CN113603288A - High-salinity and high-hardness underground water physicochemical hardness removal method - Google Patents
High-salinity and high-hardness underground water physicochemical hardness removal method Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 116
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- 238000000034 method Methods 0.000 title claims abstract description 47
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 84
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
- 238000000909 electrodialysis Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 14
- 238000004062 sedimentation Methods 0.000 claims abstract description 14
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- 239000008367 deionised water Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
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- 238000001354 calcination Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
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- 239000012065 filter cake Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 230000032683 aging Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 3
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- 238000011049 filling Methods 0.000 claims description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- 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
- C02F1/44—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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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F2001/007—Processes including a sedimentation step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention relates to the technical field of mineral water hardness removal, in particular to a high-salinity and high-hardness underground water physical and chemical hardness removal method based on prepared GO-Ce/ZrO2@TiO2On the basis of the modified ultrafiltration membrane, the calcium ions after chemical softening and hardness removal are further reduced to below 5mg/L through the process flow of water → a pre-sedimentation regulating tank → a flocculation sedimentation tank → a high-density sedimentation tank → a valveless filter tank → an ultrafiltration system → a reverse osmosis system → an electrodialysis system. The adopted modified ultrafiltration membraneThe method can further intercept fine particles generated by chemical precipitation under strong alkaline conditions, so that an ion exchange softening system which is necessary to meet the requirement of electrodialysis concentration water inlet on RO concentrated water after conventional chemical softening is replaced, and the whole salt load of the system is greatly reduced.
Description
Technical Field
The invention relates to the technical field of mineral water hardness removal, in particular to a high-salinity and high-hardness underground water physicochemical hardness removal method.
Background
China coal mine resources are generally concentrated in northern water-poor areas, but coal mining water and peripheral industrial water (such as power plant water) are in huge demand. During the coal mining process, a large amount of underground water of a mine can be generated, and the coal mining method is characterized by high content of suspended matters, high mineralization degree and high hardness. The development of an effective comprehensive treatment and reuse technology of underground water is beneficial to balancing the supply and demand contradiction of coal mining water and solving the problem of mine wastewater discharge pollution, thereby becoming a research hotspot in the field of water treatment.
The key points of treating and recycling the mine underground water are hardness removal and salt recovery. The conventional treatment technology is generally realized by coupling methods such as chemical softening, ultrafiltration, reverse osmosis and the like. But in many engineering practices in areas such as Xinjiang in China, the conventional means for treating mine underground water with high mineralization and high hardness often show insufficient softening effect, calcium and magnesium scale ions cause blockage of a subsequent salt collecting system, and the problems that hardness removal and salt collection cannot be realized simultaneously and the like are found. The electrodialysis desalination technology can realize high-efficiency salt recovery, but an electrodialysis system generally requires that the concentration of calcium ions in inlet water is less than 30mg/L, and has extremely high requirements on a water hardness removal process. The double-alkali method can fully realize water hardness removal, but the formed strong-alkali environment puts higher requirements on the alkali resistance of the ultrafiltration membrane component.
Therefore, aiming at the treatment requirements of the underground water of the high-salinity and high-hardness mine, the development of a physicochemical hardness removal method of the underground water with high salinity and high hardness needs to be urgently needed, the double alkali method and the electrodialysis desalination technology are effectively coupled, the water hardness is fully reduced, and the effective operation of the salt collecting unit of the system is considered.
Disclosure of Invention
In order to achieve the purpose, the invention designs a high-efficiency physicochemical hardness removal method for high-salinity and high-hardness underground water based on the prepared modified ultrafiltration membrane, solves the problem that the calcium ion concentration of softened ultrahigh-hardness mine water cannot meet the water inlet requirement of an electrodialysis system in actual engineering practice, and adopts the following specific technical scheme:
the existing underground water hardness removal process flow comprises the following steps: the process of the pre-settling tank → the flocculation sedimentation tank → the high-density sedimentation tank → the valveless filter tank → the reverse osmosis system → the electrodialysis system is used for removing hardness of the raw water.
The technical innovation of the invention is as follows:
an ultrafiltration system is arranged between the valveless filter and the reverse osmosis system;
the ultrafiltration system is provided with a modified ultrafiltration membrane, and can intercept and intercept fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed in the effluent water from the valveless filter under the condition of high pH in the operating environment with the pH being more than or equal to 11.5, so that the concentration of calcium ions in the water flowing out of the ultrafiltration system and into the reverse osmosis system is less than or equal to 10 mg/L.
Further, SO in the raw water4 2-The concentration of Ca is more than or equal to 3122mg/L2+The concentration of the water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum water inflow per day of raw water is 10800m3D; the pre-settling adjustment, flocculation precipitation, high-density precipitation and valveless filter tank are used as pretreatment links; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as an advanced treatment link.
Furthermore, the number of the pre-settling adjusting tanks in the pretreatment link is 1, the pre-settling adjusting tanks are divided into 2 grids, the size range of a single grid is 30m multiplied by 10m to 60m multiplied by 15m, and the tank capacity range is 2400m3～7200m3And a truss type mud scraper is arranged in the pool;
the flocculation sedimentation tank in the pretreatment link is arranged with 1 seat in number and divided into 2 grids, the size of each grid is not less than the range of 5 mx 10 m-7 mx 15m, the flocculation sedimentation tank is divided into 2 grids, the flow of each grid is 160m3/h～350m3H, arranging a polypropylene honeycomb inclined pipe in the pool, wherein the aperture phi is 35mm, the inclined length is 1000mm, and the inclination angle is 60 degrees;
the high-density sedimentation in the pretreatment link adopts inclined plate filling, the inclined plate inclination angle is 60 degrees, and the water outlet mode is triangular weir non-submerged outflow;
the valveless filter adopts a single-layer quartz sand filter material, the particle size is 0.5-1.0mm, the thickness is 700mm, and the thickness of the lower pebble cushion layer is 450 mm.
Furthermore, the ultrafiltration system in the advanced treatment link comprises 3 sets of water production capacity with net capacity of 100m3/h～200m3An ultrafiltration unit of/h;
the reverse osmosis system in the advanced treatment link contains 4 sets of water producing capacity of 80m3/h～120m3A reverse osmosis device per hour, and adding 3-6 mg/L of scale inhibitor;
the single-membrane treatment capacity of an electrodialysis system in the advanced treatment link per square meter is 8-12 eq/m2Hr, effective membrane area 18000-20000 m2。
Further, the method for preparing the modified ultrafiltration membrane comprises the following steps:
s1 preparation of modified TiO2Particles
S1-1, adoptive species
Method for preparing monodisperse TiO by controlling the synthesis temperature of the material and the pH value of the solvent2Microspheres;
s1-2, carrying out alcoholysis on commercial lignin to obtain small molecular lignin fragments, and grafting amine on the lignin fragments by using a Mannich reaction to prepare modified lignin amine;
s1-3, and the method of cohydrolysis and calcination is adopted to dope porous Ce with ZrO2Post-coated TiO2To obtain Ce/ZrO2@TiO2Particles;
s2 preparation of modified ultrafiltration membrane
S2-1, preparing graphene oxide by a modified Hummers method;
s2-2, adopting an immersion method to mix the Ce/ZrO prepared in the step S1-32@TiO2Dispersing the particles in the graphene oxide sheet layer prepared in the step S2-1 to obtain GO-Ce/ZrO2@TiO2A composite material;
s2-3, using the GO-Ce/ZrO prepared in the step S2-2 by an IP method2@TiO2Composite material for PSF ultrafiltration membraneSurface modification to obtain GO-Ce/ZrO2@TiO2And (3) modifying the ultrafiltration membrane.
Further, the specific scheme of the step S1-3 is as follows:
s1-3-1, first, the TiO prepared in the step S1-12Adding the microspheres into absolute ethyl alcohol, stirring uniformly, transferring into deionized water, and finally adding the modified lignin amine prepared in the step S1-2 to prepare a mixed solution; in the mixed solution, TiO2The mass ratio of the microspheres to the modified lignin amine is 2.89: 1, the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 4;
s1-3-2, ultrasonically dispersing the mixed solution prepared in the step S131 for 30min, and dropwise adding 28% ammonia water until the pH value of the mixed solution system is 9;
s1-3-3, mixing the components in a mass ratio of 8: 1 ZrOCl2·H2O and Ce (SO)4)2·4H2Dissolving O in deionized water to obtain solution, wherein ZrOCl is contained in the deionized water2·H2The concentration of O is 0.031 g/mL;
s1-3-4, mixing the components in a volume ratio of 1: 13, dropwise adding the solution prepared in the step S133 into the mixed system prepared in the step S1-3-2, stirring for 2 hours, standing and aging for 4 hours, centrifugally washing and filtering, vacuum-drying the obtained filter cake at 60 ℃ for 12 hours, taking out and grinding, and calcining the ground powder at 500 ℃ for 2 hours to obtain Ce/ZrO2@TiO2Particles.
Further, the specific scheme of the step S2-2 is as follows:
s2-2-1, adding the graphene oxide prepared in the step S2-1 into ethanol/water with the volume ratio of 5: 1 for 30min, and then adding the Ce/ZrO prepared in the step S1-3-42@TiO2Performing strong ultrasonic treatment on the particles for 30 min; graphene oxide and Ce/ZrO in the mixed solution2@TiO2The mass ratio of the particles is 1.75: 1;
s2-2-2, standing the mixed solution prepared in the step S2-2-1 at room temperature for 24 hours, washing with ethanol, and drying at 55 ℃ for 12 hours to obtain GO-Ce/ZrO2@TiO2A composite material;
further, the specific scheme of the step S2-3 is as follows:
s2-3-1, fixing the PSF film between acrylic acid frames to prepare a support film, and mixing the PSF film and the acrylic acid frames in a volume ratio of 1: 2 wt.% of PIP and 0.01-0.03 wt.% of GO-Ce/ZrO2@TiO2Pouring the composite material aqueous solution to the top of the support film, soaking for 10min at 25 ℃, and removing the solution on the surface of the support film by using a rolling soft rubber roller until no visible liquid drop exists after the soaking;
s2-3-2, re-fixing the support membrane processed in the step S2-3-1 between new acrylic frames to prepare a new support membrane, pouring a TMC/n-hexane solution with the concentration of 0.01% to the top of the new support membrane, soaking at 25 ℃ for 1min, pouring an excessive TMC/n-hexane solution to the surface of the new support membrane, finally detaching the acrylic frames, and taking out the membrane; drying the film at 80 deg.C for 6min to obtain GO-Ce/ZrO2@TiO2And (3) modifying the ultrafiltration membrane.
Compared with the existing mineral water hardness removal, the invention has the beneficial effects that:
the invention aims at the characteristics of high mineralization and high hardness of mine underground water, and prepares a modified ultrafiltration membrane with good alkali resistance, high water flux and good anti-fouling effect. Based on the modified ultrafiltration membrane, the invention designs a set of hardness removal method aiming at mine underground water with high mineralization degree and high hardness, realizes effective coupling of a double alkali method and an electrodialysis desalination technology, can effectively reduce the concentration of calcium ions to be below 5mg/L, and saves an ion exchange softening system which is required to be adopted conventionally to realize great reduction of the whole salt load of the system. By implementing the technical means, the water hardness removal effect can be effectively enhanced, the stable operation of the subsequent deep salt collecting unit is considered, and the zero emission treatment of the underground water of the mine is realized.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to further illustrate the adopted modes and the obtained effects of the invention, the technical scheme of the invention is clearly and completely described by combining the embodiment and the experimental example.
Example 1
Example 1 the main objective is to illustrate the specific process of the invention for the preparation of a modified ultrafiltration membrane:
s1 preparation of modified TiO2Particles
S1-1 preparation of monodisperse TiO2Microspheres
S1-1-1, adding 0.5mL of tetrabutyl titanate into 45mL of absolute ethyl alcohol at 25 ℃, magnetically stirring for 20min, and dropwise adding 0.4mL of ammonia water with the mass fraction of 28% into the solution during stirring to obtain a mixed solution;
s1-1-2, transferring the uniformly stirred mixed solution into a polytetrafluoroethylene-lined autoclave, preserving the heat for 2 hours at 130 ℃, cooling to room temperature, and collecting a sample; centrifuging, washing and drying the sample to obtain white powdery TiO2Microspheres;
s1-2, preparation of modified lignin amine
S1-2-1, adding 10g of lignin into 30mL of absolute ethyl alcohol, dropwise adding 0.75mL of concentrated HCl while stirring, heating and refluxing for 4h, filtering, and washing to obtain brown fine powdery activated lignin;
s1-2-2, adding 5g of activated lignin and 0.5g of NaOH powder into 30mL of deionized water, and stirring and reacting at 70 ℃ for 1h to obtain a mixed solution;
s1-2-3, adding 1.2mL of formaldehyde solution and 2.4g of hexamethylene diamine into the mixed solution prepared in the step S1-2-2, heating in a water bath at 75 ℃ for 4h, cooling to room temperature, and filtering to obtain a filtrate;
s1-2-4, adding excessive K with the mass fraction of 10% into the filtrate3Fe(CN)6Filtering the obtained precipitate, washing and drying to obtain modified lignin amine;
s1-3, preparation of Ce/ZrO2@TiO2Particles
S1-3-1, 0.2g of the TiO prepared in step S1-1 was first introduced2Adding the microspheres into 20mL of absolute ethyl alcohol, stirring uniformly, transferring into 80mL of deionized water, and finally adding 0.07g of modified lignin amine prepared in the step S1-2 to prepare a mixed solution;
s1-3-2, ultrasonically dispersing the mixed solution prepared in the step S1-3-1 for 30min, and dropwise adding 28% ammonia water until the pH value of the mixed solution system is 9;
s1-3-3, 0.1614g ZrOCl2·H2O and 0.0203g Ce (SO)4)2·4H2Dissolving O in 20mL of deionized water to obtain a solution;
s1-3-4, dropwise adding the solution prepared in the step S1-3-3 into the mixed system prepared in the step S1-3-2, stirring for 2 hours, standing and aging for 4 hours, centrifuging, washing and filtering, vacuum drying the obtained filter cake at 60 ℃ for 12 hours, taking out and grinding, calcining the ground powder at 500 ℃ for 2 hours to obtain Ce/ZrO2@TiO2Particles;
s2 preparation of modified ultrafiltration membrane
S2-1, preparation of graphene oxide
S2-1-1, mixing 1g of graphite powder and 0.5g of NaNO3Slowly add 23mL of concentrated H2SO4In the reaction solution, after stirring for 1h in ice bath, 3g of KMnO is slowly added4Controlling the temperature of the mixed solution to react for 2 hours at 8 ℃;
s2-1-2, stirring the mixed solution prepared in the step S2-1-1 in a water bath at 38 ℃ for 30min, then dropping 46mL of deionized water, and stirring in the water bath at 95 ℃ for 20 min;
s2-1-3, adding 3mL of H into the mixed solution after ice bath treatment in the step S2-1-22O2Stopping the reaction with 150mL of deionized water, centrifuging, washing the centrifuged product with 5 wt.% hydrochloric acid and deionized water until the pH value of the system is 6, and drying in vacuum at 45 ℃ to obtain graphene oxide;
s2-2, preparation of GO-Ce/ZrO2@TiO2Composite material
S2-2-1, adding 5.25g of graphene oxide prepared in the step S2-1 into ethanol/water with the volume ratio of 5: 1 for 30min, and then 3g of Ce/ZrO prepared in step S1-3-4 is added2@TiO2Performing strong ultrasonic treatment on the particles for 30 min;
s2-2-2, standing the mixed solution prepared in the step S2-2-1 at room temperature for 24 hours, washing with ethanol, and drying at 55 ℃ for 12 hours to obtain GO-Ce/ZrO2@TiO2A composite material;
s2-3, preparation of GO-Ce/ZrO2@TiO2Modified ultrafiltration membrane
S2-3-1、Fix the PSF film between acrylic frames to make a support film, 10mL 2 wt.% PIP and 20mL 0.03 wt.% GO-Ce/ZrO2@TiO2Pouring the composite material aqueous solution to the top of the support film, soaking for 10min at 25 ℃, and removing the solution on the surface of the support film by using a rolling soft rubber roller until no visible liquid drop exists after the soaking;
s2-3-2, re-fixing the support membrane processed in the step S2-3-1 between new acrylic frames to prepare a new support membrane, pouring a TMC/n-hexane solution with the concentration of 0.01% to the top of the new support membrane, soaking at 25 ℃ for 1min, pouring an excessive TMC/n-hexane solution to the surface of the new support membrane, finally detaching the acrylic frames, and taking out the membrane; drying the film at 80 deg.C for 6min to obtain GO-Ce/ZrO2@TiO2And (3) modifying the ultrafiltration membrane.
Example 2
Example 2 illustrates a specific de-hardening process designed according to the present invention for groundwater based on the modified ultrafiltration membrane prepared in example 1:
an ultrafiltration system is arranged between the valveless filter and the reverse osmosis system;
the ultrafiltration system is provided with a modified ultrafiltration membrane, and can intercept and intercept fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed in the effluent water from the valveless filter under the condition of high pH in the operating environment with the pH being more than or equal to 11.5, so that the concentration of calcium ions in the water flowing out of the ultrafiltration system and into the reverse osmosis system is less than or equal to 10 mg/L.
Specifically, SO in the raw water4 2-The concentration of Ca is more than or equal to 3122mg/L2+The concentration of the water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum water inflow per day of raw water is 10800m3D; the pre-settling adjustment, flocculation precipitation, high-density precipitation and valveless filter tank are used as pretreatment links; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as an advanced treatment link.
Specifically, the number of the pre-settling adjusting tanks in the pretreatment link is 1, the pre-settling adjusting tanks are divided into 2 grids, the size range of a single grid is 30m multiplied by 10m, and the tank capacity range is 2400m3And a truss type mud scraper is arranged in the pool;
the flocculation sedimentation tank in the pretreatment link is arranged with 1 seat in number and divided into 2 lattices, the size of each lattice is not less than the range of 5m multiplied by 10m, the flow of each lattice is 160m3H, arranging a polypropylene honeycomb inclined pipe in the pool, wherein the aperture phi is 35mm, the inclined length is 1000mm, and the inclination angle is 60 degrees;
specifically, the high-density sediment in the pretreatment link adopts inclined plate filler, the inclination angle of the inclined plate is 60 degrees, and the water outlet mode is triangular weir non-submerged outflow;
the valveless filter adopts a single-layer quartz sand filter material, the particle size is 0.5mm, the thickness is 700mm, and the thickness of the lower pebble cushion layer is 450 mm.
Specifically, the ultrafiltration system in the advanced treatment link comprises 3 sets of water production capacity with net capacity of 100m3An ultrafiltration unit of/h;
the reverse osmosis system in the advanced treatment link contains 4 sets of water producing capacity of 80m3A reverse osmosis device per hour, and 3mg/L of scale inhibitor is added;
the electrodialysis system in the advanced treatment link has the single-membrane treatment capacity of 8eq/m per square meter2Hr, effective membrane area 18000m2。
Example 3
Example 3 illustrates a specific hardness removal process for groundwater designed according to the present invention based on a commercially available us-based PES ultrafiltration membrane:
an ultrafiltration system is arranged between the valveless filter and the reverse osmosis system;
the ultrafiltration system is provided with a modified ultrafiltration membrane, and can intercept and intercept fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed in the effluent water from the valveless filter under the condition of high pH in the operating environment with the pH being more than or equal to 11.5, so that the concentration of calcium ions in the water flowing out of the ultrafiltration system and into the reverse osmosis system is less than or equal to 10 mg/L.
Specifically, SO in the raw water4 2-The concentration of Ca is more than or equal to 3122mg/L2+The concentration of the water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum water inflow per day of raw water is 10800m3D; the pre-settling adjustment, flocculation precipitation, high-density precipitation and valveless filter tank are used as pretreatment links; the above-mentioned superThe filtration system, the reverse osmosis system and the electrodialysis system are taken as an advanced treatment link.
Specifically, the number of the pre-settling adjusting tanks in the pretreatment link is 1, the pre-settling adjusting tanks are divided into 2 grids, the size range of a single grid is 60m multiplied by 15m, and the tank capacity range is 7200m3And a truss type mud scraper is arranged in the pool;
the flocculation sedimentation tank in the pretreatment link is arranged with 1 seat in number and divided into 2 lattices, the size of each lattice is not less than the range of 7m multiplied by 15m, and the flow of each lattice is 350m3H, arranging a polypropylene honeycomb inclined pipe in the pool, wherein the aperture phi is 35mm, the inclined length is 1000mm, and the inclination angle is 60 degrees;
specifically, the high-density sediment in the pretreatment link adopts inclined plate filler, the inclination angle of the inclined plate is 60 degrees, and the water outlet mode is triangular weir non-submerged outflow;
the valveless filter adopts a single-layer quartz sand filter material, the particle size is 1.0mm, the thickness is 700mm, and the thickness of the lower pebble cushion layer is 450 mm.
Specifically, the ultrafiltration system in the advanced treatment link comprises 3 sets of water production capacity with net capacity of 200m3An ultrafiltration unit of/h;
the reverse osmosis system in the advanced treatment link contains 4 sets of water producing capacity of 120m3A reverse osmosis device per hour, and 6mg/L of scale inhibitor is added;
the single-membrane treatment capacity of an electrodialysis system in the advanced treatment link per square meter is 12eq/m2Hr, effective membrane area 20000m2。
Examples of the experiments
The experimental examples are described on the basis of the scheme described in example 2, and are intended to illustrate the GO-Ce/ZrO prepared according to the invention2@TiO2The specific performance of the ultrafiltration membrane is modified.
1. Design of experiments
To clarify the GO-Ce/ZrO prepared by the present invention2@TiO2The following experimental group was designed to modify the specific properties of the ultrafiltration membranes, and for visual comparison, a commercial ultrafiltration membrane was used as a blank in this example, and the basic parameters of the commercial ultrafiltration membrane are shown in table 1.
TABLE 1 control group commercial ultrafiltration membrane basic parameters
Blank group: commercial PSF ultrafiltration membranes in table 1;
experimental group 1: adding TiO into the mixture2Anchoring on the surface of a PSF film to prepare TiO2Modifying the ultrafiltration membrane;
experimental group 2: using Ce-doped ZrO2Coated in TiO2The appearance of the shell is a core-shell structure, and Ce/ZrO2@TiO2Anchoring on the surface of a PSF film to prepare Ce/ZrO2@TiO2Modifying the ultrafiltration membrane;
experimental group 3: using the protocol described in example 1: mixing Ce/ZrO2@TiO2The particles are dispersed in graphene oxide lamella to synthesize GO-Ce/ZrO2@TiO2Composite particles of GO-Ce/ZrO2@TiO2Anchoring the composite particles on the surface of a PSF film to prepare GO-Ce/ZrO2@TiO2Modifying the ultrafiltration membrane; GO-Ce/ZrO2@TiO2The concentration of the composite material aqueous solution is 0.03 wt.%, GO-Ce/ZrO2@TiO2The volume ratio of the composite material aqueous solution to PIP is 2: 1.
2. average pore diameter and porosity
Blank groups, experiment groups 1, 2, 3, 4 and 5 are selected, and the average pore diameter and porosity of each group of modified ultrafiltration membranes are measured, and specific data are shown in table 2.
TABLE 2 average pore size and porosity of various groups of modified ultrafiltration membranes
Comparing the data in the blank experimental group 1, it can be seen that when TiO is used alone2When the PSF membrane is modified, the average pore diameter and porosity of the ultrafiltration membrane are both increased because hydrophilic inorganic materials are mixed with the PSF polymer matrix, so that the exchange of a solvent and a non-solvent is accelerated in the phase inversion process, and a macroporous structure is favorably generated, thereby improving the ultrafiltration membraneTotal porosity of (c).
Comparing the data in the blank group, the experimental group 1 and the experimental group 2, it can be seen that the ZrO is enlarged by using the lignin amine as the pore-forming agent2Mass transfer channels inside the solid shell while doping Ce into ZrO2The crystal lattice can stabilize the tetragonal crystal phase structure and effectively increase the pore structure, thereby enabling the Ce/ZrO to have a uniform structure2@TiO2The aperture and porosity of the modified ultrafiltration membrane are increased.
Comparing the data in the blank group, the experimental group 1, the experimental group 2 and the experimental group 3, it can be seen that the average pore size and the porosity of the ultrafiltration membrane are both significantly improved (average pore size: 24.51nm, porosity: 75.37%), because when the matrix of the sheet structure PSF polymer of GO is mixed, a folding mechanism is formed in the sub-layer of the membrane, thereby increasing the average pore size and the porosity of the ultrafiltration membrane.
Comparing the data in experiment group 5, experiment group 4 and experiment group 3, it can be seen that when GO-Ce/ZrO2@TiO2When the concentration of the composite material aqueous solution is gradually increased, the porosity of the ultrafiltration membrane shows a change trend of increasing (71.51% → 76.33%) and then decreasing (76.33% → 75.37%), and the average pore size of the ultrafiltration membrane also shows the same change trend (23.41nm → 24.98nm → 24.51 nm). The reason why this phenomenon occurs is presumed to be: GO-Ce/ZrO2@TiO2The higher the concentration of the composite material aqueous solution on the membrane surface is, the higher the concentration of the polymer at the membrane interface is diluted, so that the porosity of the composite membrane is increased; but too high a concentration of GO-Ce/ZrO2@TiO2In the composite material aqueous solution, agglomeration phenomena occur among particles to different degrees, so that the diffusion speed of a non-solvent is reduced during phase separation, and the porosity and the average pore diameter of the ultrafiltration membrane are reduced.
In summary, in the experimental examples, GO-Ce/ZrO2@TiO2The preferred concentration of the aqueous composite solution is 0.02 wt.%.
3. Pure water flux test
A control group, an experimental group 1, an experimental group 2 and an experimental group 3 are selected, pure water flux of different modified ultrafiltration membranes is compared, a cross-flow filtration system with a laboratory scale is used for testing the separation performance of the ultrafiltration membranes of each experimental group under the feeding pressure of 0.7MPa and the temperature of 25 ℃, and specific data are shown in a table 3.
TABLE 3 basic parameters of control commercial modified ultrafiltration membranes
From the data in table 3, it can be seen that the water flux of the modified ultrafiltration membrane is significantly higher than that of the pure PSF membrane.
In addition, due to TiO2The mesoporous structure of the modified ultrafiltration membrane provides a special water channel for water to pass through the membrane, so that the water flux of the modified ultrafiltration membrane is (398.4 L.m)-2·h-1) Higher than pure PSF film (229.3 L.m)-2·h-1)；Ce/ZrO2@TiO2The modified ultrafiltration membrane has more abundant oxygen-containing functional groups than a single inorganic material, so that the surface of the membrane has more excellent hydrophilicity (511.2L m)-2·h-1)；GO-Ce/ZrO2@TiO2The modified ultrafiltration membrane is most hydrophilic on the membrane surface because it possesses additional water channels provided by the stacked GO lamellar structure (642.7L · m)-2·h-1) Thus, the invention proves that the modified ultrafiltration membrane with ultrahigh water flux is successfully prepared.
3. HA contamination resistance test
A blank group, an experimental group 1, an experimental group 2 and an experimental group 3 are selected, a pure PSF membrane and a modified ultrafiltration membrane are continuously filtered for 10mg/L of HA solution, the HA pollution resistance of the membrane is evaluated according to the flux change of the pure PSF membrane and the modified ultrafiltration membrane in the filtering process, and the results are shown in a table 4.
TABLE 4 flux change for continuous filtration of 10mg/LHA solution with ultrafiltration membrane
From the data in table 4, the flux of all membranes continuously decayed during the filtration process of 200min, because a small part of HA molecules are continuously deposited on the membrane surface and embedded into the inner pore channels of the membrane during the continuous filtration process, and part of the membrane pores are blocked.
However, the flux of the unmodified pure PSF membrane is reduced at a relatively obvious speed, the flux is reduced to 68% of the original flux after 200min, the ultrafiltration membrane after inverse modification is reduced at a relatively slow speed, and the original flux is respectively maintained at 76% (experiment group 1), 83% (experiment group 2) and 91% (experiment group 3) after continuous filtration for 200 min. This also demonstrates that the modified ultrafiltration membranes have excellent HA contamination resistance, where GO-Ce/ZrO2@TiO2The modified ultrafiltration membrane has the most excellent performance.
5. Practical application
The practical application of the invention utilizes project design purchasing and construction management general contract project for No. five well water treatment in the West area of the great south lake, the place is the east part of the West area of the great south lake of the south Tu Ha coal field in Xinjiang Hami city, and the company is Xuan mine group Hami energy limited company.
The design water quality parameters are shown in Table 5.
Table 5 designs the quality parameters of the influent water
The water quality standard of the miscellaneous water:
TDS: less than or equal to 1000mg/L, pH: 6-9, SS: less than or equal to 10mg/L, calcium hardness: less than or equal to 250mg/L, alkalinity: less than or equal to 200 mg/L.
GO-Ce/ZrO prepared by adopting method2@TiO2The ultrafiltration membrane is modified, and simultaneously, an ion exchange unit is added before electrodialysis water inlet, and the calcium removal effect of each process unit is shown in table 6.
TABLE 6 calcium removal Effect of the Process units
As can be seen from the data in Table 6, the present invention employs GO-Ce/ZrO in an alkaline state (pH. gtoreq.11.5)2@TiO2The modified ultrafiltration membrane physically intercepts fine particles such as calcium carbonate, magnesium hydroxide and the like, calcium hydroxide and the like which are not completely precipitated in chemical softening, and can further interceptMost of the calcium and magnesium precipitates already precipitated, thereby further reducing the concentration of the soluble calcium ions of the RO feed water.
Originally, the calcium ions of chemically softened water can reach more than 40mg/L, after alkali-resistant ultrafiltration interception, the calcium ions of the water can reach less than 5mg/L, after further concentration by RO, the concentration of the calcium ions of electrodialysis is about 30mg/L, and the requirement of the calcium ions of the water entering the electrodialysis can be met without ion exchange.
The invention is not only suitable for the desalination concentration of high salinity and high hardness water, but also widely suitable for the multistage desalination concentration process required in various zero emission projects at present.
In the waste water zero discharge or near zero discharge project, the discharge amount of RO concentrated water is often reduced by adopting a multi-stage desalting concentration process, the RO concentration process can only enrich sulfate radicals, calcium, magnesium and the like into the concentrated water, and because the sulfate radicals in the RO concentrated water can not be reduced and can only be continuously concentrated and enriched, the concentration of calcium ions in RO inlet water needs to be reduced to avoid the scaling of calcium sulfate at the side of the concentrated water.
Claims (8)
1. A high-salinity and high-hardness underground water physicochemical hardness removal method is characterized by comprising the following steps: the process of the pre-settling tank → the flocculation sedimentation tank → the high-density sedimentation tank → the valveless filter tank → the reverse osmosis system → the electrodialysis system is used for removing hardness of the raw water, and in the process flow:
an ultrafiltration system is arranged between the valveless filter and the reverse osmosis system;
the ultrafiltration system is provided with a modified ultrafiltration membrane, and can intercept fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed in the effluent water from the valveless filter under the condition of high pH in the operating environment with the pH being more than or equal to 11.5, so that the concentration of calcium ions in the water flowing out of the ultrafiltration system and flowing into the reverse osmosis system is less than or equal to 10 mg/L.
2. A highly mineralized and hard material according to claim 1The method for efficiently removing hardness of underground water by physicochemical treatment is characterized in that SO in the raw water4 2-The concentration of Ca is more than or equal to 3122mg/L2+The concentration of the water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum water inflow per day of raw water is 10800m3D; the pre-settling adjustment, flocculation precipitation, high-density precipitation and valveless filter tank are used as pretreatment links; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as an advanced treatment link.
3. The method as claimed in claim 2, wherein the number of pre-settling adjusting tanks in the pretreatment step is 1, the pre-settling adjusting tanks are divided into 2 cells, the size range of a single cell is 30m x 10m to 60m x 15m, and the tank capacity range is 2400 to 7200m3And a truss type mud scraper is arranged in the pool;
the flocculation sedimentation tank in the pretreatment link is arranged with 1 seat in number and divided into 2 grids, the size of each grid is not less than the range of 5 mx 10 m-7 mx 15m, and the flow of each grid is 160-350 m3H, arranging a polypropylene honeycomb inclined pipe in the pool, wherein the aperture phi is 35mm, the inclined length is 1000mm, and the inclination angle is 60 degrees;
the high-density sedimentation in the pretreatment link adopts inclined plate filling, the inclined plate inclination angle is 60 degrees, and the water outlet mode is triangular weir non-submerged outflow;
the valveless filter adopts a single-layer quartz sand filter material, the particle size is 0.5-1.0mm, the thickness is 700mm, and the thickness of a pebble cushion layer below the pebble cushion layer is 450 mm.
4. The method as claimed in claim 2, wherein the ultrafiltration system in the advanced treatment step comprises 3 sets of water production capacity per unit volume of 100-200 m3An ultrafiltration unit of/h;
the reverse osmosis system in the advanced treatment link contains 4 sets of water producing capacity of 80-120 m3A reverse osmosis device per hour, and adding 3-6 mg/L of scale inhibitor;
the single-membrane treatment capacity of an electrodialysis system in the advanced treatment link per square meter is 8-12 eq/m2Hr, effective membrane area 18000-20000 m2。
5. The physicochemical hardness removal method for the hypersalinity and high hardness groundwater according to claim 1, characterized in that the modified ultrafiltration membrane used by the ultrafiltration system is prepared by the following specific method: the porous Ce-doped ZrO is prepared by adopting a cohydrolysis and calcination method2Post-coated TiO2To obtain Ce/ZrO2@TiO2Particles; the Ce/ZrO is mixed2@TiO2The particles are dispersed in graphene oxide lamella to prepare GO-Ce/ZrO2@TiO2A composite material; using said GO-Ce/ZrO2@TiO2The composite material modifies the surface of a PSF ultrafiltration membrane to prepare GO-Ce/ZrO2@TiO2And (3) modifying the ultrafiltration membrane.
6. The method for physicochemical de-hardening of hypersaline and high hardness groundwater as claimed in claim 5, wherein the Ce/ZrO-Si is selected from the group consisting of2@TiO2The specific preparation steps for particle preparation are as follows: adding TiO into the mixture2Washing the particles with alcohol and water, adding the particles into amino modified lignin amine, and performing ultrasonic dispersion to obtain a mixed system; ZrOCl2·H2O and Ce (SO)4)2·4H2Dissolving O in deionized water to obtain a solution, dripping the solution into the mixed system, stirring, aging and centrifuging to obtain a filter cake; drying, grinding and calcining the filter cake to obtain Ce/ZrO2@TiO2Particles.
7. The method for physicochemical de-hardening of hypersalinity and high hardness groundwater as claimed in claim 5, wherein the GO-Ce/ZrO2@TiO2The specific preparation steps of the composite material are as follows: adding graphene oxide into an ethanol/water mixed solution, and adding the Ce/ZrO after ultrasonic dispersion2@TiO2The particles are subjected to strong ultrasound, standing, ethanol washing and drying to obtain GO-Ce/ZrO2@TiO2A composite material.
8. The method for physicochemical de-hardening of hypersalinity and high hardness groundwater as claimed in claim 5, wherein the GO-Ce/ZrO2@TiO2The specific preparation steps of the modified ultrafiltration membrane are as follows: fixing PSF film between acrylic frames to form support film, and mixing PIP with GO-Ce/ZrO2@TiO2Pouring the composite material aqueous solution to the top of the support film, and removing the solution on the surface of the support film after soaking; re-fixing the treated support membrane to prepare a new support membrane, pouring TMC/n-hexane solution to the top of the new support membrane, soaking, pouring excessive TMC/n-hexane solution, taking out the membrane, and drying to obtain GO-Ce/ZrO2@TiO2And (3) modifying the ultrafiltration membrane.
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| CN117023843A (en) * | 2023-07-19 | 2023-11-10 | 大庆师范学院 | Comprehensive treatment device for realizing zero discharge of waste water in graphite industry and application method |
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