CN113880317B - Biological desalination method in seawater desalination process - Google Patents
Biological desalination method in seawater desalination process Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 158
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 238000011033 desalting Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 230000001954 sterilising effect Effects 0.000 claims abstract description 14
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 14
- 239000012629 purifying agent Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 62
- ZKEYULQFFYBZBG-UHFFFAOYSA-N lanthanum carbide Chemical compound [La].[C-]#[C] ZKEYULQFFYBZBG-UHFFFAOYSA-N 0.000 claims description 61
- 239000012528 membrane Substances 0.000 claims description 50
- 239000013384 organic framework Substances 0.000 claims description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 40
- 229910052782 aluminium Inorganic materials 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000002028 Biomass Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 239000002699 waste material Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000012265 solid product Substances 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 14
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- -1 lanthanum hydride Chemical compound 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000008213 purified water Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
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- 238000005303 weighing Methods 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000012510 hollow fiber Substances 0.000 claims description 5
- 238000001471 micro-filtration Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims 1
- 240000008042 Zea mays Species 0.000 claims 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims 1
- 235000005822 corn Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 241000209094 Oryza Species 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000002916 wood waste Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention discloses a biological desalination method in a seawater desalination process, which comprises the following steps: step one, primary filtration of seawater: removing large-particle-size impurities in the seawater by using a primary filter layer; step two, seawater purification and reduction: sequentially adding a purifying agent and a reducing agent into seawater; step three, secondary filtration of seawater: removing small-particle-size impurities in the seawater by using a secondary filter layer; step four, seawater desalination treatment: desalting by using a biological desalting layer to obtain desalted seawater; step five, seawater sterilization treatment: treating the desalted seawater by using a degerming device to obtain degerming seawater; step six, detecting the seawater. Compared with the conventional seawater desalination treatment, the seawater desalination process of the invention uses the self-made biological desalination layer, and the biological desalination layer has better desalination effect.
Description
Technical Field
The invention relates to the field of seawater treatment, in particular to a biological desalination method in a seawater desalination process.
Background
China is a country lacking in fresh water resources, the population is growing continuously, the urbanization process is accelerated, the industrial development is rapid, the demand for water is increased at an incredible speed, and the pollution of water bodies greatly reduces the available fresh water. Meanwhile, the climate change increases the frequency and intensity of drought and flood and also aggravates the problem of water resources. Therefore, the method has the advantages of actively developing and utilizing unconventional water resources such as seawater and brackish water while vigorously developing the conventional water resources, saving water and recycling reclaimed water, converting the concept and mode of water resource utilization, improving the water resource utilization efficiency and having very important significance for relieving the contradiction between water resource supply and demand in China.
In recent years, biomass-based wood waste is produced in large quantities, but the recycled part of the biomass-based wood waste only accounts for a small proportion, and agricultural and forestry biomass (including straws and forestry residues) serving as waste accounts for 69% of the total amount every year as a big agricultural country in China, so that the environment is not improved easily, and great resource waste is caused; based on the method, the biomass waste is treated and then used for seawater desalination and desalination, so that a good effect is achieved.
Disclosure of Invention
Aiming at the problem that a large amount of biomass waste can not be further utilized in the prior art, the invention provides a biological desalination method in a seawater desalination process.
The purpose of the invention is realized by adopting the following technical scheme:
a biological desalination method in a seawater desalination process comprises the following steps:
step one, primary filtration of seawater:
removing large-particle-size impurities in the seawater by using a primary filter layer to obtain primary filtered seawater;
step two, seawater purification and reduction:
sequentially adding a purifying agent and a reducing agent into the seawater, and treating to obtain purified and reduced seawater;
step three, secondary filtration of seawater:
removing small-particle-size impurities in the purified and reduced seawater by using a secondary filter layer to obtain secondary filtered seawater;
step four, seawater desalination treatment:
desalting the secondary filtered seawater by using a biological desalting layer to obtain desalted seawater;
step five, seawater sterilization treatment:
treating the desalted seawater by using a degerming device to obtain desalted seawater;
step six, seawater detection:
and carrying out index detection on the desalinated seawater.
Preferably, the first-stage filter layer is a polypropylene membrane with the pore diameter of 5-10 mu m.
Preferably, the primary filter layer is subjected to pressure treatment in the filtering process, so that the flow rate of passing seawater is 1.2-1.6 m3/h。
Preferably, the purifying agent is liquid chlorine or sodium hypochlorite, and the concentration of the purifying agent in the seawater raw water after the purifying agent is added is 5-10 mg/L.
Preferably, the reducing agent is sodium sulfite.
Preferably, in the step of seawater purification and reduction, the added purifying agent is uniformly mixed, then is kept stand for 2-5 hours, the lower-layer precipitate is removed, and then a reducing agent is added, wherein the adding amount of the reducing agent is based on keeping the residual chlorine in the seawater to be less than 1 ppm.
Preferably, the secondary filter layer is a hollow fiber microfiltration membrane with the aperture of 800-1000 nm.
Preferably, the secondary filter layer is subjected to pressure treatment in the filtering process to ensureThe flow rate of passing seawater is 1-1.5 m3/h。
Preferably, the biological desalination layer is a modified polysulfone membrane, and the modified polysulfone membrane is obtained by modifying a polysulfone membrane by a lanthanum carbide/aluminum-based organic framework material.
Preferably, ultraviolet light sterilization is arranged in the sterilization equipment.
Preferably, the preparation method of the lanthanum carbide/aluminum-based organic framework material comprises the following steps:
s1, preparing biochar:
cleaning waste agriculture and forestry biomass, drying the waste agriculture and forestry biomass in an oven at the temperature of 80-100 ℃, crushing the waste agriculture and forestry biomass into powder, transferring the powder into a graphite furnace, heating the powder to 400-600 ℃ under the protection of nitrogen, preserving the heat for 3-6 hours, cooling the powder along with the furnace, and crushing the powder into nano-particles to obtain biochar;
s2, preparing lanthanum carbide:
uniformly mixing biochar and lanthanum hydride according to a mass ratio of 1: 12-14, placing the mixture in a graphite furnace, heating to 1120-1150 ℃ under the protection of rare gas, and carrying out heat preservation treatment for 2-3 hours to obtain lanthanum carbide;
s3, preparing a lanthanum carbide/aluminum-based organic framework material:
(1) mixing lanthanum carbide and N, N' -dimethylformamide according to the mass ratio of 1: 6-10, and performing ultrasonic dispersion uniformly to obtain a lanthanum carbide mixture;
(2) mixing aluminum nitrate, terephthalic acid and N, N' -dimethylformamide according to the mass ratio of 3.2-3.8: 1: 6-10, and performing ultrasonic dispersion uniformly to obtain organic frame precursor liquid;
(3) uniformly mixing organic framework precursor liquid and a lanthanum carbide mixture according to a mass ratio of 10-12: 1, pouring the mixture into a high-pressure reaction kettle, treating the high-pressure reaction kettle at 230-250 ℃ for 72-96 h, naturally cooling, centrifugally collecting a solid product, washing the solid product with ethanol for at least three times, and drying the washed solid product under reduced pressure to obtain the lanthanum carbide/aluminum-based organic framework material.
Preferably, the waste agricultural and forestry biomass comprises at least one of straw, rice hulls, wood chips, bark, corncobs and husks.
Preferably, the particle size of the biochar is 200-500 nm.
Preferably, the preparation method of the modified polysulfone membrane comprises the following steps:
weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1: 5-8, stirring until the polysulfone and dimethyl sulfoxide are completely dissolved, sequentially adding ethylene glycol dimethacrylate and a lanthanum carbide/aluminum-based organic framework material, performing ultrasonic homogenization, defoaming and casting to form a film, soaking the film-formed product in a sodium hydroxide solution for 8-10 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying to obtain a modified polysulfone film; wherein, the mass of the ethylene glycol dimethacrylate accounts for 1 to 3 percent of the mass of the polysulfone, and the mass of the lanthanum carbide/aluminum-based organic framework material accounts for 5.6 to 8.8 percent of the mass of the polysulfone.
The invention has the beneficial effects that:
the invention discloses a biological desalination method in a seawater desalination process, which uses a multi-stage layer-by-layer filtration method, wherein seawater is subjected to coarse filtration, purification and reduction, fine filtration, desalination and sterilization in sequence, and finally all the seawater after desalination can meet the indexes. Compared with the conventional seawater desalination treatment, the seawater desalination process of the invention uses the self-made biological desalination layer, and the biological desalination layer has better desalination effect.
According to the invention, the seawater is firstly subjected to a first-stage filtering layer to remove large-particle-size impurities in the seawater, then is subjected to a second-stage filtering layer to remove small-particle-size impurities, double-layer impurity removal and filtering are carried out to ensure that the seawater is cleaner, then the seawater is desalted through a biological desalting layer, then the desalted seawater is subjected to sterilization treatment, and whether the index is met or not is detected.
The biological desalting layer is prepared by taking a polysulfone membrane as a matrix and taking biochar prepared and compounded with an aluminum-based organic framework material as an additive, and has a good desalting effect. Specifically, the polysulfone membrane is modified, a lanthanum carbide/aluminum-based organic framework material is added, the lanthanum carbide/aluminum-based organic framework material is obtained by coating lanthanum carbide with an aluminum-based organic framework material, the aluminum-based organic framework material has a certain salt absorption effect, the salt absorption performance is enhanced after the lanthanum carbide is coated, and the lanthanum carbide is prepared by sintering waste agriculture and forestry biomass to form biochar and then reacting the biochar with lanthanum hydride.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The invention is further described below with reference to the following examples.
Example 1
A biological desalination method in a seawater desalination process comprises the following steps:
step one, primary filtration of seawater:
the flow rate of seawater passing through the membrane under pressure was 1.4m, using a polypropylene membrane having a pore size of 8 μm3Removing large-particle-size impurities in the seawater to obtain primary filtered seawater;
step two, seawater purification and reduction:
adding sodium hypochlorite into seawater, uniformly mixing, standing for 3h, removing lower-layer precipitate, adding sodium sulfite, and treating to obtain purified and reduced seawater; wherein the concentration of sodium hypochlorite in the raw seawater water after the sodium hypochlorite is added is 8mg/L, and the adding amount of the sodium sulfite is based on keeping the residual chlorine in the seawater to be less than 1 ppm;
step three, secondary filtration of seawater:
the flow rate of the purified and reduced seawater was 1.2m by pressurizing with a hollow fiber microfiltration membrane having a pore size of 900nm3Removing small-particle-size impurities in the purified and reduced seawater to obtain secondary filtered seawater;
step four, seawater desalination treatment:
desalting the second-stage filtered seawater by reverse osmosis with modified polysulfone membrane, pressurizing with high-pressure pump and energy recovery equipment to make seawater flow through biological desalting membrane at 1m3Obtaining desalted seawater;
step five, seawater sterilization treatment:
treating the desalted seawater by using an ultraviolet sterilization degerming device to obtain desalted seawater;
step six, seawater detection:
and carrying out index detection on the desalinated seawater.
The modified polysulfone membrane is obtained by modifying a polysulfone membrane with a lanthanum carbide/aluminum-based organic framework material, and the preparation method of the lanthanum carbide/aluminum-based organic framework material comprises the following steps:
s1, preparing biochar:
cleaning waste agriculture and forestry biomass, drying the waste agriculture and forestry biomass in an oven at the temperature of 80-100 ℃, crushing the waste agriculture and forestry biomass into powder, transferring the powder into a graphite furnace, heating the powder to 500 ℃ under the protection of nitrogen, preserving the heat for 4 hours, cooling the powder along with the furnace, and crushing the powder into nano-particles to obtain biochar with the particle size of 200-500 nm; wherein the waste agriculture and forestry biomass comprises at least one of straw, rice hull, wood chip, bark, corncob and fruit shell;
s2, preparing lanthanum carbide:
uniformly mixing biochar and lanthanum hydride according to a mass ratio of 1:13, placing the mixture in a graphite furnace, heating to 1135 ℃ under the protection of rare gas, and carrying out heat preservation treatment for 2.5 hours to obtain lanthanum carbide;
s3, preparing a lanthanum carbide/aluminum-based organic framework material:
(1) mixing lanthanum carbide and N, N' -dimethylformamide according to the mass ratio of 1:8, and performing ultrasonic dispersion uniformly to obtain a lanthanum carbide mixture;
(2) mixing aluminum nitrate, terephthalic acid and N, N' -dimethylformamide according to the mass ratio of 3.5:1:8, and performing ultrasonic dispersion uniformly to obtain organic framework precursor liquid;
(3) uniformly mixing organic framework precursor liquid and a lanthanum carbide mixture according to a mass ratio of 11:1, pouring the mixture into a high-pressure reaction kettle, treating the high-pressure reaction kettle at 240 ℃ for 84 hours, naturally cooling, centrifugally collecting a solid product, washing the solid product with ethanol for at least three times, and drying the washed solid product under reduced pressure to obtain the lanthanum carbide/aluminum-based organic framework material.
The preparation method of the modified polysulfone membrane comprises the following steps:
weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1:7, stirring until the polysulfone and the dimethyl sulfoxide are completely dissolved, sequentially adding ethylene glycol dimethacrylate and a lanthanum carbide/aluminum-based organic framework material, performing ultrasonic homogenization, defoaming and casting to form a membrane, soaking the membrane-formed product in a sodium hydroxide solution for 9 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying to obtain a modified polysulfone membrane; wherein the mass of the ethylene glycol dimethacrylate is 2 percent of that of the polysulfone, and the mass of the lanthanum carbide/aluminum-based organic framework material is 7.2 percent of that of the polysulfone.
Example 2
A biological desalination method in a seawater desalination process comprises the following steps:
step one, primary filtration of seawater:
the flow rate of seawater passing through the membrane under pressure was 1.2m, using a polypropylene membrane having a pore size of 5 μm3Removing large-particle-size impurities in the seawater to obtain primary filtered seawater;
step two, seawater purification and reduction:
adding liquid chlorine into seawater, uniformly mixing, standing for 2h, removing lower-layer precipitate, adding sodium sulfite, and treating to obtain purified and reduced seawater; wherein the concentration of the liquid chlorine in the raw seawater after the liquid chlorine is put into the raw seawater is 5mg/L, and the input amount of sodium sulfite is based on keeping the residual chlorine in the seawater to be less than 1 ppm;
step three, secondary filtration of seawater:
the flow rate of the purified and reduced seawater is 1m by pressurizing with hollow fiber microfiltration membrane with 800nm pore diameter3Removing small-particle-size impurities in the purified and reduced seawater to obtain secondary filtered seawater;
step four, seawater desalination treatment:
desalting the second-stage filtered seawater by reverse osmosis with modified polysulfone membrane, pressurizing with high-pressure pump and energy recovery equipment to make seawater flow through biological desalting membrane at 0.8m3H, obtaining desaltedSeawater;
step five, seawater sterilization treatment:
treating the desalted seawater by using an ultraviolet sterilization degerming device to obtain desalted seawater;
step six, seawater detection:
and carrying out index detection on the desalinated seawater.
The modified polysulfone membrane is obtained by modifying a polysulfone membrane with a lanthanum carbide/aluminum-based organic framework material, and the preparation method of the lanthanum carbide/aluminum-based organic framework material comprises the following steps:
s1, preparing biochar:
cleaning waste agriculture and forestry biomass, drying the waste agriculture and forestry biomass in an oven at the temperature of 80-100 ℃, crushing the waste agriculture and forestry biomass into powder, transferring the powder into a graphite furnace, heating the powder to 400 ℃ under the protection of nitrogen, preserving the heat for 6 hours, cooling the powder along with the furnace, and crushing the powder into nano-particles to obtain biochar with the particle size of 200-500 nm; wherein the waste agriculture and forestry biomass comprises at least one of straw, rice hull, wood chip, bark, corncob and fruit shell;
s2, preparing lanthanum carbide:
uniformly mixing biochar and lanthanum hydride according to a mass ratio of 1:12, placing the mixture in a graphite furnace, heating to 1120 ℃ under the protection of rare gas, and carrying out heat preservation treatment for 3 hours to obtain lanthanum carbide;
s3, preparing a lanthanum carbide/aluminum-based organic framework material:
(1) mixing lanthanum carbide and N, N' -dimethylformamide according to the mass ratio of 1:6, and performing ultrasonic dispersion uniformly to obtain a lanthanum carbide mixture;
(2) mixing aluminum nitrate, terephthalic acid and N, N' -dimethylformamide according to the mass ratio of 3.2:1:6, and performing ultrasonic dispersion uniformly to obtain organic framework precursor liquid;
(3) uniformly mixing organic framework precursor liquid and a lanthanum carbide mixture according to a mass ratio of 10:1, pouring the mixture into a high-pressure reaction kettle, treating the high-pressure reaction kettle at 230 ℃ for 72 hours, naturally cooling, centrifugally collecting a solid product, washing the solid product with ethanol for at least three times, and drying the washed solid product under reduced pressure to obtain the lanthanum carbide/aluminum-based organic framework material.
The preparation method of the modified polysulfone membrane comprises the following steps:
weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1:5, stirring until the polysulfone and the dimethyl sulfoxide are completely dissolved, sequentially adding ethylene glycol dimethacrylate and a lanthanum carbide/aluminum-based organic framework material, performing ultrasonic homogenization, defoaming and casting to form a membrane, soaking the membrane-formed product in a sodium hydroxide solution for 8 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying to obtain a modified polysulfone membrane; wherein the mass of the ethylene glycol dimethacrylate accounts for 1 percent of the mass of the polysulfone, and the mass of the lanthanum carbide/aluminum-based organic framework material accounts for 5.6 percent of the mass of the polysulfone.
Example 3
A biological desalination method in a seawater desalination process comprises the following steps:
step one, primary filtration of seawater:
the flow rate of seawater passing through the membrane under pressure was 1.6m, using a polypropylene membrane having a pore size of 10 μm3Removing large-particle-size impurities in the seawater to obtain primary filtered seawater;
step two, seawater purification and reduction:
adding sodium hypochlorite into seawater, uniformly mixing, standing for 5h, removing lower-layer precipitate, adding sodium sulfite, and treating to obtain purified and reduced seawater; wherein the concentration of the sodium hypochlorite in the seawater raw water after the sodium hypochlorite is added is 10mg/L, and the adding amount of the sodium sulfite is based on keeping the residual chlorine in the seawater to be less than 1 ppm;
step three, secondary filtration of seawater:
the flow rate of the purified and reduced seawater was 1.5m by pressurizing with a hollow fiber microfiltration membrane having a pore size of 1000nm3Removing small-particle-size impurities in the purified and reduced seawater to obtain secondary filtered seawater;
step four, seawater desalination treatment:
desalting the second-stage filtered seawater by reverse osmosis with modified polysulfone membrane, pressurizing with high-pressure pump and energy recovery equipment to make seawater flow through biological desalting membrane at 1.2m3Obtaining desalted seawater;
step five, seawater sterilization treatment:
treating the desalted seawater by using an ultraviolet sterilization degerming device to obtain desalted seawater;
step six, seawater detection:
and carrying out index detection on the desalinated seawater.
The modified polysulfone membrane is obtained by modifying a polysulfone membrane with a lanthanum carbide/aluminum-based organic framework material, and the preparation method of the lanthanum carbide/aluminum-based organic framework material comprises the following steps:
s1, preparing biochar:
cleaning waste agriculture and forestry biomass, drying the waste agriculture and forestry biomass in an oven at the temperature of 80-100 ℃, crushing the waste agriculture and forestry biomass into powder, transferring the powder into a graphite furnace, heating the powder to 600 ℃ under the protection of nitrogen, preserving the heat for 3 hours, cooling the powder along with the furnace, and crushing the powder into nano-particles to obtain biochar with the particle size of 200-500 nm; wherein the waste agriculture and forestry biomass comprises at least one of straw, rice hull, wood chip, bark, corncob and fruit shell;
s2, preparing lanthanum carbide:
uniformly mixing biochar and lanthanum hydride according to a mass ratio of 1:14, placing the mixture in a graphite furnace, heating to 1150 ℃ under the protection of rare gas, and carrying out heat preservation treatment for 3 hours to obtain lanthanum carbide;
s3, preparing a lanthanum carbide/aluminum-based organic framework material:
(1) mixing lanthanum carbide and N, N' -dimethylformamide according to the mass ratio of 1:10, and performing ultrasonic dispersion uniformly to obtain a lanthanum carbide mixture;
(2) mixing aluminum nitrate, terephthalic acid and N, N' -dimethylformamide according to the mass ratio of 3.8:1:10, and performing ultrasonic dispersion uniformly to obtain organic framework precursor liquid;
(3) uniformly mixing organic framework precursor liquid and a lanthanum carbide mixture according to the mass ratio of 12:1, pouring the mixture into a high-pressure reaction kettle, treating the high-pressure reaction kettle at 250 ℃ for 96 hours, naturally cooling, centrifugally collecting a solid product, washing the solid product with ethanol for at least three times, and drying the washed solid product under reduced pressure to obtain the lanthanum carbide/aluminum-based organic framework material.
The preparation method of the modified polysulfone membrane comprises the following steps:
weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1:8, stirring until the polysulfone and the dimethyl sulfoxide are completely dissolved, sequentially adding ethylene glycol dimethacrylate and a lanthanum carbide/aluminum-based organic framework material, performing ultrasonic homogenization, defoaming and casting to form a film, soaking the film-formed product in a sodium hydroxide solution for 8-10 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying to obtain a modified polysulfone film; wherein the mass of the ethylene glycol dimethacrylate is 3 percent of that of the polysulfone, and the mass of the lanthanum carbide/aluminum-based organic framework material is 8.8 percent of that of the polysulfone.
Comparative example 1
A biological desalination method in a seawater desalination process, which has the same steps as the embodiment 1, and is characterized in that:
step four, seawater desalination treatment:
performing desalination treatment on the secondary filtered seawater by using a polysulfone membrane to obtain desalinated seawater;
the preparation method of the polysulfone membrane comprises the following steps: weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1:7, stirring until the polysulfone and the dimethyl sulfoxide are completely dissolved, adding ethylene glycol dimethacrylate, defoaming and casting to form a film after ultrasonic homogenization, placing the film-formed product into a sodium hydroxide solution for soaking treatment for 9 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying treatment to obtain a polysulfone film; wherein the mass of the ethylene glycol dimethacrylate is 2 percent of that of the polysulfone.
Comparative example 2
A biological desalination method in a seawater desalination process, which has the same steps as the embodiment 1, and is characterized in that:
step four, seawater desalination treatment:
carrying out desalination treatment on the secondary filtered seawater by using a modified polysulfone membrane to obtain desalinated seawater;
the modified polysulfone membrane is obtained by modifying a polysulfone membrane by an aluminum-based organic framework material, and the preparation method of the aluminum-based organic framework material comprises the following steps:
(1) mixing aluminum nitrate, terephthalic acid and N, N' -dimethylformamide according to the mass ratio of 3.8:1:10, and performing ultrasonic dispersion uniformly to obtain organic framework precursor liquid;
(2) pouring organic framework precursor liquid into a high-pressure reaction kettle, treating the high-pressure reaction kettle at 250 ℃ for 96 hours, naturally cooling, centrifugally collecting a solid product, washing the solid product with ethanol for at least three times, and drying the washed solid product under reduced pressure to obtain the lanthanum carbide/aluminum-based organic framework material.
The preparation method of the modified polysulfone membrane comprises the following steps:
weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1:8, stirring until the polysulfone and dimethyl sulfoxide are completely dissolved, sequentially adding ethylene glycol dimethacrylate and an aluminum-based organic framework material, performing ultrasonic homogenization, defoaming and casting to form a membrane, placing the membrane-formed product into a sodium hydroxide solution, soaking for 8-10 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying to obtain a modified polysulfone membrane; wherein the mass of the ethylene glycol dimethacrylate is 3% of the mass of the polysulfone, and the mass of the aluminum-based organic framework material is 8.8% of the mass of the polysulfone.
To illustrate the present invention more clearly, the desalination experiments were conducted on seawater according to the methods of examples 1 to 3 and comparative examples 1 to 2 of the present invention, in which the thicknesses of the primary and secondary filtration layers were set to (50. + -. 0.5) μm and the thickness of the bio-desalination layer was set to (20. + -. 0.2) μm. The results of the test at normal temperature are as follows:
TABLE 1 measurement of total soluble solid content and salt rejection
As can be seen from Table 1, the methods of examples 1 to 3 of the present invention have higher salt rejection rates, all of which can reach 99% or more.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A biological desalination method in a seawater desalination process is characterized by comprising the following steps:
step one, primary filtration of seawater:
removing large-particle-size impurities in the seawater by using a primary filter layer to obtain primary filtered seawater;
step two, seawater purification and reduction:
sequentially adding a purifying agent and a reducing agent into the seawater, and treating to obtain purified and reduced seawater;
step three, secondary filtration of seawater:
removing small-particle-size impurities in the purified and reduced seawater by using a secondary filter layer to obtain secondary filtered seawater;
step four, seawater desalination treatment:
desalting the secondary filtered seawater by using a biological desalting layer to obtain desalted seawater;
step five, seawater sterilization treatment:
treating the desalted seawater by using a degerming device to obtain desalted seawater;
step six, seawater detection:
performing index detection on the desalinated seawater;
the biological desalting layer is a modified polysulfone membrane, and the modified polysulfone membrane is obtained by modifying a polysulfone membrane through a lanthanum carbide/aluminum-based organic framework material;
the preparation method of the lanthanum carbide/aluminum-based organic framework material comprises the following steps:
s1, preparing biochar:
cleaning waste agriculture and forestry biomass, drying the waste agriculture and forestry biomass in an oven at the temperature of 80-100 ℃, crushing the waste agriculture and forestry biomass into powder, transferring the powder into a graphite furnace, heating the powder to 400-600 ℃ under the protection of nitrogen, preserving the heat for 3-6 hours, cooling the powder along with the furnace, and crushing the powder into nano particles to obtain biochar;
s2, preparing lanthanum carbide:
uniformly mixing biochar and lanthanum hydride according to a mass ratio of 1: 12-14, placing the mixture in a graphite furnace, heating to 1120-1150 ℃ under the protection of rare gas, and carrying out heat preservation treatment for 2-3 hours to obtain lanthanum carbide;
s3, preparing a lanthanum carbide/aluminum-based organic framework material:
(1) mixing lanthanum carbide and N, N' -dimethylformamide according to the mass ratio of 1: 6-10, and performing ultrasonic dispersion uniformly to obtain a lanthanum carbide mixture;
(2) mixing aluminum nitrate, terephthalic acid and N, N' -dimethylformamide according to the mass ratio of 3.2-3.8: 1: 6-10, and performing ultrasonic dispersion uniformly to obtain organic frame precursor liquid;
(3) uniformly mixing organic framework precursor liquid and a lanthanum carbide mixture according to a mass ratio of 10-12: 1, pouring the mixture into a high-pressure reaction kettle, treating the high-pressure reaction kettle at 230-250 ℃ for 72-96 h, naturally cooling, centrifugally collecting a solid product, washing the solid product with ethanol for at least three times, and drying the washed solid product under reduced pressure to obtain a lanthanum carbide/aluminum-based organic framework material;
the preparation method of the modified polysulfone membrane comprises the following steps:
weighing polysulfone and dimethyl sulfoxide, mixing according to a mass ratio of 1: 5-8, stirring until the polysulfone and dimethyl sulfoxide are completely dissolved, sequentially adding ethylene glycol dimethacrylate and a lanthanum carbide/aluminum-based organic framework material, performing ultrasonic homogenization, defoaming and casting to form a film, soaking the film-formed product in a sodium hydroxide solution for 8-10 hours, washing with purified water until a washing solution is neutral, and performing reduced pressure drying to obtain a modified polysulfone film; wherein the mass of the ethylene glycol dimethacrylate is 1-3% of the mass of the polysulfone, and the mass of the lanthanum carbide/aluminum-based organic framework material is 5.6-8.8% of the mass of the polysulfone.
2. The biological desalination method in the seawater desalination process according to claim 1, wherein the first-stage filter layer is a polypropylene membrane with a pore size of 5-10 μm.
3. The biological desalination method in the seawater desalination process as claimed in claim 1, wherein the purifying agent is liquid chlorine or sodium hypochlorite, and the concentration of the purifying agent in the seawater raw water after the purifying agent is added is 5-10 mg/L.
4. The method as claimed in claim 1, wherein the reducing agent is sodium sulfite.
5. The biological desalination method in the seawater desalination process according to claim 1, wherein in the seawater purification and reduction step, the fed purifying agent is uniformly mixed, then the mixture is kept stand for 2-5 h, the lower layer of precipitate is removed, and then a reducing agent is fed, wherein the feeding amount of the reducing agent is based on keeping the residual chlorine in the seawater to be less than 1 ppm.
6. The biological desalination method in the seawater desalination process as claimed in claim 1, wherein the secondary filtration layer is a hollow fiber microfiltration membrane with a pore size of 800-1000 nm.
7. The biological desalination method of claim 1, wherein the sterilization device is configured to sterilize ultraviolet light.
8. The method of claim 1, wherein the waste agricultural biomass comprises at least one of straw, rice hulls, wood chips, bark, corn cobs, and fruit shells.
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