CN113603288B - Physical and chemical hardness removal method for high-mineralization high-hardness groundwater - Google Patents
Physical and chemical hardness removal method for high-mineralization high-hardness groundwater Download PDFInfo
- Publication number
- CN113603288B CN113603288B CN202110942696.XA CN202110942696A CN113603288B CN 113603288 B CN113603288 B CN 113603288B CN 202110942696 A CN202110942696 A CN 202110942696A CN 113603288 B CN113603288 B CN 113603288B
- Authority
- CN
- China
- Prior art keywords
- tio
- zro
- water
- hardness
- ultrafiltration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000126 substance Substances 0.000 title claims abstract description 11
- 239000003673 groundwater Substances 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 92
- 239000012528 membrane Substances 0.000 claims abstract description 84
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 62
- 238000004062 sedimentation Methods 0.000 claims abstract description 42
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
- 238000000909 electrodialysis Methods 0.000 claims abstract description 20
- 238000005189 flocculation Methods 0.000 claims abstract description 16
- 230000016615 flocculation Effects 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229920005610 lignin Polymers 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 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
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011575 calcium Substances 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
- 239000000463 material Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 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
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000002455 scale inhibitor Substances 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000026676 system process Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 8
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 14
- 230000004907 flux Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect 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
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009430 construction management Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013400 design of experiment Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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-mineralization high-hardness groundwater materialization hardness removal method based on the prepared GO-Ce/ZrO 2 @TiO 2 Based on 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 and an electrodialysis system. The adopted modified ultrafiltration membrane can further intercept fine particles generated by chemical precipitation under the strong alkaline condition, thereby replacing an ion exchange softening system which is needed to be adopted by RO concentrated water after conventional chemical softening in order to meet the electrodialysis concentration water inlet requirement, and greatly reducing the integral salt load of the system.
Description
Technical Field
The invention relates to the technical field of mineral water hardness removal, in particular to a physical and chemical hardness removal method for high-mineralization high-hardness groundwater.
Background
Coal mine resources in China are generally concentrated in northern water-poor areas, but the demand of coal mining water and peripheral industrial water (such as power plant water) is huge. During the coal mining process, a large amount of mine underground water is produced, and the method is characterized by high suspended matter content, high mineralization degree and high hardness. The development of an effective comprehensive treatment and recycling technology for underground water is beneficial to balancing the contradiction between supply and demand of water for coal mining, and solves the problem of emission pollution of mine wastewater, so that the technology becomes a research hot spot in the field of water treatment.
The key point of the treatment and recycling of the mine underground water is the hardness removal and salt recovery. The conventional treatment technology is commonly realized by coupling methods such as chemical softening, ultrafiltration, reverse osmosis and the like. However, in many engineering practices in Xinjiang and other areas in China, the conventional means for treating mine underground water with high mineralization degree and high hardness often show the problems that the softening effect is insufficient, the subsequent salt collecting system is blocked due to calcium and magnesium scale ions, the hardness is removed, salt collection cannot be achieved, and the like. The electrodialysis desalination technology can realize efficient salt recovery, but electrodialysis systems generally require that the concentration of calcium ions in water is less than 30mg/L, and have extremely high requirements on the water hardness removal technology. The dual-alkali method can fully realize the hardness removal of water quality, but the formed strong alkaline environment has higher requirements on the alkali resistance of the ultrafiltration membrane component.
Therefore, aiming at the treatment requirement of the high-mineralization high-hardness mine underground water, development of a physical and chemical hardness removal method for the high-mineralization high-hardness mine underground water is needed, the double-alkali method and the electrodialysis desalination technology are effectively coupled, the water hardness is fully reduced, and meanwhile, the effective operation of a system salt collecting unit is considered.
Disclosure of Invention
In order to achieve the purpose, the invention designs a high-efficiency materialization and hardness removal method for high-mineralization high-hardness underground water based on the prepared modified ultrafiltration membrane, solves the problem that the calcium ion concentration still cannot meet the water inlet requirement of an electrodialysis system after the mine water with the ultra-high hardness is softened in actual engineering practice, and has the specific technical scheme as follows:
the existing groundwater hardening removal process flow is as follows: the method comprises the steps of using a pre-sedimentation regulating tank, a flocculation sedimentation tank, a high-density sedimentation tank, a valveless filter tank, a reverse osmosis system and an electrodialysis system process to remove hardness of 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 retain fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed under the high pH condition in the effluent water of the valveless filter under the operating environment with the pH value of 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 10mg/L.
Further, SO in the raw water 4 2- The concentration of (C) is more than or equal to 3122mg/L, ca 2+ The concentration of the raw water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum daily water inflow of raw water is 10800m 3 /d; the pre-sedimentation adjustment, flocculation sedimentation, high-density sedimentation and valveless filter are used as pretreatment links; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as advanced treatment links.
Further, the number of the preliminary sedimentation regulating tanks in the pretreatment link is 1, the preliminary sedimentation regulating tanks are divided into 2 grids, the size range of each unit is 30m multiplied by 10m to 60m multiplied by 15m, and the tank capacity range is 2400m 3～ 7200m 3 And a truss type mud scraper is arranged in the pool;
the number of flocculation sedimentation tanks in the pretreatment link is 1, the flocculation sedimentation tanks are divided into 2 grids, the size of each grid is not smaller than the range of 5m multiplied by 10m to 7m multiplied by 15m, the flocculation sedimentation tanks are divided into 2 grids, and the flow rate of each grid is 160m 3 /h～350m 3 A polypropylene honeycomb inclined tube is arranged in the cell, the aperture phi is 35mm, the inclined length is 1000mm, and the inclined angle is 60 degrees;
the high-density sedimentation in the pretreatment link adopts inclined plate filler, the inclined plate inclination angle is 60 degrees, and the water outlet mode is non-submerged outflow of the triangular weir;
the valveless filter adopts a single-layer quartz sand filter material, the grain diameter is 0.5-1.0mm, the thickness is 700mm, and the thickness of a pebble cushion layer is 450mm.
Further, the ultrafiltration system in the advanced treatment link comprises 3 sets of ultrafiltration systems with a net water production capacity of 100m 3 /h～200m 3 An ultrafiltration device of/h;
the reverse osmosis system in the advanced treatment link comprises 4 sets of water production capacity of 80m 3 /h～120m 3 The reverse osmosis device of/h is designed and added with 3-6 mg/L of scale inhibitor;
the electrodialysis system in the advanced treatment link has a single membrane treatment capacity of 8-12 eq/m per square meter 2 Hr, effective membrane area 18000-20000 m 2 。
Further, the method for preparing the modified ultrafiltration membrane comprises the following steps:
s1, preparing modified TiO 2 Particles
S1-1, adopt classMethod for preparing monodisperse TiO by controlling synthesis temperature of material and pH value of solvent 2 A microsphere;
s1-2, carrying out alcoholysis on commercialized lignin into micromolecular lignin fragments, and then preparing modified lignin amine on the lignin fragments by grafting amine groups through Mannich reaction;
s1-3, doping porous Ce with ZrO by adopting a method of cohydrolysis and calcination 2 Post-coated TiO 2 Ce/ZrO was obtained 2 @TiO 2 Particles;
s2, preparing modified ultrafiltration membrane
S2-1, preparing graphene oxide by adopting a modified Hummers method;
s2-2, adopting a submerged method to prepare Ce/ZrO in the step S1-3 2 @TiO 2 The particles are dispersed in the graphene oxide sheet layer prepared in the step S2-1 to prepare the GO-Ce/ZrO 2 @TiO 2 A composite material;
s2-3, adopting an IP method, and using the GO-Ce/ZrO prepared in the step S2-2 2 @TiO 2 The composite material modifies the surface of the PSF ultrafiltration membrane to prepare the GO-Ce/ZrO 2 @TiO 2 Modifying the ultrafiltration membrane.
Further, the specific scheme of the step S1-3 is as follows:
s1-3-1, firstly, tiO prepared in the step S1-1 2 Adding the microspheres into absolute ethyl alcohol, uniformly stirring, then 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, tiO 2 The 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, a step of;
s1-3-2, dropwise adding 28% ammonia water by mass fraction into the mixed solution prepared in the ultrasonic dispersion step S131 for 30min until the pH value of the mixed solution system is 9;
s1-3-3, wherein the mass ratio is 8: zrOCl of 1 2 ·H 2 O and Ce (SO) 4 ) 2 ·4H 2 O is dissolved in deionized water to obtain solution, and ZrOCl in the deionized water 2 ·H 2 The concentration of O is 0.031g/mL;
s1-3-4, wherein the volume ratio is 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 for 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/ZrO 2 @TiO 2 And (3) particles.
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 with a water volume ratio of 5:1, and then adding Ce/ZrO prepared in the step S1-3-4 2 @TiO 2 Particles, strong ultrasonic for 30min; graphene oxide and Ce/ZrO in the mixed solution 2 @TiO 2 The mass ratio of the particles is 1.75:1, a step of;
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/ZrO 2 @TiO 2 A composite material;
further, the specific scheme of the step S2-3 is as follows:
s2-3-1, fixing a PSF film between acrylic frames to prepare a support film, wherein the volume ratio is 1: 2w of 2% PIP and 0.01 to 0.03wt.% GO-Ce/ZrO 2 @TiO 2 Pouring 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 after soaking until no visible liquid drops exist;
s2-3-2, re-fixing the support film treated in the step S2-3-1 between new acrylic acid frames to prepare a new support film, pouring TMC/n-hexane solution with the concentration of 0.01% to the top of the new support film, soaking for 1min at 25 ℃, pouring excessive TMC/n-hexane solution into the surface of the new support film, and finally disassembling the acrylic acid frames to take out the film; drying the film taken out from the step at 80 ℃ for 6min to obtain GO-Ce/ZrO 2 @TiO 2 Modifying the ultrafiltration membrane.
Compared with the existing mineral water for removing hardness, the invention has the beneficial effects that:
aiming at the characteristics of high-mineralization high-hardness mine underground water, the invention prepares the modified ultrafiltration membrane with good alkali resistance, high water flux and good anti-pollution effect. Based on the modified ultrafiltration membrane, the invention designs a mine underground water hardness removal method aiming at 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 below 5mg/L, and omits an ion exchange softening system which is conventionally required to be adopted so as to greatly reduce the overall salt load of the system. By implementing the technical means of the invention, the water hardness removal effect can be effectively enhanced, and meanwhile, the stable operation of the subsequent deep salt collecting unit is considered, so that 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 explain the manner and effects of the invention, a technical solution of the invention will be clearly and completely described in the following in connection with examples and experimental examples.
Example 1
Example 1 is intended to illustrate a specific method of preparing a modified ultrafiltration membrane in accordance with the present invention:
s1, preparing modified TiO 2 Particles
S1-1, preparation of monodisperse TiO 2 Microsphere(s)
S1-1-1, adding 0.5mL of tetrabutyl titanate into 45mL of absolute ethyl alcohol at 25 ℃ and magnetically stirring for 20min, and dropwise adding 0.4mL of 28% ammonia water into the solution in the stirring process to obtain a mixed solution;
s1-1-2, transferring the uniformly stirred mixed solution into an autoclave with a polytetrafluoroethylene lining, preserving heat for 2 hours at 130 ℃, cooling to room temperature, and collecting a sample; the sample is centrifuged, washed and dried to obtain white powdery TiO 2 A microsphere;
s1-2, preparing modified lignin amine
S1-2-1, adding 10g of lignin into 30mL of absolute ethyl alcohol, dripping 0.75mL of concentrated HCl while stirring, heating and refluxing for 4 hours, filtering, and washing to obtain tan fine powdered 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 for 1h at 70 ℃ to obtain a mixed solution;
s1-2-3, adding 1.2mL of formaldehyde solution and 2.4g of hexamethylenediamine into the mixed solution prepared in the step S1-2-2, heating in a water bath at 75 ℃ for 4 hours, cooling to room temperature, and filtering to obtain filtrate;
s1-2-4, adding 10% by mass of excessive K into the filtrate 3 Fe(CN) 6 Filtering the obtained precipitate, washing and drying to obtain modified lignin amine;
s1-3, preparation of Ce/ZrO 2 @TiO 2 Particles
S1-3-1, 0.2g of TiO prepared in step S1-1 is first of all 2 Adding the microspheres into 20mL of absolute ethyl alcohol, uniformly stirring, 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, dropwise adding 28% ammonia water by mass fraction into the mixed solution prepared in the ultrasonic dispersion step S1-3-1 for 30min until the pH value of the mixed solution system is 9;
s1-3-3, 0.1614g ZrOCl 2 ·H 2 O and 0.0203g Ce (SO) 4 ) 2 ·4H 2 O is dissolved 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 for aging for 4 hours, centrifugally 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/ZrO 2 @TiO 2 Particles;
s2, preparing modified ultrafiltration membrane
S2-1, preparation of graphene oxide
S2-1-1, 1g graphite powder and 0.5g NaNO 3 Slowly add 23mL of concentrated H 2 SO 4 In the process, 3g KMnO was slowly added after stirring in an ice bath for 1h 4 Controlling 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 dripping 46mL of deionized water, and stirring in the water bath at 95 ℃ for 20min;
s2-1-3, adding 3mL of H into the mixed solution processed in the step S2-1-2 in an ice bath 2 O 2 Terminating the reaction with 150mL deionized water, washing the centrifugal product to a system pH=6 by using 5wt.% hydrochloric acid and deionized water after centrifugation, and vacuum drying at 45 ℃ to obtain graphene oxide;
s2-2, preparation of GO-Ce/ZrO 2 @TiO 2 Composite material
S2-2-1, adding 5.25g of graphene oxide prepared in the step S2-1 into ethanol/water with a volume ratio of 5:1, and then adding 3g of Ce/ZrO prepared in the step S1-3-4 2 @TiO 2 Particles, strong ultrasonic for 30min;
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/ZrO 2 @TiO 2 A composite material;
s2-3, preparation of GO-Ce/ZrO 2 @TiO 2 Modified ultrafiltration membrane
S2-3-1, fixing PSF film between acrylic frames to make support film, combining 10mL 2wt.% PIP and 20mL 0.03wt.% GO-Ce/ZrO 2 @TiO 2 Pouring 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 after soaking until no visible liquid drops exist;
s2-3-2, re-fixing the support film treated in the step S2-3-1 between new acrylic acid frames to prepare a new support film, pouring TMC/n-hexane solution with the concentration of 0.01% to the top of the new support film, soaking for 1min at 25 ℃, pouring excessive TMC/n-hexane solution into the surface of the new support film, and finally disassembling the acrylic acid frames to take out the film; drying the film taken out from the step at 80 ℃ for 6min to obtain GO-Ce/ZrO 2 @TiO 2 Modifying the ultrafiltration membrane.
Example 2
Example 2 a specific process flow for the removal of hardness from groundwater designed in accordance with the invention is described 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 retain fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed under the high pH condition in the effluent water of the valveless filter under the operating environment with the pH value of 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 10mg/L.
Specifically, the SO in the raw water 4 2- The concentration of (C) is more than or equal to 3122mg/L, ca 2+ The concentration of the raw water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum daily water inflow of raw water is 10800m 3 /d; the pre-sedimentation adjustment, flocculation sedimentation, high-density sedimentation and valveless filter are used as pretreatment links; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as advanced treatment links.
Specifically, the number of the preliminary sedimentation regulating tanks in the pretreatment link is 1, the preliminary sedimentation regulating tanks are divided into 2 grids, the size range of each unit is 30m multiplied by 10m, and the tank capacity range is 2400m 3 And a truss type mud scraper is arranged in the pool;
the number of flocculation sedimentation tanks in the pretreatment link is 1, the flocculation sedimentation tanks are divided into 2 grids, and the sizes of the single grids are not equalLess than the range of 5m multiplied by 10m, and the unit flow is 160m 3 A polypropylene honeycomb inclined tube is arranged in the cell, the aperture phi is 35mm, the inclined length is 1000mm, and the inclined angle is 60 degrees;
specifically, the high-density sedimentation in the pretreatment link adopts inclined plate filler, the inclined plate inclination angle is 60 degrees, and the water outlet mode is a triangular weir non-submerged outflow;
the valveless filter adopts a single-layer quartz sand filter material, the grain diameter is 0.5mm, the thickness is 700mm, and the thickness of a pebble cushion layer is 450mm.
Specifically, the ultrafiltration system in the advanced treatment link comprises 3 sets of ultrafiltration systems with a net water production capacity of 100m 3 An ultrafiltration device of/h;
the reverse osmosis system in the advanced treatment link comprises 4 sets of water production capacity of 80m 3 The reverse osmosis device of/h is designed and added with 3mg/L of scale inhibitor;
the electrodialysis system in the advanced treatment link has a single membrane treatment capacity of 8eq/m per square meter 2 Hr, effective membrane area 18000m 2 。
Example 3
Example 3 illustrates a specific process flow for the removal of hardness from groundwater designed in accordance with the present invention based on commercially available PES ultrafiltration membranes of the american type:
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 retain fine precipitated particles such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like formed under the high pH condition in the effluent water of the valveless filter under the operating environment with the pH value of 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 10mg/L.
Specifically, the SO in the raw water 4 2- The concentration of (C) is more than or equal to 3122mg/L, ca 2+ The concentration of the raw water is more than or equal to 1002mg/L, the hardness is more than or equal to 4253mg/L, and the maximum daily water inflow of raw water is 10800m 3 /d; the pre-sedimentation adjustment, flocculation sedimentation, high-density sedimentation and valveless filter are used as pretreatment links; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as advanced treatment links.
Specifically, what isThe number of the preliminary sedimentation regulating tanks in the pretreatment link is 1, the preliminary sedimentation regulating tanks are divided into 2 grids, the size range of each grid is 60m multiplied by 15m, and the tank capacity range is 7200m 3 And a truss type mud scraper is arranged in the pool;
the number of flocculation sedimentation tanks in the pretreatment link is 1, the flocculation sedimentation tanks are divided into 2 grids, the size of each grid is not smaller than the range of 7m multiplied by 15m, and the flow rate of each grid is 350m 3 A polypropylene honeycomb inclined tube is arranged in the cell, the aperture phi is 35mm, the inclined length is 1000mm, and the inclined angle is 60 degrees;
specifically, the high-density sedimentation in the pretreatment link adopts inclined plate filler, the inclined plate inclination angle is 60 degrees, and the water outlet mode is a triangular weir non-submerged outflow;
the valveless filter adopts a single-layer quartz sand filter material, the grain diameter is 1.0mm, the thickness is 700mm, and the thickness of a pebble cushion layer is 450mm.
Specifically, the ultrafiltration system in the advanced treatment link comprises 3 sets of ultrafiltration systems with a net water production capacity of 200m 3 An ultrafiltration device of/h;
the reverse osmosis system in the advanced treatment link comprises 4 sets of water production capacity of 120m 3 The reverse osmosis device of/h is designed and added with 6mg/L of scale inhibitor;
the electrodialysis system in the advanced treatment link has a single membrane treatment capacity of 12eq/m per square meter 2 Hr, effective membrane area 20000m 2 。
Experimental example
The description of this experimental example is based on the description scheme in example 2, and is intended to clarify the GO-Ce/ZrO preparation of the present invention 2 @TiO 2 Specific properties of the modified ultrafiltration membrane.
1. Design of experiment
To clarify the GO-Ce/ZrO preparation of the present invention 2 @TiO 2 The following experimental groups were designed for visual comparison of specific properties of the modified ultrafiltration membrane, and in this example, a commercial ultrafiltration membrane was used as a blank group, and basic parameters of the commercial ultrafiltration membrane are shown in table 1.
Table 1 basic parameters of commercial ultrafiltration membranes for control group
Blank group: commercial PSF ultrafiltration membranes in table 1;
experiment group 1: tiO is mixed with 2 Anchored on the surface of PSF film to prepare TiO 2 Modifying an ultrafiltration membrane;
experiment group 2: using Ce-doped ZrO 2 Coating on TiO 2 Forming a core-shell structure, and adding Ce/ZrO 2 @TiO 2 Anchored on the surface of PSF film to prepare Ce/ZrO 2 @TiO 2 Modifying an ultrafiltration membrane;
experiment group 3: the protocol described in example 1 was used: ce/ZrO 2 @TiO 2 The particles are dispersed in graphene oxide sheets to synthesize GO-Ce/ZrO 2 @TiO 2 Composite particles of GO-Ce/ZrO 2 @TiO 2 Composite particles are anchored on the surface of a PSF film to prepare GO-Ce/ZrO 2 @TiO 2 Modifying an ultrafiltration membrane; GO-Ce/ZrO 2 @TiO 2 The concentration of the aqueous solution of the composite material was 0.03wt.%, GO-Ce/ZrO 2 @TiO 2 The volume ratio of the composite material aqueous solution to PIP is 2:1.
2. average pore size and porosity
Blank group, experiment group 1, experiment group 2, experiment group 3, experiment group 4 and experiment group 5 were selected, and the average pore diameter and porosity of each group of modified ultrafiltration membranes were determined, and specific data are shown in table 2.
TABLE 2 average pore size and porosities of modified Ultrafiltration membranes of each group
Comparing the data from the blank group, experimental group 1, it can be seen that when TiO alone is used 2 When the PSF membrane is modified, the average pore diameter and the porosity of the ultrafiltration membrane are increased, because the hydrophilic inorganic material is mixed with the matrix of the PSF polymer, so that the exchange of the solvent and the non-solvent is accelerated in the phase inversion process, a macroporous structure is generated, and the total porosity of the ultrafiltration membrane is improved.
Comparing the data in blank, experimental group 1 and experimental group 2, it can be seen thatLignin amine is used as pore-forming agent to enlarge ZrO 2 Mass transfer channels inside the solid shell, while doping Ce to ZrO 2 To stabilize the tetragonal phase structure in the crystal lattice, can effectively increase the pore structure, thereby leading Ce/ZrO 2 @TiO 2 The pore diameter and the porosity of the modified ultrafiltration membrane are increased.
Comparing the data in blank, experimental group 1, experimental group 2 and experimental group 3, it can be seen that the average pore size and porosity of the ultrafiltration membrane are significantly improved (average pore size: 24.51nm, porosity: 75.37%), because when the matrices of the lamellar structure PSF polymer of GO are mixed, a wrinkle mechanism is formed in the sublayers of the membrane, thereby increasing the average pore size and 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/ZrO 2 @TiO 2 When the concentration of the aqueous solution of the composite material is gradually increased, the porosity of the ultrafiltration membrane is changed in a trend of increasing (71.51% -76.33%) and then shrinking (76.33% -75.37%), and the average pore diameter of the ultrafiltration membrane is also changed in the same trend (23.41 nm-24.98 nm-24.51 nm). The reason for this phenomenon is presumed to be: GO-Ce/ZrO 2 @TiO 2 The higher the concentration of the composite material aqueous solution on the surface of the membrane is, the polymer concentration at the membrane interface is diluted, so that the porosity of the composite membrane is increased; but too high a concentration of GO-Ce/ZrO 2 @TiO 2 The composite material aqueous solution can agglomerate to different degrees, so that the diffusion speed of the non-solvent is reduced during phase separation, and the porosity and average pore diameter of the ultrafiltration membrane are reduced.
In summary, in experimental examples, GO-Ce/ZrO 2 @TiO 2 The preferred concentration of the aqueous composite solution is 0.02wt.%.
3. Pure water flux test
The pure water flux of different modified ultrafiltration membranes was compared by selecting a control group, an experimental group 1, an experimental group 2 and an experimental group 3, and the separation performance of the ultrafiltration membranes of each experimental group at 0.7MPa feeding pressure and 25 ℃ was tested by using a laboratory-scale cross-flow filtration system, and specific data are shown in Table 3.
Table 3 basic parameters of commercial modified Ultrafiltration membranes of control group
From the data in Table 3, the water flux of the modified ultrafiltration membrane was significantly higher than that of the pure PSF membrane.
In addition, due to TiO 2 The mesoporous structure of the modified ultrafiltration membrane provides a special water channel for the water transmembrane, so the water flux (398.4 L.m) -2 ·h -1 ) Higher than pure PSF film (229.3 L.m -2 ·h -1 )；Ce/ZrO 2 @TiO 2 The modified ultrafiltration membrane has more excellent hydrophilicity (511.2 L.m) on the membrane surface because the membrane has oxygen-containing functional groups which are more abundant than those of single inorganic material -2 ·h -1 )；GO-Ce/ZrO 2 @TiO 2 The modified ultrafiltration membrane has the most excellent hydrophilicity of the membrane surface because it has additional water channels provided by the stacked GO lamellar structure (642.7 L.multidot.m -2 ·h -1 ) Thus proving that the invention successfully prepares the modified ultrafiltration membrane with ultrahigh water flux.
3. HA contamination resistance test
Blank, experiment 1, experiment 2 and experiment 3 were selected, and the HA solution of 10mg/L was continuously filtered through a pure PSF membrane and a modified ultrafiltration membrane, and the HA contamination resistance of the membrane was evaluated by the flux change during the filtration, and the results are shown in Table 4.
TABLE 4 flux variation of ultrafiltration membrane with continuous filtration of 10mg/LHA solution
From the data in table 4, all membranes continue to attenuate in flux during 200min filtration, as a small portion of HA molecules are continually deposited on the membrane surface and embedded in the membrane internal pores during continuous filtration, blocking a portion of the membrane pores.
But the flux of the unmodified pure PSF membrane is reduced remarkably, and the flux is reduced to 68% of the original flux after 200minThe ultrafiltration membrane after the reverse modification has a slower falling speed, and maintains 76% (experimental group 1), 83% (experimental group 2) and 91% (experimental group 3) of the original flux after continuous filtration for 200 min. This also demonstrates that the modified ultrafiltration membrane HAs excellent resistance to HA contamination, wherein GO-Ce/ZrO 2 @TiO 2 The modified ultrafiltration membrane has the most excellent performance.
5. Practical application
The invention is applied to the water treatment and purchase and construction management general contractor project of the No. five well mine in the south lake and west area of Danan province, wherein the site is the eastern part of the south lake and mine area of Hami, xinjiang and the company is Xuemi group Hami energy Limited company.
The design water quality parameters are shown in Table 5.
Table 5 design of Inlet Water quality parameters
Water quality standard of miscellaneous water:
TDS: less than or equal to 1000mg/L, pH:6 to 9, SS: less than or equal to 10mg/L, calcium hardness: less than or equal to 250mg/L, alkalinity: not more than 200mg/L.
GO-Ce/ZrO prepared by the method 2 @TiO 2 The ultrafiltration membrane is modified, and an ion exchange unit is added before electrodialysis water inflow, and the calcium removal effect of each process unit is shown in Table 6.
TABLE 6 calcium removal effect of each Process Unit
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 @TiO 2 The modified ultrafiltration membrane physically intercepts fine particles such as complete calcium carbonate, magnesium hydroxide and the like, calcium hydroxide and the like which are not precipitated in chemical softening, and can further intercept most of precipitated calcium-magnesium precipitates, thereby further reducing the concentration of dissolved calcium ions in RO inflow water.
The chemical softening water calcium ion is expected to reach more than 40mg/L, after alkali-resistant ultrafiltration interception, the water calcium ion can reach less than 5mg/L, after RO is further concentrated, the concentration of the electrodialysis calcium ion is about 30mg/L, and the concentration requirement of the electrodialysis water calcium ion can be met without ion exchange.
The invention is not only suitable for desalting and concentrating the high-mineralization high-hardness water, but also widely suitable for multistage desalting and concentrating processes required in various zero-emission projects at present.
In the zero emission or near zero emission engineering of wastewater, a multistage desalting and concentrating process is often needed to reduce the emission of RO concentrated water, but the RO concentrating process only can enrich sulfate radicals, calcium magnesium and the like into the concentrated water, and because the sulfate radicals in the RO concentrated water cannot be reduced, the concentration of calcium ions in RO water can only be concentrated and enriched continuously, so that the concentration of calcium ions in RO water is required to be reduced, and scaling of calcium sulfate on the concentrated water side is avoided.
Claims (3)
1. A physical and chemical hardness removal method for high-mineralization high-hardness groundwater is characterized by comprising the following steps: the method comprises the steps of using a pre-sedimentation regulating tank, a flocculation sedimentation tank, a high-density sedimentation tank, a valveless filter tank, a reverse osmosis system and an electrodialysis system process to remove hardness of raw water, wherein 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 calcium carbonate, magnesium carbonate, calcium hydroxide and magnesium hydroxide tiny precipitation particles formed under the condition of high pH in the effluent water from the valveless filter tank can be trapped under the operation environment that the pH is 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 5mg/L;
SO in the raw water 4 2- The concentration of Ca is less than or equal to 3122mg/L 2+ The concentration of the raw water is less than or equal to 1002mg/L, the hardness is less than or equal to 4253mg/L, and the maximum daily water inflow of raw water is 10800m 3 /d; the pre-sedimentation is regulated, the flocculation sedimentation is carried out, the high-density sedimentation is carried out, and the valve-free filtration is carried outThe pool is used as a pretreatment link; the ultrafiltration system, the reverse osmosis system and the electrodialysis system are used as deep treatment links;
the preparation method of the modified ultrafiltration membrane used by the ultrafiltration system comprises the following steps: adopts a method of cohydrolysis and calcination to lead Ce to be doped with ZrO 2 Post-coated TiO 2 Ce/ZrO was obtained 2 @TiO 2 Particles; the Ce/ZrO 2 @TiO 2 Particles are dispersed in the graphene oxide sheet layer to prepare the GO-Ce/ZrO 2 @TiO 2 A composite material; using the GO-Ce/ZrO 2 @TiO 2 The composite material modifies the surface of the PSF ultrafiltration membrane to prepare the GO-Ce/ZrO 2 @TiO 2 Modifying an ultrafiltration membrane;
the Ce/ZrO 2 @TiO 2 The preparation steps of the particle preparation are as follows: tiO is mixed with 2 Adding the particles into amino modified lignin amine after alcohol washing and water washing, performing ultrasonic dispersion to obtain a mixed system, and then dropwise adding 28% ammonia water until the pH value of the mixed solution system is 9; zrOCl 2 ·H 2 O and Ce (SO) 4 ) 2 ·4H 2 O is dissolved in deionized water to obtain a solution, the solution is dripped into the mixed system, and a filter cake is obtained through stirring, aging and centrifugation; drying, grinding and calcining the filter cake to obtain Ce/ZrO 2 @TiO 2 Particles;
the GO-Ce/ZrO 2 @TiO 2 The preparation method of the composite material comprises the following steps: adding graphene oxide into an ethanol/water mixed solution, performing ultrasonic dispersion, and adding the Ce/ZrO 2 @TiO 2 The particles are subjected to strong ultrasonic treatment, standing, ethanol washing and drying to obtain the GO-Ce/ZrO 2 @TiO 2 A composite material;
the GO-Ce/ZrO 2 @TiO 2 The preparation method of the modified ultrafiltration membrane comprises the following steps: fixing PSF film between acrylic frames to form support film, and fixing PIP and GO-Ce/ZrO 2 @TiO 2 Pouring the composite material aqueous solution to the top of the support film, and removing the solution on the surface of the support film after infiltration; re-fixing the treated support film to form a new support film, pouring TMC/n-hexane solution to the top of the new support film, soaking, pouring excessive TMC/n-hexane solution, taking out the film,drying to obtain GO-Ce/ZrO 2 @TiO 2 Modifying the ultrafiltration membrane.
2. The method for materializing and removing hardness of high-mineralization high-hardness groundwater according to claim 1, wherein the number of pre-sedimentation regulating tanks in the pretreatment step is 1, the number of the pre-sedimentation regulating tanks is divided into 2 grids, the size range of each single grid is 30m multiplied by 10m to 60m multiplied by 15m, and the tank capacity range is 2400m to 7200m 3 And a truss type mud scraper is arranged in the pool;
the number of flocculation sedimentation tanks in the pretreatment link is 1, the flocculation sedimentation tanks are divided into 2 grids, the size of each grid is not smaller than the range of 5m multiplied by 10m to 7m multiplied by 15m, and the flow rate of each grid is 160 to 350m 3 A polypropylene honeycomb inclined tube is arranged in the cell, the aperture phi is 35mm, the inclined length is 1000mm, and the inclined angle is 60 degrees;
the high-density sedimentation in the pretreatment link adopts inclined plate filler, the inclined plate inclination angle is 60 degrees, and the water outlet mode is non-submerged outflow of the triangular weir;
the valveless filter adopts a single-layer quartz sand filter material, the grain diameter is 0.5-1.0mm, the thickness is 700mm, and the thickness of a pebble cushion layer is 450mm.
3. The method for physical and chemical removal of high-mineralization high-hardness groundwater according to claim 1, wherein the ultrafiltration system in the advanced treatment process comprises 3 sets of ultrafiltration systems with a net water production capacity of 100-200 m 3 An ultrafiltration device of/h;
the reverse osmosis system in the advanced treatment link comprises 4 sets of water production capacity of 80-120 m 3 The reverse osmosis device of/h is designed and added with 3-6 mg/L of scale inhibitor;
the electrodialysis system in the advanced treatment link has a single membrane treatment capacity of 8-12 eq/m per square meter 2 Hr, effective membrane area 18000-20000 m 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110942696.XA CN113603288B (en) | 2021-08-17 | 2021-08-17 | Physical and chemical hardness removal method for high-mineralization high-hardness groundwater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110942696.XA CN113603288B (en) | 2021-08-17 | 2021-08-17 | Physical and chemical hardness removal method for high-mineralization high-hardness groundwater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113603288A CN113603288A (en) | 2021-11-05 |
| CN113603288B true CN113603288B (en) | 2023-11-24 |
Family
ID=78340951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110942696.XA Active CN113603288B (en) | 2021-08-17 | 2021-08-17 | Physical and chemical hardness removal method for high-mineralization high-hardness groundwater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113603288B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233706A (en) * | 2015-09-23 | 2016-01-13 | 三达膜科技（厦门）有限公司 | Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof |
| CN109908770A (en) * | 2019-01-31 | 2019-06-21 | 天津大学 | Tungstated cerium dopping zirconia-coated titanium dioxide solids super acids filler |
| CN110683678A (en) * | 2019-10-28 | 2020-01-14 | 新疆天蓝水清环境服务有限公司 | Combined process for removing hardness of high-hardness high-salt-content concentrated water |
| CN112520912A (en) * | 2020-11-05 | 2021-03-19 | 南京大学 | High-salt high-hardness mine water near-zero discharge process |
-
2021
- 2021-08-17 CN CN202110942696.XA patent/CN113603288B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233706A (en) * | 2015-09-23 | 2016-01-13 | 三达膜科技（厦门）有限公司 | Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof |
| CN109908770A (en) * | 2019-01-31 | 2019-06-21 | 天津大学 | Tungstated cerium dopping zirconia-coated titanium dioxide solids super acids filler |
| CN110683678A (en) * | 2019-10-28 | 2020-01-14 | 新疆天蓝水清环境服务有限公司 | Combined process for removing hardness of high-hardness high-salt-content concentrated water |
| CN112520912A (en) * | 2020-11-05 | 2021-03-19 | 南京大学 | High-salt high-hardness mine water near-zero discharge process |
Non-Patent Citations (1)
| Title |
|---|
| 多孔钨酸化CexZr1-xO2固体超强酸包覆TiO2对聚砜膜性能影响研究;孙帅;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20210615(第6期);摘要、第2.1节、第3.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113603288A (en) | 2021-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107469633B (en) | Method for preparing membrane with enhanced water flux | |
| CN109266851B (en) | Method for extracting lithium through magnetic microporous lithium adsorbent | |
| CN109692581B (en) | Two-dimensional layered Ti3C2Membrane, preparation method and application thereof | |
| WO2014153965A1 (en) | Composite flocculating agent and method for processing radioactive elements iron, cobalt, manganese and silver in nuclear wastewater | |
| JP4880656B2 (en) | Water treatment apparatus and water treatment method | |
| CN110841487B (en) | Preparation method of seawater desalination membrane | |
| CN113603288B (en) | Physical and chemical hardness removal method for high-mineralization high-hardness groundwater | |
| CN113262648B (en) | Lithium ion selective permeation membrane and application thereof | |
| CN112520912A (en) | High-salt high-hardness mine water near-zero discharge process | |
| Miao et al. | Novel LIS-doped mixed matrix membrane absorbent with high structural stability for sustainable lithium recovery from geothermal water | |
| Liu et al. | Mitigation of NOM fouling of ultrafiltration membranes by pre-deposited heated aluminum oxide particles with different crystallinity | |
| CN114315030B (en) | Papermaking tail water membrane integrated step waste salt recycling method and reclaimed water recycling method | |
| Pan et al. | Sewage sludge ash-based thermo-responsive hydrogel as a novel draw agent towards high performance of water flux and recovery for forward-osmosis | |
| Gabelich et al. | Concentrate treatment for inland desalting | |
| JP3340029B2 (en) | Method of treating wastewater containing SiO2 | |
| CN110467301A (en) | A kind of shale gas fracturing outlet liquid processing method and system and device | |
| CN110950409A (en) | Heavy medium coagulating sedimentation water treatment method | |
| CN100515961C (en) | Process for removing silicon from thick oil sewage | |
| Fan et al. | Fabrication and evaluation of an attapulgite membrane as the filter for recycling blowdown water from industrial boilers | |
| CN108905656B (en) | Preparation method and application of grafted poly (sodium polystyrene sulfonate) polysulfone microporous filter membrane | |
| CN110711494A (en) | Tubular membrane assembly and system for purifying suspension liquid with high solid waste content | |
| CN105668863A (en) | Method for treating fluoride containing waste water in silicon wafer production process | |
| CN206624737U (en) | A kind of organic wastewater reverse osmosis concentrated water oxidation and desalination system | |
| CN114988438A (en) | Lithium carbonate circulation lithium extraction process | |
| Zhang et al. | Membrane flux dynamics in the submerged ultrafiltration hybrid treatment process during particle and natural organic matter removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |