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.