CN113603187B - High-hardness underground water physicochemical hardness removal method based on composite modified macroporous resin - Google Patents
High-hardness underground water physicochemical hardness removal method based on composite modified macroporous resin Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 160
- 229920005989 resin Polymers 0.000 title claims abstract description 160
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 39
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- 238000007710 freezing Methods 0.000 claims description 29
- 230000008014 freezing Effects 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 27
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 26
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 25
- 239000011780 sodium chloride Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 14
- 230000009466 transformation Effects 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
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- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
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- 229910001424 calcium ion Inorganic materials 0.000 abstract description 28
- 239000011575 calcium Substances 0.000 abstract description 25
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000909 electrodialysis Methods 0.000 abstract description 12
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
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- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000011001 backwashing Methods 0.000 description 4
- 229960001701 chloroform Drugs 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
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- 238000005342 ion exchange Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000013400 design of experiment Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000012520 frozen sample Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 235000021581 juice product Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000011342 resin composition Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
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Images
Classifications
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/09—Inorganic material
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of mineral water hardness removal, in particular to a high-hardness underground water physicochemical hardness removal method based on composite modified macroporous resin; on the basis of greatly reducing calcium and magnesium ions in RO concentrated water by adopting composite modified macroporous resin with orderly arranged three-dimensional apertures, the hardness of raw water can be reduced to 1.5mg/L from 300mg/L through the process flow of the raw water → a pre-settling regulating tank → a flocculation precipitation tank → a high-density precipitation tank → a valveless filter tank → an ultrafiltration system → a reverse osmosis system → a hardness removal system → an electrodialysis system, namely, the calcium ions are reduced to 0.5mg/L from 120mg/L, the requirement that the calcium ions in water entering the electrodialysis system are less than 1.84mg/L can be met, and the scaling risk of calcium sulfate formation of the electrodialysis system is effectively avoided.
Description
Technical Field
The invention relates to the technical field of mineral water hardness removal, in particular to a high-hardness underground water physicochemical hardness removal method based on composite modified macroporous resin.
Background
The practical application of the invention is a No. five well and mine water treatment and utilization project of the West area of the great south lake, and in the process of construction diagram design and ordering and purchasing of electrodialysis equipment, it is found that calcium ions produced by ultrafiltration can reach about 40mg/L due to too high hardness of raw water in water quality, after RO system concentration is carried out, the calcium ion content of electrodialysis inflow water can reach 114mg/L, and electrodialysis manufacturers require that the calcium ion index of the inflow water of an electrodialysis normal system is less than 30mg/L.
For the above reasons, the project of the present invention needs a hard water softening resin capable of effectively removing divalent cations in RO concentrate, and the resin is preferably a weakly acidic resin due to the requirements of the subsequent processes of the project. Currently commercially available cation exchange resins achieve removal of heavy metal ions mainly through ion exchange of-SOH or-COOH, but have the following problems:
the main control mechanism of ion exchange is resin intraparticle diffusion, but the passages of resin intraparticle diffusion are susceptible to Ca 2+ 、Mg 2+ Blockage interferes, and the heavy metal removal efficiency is influenced.
At present toA common solution to the above problem is to design a macroporous resin (macroporous resin is a generic term for an ion exchange resin having a capillary structure inside resin sphere particles) to reduce Ca 2+ 、Mg 2+ The influence of (c). For the reasons mentioned above, such resins are mainly used for Pb 2+ 、Cu 2+ 、Ni 2+ And (4) removing.
The macroporous resins disclosed in the prior art are all produced in disorder, and the internal pore diameter of the particles except the surface may be in a closed pore state, so that the resin particle internal diffusion efficiency cannot be further improved, and Ca is not contained in the resin particles 2+ 、Mg 2+ Is less effective than other divalent cations commonly found in mineral waters.
For the reasons, the invention aims to design the resin particles with orderly arranged inner pore diameters, reduce the problems of closed pores and low pore diameter utilization rate caused by disordered arrangement of the pore diameters, improve the internal diffusion efficiency of the resin particles and improve the Ca resistance of the resin 2+ 、Mg 2+ The removal effect of (1).
Disclosure of Invention
In order to realize the aim, the invention provides a high-hardness groundwater physicochemical hardness removal method based on composite modified macroporous resin 2+ 、Mg 2+ The specific technical scheme is as follows:
1. hardness removal system
The invention discloses a high-hardness underground water physicochemical hardness removal method based on composite modified macroporous resin 2+ The concentration is more than or equal to 114mg/L, mg 2+ Hardness of RO concentrated water with the concentration of more than or equal to 68mg/L is removed, and in the system:
the softener can remove divalent cations in RO concentrated water through the composite modified macroporous resin arranged in the softener, so that Ca in the water body flowing out of the hardness removal system 2+ The concentration is less than or equal to 0.5mg/L.
Further, the method can be used for preparing a novel materialThe generation amount of the RO concentrated water is 198m 3 H, the corresponding design treatment water amount of the hardness removal system is 198m 3 /h。
Furthermore, the regenerant used by the hardness removal system is hydrochloric acid with the concentration of 5%, the regeneration flow rate is 4-5 m/s, the regenerant used by the hardness removal system is hydrochloric acid with the concentration of 5%, the regeneration time is 45min, and the regeneration period is 15-18 h.
Furthermore, the transformation agent used by the hardness removal system is sodium hydroxide with the concentration of 5%, the transformation flow rate is 4-5 m/s, and the transformation time is 45min.
Furthermore, the backwashing agent used by the hard removing system is backflow soft water, the backwashing flow rate is 5-10 m/s, and the transformation time is 15min.
2. Specific preparation method of composite modified macroporous resin
S1, preparing a GO two-dimensional template by adopting a quenching method;
s2, preparing a modified graphene oxide framework
In-situ polymerizing carboxylic acid and amide monomers on the GO two-dimensional template prepared in the step S1, and neutralizing the carboxylic acid and amide monomers by using a NaOH solution to obtain a modified graphene oxide skeleton, namely a P @ GO template;
s3, preparing the composite modified macroporous resin
S3-1, with H + Preparing sulfonyl chloride resin by using type polystyrene sulfonic acid resin as a raw material;
s3-2, mixing the sulfonyl chloride resin prepared in the step S3-1, the P @ GO template prepared in the step S2 and hexamethylene diamine/CH 2 Cl 2 Mixing, dissolving and reacting to prepare P @ GO intermediate resin; preparing ordered self-supporting pore diameters in the P @ GO intermediate resin by adopting an ion regulation and control ice mold method to obtain a composite macroporous resin;
s3-3, washing the composite macroporous resin prepared in the step S3-2, and removing residual reactants to obtain the composite modified macroporous resin.
Further, the specific scheme of step S1 is as follows:
s1-1, mixing graphene oxide powder with a NaCl solution in a vacuum box, and then splashing the mixture on a precooling slide at the temperature of-60 ℃ at the height of 1-1.5 m to form a single-layer polycrystalline slice; the concentration of the graphene oxide in the mixed solution is 0.4-1.3 g/L, and the concentration of NaCl is 0.3-1.1 g/L;
s1-2, freezing the single-layer polycrystalline slice prepared in the step S1-1 at an annealing temperature of-30 to-10 ℃ for 1h, and carrying out freeze drying to obtain the GO two-dimensional template.
The principle of step S1 is: when the mixed droplets were splashed onto a pre-cooled slide at-60 ℃, the droplets quickly spread onto the surface and immediately frozen into a thin sheet of polycrystalline ice. Because the temperature of the precooled slide glass is lower than the homogeneous nucleation critical temperature of ice, the homogeneous nucleation of ice occurs at the moment of freezing the liquid drops, a large number of micro ice crystals are generated, a layer of polycrystalline ice sheets is formed, and the graphene oxide sheets are uniformly dispersed among the ice crystals. The temperature is then maintained at the higher annealing temperature for a period of time during which large ice crystals grow to consume the smaller ice crystals, the average size of the ice crystals increases and the overall population decreases. Along with the process of recrystallizing ice crystal growth, the graphene oxide sheets are pushed into the gaps of the ice product, and after the recrystallization process tends to be stable, the sample is freeze-dried to obtain a corresponding GO two-dimensional template.
Further, the thickness of the pre-cooling slide glass used in the step S1-1 is 0.09-0.12 mm to ensure good thermal conductivity, and isopropanol, acetone and absolute ethyl alcohol are sequentially used for ultrasonic cleaning for 20min before use to ensure the cleanliness of the frozen surface.
Further, the specific scheme of the step 2 is as follows:
s2-1, pouring methacrylamide, N-methylene bisacrylamide and acrylic acid into distilled water, and performing ultrasonic mixing uniformly at 35 ℃ to obtain a mixed solution; in the mixed solution, the concentration of methacrylamide is 5g/L, and the mass ratio of acrylamide, N-methylene bisacrylamide and acrylic acid is 1:1:3;
s2-2, adding the GO two-dimensional template prepared in the step S1 into the mixed solution prepared in the step S2-1, and magnetically stirring for 30min at 40 ℃; the concentration of the GO two-dimensional template in the mixed solution is 100g/L;
s2-3, adding potassium persulfate into the mixed solution obtained after magnetic stirring in the step S2-2, and reacting for 2.5 hours at a constant temperature of 50 ℃; in the step, the concentration of the sodium persulfate in the mixed solution is 1.1g/L;
s2-4, firstly filtering the mixed liquid in the step S2-3 to obtain a filtered product, washing the filtered product with distilled water until the supernatant is clear, then standing the filtered product in a sodium hydroxide solution with the pH =10 for 30min, filtering, washing the filtered product with the distilled water until the pH of a washing liquid is 7.5-8.0, and finally drying the washed filtered product at 60 ℃ for 12h to obtain the P @ GO template.
The P @ GO template prepared in step 2 has the following characteristics:
(1) The P @ GO template has good adsorption performance on calcium and magnesium ions in water;
(2) The preparation process of the P @ GO template is green and environment-friendly, and the carboxylic acid and amide copolymers loaded on the inner surface and the outer surface of the P @ GO template are not easy to elute;
(3) The P @ GO template has a long service life.
Further, the specific scheme of the step S3-1 is as follows:
s3-1-1, reacting H + Mixing polystyrene sulfonic acid resin with chloroform, and swelling for 24h; h in the trichloromethane + The concentration of the polystyrene sulfonic acid resin is 200g/L;
s3-1-2, mixing the mixed liquor in the step S3-1-1 with a mixed liquor with a volume ratio of 1:1 SOCl 2 /CHCl 3 Mixing the mixed solution, refluxing for 8h at 80 ℃ by micro-boiling, and filtering to obtain solid particles after the reaction is finished; the mixed solution in the step S3-1-1 is mixed with SOCl 2 /CHCl 3 The mixing volume ratio of the mixed solution is 1:1;
s3-1-3, with CH 2 Cl 2 And (3) washing the solid particles prepared in the step (S3-1-2) for 5-7 times, and drying in vacuum to obtain the sulfonyl chloride resin.
Further, the specific scheme of the step S3-2 is as follows:
s3-2-1, mixing the sulfonyl chloride resin prepared in the step S3-1, the P @ GO template prepared in the step S2 and a mixture of the sulfonyl chloride resin and the P @ GO template in a volume ratio of 1:1 of hexamethylenediamine/CH 2 Cl 2 Mixing the mixed solution, and slightly boiling and refluxing for 1h at 60 ℃ to obtain P @ GO intermediate resin; the said and hexamethylenediamine/CH 2 Cl 2 The concentration of the sulfonyl chloride resin in the mixed solution is 120-160 g/L, and the concentration of the P @ GO template is 30-60 g/L;
s3-2-2, adding a NaCl solution with the concentration of 0.3-1.2 g/L into the P @ GO intermediate resin prepared in the step S3-2-1 to prepare a precursor solution, precooling the precursor solution to 0 ℃, and then filling the precursor solution into a reaction container for directional freezing to obtain a product; the temperature gradient of the directional freezing is-10 ℃, 15 ℃, 20 ℃,30 ℃, 40 ℃,60 ℃ and 80 ℃;
s3-2-3, continuously freezing the product subjected to the directional freezing treatment in the step S3-2-2 at the temperature of minus 40 ℃ for 12 hours, and continuously freezing and drying for 48 hours to obtain the composite macroporous resin.
The principle of preparing the oriented ordered pore size resin in the step S3-2 is as follows:
the whole mixed system is directionally frozen at different freezing temperatures (-10 ℃, -15 ℃, -20 ℃, -30 ℃, -40 ℃, -60 ℃, -80 ℃). In the directional freezing process, a single upward temperature gradient can be generated in the vertical direction, the solvent water firstly triggers nucleation and crystallization on the freezing surface of the P @ GO template close to the cold source, and then the ice crystals grow upwards along the vertical direction and are microtubular ice crystals. In the process of ice crystal growth, the precursor liquid generates microphase separation: the solvent water crystallizes in a large range to form a frozen phase; the components in the precursor liquid are squeezed between the ice crystals and are gathered in micro liquid phase in the gaps of the ice crystals, and assembled and compressed to form a three-dimensional framework among the ice crystals. Then, the completely frozen sample is transferred to a refrigerator at-40 ℃ for further freezing for 12h, and the three-dimensional pore size is further formed stably. Finally, the ice crystals are completely removed by freeze drying for 48 hours.
Further, the reaction container used in the step S3-2-2 is composed of a precooling slide glass and a polytetrafluoroethylene tube bonded on the precooling slide glass, and the wall thickness of the polytetrafluoroethylene tube is 2.5-3 mm.
Further, the specific scheme of step S3-3 is as follows:
s3-3-1, using CH 2 Cl 2 Washing the composite macroporous resin prepared in the step S3-2 for 5-7 times, and then washing with absolute ethyl alcohol for 4-5 times;
s3-3-2, soaking the composite macroporous resin washed in the step S3-3-1 in a sodium hydroxide solution with the pH =10 for 30min, and filtering to obtain a filtered product;
s3-3-3, washing the filtered product in the step S3-3-2 by using deionized water until the pH value of a washing liquid is reduced to 7.5, and then drying the filtered product at 45 ℃ until the weight is constant to obtain the composite modified macroporous resin.
Compared with the existing groundwater physicochemical hardness removal method, the invention has the beneficial effects that:
(1) The groundwater physicochemical hardness removal system designed by the invention can remove Ca 2+ The concentration is more than or equal to 114mg/L, mg 2+ The RO concentrated water with the concentration more than or equal to 68mg/L is subjected to hardness removal, so that Ca in the water body flowing out of the hardness removal system 2+ The concentration is less than or equal to 0.5mg/L, and the calcium ion index of the water inlet of the electrodialysis normal system required by an electrodialysis manufacturer is met.
(2) The invention aims to improve the Ca content of macroporous weak acid cation exchange resin 2+ 、Mg 2+ The removal effect, use P @ GO template to establish orderly arranged's three-dimensional aperture as the benchmark inside the resin particle, increase the internal diffusivity of resin particle, improve Ca 2+ 、Mg 2+ The removal rate of (3).
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a graph showing the dynamic adsorption curve of calcium and magnesium ions by a resin in an experimental example of the present invention;
FIG. 3 is a graph showing the effect of the amount of resin on the removal rate of calcium ions from water in the experimental examples 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
The main purpose of example 1 is to illustrate the data indexes of the hardness removal system designed by the present invention.
The invention discloses a high-hardness underground water physicochemical hardness removal method based on composite modified macroporous resin 2+ The concentration is more than or equal to 114mg/L, mg 2+ The hardness of the RO concentrated water with the concentration of more than or equal to 68mg/L is removed, and the technical innovation of the invention is as follows:
in the system, the softener is provided with the composite modified macroporous resin. Through the composite modified macroporous resin, the softener can remove divalent cations in RO concentrated water, so that Ca in the water body flowing out of the hardness removal system 2+ The concentration is less than or equal to 0.5mg/L.
Specifically, the generation amount of the RO concentrated water is 198m 3 H, the corresponding design treatment water amount of the hardness removal system is 198m 3 /h。
Specifically, the regenerant used in the hardness removal system is hydrochloric acid with the concentration of 5%, the regeneration flow rate is 4-5 m/s, the regeneration time is 45min, and the regeneration period is 15-18 h.
Specifically, the transformation agent used by the hardness removal system is sodium hydroxide with the concentration of 5%, the transformation flow rate is 4-5 m/s, and the transformation time is 45min.
Specifically, the backwashing agent used by the hard removal system is backflow soft water, the backwashing flow rate is 5-10 m/s, and the transformation time is 15min.
Example 2
Example 2 is mainly intended to illustrate a specific preparation method of the composite modified macroporous resin designed by the invention, and the contents are as follows:
s1, preparing GO two-dimensional template
S1-1, mixing graphene oxide powder and a NaCl solution in a vacuum box, and then splashing the mixture on a pre-cooled slide at the temperature of minus 60 ℃ at the height of 1m to form a single-layer polycrystalline slice; the concentration of the graphene oxide in the mixed solution is 0.4g/L, and the concentration of NaCl is 0.3g/L;
s1-2, freezing the single-layer polycrystalline slice prepared in the step S1-1 at an annealing temperature of-30 ℃ for 1h, and obtaining a GO two-dimensional template after freeze drying;
s2, preparing a modified graphene oxide framework
S2-1, pouring 5g of methacrylamide, 5g of N, N-methylene bisacrylamide and 15g of acrylic acid into 1L of distilled water, and uniformly mixing by ultrasonic waves at the temperature of 35 ℃ to obtain a mixed solution;
s2-2, adding 100g of the GO two-dimensional template prepared in the step S1 into the mixed solution prepared in the step S2-1, and magnetically stirring for 30min at 40 ℃;
s2-3, adding 1.1g of potassium persulfate into the mixed solution obtained after magnetic stirring in the step S2-2, and reacting for 2.5 hours at a constant temperature of 50 ℃;
s2-4, firstly filtering the mixed liquid in the step S2-3 to obtain a filtered product, washing the filtered product with distilled water until the supernatant is clear, then standing the filtered product in a sodium hydroxide solution with the pH =10 for 30min, filtering, washing the filtered product with distilled water until the pH of a washing liquid is 7.5, and finally drying the washed filtered product at 60 ℃ for 12h to obtain a P @ GO template;
s3, preparing the composite modified macroporous resin
S3-1, preparing sulfonyl chloride resin, specifically comprising the following steps:
s3-1-1, mixing 200g 732-CR with 1L of trichloromethane, and swelling for 24 hours;
the 732 cation exchange resin (732-CR) is provided by Shanghai resin factory, and its physicochemical properties are shown in Table 1.
Physicochemical Properties of Table 1 732-CR
S3-1-2, mixing 1L of the mixed solution in the step S3-1-1 with 1L of the mixed solution in a volume ratio of 1:1 SOCl 2 /CHCl 3 Mixing the mixed solution, refluxing for 8h at 80 ℃ by micro-boiling, and filtering to obtain solid particles after the reaction is finished;
s3-1-3, with CH 2 Cl 2 And (3) washing the solid particles prepared in the step (S3-1-2) for 5 times, and performing vacuum drying to obtain the sulfonyl chloride resin.
S3-2, preparing the composite macroporous resin, which comprises the following specific steps:
s3-2-1, mixing 120g of sulfonyl chloride resin prepared in the step S3-1, 30g of P @ GO template prepared in the step S2 and 1L of sulfonyl chloride resin in a volume ratio of 1: hexamethylenediamine of 1-CH 2 Cl 2 Mixing the mixed solution, and slightly boiling and refluxing for 1h at 60 ℃ to obtain P @ GO intermediate resin;
s3-2-2, adding a NaCl solution with the concentration of 0.3g/L into the P @ GO intermediate resin prepared in the step S3-2-1 to prepare a precursor liquid, precooling the precursor liquid to 0 ℃, and then loading the precursor liquid into a reaction container for directional freezing to obtain a product; the temperature gradient of the directional freezing is-10 ℃, 15 ℃, 20 ℃,30 ℃, 40 ℃,60 ℃ and 80 ℃;
s3-2-3, continuously freezing the product subjected to the directional freezing treatment in the step S3-2-2 at the temperature of minus 40 ℃ for 12 hours, and continuously freezing and drying for 48 hours to obtain the composite macroporous resin;
s3-3, preparing the composite modified macroporous resin, which comprises the following specific steps:
s3-3-1, using CH 2 Cl 2 Washing the composite macroporous resin prepared in the step S3-2 for 5 times, and then washing with absolute ethyl alcohol for 4 times;
s3-3-2, soaking the composite macroporous resin washed in the step S3-3-1 in a sodium hydroxide solution with the pH =10 for 30min, and filtering to obtain a filtered product;
s3-3-3, washing the filtered product in the step S3-3-2 by using deionized water until the pH value of the washing liquid is reduced to 7.5, and then drying the filtered product at 45 ℃ until the weight is constant to obtain the composite modified macroporous resin.
Specifically, the thickness of the precooled slide glass used in the step S1-1 is 0.09mm to ensure good thermal conductivity, and isopropanol, acetone and absolute ethyl alcohol are sequentially used for ultrasonic cleaning for 20min before use to ensure the cleanliness of the frozen surface.
Specifically, the reaction container used in the step S3-2-2 is composed of a pre-cooling slide glass and a polytetrafluoroethylene tube bonded to the pre-cooling slide glass, and the wall thickness of the polytetrafluoroethylene tube is 2.5mm.
Example 3
Example 3 is based on the scheme described in example 2, and aims to illustrate a specific preparation method of the composite modified macroporous resin under another parameter:
s1, preparing GO two-dimensional template
S1-1, mixing graphene oxide powder and a NaCl solution in a vacuum box, and then splashing the mixture on a pre-cooled slide at the temperature of minus 60 ℃ at the height of 1m to form a single-layer polycrystalline slice; the concentration of the graphene oxide in the mixed solution is 1.3g/L, and the concentration of NaCl is 1.1g/L;
s1-2, freezing the single-layer polycrystalline slice prepared in the step S1-1 at an annealing temperature of-10 ℃ for 1h, and obtaining a GO two-dimensional template after freeze drying;
s2, preparing a modified graphene oxide framework
S2-1, pouring 20g of methacrylamide, 20g of N, N-methylene bisacrylamide and 60g of acrylic acid into 2L of distilled water, and performing ultrasonic mixing uniformly at 35 ℃ to obtain a mixed solution;
s2-2, adding 200g of the GO two-dimensional template prepared in the step S1 into the mixed liquid prepared in the step S2-1, and magnetically stirring for 30min at 40 ℃;
s2-3, adding 2.2g of potassium persulfate into the mixed solution obtained after magnetic stirring in the step S2-2, and reacting at the constant temperature of 50 ℃ for 2.5 hours;
s2-4, firstly filtering the mixed liquid in the step S2-3 to obtain a filtered product, washing the filtered product with distilled water until the supernatant is clear, then standing the filtered product in a sodium hydroxide solution with the pH =10 for 30min, filtering, washing the filtered product with distilled water until the pH of a washing liquid is 8.0, and finally drying the washed filtered product at 60 ℃ for 12h to obtain a P @ GO template;
s3, preparing the composite modified macroporous resin
S3-1, preparing sulfonyl chloride resin, and specifically comprising the following steps:
s3-1-1, mixing 200g of 732-CR with 2L of trichloromethane, and swelling for 24 hours;
s3-1-2, mixing 2L of the mixed solution in the step S3-1-1 with 2L of the mixed solution in a volume ratio of 1:1 SOCl 2 /CHCl 3 Mixing the mixed solution, refluxing for 8h at 80 deg.C, and filtering to obtain solid particles;
s3-1-3, with CH 2 Cl 2 And (3) washing the solid particles prepared in the step (S3-1-2) for 7 times, and performing vacuum drying to obtain sulfonyl chloride resin.
S3-2, preparing the composite macroporous resin, which comprises the following specific steps:
s3-2-1, step 160gSulfonyl chloride resin prepared by S3-1, 60g of the P @ GO template prepared by the step S2, and 1L of the sulfonyl chloride resin in a volume ratio of 1:1 of hexamethylenediamine/CH 2 Cl 2 Mixing the mixed solution, and slightly boiling and refluxing for 1h at 60 ℃ to obtain P @ GO intermediate resin;
s3-2-2, adding a NaCl solution with the concentration of 1.2g/L into the P @ GO intermediate resin prepared in the step S3-2-1 to prepare a precursor liquid, precooling the precursor liquid to 0 ℃, and then loading the precursor liquid into a reaction container for directional freezing to obtain a product; the temperature gradient of the directional freezing is-10 ℃, 15 ℃, 20 ℃,30 ℃, 40 ℃,60 ℃ and 80 ℃;
s3-2-3, continuously freezing the product subjected to the directional freezing treatment in the step S3-2-2 at the temperature of minus 40 ℃ for 12 hours, and continuously freezing and drying for 48 hours to obtain composite macroporous resin;
s3-3, preparing the composite modified macroporous resin, which comprises the following specific steps:
s3-3-1, using CH 2 Cl 2 Washing the composite macroporous resin prepared in the step S3-2 for 5 times, and then washing the composite macroporous resin with absolute ethyl alcohol for 5 times;
s3-3-2, soaking the composite macroporous resin washed in the step S3-3-1 in a sodium hydroxide solution with the pH =10 for 30min, and filtering to obtain a filtered product;
s3-3-3, washing the filtered product in the step S3-3-2 by using deionized water until the pH value of a washing liquid is reduced to 7.5, and then drying the filtered product at 45 ℃ until the weight is constant to obtain the composite modified macroporous resin.
Specifically, the thickness of the pre-cooling slide glass used in the step S1-1 is 0.12mm to ensure good thermal conductivity, and before use, the pre-cooling slide glass is sequentially cleaned by isopropanol, acetone and absolute ethyl alcohol for 20min to ensure the cleanliness of the frozen surface.
Specifically, the reaction container used in the step S3-2-2 is composed of a pre-cooling slide glass and a polytetrafluoroethylene tube bonded to the pre-cooling slide glass, and the wall thickness of the polytetrafluoroethylene tube is 3mm.
Examples of the experiments
The experimental example is described based on the scheme described in example 2, and aims to clarify the specific properties of the composite modified macroporous resin prepared by the invention.
1. Design of experiments
To illustrate the specific properties of the composite modified macroporous resins prepared in accordance with the present invention, the following experimental set was designed, and for visual comparison, a commercial resin-732-CR was used as a blank set in this example, and the basic parameters of the commercial resin are shown in Table 1 above.
Blank group: commercial resin-732-CR in Table 1;
experimental group 1: using the protocol described in example 1, sulfonyl chloride resin was prepared from sulfonyl chloride resin without using an ice mold method;
experimental group 2: using the protocol described in example 1, with hexamethylenediamine/CH 2 Cl 2 Preparing hexamethylenediamine modified polystyrene macroporous resin by using the mixed solution and sulfonyl chloride resin as raw materials without adopting an ice mould method;
experimental group 3: using the protocol described in example 1, with sulfonyl chloride resin, GO two-dimensional template, hexamethylenediamine/CH 2 Cl 2 Preparing GO/composite modified macroporous resin by using the mixed solution as a raw material without adopting an ice mold method;
experimental group 4: using the protocol described in example 1, with sulfonyl chloride resin, P @ GO template, hexamethylenediamine/CH 2 Cl 2 Preparing PGO/composite modified macroporous resin by using the mixed solution as a raw material without adopting an ice mold method;
experimental group 5: using the protocol described in example 1, with sulfonyl chloride resin, P @ GO template, hexamethylenediamine/CH 2 Cl 2 Preparing P @ GO/composite modified macroporous resin by using the mixed solution as a raw material by adopting an ice mold method;
2. influence of different synthetic methods on numerical specific surface area
Blank groups and experimental groups 1-6 are selected, the specific surface area of each group of resin is measured, and specific data are shown in table 2.
TABLE 2 Carrier hydrophilicity
Referring to the data in Table 2, it can be seen that the current commercial 732-CR specific surface area is443m 2 The reason why the specific surface area of the sulfonyl chloride resin prepared in experimental group 1 is lower than that of 732-CR is presumed to be that the 732-CR is re-swollen to destroy the original pore size structure of 732-CR without constituting a new pore size structure, resulting in a decrease in specific surface area.
Comparing the experimental groups 2, 3 and 4 with the blank group, it can be found that the specific surface area of the resin prepared by the experimental groups 2, 3 and 4 is slightly higher than 732-CR, but the difference is not large, and the difference of the specific surface area of the resin between the experimental groups 2, 3 and 4 is also small, and whether the GO two-dimensional template and the P @ GO template are added or not is presumed, the specific surface area of the resin cannot be changed, and the decisive effect on the formation of the pore size structure of the resin is not achieved.
It is to be noted that the specific surface area of the resin prepared in Experimental group 5 was much higher than that of the other groups (the specific surface area of the resin in Experimental group 5 was 513m 2 The/g) method is adopted, so that the components in the precursor liquid are squeezed between the ice crystals in the directional freezing process and are gathered in micro liquid phase in the gaps of the ice crystals, and the pore diameters of the three-dimensional structures are formed.
Therefore, in the present experimental example, the method of preparing the resin having a large specific surface area is preferably an ice mold method.
2. Influence of NaCl solution concentration in precursor solution on resin morphology
Based on the scheme in the experimental group 5, the following experimental group is designed to explore the influence of the concentration of the NaCl solution in the precursor solution on the morphology of the resin, and the specific data are shown in table 3.
TABLE 3 influence of NaCl solution concentration in the precursor solution on the morphology of the resin
Referring to the data in table 3, regarding the variation of the pore size of the resin, it can be seen that when the concentration of the NaCl solution is 0.1g/L, the pore size of the prepared resin is 0.3nm at the minimum and 4.3nm at the maximum, i.e. the difference of pore sizes is very large (difference is 4.0 nm), and the directional pore-forming effect is not good; when the concentration of the NaCl solution is gradually increased to 1.9g/L, the pore diameter of the prepared resin is 2.1nm at the minimum and 2.8nm at the maximum, and the minimum pore and the maximum pore are reduced, namely the difference of the pore diameters is reduced (the difference is 0.7 nm), which shows that the prepared resin has better directional pore-forming effect and the pore diameters with uniform particle sizes are obtained. However, it is noted that when the NaCl solution concentration is increased to 1.2g/L, the values of the smallest pores and the largest pores of the obtained resin are both decreased (the pore diameter is 0.8nm at the minimum and 1.9nm at the maximum), and the difference in pore diameter is suddenly increased (the difference is 1.1 nm).
Referring to the data in Table 3, in terms of the thickness change between the pore diameters of the resin, it can be seen that the pore diameter thickness of the resin obtained becomes gradually thicker (0.3 to 3.2 nm) as the concentration of the NaCl solution is gradually increased.
In combination with the above, as the concentration of the NaCl solution is gradually increased, the pore diameter thickness of the resin is gradually increased from thin to thick. When the concentration of the NaCl solution is 0.1g/L, although the reticular pore diameter is obtained and the resin structure is compactly reinforced, the pore diameter distribution is not uniform, which can cause poor mechanical transformation performance; as the NaCl solution concentration gradually increased to 1.9g/L, more resin components were repelled by the particle ice crystals, compressed between the ice crystals, and thus exhibited a more uniform and ordered pore size distribution. However, when the concentration of NaCl solution is increased to 1.2g/L, the pore diameter is blocked due to the thickness of the partition wall between the pore diameters, the ordered generation of the pore diameters is damaged, and the phenomenon is shown that the difference of the pore diameters is suddenly increased.
Therefore, in this experimental example, in order to obtain a resin material having small pore diameter variation and uniform pore diameter, the concentration of NaCl solution is preferably 1.9g/L.
3. Dynamic analysis of calcium and magnesium ions by resin under flowing water condition
Fig. 2 is a dynamic adsorption curve of calcium and magnesium ions by the composite modified macroporous resin prepared by the method under different flow rates. In this experimental example, a simulated calcium-magnesium ion mixed solution having a concentration of 500ppm (in terms of calcium carbonate) and 4:1 was used. The outlet flow rates were 5.0, 15.0, 30.0mL/min, respectively.
Comparing the three dynamic adsorption curves, it can be seen that the smaller the flow rate, the better the adsorption effect of the resin, and the higher the removal rate of calcium and magnesium ions, which can reach 99.6% at most, and the other two adsorption curves are 92.3% and 87.4% in sequence. It is worth noting that the adsorption effect of the resin gradually deteriorates and the removal rate of calcium and magnesium ions gradually decreases as the adsorption time increases. This is because as the adsorption proceeds, the resin adsorbs a certain amount of adsorbate, and some functional groups in the resin are already aggregated with calcium and magnesium ions, resulting in a gradually reduced adsorption rate. Therefore, in practical use, the outlet flow rate of the drinking water is controlled, so that the treated resin can meet the requirement of hardness of the drinking water, and the service life of the resin can be prolonged to the maximum extent.
4. Influence of resin dosage on removal rate of calcium ions in water
FIG. 3 is a graph showing the effect of the amount of the modified macroporous resin composition prepared in the present application on the removal rate of calcium ions in water. From fig. 3, it can be seen that, by changing the amount of the composite modified macroporous resin added while keeping the calcium ion concentration at 500ppm (in terms of calcium carbonate) and the volume of water at 100mL, the removal rate of calcium ions increases with the increase of the amount of the resin used, and when the amount of the composite modified macroporous resin added is 0.11g, the removal rate of calcium ions in water reaches nearly 100%.
5. Practical application
The practical application of the invention utilizes the project design purchasing and construction management general contract project for the water treatment of the No. five well mine in the West area of the great south lake by the Kam coal field southeast district of the south China, xinjiang, and the company is the Kam energy limited company of the Xuan mine group.
Item information: treatment scale: producing 100m of water 3 The method comprises the following steps of (1) constructing 4 sets of the Perx 5 sets at a time, and reserving 1 set of the positions; the hardness of underground mine water is high, most of the underground mine water is permanent hardness, and the underground mine water needs to be softened by caustic soda and then enters reverse osmosis after being pretreated after the hardness is removed. The details of the hardness removal system are shown in Table 4.
TABLE 4 hard system details
Raw water type: the third-level wastewater has SDI less than 2.5.
The water quality parameters of each stream within the RO are shown in table 5.
TABLE 5 Water quality parameters of the streams in RO
The effect of the hardness removal system on removing calcium from RO water based on the composite modified macroporous resin prepared by the invention is shown in Table 6.
TABLE 6 calcium removal Effect of hardness removal System
The data in Table 6 show that, in an alkaline state (pH is more than or equal to 11.5), the composite modified macroporous resin is adopted to greatly reduce calcium and magnesium ions in RO concentrated water, the hardness of raw water can be reduced from 300mg/L to 1.5mg/L, namely the hardness of calcium ions is reduced from 120mg/L to 0.5mg/L, the requirement that the calcium ions in water entering electrodialysis is less than 1.84mg/L can be met, and the scaling risk caused by calcium sulfate of an electrodialysis system is effectively avoided.
The principle of the RO concentrated water calcium removal process can be known as follows: only the effluent of the ion exchange resin can more thoroughly remove calcium ions, and the requirement of calcium ion concentration of the electrodialysis influent water is met, so in the experimental example, the RO concentrated water softening scheme is preferably performed by adopting composite modified macroporous resin, and regeneration is performed by adopting 3% -5% de HCL, the regeneration liquid is enriched with divalent cations such as high-concentration calcium, magnesium and the like, and can be continuously returned to the system for chemical softening removal.
In addition, in the application engineering of the invention, the concentration of the fluorinion in the raw water is 0.9mg/L, the concentration of the fluorinion after RO concentration is 2.55mg/L, and CaF 2 KSP constant of 2.7X 10 -11 The solubility of calcium fluoride is 14mg/L, the fluorine ion is 7.16mg/L, the calcium ion is 7.54mg/L, and the calcium ion exceeding the concentration can form fluoridation to form the scale, thereby effectively removing the scaleCalcium ions in the RO concentrated water are very important for the normal operation of the system.
Although barium ions and strontium ions are not detected in raw water of the engineering, barium sulfate, strontium sulfate, calcium carbonate and the like are substances which are easy to form scales, divalent cations such as calcium, magnesium, barium, strontium and the like are also very necessary to be removed through ion exchange softening, and meanwhile, the ion exchange softening is a process which is often adopted in a zero-emission process, so that the process of removing the divalent calcium and magnesium ions by adopting the modified macroporous resin to RO concentrated water is very important to the engineering and is a process which must be adopted.
Claims (8)
1. The preparation method of the composite modified macroporous resin is characterized by comprising the following steps:
s1, preparing a GO two-dimensional template by adopting a quenching method;
s2, preparing a modified graphene oxide framework
In-situ polymerizing carboxylic acid and amide monomers on the GO two-dimensional template prepared in the step S1, and neutralizing the carboxylic acid and amide monomers by using a NaOH solution to obtain a modified graphene oxide skeleton, namely a P @ GO template;
s3, preparing the composite modified macroporous resin
S3-1, and H + Preparing sulfonyl chloride resin by using type polystyrene sulfonic acid resin as a raw material;
s3-2, mixing the sulfonyl chloride resin prepared in the step S3-1, the P @ GO template prepared in the step S2 and hexamethylene diamine/CH 2 Cl 2 Mixing solution and mixing reaction to prepare P @ GO intermediate resin; preparing ordered self-supporting pore diameters in the P @ GO intermediate resin by adopting an ion regulation and control ice mold method to obtain a composite macroporous resin;
and S3-3, washing the composite macroporous resin prepared in the step S3-2, and removing residual reactants to obtain the composite modified macroporous resin.
2. The method for preparing the composite modified macroporous resin as claimed in claim 1, wherein the specific scheme of the step 2 is as follows:
s2-1, pouring methacrylamide, N-methylene bisacrylamide and acrylic acid into distilled water, and performing ultrasonic mixing uniformly at 35 ℃ to obtain a mixed solution; in the mixed solution, the concentration of methacrylamide is 5g/L, and the mass ratio of methacrylamide, N-methylene-bisacrylamide and acrylic acid is 1:1:3;
s2-2, adding the GO two-dimensional template prepared in the step S1 into the mixed liquid prepared in the step S2-1, and magnetically stirring for 30min at 40 ℃; the concentration of the GO two-dimensional template in the mixed solution is 100g/L;
s2-3, adding potassium persulfate into the mixed solution obtained after magnetic stirring in the step S2-2, and reacting at a constant temperature of 50 ℃ for 2.5h; in the step, the concentration of potassium persulfate in the mixed solution is 1.1g/L;
s2-4, firstly filtering the mixed liquid in the step S2-3 to obtain a filtered product, washing the filtered product with distilled water until the supernatant is clear, then standing the filtered product in a sodium hydroxide solution with the pH =10 for 30min, filtering, washing the filtered product with distilled water until the pH of the washing liquid is 7.5 to 8.0, and finally drying the washed filtered product at 60 ℃ for 12h to obtain a P @ GO template.
3. The method for preparing the composite modified macroporous resin as claimed in claim 1, wherein the specific scheme of the step S3-2 is as follows:
s3-2-1, mixing sulfonyl chloride resin prepared in the step S3-1, a P @ GO template prepared in the step S2, and a sulfonyl chloride resin prepared in the step S3-1, in a volume ratio of 1:1 of hexamethylenediamine/CH 2 Cl 2 Mixing the mixed solution, and slightly boiling and refluxing at 60 ℃ for 1h to obtain P @ GO intermediate resin; the said and hexamethylenediamine/CH 2 Cl 2 The concentration of the sulfonyl chloride resin in the mixed solution is 120 to 160g/L, and the concentration of the P @ GO template is 30 to 60g/L;
s3-2-2, adding a NaCl solution with the concentration of 0.3 to 1.2g/L into the P @ GO intermediate resin prepared in the step S3-2-1 to prepare a precursor liquid, precooling the precursor liquid to 0 ℃, and then filling the precursor liquid into a reaction container for directional freezing to obtain a product; the temperature gradient of the directional freezing is-10 ℃, 15 ℃, 20 ℃,30 ℃, 40 ℃,60 ℃ and 80 ℃;
s3-2-3, continuously freezing the product subjected to the directional freezing treatment in the step S3-2-2 at the temperature of minus 40 ℃ for 12h, and continuously freezing and drying for 48h to obtain the composite macroporous resin.
4. The use of a composite modified macroporous resin, wherein the composite modified macroporous resin is prepared as in claim 1, and the composite modified macroporous resin is used in a hardness removal system of high-hardness underground water, and can enable Ca in a water body flowing out of the hardness removal system 2+ The concentration is less than or equal to 0.5mg/L;
the high-hardness underground water is Ca 2+ The concentration is more than or equal to 114mg/L, mg 2+ RO concentrated water with the concentration of more than or equal to 68 mg/L.
5. The use of the composite modified macroporous resin as claimed in claim 4, wherein the RO concentrated water is produced in an amount of 198m 3 The design treatment water quantity of the corresponding hardness removal system is 198m 3 /h。
6. The use of the composite modified macroporous resin as claimed in claim 4, wherein the regenerant used in the hardness-removing system is hydrochloric acid with a concentration of 5%, the regeneration flow rate is 4 to 5m/s, the regeneration time is 45min, and the regeneration period is 15 to 18h.
7. The use of the composite modified macroporous resin as claimed in claim 4, wherein the transformation agent used in the hardness-removing system is sodium hydroxide with a concentration of 5%, the transformation flow rate is 4 to 5m/s, and the transformation time is 45min.
8. The application of the composite modified macroporous resin as claimed in claim 4, wherein the backwash agent used in the hardness removal system is soft reflux water, the backwash flow rate is 5 to 10m/s, and the transformation time is 15min.
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