membrane technologies, which mainly removes suspended pollutants, soluble organic pollutants and divalent cations in the shale gas wastewater to realize the recycling of the shale gas wastewater in shale gas exploitation, simplifies the treatment process of the shale gas wastewater, relieves membrane pollution in the treatment process and reduces the treatment cost.
The invention relates to a shale gas wastewater internal recycling treatment method based on adsorption and membrane technologies, which sequentially comprises the following steps:
(1) adsorption treatment
Adsorption treatment mainly removes soluble organic pollutants and suspended pollutants, and has two modes:
adding an aerogel powder adsorbent into the shale gas wastewater, adsorbing under stirring, and standing to settle suspended pollutants and the powder adsorbent adsorbed with soluble organic pollutants in the wastewater;
or the aerogel particle adsorbent is filled in the adsorption bed reactor, then the shale gas wastewater passes through the adsorption bed reactor in a continuous water inlet and continuous water outlet operation mode, and the aerogel particle adsorbent is used for adsorbing and removing soluble organic pollutants and filtering and intercepting suspended pollutants;
(2) ultra-filtration treatment
Carrying out ultrafiltration treatment on the supernatant obtained by the adsorption treatment of the aerogel powder adsorbent or the effluent of the adsorption bed reactor, wherein the treatment mainly removes residual powder adsorbent and suspended pollutants from the supernatant obtained by the treatment of the aerogel powder adsorbent, and the treatment mainly removes residual suspended pollutants and soluble organic pollutants from the effluent of the fixed bed reactor;
(3) nanofiltration treatment
And (3) performing nanofiltration treatment on the effluent of the ultrafiltration treatment, wherein the treatment mainly removes divalent cations.
According to the shale gas wastewater internal recycling treatment method based on adsorption and membrane technologies, in the step (1), the aerogel powder adsorbent is a charcoal aerogel powder adsorbent, and the aerogel particle adsorbent is a charcoal aerogel particle adsorbent, which are all obtained by self-control.
The preparation method of the charcoal aerogel powder adsorbent comprises the following steps:
uniformly mixing chitosan powder and an alkaline mixed solution to form a first slurry, wherein the mass concentration of the chitosan powder in the first slurry is 2.0-6.0%, the alkaline mixed solution is composed of potassium hydroxide, urea and deionized water, the mass concentration of the potassium hydroxide in the alkaline mixed solution is 4.0-11.5%, and the mass concentration of the urea in the alkaline mixed solution is 4.0-12.0%; repeatedly freezing and thawing the first slurry at-20 ℃ until chitosan is completely dissolved to form second slurry, then baking the second slurry in a tubular furnace at 600-800 ℃ for 2h after freeze drying, cooling to room temperature along with the furnace after baking is finished, grinding the baked product into powder, and washing away unreacted potassium hydroxide and urea by using deionized water to obtain the biochar aerogel powder adsorbent.
The first preparation method of the biological carbon aerogel particle adsorbent comprises the following steps:
dissolving chitosan powder in acetic acid water solution with volume concentration of 2.0-5.0% to form chitosan-acetic acid solution, wherein the mass concentration of the chitosan powder in the chitosan-acetic acid solution is 2.0-4.0%; dropping a chitosan-acetic acid solution into a sodium hydroxide aqueous solution with the mass concentration of 2.0-4.0% by using an injector to form chitosan hydrogel spheres, standing for 12 hours, taking out the hydrogel spheres, freeze-drying, calcining the freeze-dried spheres in a tubular furnace at 600-800 ℃ for 2 hours, and cooling to room temperature along with the furnace after calcining to obtain the biological carbon aerogel particle adsorbent named as aerogel particle # 1.
The second preparation method of the biological carbon aerogel particle adsorbent comprises the following steps:
(11) uniformly mixing chitosan powder and an alkaline mixed solution to form a first slurry, wherein the mass concentration of the chitosan powder in the first slurry is 2.0-6.0%, the alkaline mixed solution is composed of potassium hydroxide, urea and deionized water, the mass concentration of the potassium hydroxide in the alkaline mixed solution is 4.0-11.5%, and the mass concentration of the urea in the alkaline mixed solution is 4.0-12.0%; repeatedly freezing and thawing the first slurry at-20 ℃ until chitosan is completely dissolved to form second slurry, then baking the second slurry in a tubular furnace at 600-800 ℃ for 2h after freeze drying, cooling to room temperature along with the furnace after baking is finished, grinding the baked product into powder, and washing away unreacted potassium hydroxide and urea by using deionized water to obtain the charcoal aerogel powder adsorbent;
(12) dissolving sodium alginate powder in deionized water to form a sodium alginate solution with the mass concentration of 2.0-4.0%; uniformly dispersing the charcoal aerogel powder adsorbent prepared in the step (11) in a sodium alginate aqueous solution to form a first mixed solution, wherein the mass ratio of the charcoal aerogel powder adsorbent to the volume of the sodium alginate solution is 0.01-0.05: 10, the unit of the mass of the biochar aerogel powder is g, the unit of the volume of the sodium alginate solution is mL, then the surfactant F-127 is added into the first mixed solution and uniformly mixed to form a second mixed solution, the adding amount of the F-127 enables the mass concentration of the F-127 in the second mixed solution to be 1.0%, then benzyl benzoate is uniformly dispersed in the second mixed solution to form a third mixed solution, and the benzyl benzoate are uniformly dispersed in the second mixed solution to form a third mixed solutionThe volume ratio of the second mixed solution is 0.5-1: 1; dripping the third mixed solution into CaCl with the mass concentration of 2.0-4.0% by using an injector2Forming spherical hydrogel in an aqueous solution, transferring the spherical hydrogel into an isopropanol solution, soaking and cleaning to remove oil drops embedded in the spherical hydrogel, and placing the obtained porous spherical hydrogel in CaCl with the mass concentration of 2.0-4.0%2Soaking in the aqueous solution for 1h, taking out after soaking, washing with deionized water to remove residual calcium ions and chloride ions, and freeze-drying to obtain the charcoal aerogel particle adsorbent named as aerogel particle # 2.
The shale gas wastewater internal recycling treatment method based on adsorption and membrane technology comprises the steps that in the step (1), the addition amount of aerogel powder adsorbent is 150-600 mg/L, the adsorption time is 15-30 minutes under stirring, the stirring rotation speed is 200-400 rpm, and the standing time is 0.5-4 hours.
According to the shale gas wastewater internal recycling treatment method based on adsorption and membrane technologies, the adsorption bed reactor in the step (1) is a fixed bed reactor or a fluidized bed reactor, when the adsorption bed reactor is the fixed bed reactor, the packing rate of the aerogel particle adsorbent is 20-50%, and the empty bed contact time of the shale gas wastewater is 30-60 minutes; when the fluidized bed reactor is used, the filling rate of the aerogel particle adsorbent is 10-60%, dissolved oxygen is controlled at 2-4 mg/L by aeration during stable operation, and the hydraulic retention time is 6-20 hours.
The shale gas wastewater internal recycling treatment method based on adsorption and membrane technology comprises the step (2) of carrying out ultrafiltration treatment on the polyvinylidene fluoride membrane or the polypropylene membrane as an ultrafiltration membrane, wherein the operation mode is constant flux operation, and the water flux is 20-60L/(m)2H), ensuring that the transmembrane pressure difference on two sides of the ultrafiltration membrane is less than a limit value in the running process of ultrafiltration treatment. The service time of the ultrafiltration membrane is determined by the limited transmembrane pressure difference on two sides of the ultrafiltration membrane, and the limited value of the transmembrane pressure difference on two sides of different ultrafiltration membranes is different. When the transmembrane pressure difference value on the two sides of the ultrafiltration membrane is detected to be larger than or equal to the limit value, the ultrafiltration membrane should be replaced (the replaced ultrafiltration membrane can be cleaned and reused).
According to the shale gas wastewater internal recycling treatment method based on the adsorption and membrane technology, the nanofiltration membrane subjected to nanofiltration treatment in the step (3) is a polyamide membrane, and comprises a VNF1, NF90 or NF270 membrane; the operation mode is constant pressure operation, the driving pressure is 100-400 psi, the water flow direction is perpendicular to the surface of the nanofiltration membrane, and the water recovery rate is 50-85%.
Compared with the prior art, the invention has the following beneficial effects:
1. the method can realize the efficient removal of soluble organic carbon and divalent cations in the shale gas wastewater (see examples 1, 3 and 5), so that the water quality after treatment reaches the internationally recognized shale gas exploitation water standard, and the outstanding problems of large water requirement, high wastewater yield and strong environmental risk in shale gas exploitation are solved.
2. The method has the advantages that the process steps of adsorption, ultrafiltration and nanofiltration are adopted, the process flow is simplified, the field application of integrated equipment is easy to form, the treatment effect is reliable, the water impact load resistance is high, and the method has good adaptability to complex and various water qualities.
3. The adsorbent used in the invention is a self-made biological carbon aerogel adsorbent, has the characteristics of environmental protection, easy preparation, high adsorption capacity and high adsorption rate, and is suitable for adsorption pretreatment of shale gas wastewater.
4. The method has the advantages that the biochar aerogel particle adsorbent is used in the adsorption treatment step and filled into the adsorption bed reactor, so that the shale gas wastewater can run in a continuous water inlet and continuous water outlet mode, compared with the biochar aerogel powder adsorbent, the method is more suitable for the characteristics of small-scale concentrated wastewater distribution of shale gas exploitation, the occupied area is saved, more suspended pollutants can be filtered and intercepted (see table 2 in example 1, table 4 in example 3 and table 6 in example 5) while the soluble organic pollutants are adsorbed and removed, or the coupling biological method is used for intensively removing the soluble organic matters in the shale gas wastewater.
5. The method of the invention carries out adsorption treatment before ultrafiltration, so that a large amount of soluble organic pollutants and suspended pollutants in the shale gas wastewater are removed, thus obviously relieving membrane pollution in subsequent ultrafiltration and nanofiltration, increasing stable operation time and reducing the cost of membrane cleaning and membrane replacement.
Detailed Description
The shale gas wastewater recycling treatment method based on adsorption and membrane technology of the present invention is further illustrated by the following examples.
The shale gas wastewater treated in the following examples is shale gas wastewater of three types of Sichuan basins or one of the three types of shale gas wastewater, namely shale gas wastewater #1, shale gas wastewater #2 and shale gas wastewater #3, and the pH values and the pollutant contents of the untreated shale gas wastewater #1, untreated shale gas wastewater #2 and untreated shale gas wastewater #3 are shown in the following Table 1.
Example 1
Three kinds of waste water of shale gas waste water #1, shale gas waste water #2, shale gas waste water #3 are handled to this embodiment, and the used adsorbent of adsorption treatment is charcoal aerogel powder adsorbent, and the preparation method of charcoal aerogel powder adsorbent is as follows:
uniformly mixing chitosan powder with alkaline mixed liquor to form first slurry, wherein the mass concentration of the chitosan powder in the first slurry is 4.0%, the alkaline mixed liquor is composed of potassium hydroxide, urea and deionized water, the mass concentration of the potassium hydroxide in the alkaline mixed liquor is 11.5%, and the mass concentration of the urea in the alkaline mixed liquor is 12.0%; repeatedly freezing and thawing the first slurry at-20 ℃ until chitosan is completely dissolved to form second slurry, then placing the second slurry in a tubular furnace for firing at 800 ℃ for 2h after freeze drying, cooling to room temperature along with the furnace after firing, grinding the fired product into powder, and washing away unreacted potassium hydroxide and urea by using deionized water to obtain the charcoal aerogel powder adsorbent. The detection proves that the specific surface area of the biochar aerogel powder adsorbent is 2711.71m2(g), total pore volume 1.91cm3The theoretical adsorption capacity of the adsorbent for the soluble organic carbon in the shale gas wastewater is 205.86mg DOC/g biochar aerogel adsorbent.
1. The three kinds of shale gas wastewater are sequentially treated by the following 3 process steps:
(1) adsorption treatment
Adding the biochar aerogel powder adsorbent into the shale gas wastewater, wherein the adding amount of the biochar aerogel powder adsorbent is 300mg/L, after the adding of the biochar aerogel powder adsorbent is finished, continuously stirring at the rotating speed of 200rpm for adsorption for 30 minutes, then standing for 2 hours to settle suspended pollutants in the wastewater and the powder adsorbent adsorbing the soluble organic pollutants, and the step mainly removes the soluble organic pollutants and the suspended pollutants in the shale gas wastewater;
(2) ultra-filtration treatment
Subjecting the supernatant obtained by adsorption treatment to ultrafiltration treatment, wherein the ultrafiltration membrane is polyvinylidene fluoride hollow fiber membrane, the ultrafiltration treatment is in constant flux operation mode, and the water flux is 30L/(m)2H), ultrafiltration filtering for 56 minutes, backwashing for 3.5 minutes to form 1 cycle, and operating for 10 cycles in total, wherein the transmembrane pressure difference of two sides of the ultrafiltration membrane is controlled to be less than 65kPa in the ultrafiltration treatment operation process, so that residual suspended pollutants and powder adsorbent are mainly removed;
(3) nanofiltration treatment
Performing nanofiltration treatment on the effluent after ultrafiltration treatment, wherein the nanofiltration membrane is a VNF1 membrane, the nanofiltration treatment is in a constant pressure operation mode, the driving pressure is 300psi, the water flow direction is vertical to the surface of the nanofiltration membrane, the water recovery rate is 80%, and divalent cations Ca are mainly removed2+、Mg2+、Ba2+、Sr2+And the like.
2. The three kinds of shale gas wastewater are sequentially treated by the following 2 process steps:
(1) ultra-filtration treatment
Carrying out ultrafiltration treatment on the shale gas wastewater, wherein the ultrafiltration membrane is a polyvinylidene fluoride hollow fiber membrane, the ultrafiltration treatment is in a constant flux operation mode, and the water flux is 30L/(m)2H), ultrafiltration filtering for 56 minutes, backwashing for 3.5 minutes to form 1 cycle, and operating for 10 cycles in total, wherein the transmembrane pressure difference of two sides of an ultrafiltration membrane is controlled to be less than 65kPa in the ultrafiltration treatment operation process, so that soluble organic pollutants and suspended pollutants in the shale gas wastewater are mainly filtered;
(2) nanofiltration treatment
Performing nanofiltration treatment on the effluent after the ultrafiltration treatment, wherein the nanofiltration membrane is a VNF1 membraneThe filtration treatment is a constant pressure operation mode, the driving pressure is 300psi, the water flow direction is vertical to the surface of the nanofiltration membrane, the water recovery rate is 80 percent, and the divalent cation Ca is mainly removed2+、Mg2+、Ba2+、Sr2+And the like.
The contents of the three shale gas waste waters and the pollutants in the water resulting from the treatment thereof are shown in tables 1 and 2 below.
TABLE 1
Figure BDA0003374605950000061
TABLE 2
Figure BDA0003374605950000062
As can be seen from table 1, the method of the present invention can achieve high-efficiency removal of suspended pollutants, soluble organic carbon and divalent cations (turbidity removal rate > 98%, soluble organic carbon removal rate > 86%, divalent cation removal rate > 70%) in shale gas wastewater; the method comprises the following steps: compared with the ultrafiltration-nanofiltration process for removing the adsorption, the adsorption-ultrafiltration-nanofiltration process has the advantages that the removal rate of divalent cations in the shale gas wastewater is not greatly different, but the removal rate of soluble organic carbon and suspended pollutants in the treated water can be further improved. As can be seen from Table 2, the biochar aerogel powder adsorbent can remove most of turbidity and soluble organic carbon (turbidity removal rate > 70%, soluble organic carbon removal rate > 50%), and only a small amount of divalent ions.
Example 2
This example is based on example 1, and for the method of the present invention: the membrane pollution analysis is carried out by the powder adsorbent adsorption-ultrafiltration-nanofiltration process and the ultrafiltration-nanofiltration process for removing the adsorption.
1. In the two processes of example 1, during the ultrafiltration operation, the water flux per minute and the transmembrane pressure difference on two sides of the ultrafiltration membrane are recorded by using an electronic balance and a pressure sensor, the pollution indexes TFI and HIFI of the ultrafiltration membrane of the two processes are calculated according to the recorded data, and then the TFI reduction rate (%) and the HIFI reduction rate (%) of the ultrafiltration membrane are calculated.
The formula for calculating the contamination index is (see "stable reuse of show gas water by pre-catalysis with ultrafiltration-reverse osmosis", published year 2020, volume number 392, document number 123743) published by Peng Tang et al:
Figure BDA0003374605950000071
Figure BDA0003374605950000072
in the formula Js' is normalized specific flux, TMP0、TMP0' and TMPfRespectively the initial transmembrane pressure difference of a first period of a new membrane when the shale gas wastewater passes through, the initial transmembrane pressure difference of a next period after backwashing and the final transmembrane pressure difference of each period, VsFor the volume of the permeate water, TFI (Total fouling index) is the total fouling index, and HIFI (Hydraulic irreversible fouling index) is the hydraulic irreversible fouling index.
2. The water flux per minute was recorded during the nanofiltration run for both processes of example 1 using electronic balances and sensors, and the normalized flux was calculated from the recorded data. The normalized flux is the ratio of the water flux per minute to the water flux at minute 1 in the nanofiltration run. And calculating the normalized flux increase rate (%) of the nanofiltration membrane.
The results of the calculations are shown in Table 3 below.
TABLE 3
Figure BDA0003374605950000081
As can be seen from table 3, the process of the invention: compared with the ultrafiltration-nanofiltration process for removing the adsorption, the adsorption-ultrafiltration-nanofiltration process has the advantages that the membrane pollution index of ultrafiltration is obviously reduced, the normalized flux of the nanofiltration membrane is obviously improved, and the pollution of the ultrafiltration membrane and the nanofiltration membrane is obviously improved.
Example 3
In the embodiment, the shale gas wastewater #2 is treated, the adsorbent used in the adsorption treatment is a charcoal aerogel particle adsorbent, namely aerogel particles #1, and the preparation method of the aerogel particles #1 is as follows:
dissolving chitosan powder in an acetic acid aqueous solution with the volume concentration of 5.0% to form a chitosan-acetic acid solution, wherein the mass concentration of the chitosan powder in the chitosan-acetic acid solution is 4.0%; dropping a chitosan-acetic acid solution into a sodium hydroxide aqueous solution with the mass concentration of 4.0% by using an injector to form chitosan hydrogel spheres, standing for 12 hours, taking out the hydrogel spheres, freeze-drying, calcining the freeze-dried spheres in a tubular furnace at 800 ℃ for 2 hours, and cooling to room temperature along with the furnace after calcining to obtain the aerogel particles # 1. The particles are irregular spherical particles, the apparent color is black, and the particle size is about 0.5-2 mm.
1. Treating the shale gas wastewater #2 by adopting the following 3 process steps:
(1) adsorption treatment
Filling the aerogel particles #1 in a fixed bed reactor, wherein the inner diameter of the fixed bed reactor is 2.5cm, the height of the fixed bed reactor is 30cm, and the bed filling height is 6.5cm (the filling rate of the aerogel particles #1 is 22%), then enabling the shale gas wastewater to pass through the fixed bed reactor in a continuous water inlet and continuous water outlet running mode, wherein the empty bed contact time of the shale gas wastewater is 30 minutes, and mainly removing soluble organic pollutants and suspended pollutants;
(2) ultra-filtration treatment
Performing ultrafiltration treatment on the effluent of the fixed bed reactor, wherein the ultrafiltration membrane is a polyvinylidene fluoride hollow fiber membrane, the ultrafiltration treatment is in a constant flux operation mode, and the water flux is 60L/(m)2H), ultrafiltration filtering for 56 minutes, backwashing for 3.5 minutes to form 1 cycle, and operating for 10 cycles in total, wherein the transmembrane pressure difference of two sides of the ultrafiltration membrane is controlled to be less than 65kPa in the ultrafiltration treatment operation process, so that residual soluble organic pollutants and suspended pollutants are mainly removed;
(3) nanofiltration treatment
The effluent water after ultrafiltration treatmentPerforming nanofiltration treatment, wherein the nanofiltration membrane is VNF1 membrane, the nanofiltration treatment is in constant pressure operation mode, the driving pressure is 300psi, the water flow direction is perpendicular to the surface of the nanofiltration membrane, the recovery rate is 80%, and divalent cation Ca is mainly removed2+、Mg2+、Ba2+、Sr2+And the like.
2. Treating the shale gas wastewater #2 by adopting the following 2 process steps:
(1) ultra-filtration treatment
Performing ultrafiltration treatment on the effluent of the fixed bed reactor, wherein the ultrafiltration membrane is a polyvinylidene fluoride hollow fiber membrane, the ultrafiltration treatment is in a constant flux operation mode, and the water flux is 60L/(m)2H), ultrafiltration filtering for 56 minutes, backwashing for 3.5 minutes to form 1 cycle, and operating for 10 cycles in total, wherein the transmembrane pressure difference of two sides of an ultrafiltration membrane is controlled to be less than 65kPa in the ultrafiltration treatment operation process, so that soluble organic pollutants and suspended pollutants in the shale gas wastewater are mainly filtered;
(2) nanofiltration treatment
Performing nanofiltration treatment on the effluent after ultrafiltration treatment, wherein the nanofiltration membrane is a VNF1 membrane, the nanofiltration treatment is in a constant pressure operation mode, the driving pressure is 300psi, the water flow direction is vertical to the surface of the nanofiltration membrane, the water recovery rate is 80%, and divalent cations Ca are mainly removed2+、Mg2+、Ba2+、Sr2+And the like.
The content of contaminants in the water resulting from the shale gas wastewater #2 treatment is shown in table 4 below.
TABLE 4
Figure BDA0003374605950000091
As can be seen from table 4, by using the method of the present invention, the high efficiency removal of suspended pollutants, soluble organic pollutants and divalent cations in the shale gas wastewater can be achieved, wherein the turbidity and the content of soluble organic carbon of the wastewater can be greatly reduced and a small amount of divalent cations can be removed by filling the aerogel particles #1 into the fixed bed adsorbent to treat the shale gas wastewater; the method comprises the following steps: compared with the ultrafiltration-nanofiltration process for removing the adsorption, the adsorption-ultrafiltration-nanofiltration process has the advantages that the removal effect on divalent cations in the shale gas wastewater is not greatly different, but the removal effect of the soluble organic carbon in the treated water can be improved.
Example 4
In this example, on the basis of example 3, for the method of the present invention: the particle adsorbent adsorption-ultrafiltration-nanofiltration process and the ultrafiltration-nanofiltration process for removing the adsorption are used for membrane pollution analysis.
1. In the two processes of the embodiment 3, during the ultrafiltration operation, the water flux per minute and the transmembrane pressure difference on two sides of the ultrafiltration membrane are recorded by using an electronic balance and a pressure sensor, the pollution indexes TFI and HIFI of the ultrafiltration membrane of the two processes are calculated according to the recorded data, the calculation formulas of the pollution indexes TFI and HIFI are shown in the embodiment 2, and the TFI reduction rate (%) and the HIFI reduction rate (%) of the ultrafiltration membrane are calculated.
2. The water flux per minute was recorded during the nanofiltration run for both processes of example 3 using electronic balances and sensors, and the normalized flux was calculated from the recorded data. The normalized flux is the ratio of the water flux per minute to the water flux at minute 1 in the nanofiltration run. And calculating the normalized flux increase rate (%) of the nanofiltration membrane.
The results of the calculations are shown in Table 5 below.
TABLE 5
Parameter(s) Aerogel particle #1 adsorption-ultrafiltration-nanofiltration
TFI reduction ratio (%) of Ultrafiltration Membrane 70.02
Ultrafiltration membrane HIFI reduction (%) 58.18
Normalized chemical filter membraneAmount increase rate (%) 25.15
As can be seen from table 5, the aerogel particle adsorbent has good adsorption performance and filtration capacity, and compared with the ultrafiltration-nanofiltration process for removing adsorption, the adsorption-ultrafiltration-nanofiltration process using the aerogel particle #1 has the advantages that the membrane pollution index of ultrafiltration is greatly reduced, the normalized flux of the nanofiltration membrane is obviously increased, and the pollution of both the ultrafiltration membrane and the nanofiltration membrane is obviously improved.
Example 5
In the embodiment, the shale gas wastewater #2 is treated, the adsorbent used in the adsorption treatment is a charcoal aerogel particle adsorbent, namely aerogel particles #2, and the preparation method of the aerogel particles #2 is as follows:
(11) uniformly mixing chitosan powder with alkaline mixed liquor to form first slurry, wherein the mass concentration of the chitosan powder in the first slurry is 4.0%, the alkaline mixed liquor is composed of potassium hydroxide, urea and deionized water, the mass concentration of the potassium hydroxide in the alkaline mixed liquor is 11.5%, and the mass concentration of the urea in the alkaline mixed liquor is 12.0%; repeatedly freezing and thawing the first slurry at-20 ℃ until chitosan is completely dissolved to form second slurry, then placing the second slurry in a tubular furnace for firing at 800 ℃ for 2h after freeze drying, cooling to room temperature along with the furnace after firing, grinding the fired product into powder, and washing away unreacted potassium hydroxide and urea by using deionized water to obtain the charcoal aerogel powder adsorbent;
(12) dissolving sodium alginate powder in deionized water to form a sodium alginate solution with the mass concentration of 2.0%; uniformly dispersing the charcoal aerogel powder adsorbent prepared in the step (11) in a sodium alginate aqueous solution to form a first mixed solution, wherein the mass ratio of the charcoal aerogel powder adsorbent to the volume of the sodium alginate solution is 0.01: 10, the unit of the mass of the biochar aerogel powder is g, the unit of the volume of the sodium alginate solution is mL, then the surfactant F-127 is added into the first mixed solution and evenly mixed to form a second mixed solution, and the adding amount of the F-127 is that theThe mass concentration of the benzyl benzoate in the second mixed solution is 1.0%, then the benzyl benzoate is uniformly dispersed in the second mixed solution to form a third mixed solution, and the volume ratio of the benzyl benzoate to the second mixed solution is 0.5: 1; dripping the third mixed solution into CaCl with the mass concentration of 2.0% by using an injector2Forming spherical hydrogel in the aqueous solution, transferring the spherical hydrogel into isopropanol solution, soaking and cleaning to remove oil drops embedded in the spherical hydrogel, and placing the obtained porous spherical hydrogel in CaCl with the mass concentration of 2.0%2And soaking in the aqueous solution for 1h, taking out after soaking, washing with deionized water to remove residual calcium ions and chloride ions, and freeze-drying to obtain the aerogel particles # 2.
The shale gas wastewater #2 is sequentially treated by the following 3 process steps:
(1) adsorption treatment
Filling the aerogel particles #2 in a fixed bed reactor, wherein the inner diameter of the fixed bed reactor is 2.5cm, the height of the fixed bed reactor is 30cm, and the bed filling height is 6.5cm (the filling rate of the aerogel particles #2 is 22%), then enabling the shale gas wastewater to pass through the fixed bed reactor in a continuous water inlet and continuous water outlet running mode, wherein the empty bed contact time of the shale gas wastewater is 30 minutes, and mainly removing soluble organic pollutants and suspended pollutants;
(2) ultra-filtration treatment
Performing ultrafiltration treatment on the effluent of the fixed bed reactor, wherein the ultrafiltration membrane is a polyvinylidene fluoride hollow fiber membrane, the ultrafiltration treatment is in a constant flux operation mode, and the water flux is 60L/(m)2H), ultrafiltration filtering for 56 minutes, backwashing for 3.5 minutes to form 1 cycle, and operating for 10 cycles in total, wherein the transmembrane pressure difference of two sides of the ultrafiltration membrane is controlled to be less than 65kPa in the ultrafiltration treatment operation process, so that residual soluble organic pollutants and suspended pollutants are mainly removed;
(3) nanofiltration treatment
Performing nanofiltration treatment on the effluent after ultrafiltration treatment, wherein the nanofiltration membrane is a VNF1 membrane, the nanofiltration treatment is in a constant pressure operation mode, the driving pressure is 300psi, the water flow direction is vertical to the surface of the nanofiltration membrane, the water recovery rate is 80%, and divalent cations Ca are mainly removed2+、Mg2+、Ba2+、Sr2+And the like.
The amount of contaminants in the water resulting from the shale gas wastewater #2 treatment is shown in table 6 below.
TABLE 6
Figure BDA0003374605950000111
Figure BDA0003374605950000121
As can be seen from table 6, the aerogel particle adsorbent #2 filled in the fixed bed reactor can greatly reduce the turbidity and the content of soluble organic carbon in the shale gas wastewater, and has a certain removing effect on divalent cations, and by adopting the aerogel particle #2 adsorption-ultrafiltration-nanofiltration process, the suspended pollutants, the soluble organic pollutants and the divalent cations in the shale gas wastewater can be efficiently removed, and the membrane pollution of a subsequent ultrafiltration membrane and the membrane pollution and scaling of a nanofiltration membrane can be relieved.

Claims (10)

1. A shale gas wastewater internal recycling treatment method based on adsorption and membrane technology is characterized by comprising the following steps in sequence:
(1) adsorption treatment
Adsorption treatment mainly removes soluble organic pollutants and suspended pollutants, and has two modes:
adding an aerogel powder adsorbent into the shale gas wastewater, adsorbing under stirring, and standing to settle suspended pollutants and the powder adsorbent adsorbed with soluble organic pollutants in the wastewater;
or the aerogel particle adsorbent is filled in the adsorption bed reactor, then the shale gas wastewater passes through the adsorption bed reactor in a continuous water inlet and continuous water outlet operation mode, and the aerogel particle adsorbent is used for adsorbing and removing soluble organic pollutants and filtering and intercepting suspended pollutants;
(2) ultra-filtration treatment
Carrying out ultrafiltration treatment on the supernatant obtained by the adsorption treatment of the aerogel powder adsorbent or the effluent of the adsorption bed reactor, wherein the treatment mainly removes residual powder adsorbent and suspended pollutants from the supernatant obtained by the treatment of the aerogel powder adsorbent, and the treatment mainly removes residual suspended pollutants and soluble organic pollutants from the effluent of the adsorption bed reactor;
(3) nanofiltration treatment
And (3) performing nanofiltration treatment on the effluent of the ultrafiltration treatment, wherein the treatment mainly removes divalent cations.
2. The method for internally recycling and treating the shale gas wastewater based on adsorption and membrane technology according to claim 1, wherein the aerogel powder adsorbent in the step (1) is a charcoal aerogel powder adsorbent, and the preparation method comprises the following steps: uniformly mixing chitosan powder and an alkaline mixed solution to form a first slurry, wherein the mass concentration of the chitosan powder in the first slurry is 2.0-6.0%, the alkaline mixed solution is composed of potassium hydroxide, urea and deionized water, the mass concentration of the potassium hydroxide in the alkaline mixed solution is 4.0-11.5%, and the mass concentration of the urea in the alkaline mixed solution is 4.0-12.0%; repeatedly freezing and thawing the first slurry at-20 ℃ until chitosan is completely dissolved to form second slurry, then baking the second slurry in a tubular furnace at 600-800 ℃ for 2h after freeze drying, cooling to room temperature along with the furnace after baking is finished, grinding the baked product into powder, and washing away unreacted potassium hydroxide and urea by using deionized water to obtain the biochar aerogel powder adsorbent.
3. The method for internally recycling and treating the shale gas wastewater based on adsorption and membrane technology according to claim 1, wherein the aerogel particle adsorbent in the step (1) is a charcoal aerogel particle adsorbent, and the preparation method comprises the following steps: dissolving chitosan powder in acetic acid water solution with volume concentration of 2.0-5.0% to form chitosan-acetic acid solution, wherein the mass concentration of the chitosan powder in the chitosan-acetic acid solution is 2.0-4.0%; dropping a chitosan-acetic acid solution into a sodium hydroxide aqueous solution with the mass concentration of 2.0-4.0% by using an injector to form chitosan hydrogel spheres, standing for 12 hours, taking out the hydrogel spheres, freeze-drying, calcining the freeze-dried spheres in a tubular furnace at 600-800 ℃ for 2 hours, and cooling to room temperature along with the furnace after calcining to obtain the biological carbon aerogel particle adsorbent named as aerogel particle # 1.
4. The method for internally recycling and treating the shale gas wastewater based on adsorption and membrane technology according to claim 1, wherein the aerogel particle adsorbent in the step (1) is a charcoal aerogel particle adsorbent, and the preparation method comprises the following steps:
(11) uniformly mixing chitosan powder and an alkaline mixed solution to form a first slurry, wherein the mass concentration of the chitosan powder in the first slurry is 2.0-6.0%, the alkaline mixed solution is composed of potassium hydroxide, urea and deionized water, the mass concentration of the potassium hydroxide in the alkaline mixed solution is 4.0-11.5%, and the mass concentration of the urea in the alkaline mixed solution is 4.0-12.0%; repeatedly freezing and thawing the first slurry at-20 ℃ until chitosan is completely dissolved to form second slurry, then baking the second slurry in a tubular furnace at 600-800 ℃ for 2h after freeze drying, cooling to room temperature along with the furnace after baking is finished, grinding the baked product into powder, and washing away unreacted potassium hydroxide and urea by using deionized water to obtain the charcoal aerogel powder adsorbent;
(12) dissolving sodium alginate powder in deionized water to form a sodium alginate solution with the mass concentration of 2.0-4.0%; uniformly dispersing the charcoal aerogel powder adsorbent prepared in the step (11) in a sodium alginate aqueous solution to form a first mixed solution, wherein the mass ratio of the charcoal aerogel powder adsorbent to the volume of the sodium alginate solution is 0.01-0.05: 10, the unit of the mass of the biochar aerogel powder is g, the unit of the volume of a sodium alginate solution is mL, then a surfactant F-127 is added into the first mixed solution and uniformly mixed to form a second mixed solution, the adding amount of the F-127 enables the mass concentration of the F-127 in the second mixed solution to be 1.0%, then benzyl benzoate is uniformly dispersed in the second mixed solution to form a third mixed solution, and the volume ratio of the benzyl benzoate to the second mixed solution is 0.5-1: 1; dripping the third mixed solution into CaCl with the mass concentration of 2.0-4.0% by using an injector2Forming spherical shape in aqueous solutionHydrogel, then transferring the spherical hydrogel into isopropanol solution to be soaked and cleaned to remove oil drops embedded in the spherical hydrogel, and then placing the obtained porous spherical hydrogel into CaCl with the mass concentration of 2.0-4.0%2Soaking in the aqueous solution for 1h, taking out after soaking, washing with deionized water to remove residual calcium ions and chloride ions, and freeze-drying to obtain the charcoal aerogel particle adsorbent named as aerogel particle # 2.
5. The shale gas wastewater internal recycling treatment method based on adsorption and membrane technology as claimed in claim 1 or 2, wherein the addition amount of the aerogel powder adsorbent in the step (1) is 150-600 mg/L, the adsorption time is 15-30 minutes under stirring, the stirring rotation speed is 200-400 rpm, and the standing time is 0.5-4 hours.
6. The method for recycling and treating the shale gas wastewater based on adsorption and membrane technology as claimed in claim 1, 3 or 4, wherein the adsorption bed reactor in the step (1) is a fixed bed reactor or a fluidized bed reactor, when the adsorption bed reactor is the fixed bed reactor, the packing rate of the aerogel particle adsorbent is 20-50%, and the empty bed contact time of the shale gas wastewater is 30-60 minutes; when the fluidized bed reactor is used, the filling rate of the aerogel particle adsorbent is 10-60%, dissolved oxygen is controlled at 2-4 mg/L by aeration during stable operation, and the hydraulic retention time is 6-20 hours.
7. The method for treating shale gas wastewater for internal recycling based on adsorption and membrane technology as claimed in any one of claims 1 to 4, wherein the ultrafiltration membrane of the ultrafiltration treatment in the step (2) is a polyvinylidene fluoride membrane or a polypropylene membrane, the operation mode is constant flux operation, and the water flux is 20-60L/(m) m2H), ensuring that the transmembrane pressure difference on two sides of the ultrafiltration membrane is less than a limit value in the running process of ultrafiltration treatment.
8. The method for the internal recycling treatment of shale gas wastewater based on adsorption and membrane technology as claimed in claim 5, wherein the ultrafiltration membrane of the ultrafiltration treatment in the step (2) is polymericThe operation mode of the vinylidene fluoride membrane or the polypropylene membrane is constant flux operation, and the water flux is 20-60L/(m)2H), ensuring that the transmembrane pressure difference on two sides of the ultrafiltration membrane is less than a limit value in the running process of ultrafiltration treatment.
9. The method for recycling and treating shale gas wastewater based on adsorption and membrane technology as claimed in any one of claims 1 to 4, wherein the nanofiltration membrane in step (3) is a polyamide membrane, the operation mode is constant pressure operation, the driving pressure is 100-400 psi, the water flow direction is perpendicular to the surface of the nanofiltration membrane, and the water recovery rate is 50-85%.
10. The method for recycling and treating shale gas wastewater based on adsorption and membrane technology as claimed in claim 6, wherein the nanofiltration membrane treated in step (3) is a polyamide membrane, the operation mode is constant pressure operation, the driving pressure is 100-400 psi, the water flow direction is perpendicular to the surface of the nanofiltration membrane, and the water recovery rate is 50-85%.
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