CN113174039A - Hyperbranched polymer for efficiently recovering boron and ultrafiltration process - Google Patents
Hyperbranched polymer for efficiently recovering boron and ultrafiltration process Download PDFInfo
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- CN113174039A CN113174039A CN202110636158.8A CN202110636158A CN113174039A CN 113174039 A CN113174039 A CN 113174039A CN 202110636158 A CN202110636158 A CN 202110636158A CN 113174039 A CN113174039 A CN 113174039A
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 54
- 229920000587 hyperbranched polymer Polymers 0.000 title claims abstract description 28
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 17
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000004593 Epoxy Substances 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 3
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- -1 sodium alkoxide Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 238000012653 anionic ring-opening polymerization Methods 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 abstract description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 abstract 1
- 150000001450 anions Chemical group 0.000 abstract 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 238000011068 loading method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000002738 chelating agent Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000370 acceptor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BTMHPJULXOBMEA-UHFFFAOYSA-N OCCNC(O)C(O)CO Chemical compound OCCNC(O)C(O)CO BTMHPJULXOBMEA-UHFFFAOYSA-N 0.000 description 1
- 241000041834 Orthocis Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
- 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
- B01D61/20—Accessories; Auxiliary operations
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/108—Boron compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of membrane filtration, and particularly relates to a hyperbranched polymer for efficiently recovering boron and an ultrafiltration process. The hyperbranched polymer is a hyperbranched polyhydroxylated polymer, and the hyperbranched polyhydroxylated polymer is one of hyperbranched polyglycidyl glycerol and Diol-HPEI polymer; the hyperbranched polyglycidyl is synthesized by anion ring-opening polymerization of glycidol on pentaerythritol (THME) nucleus, wherein NaOCH3 is used as a catalyst, and 1, 4-dioxane is used as a reaction medium; the Diol-HPEI polymer is synthesized by grafting glycidol onto Hyperbranched Polyethyleneimine (HPEI) molecules through epoxy amine nucleophilic addition reaction. Also discloses an ultrafiltration process of the hyperbranched polymer for efficiently recovering boron, which comprises the following steps: s1: dissolving the hyperbranched polymer in a solution containing boric acid, and adjusting the pH value; s2: and after the adjustment is finished, stirring for 50-70 minutes, and then filtering the solution by using an ultrafiltration membrane.
Description
Technical Field
The invention belongs to the technical field of membrane filtration, and particularly relates to a hyperbranched polymer for efficiently recovering boron and an ultrafiltration process.
Background
Boron, a ubiquitous element in nature, is distributed in various bodies of water mainly in the form of boric acid. Industrially, boron compounds are mainly used in the production of glass fibers, detergents, fuel cells, and the like. However, it is also toxic when its content reaches a certain level. Therefore, boron is a potential pollutant in water and an important industrial raw material, and needs to be recycled from wastewater and seawater urgently. Due to the complex morphology of boron, there is currently no efficient and economical method for separating boron from wastewater, particularly from neutral solutions, because the undissociated boric acid molecule behaves very similar to a water molecule. To date, techniques including Reverse Osmosis (RO), Electrodialysis (ED), ion exchange and electro/chemical coagulation have shown potential for separating boron from water. However, most of these techniques have certain limitations. For example, the boron rejection of reverse osmosis membranes is very sensitive to feed characteristics (e.g., pH, salinity, etc.) and operating pressure, achieving high boron rejection rates of 99% only at very high pH and low salinity, and also creates problems with high energy consumption, high caustic usage, membrane fouling, etc. Also, the presence of other ions such as Cl-and NO 3-in the electrodialysis may have a negative effect on the boron separation. Furthermore, it is very challenging to increase the current efficiency of boric acid transport and to reduce the boron concentration in the dialysate to acceptable levels. The chemical precipitation method can be used for treating high-concentration boron solution, but has the problems of long operation time, high reaction temperature, generation of a large amount of solid waste and the like.
Due to the difficulties and limitations of the above-mentioned prior art methods, new methods need to be explored to identify simpler, more economical methods. An advanced separation process combining complexation and membrane separation, namely a polymer-enhanced hybrid ultrafiltration (PEUF) process, has thus been proposed. The unwanted substances can be individually concentrated and recovered by using specific chelating polymers (i.e. chelating agents based on their complexing chemistry). The process has been widely used to separate and concentrate many inorganic species including cadmium, copper, mercury, lead, zinc, and the like.
Various water-soluble polymers have been reported in the literature as polychelants. Since commercially available polymers such as polyvinyl alcohol and polyethyleneimine show extremely low boron rejection, they must be grafted with highly effective functional groups to improve their boron chelating ability. N-methylglucamine (NMG) is a well-known functional group and has provided reactive sites in boron adsorption resins. Some researchers grafted NMG and its derivatives onto water soluble polymers used in the PEUF process and observed improved boron rejection. Recently, Yilmaz and coworkers synthesized two new boron chelating polymers, hydroxyethylamino glycerol grafted polyglycidyl methacrylate (PNS) and polyethylene-ethylene glycol-co-vinyl alcohol (COP). The maximum boron rejection was about 55% when PNS was used at a polymer loading of 1000g/g boron and a pH of 9.0. The performance is poor due to the negative effects of the carboxylate group or the lack of proton acceptors. To overcome this problem, the research group has further designed a new group of polymers, namely polyvinylamino-N, N-dipropylene glycol and its derived copolymers, which show high boron rejection of 92% and 96%, respectively. These pioneering studies on chelating polymers are indeed encouraging. However, with the exception of limited research, defects of low kinetics or low boron rejection may be found in most of the developed polymers. In order to make PEUF a viable process for boron separation, the search for new polymers is one of the most important tasks.
Disclosure of Invention
To design high performance multi-chelating agents, hyperbranched polymers may be more advantageous than linear polymers; due to its unique spherical characteristics and low intermolecular entanglement properties, hyperbranched polymers have lower solution viscosities, can eliminate membrane fouling problems, and can employ higher polymer concentrations in the PEUF process; therefore, the prepared hyperbranched polymer can realize high chelating capacity to the maximum extent by utilizing the functional groups with high density.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a hyperbranched polymer for efficiently recovering boron is a hyperbranched polyhydroxylated polymer, and the hyperbranched polyhydroxylated polymer is one of hyperbranched polyglycidyl glycerol and Diol-HPEI polymer;
the hyperbranched polyglycidyl is synthesized by anionic ring-opening polymerization of glycidol on pentaerythritol (THME) nuclei, using NaOCH31, 4-dioxane as a catalyst is used as a reaction medium;
the Diol-HPEI polymer is synthesized by grafting glycidol onto Hyperbranched Polyethyleneimine (HPEI) molecules through epoxy amine nucleophilic addition reaction.
As a preferable proposal of the invention, the preparation method of the hyperbranched polyglycidyl comprises the following steps,
a1: pentaerythritol (THME) and NaOCH3Dissolving in methanol to obtain a mixture;
a2: heating the mixture obtained from A1 to 75 +/-1 ℃, keeping the temperature, and vacuumizing for 4-5 hours to remove methanol and water and generate sodium alkoxide;
a3: after the sodium alkoxide obtained in A2 is cooled, mixing 1, 4-dioxane with the cooled sodium alkoxide, and carrying out ultrasonic treatment for 20-25 minutes to obtain a uniform solution;
a4: continuously introducing argon gas into the uniform solution obtained from A3 for 10 minutes to remove dissolved oxygen, keeping the solution in an inert atmosphere, stirring the solution, heating to 95 +/-1 ℃, slowly injecting argon-purified glycidol into the solution at the temperature, completely adding the glycidol solution, keeping the mixture at 95 +/-1 ℃, continuously stirring for 12-12.5 hours, dissolving the stirred sediment in methanol, precipitating the sediment in diethyl ether, and taking the sediment;
a5: and (3) drying the precipitate product obtained in the step (S4) in vacuum at 80 ℃, re-dissolving the dried product in deionized water, dialyzing for 3 days by using a membrane tube with the MWCO range of 6000-8000 Da, and drying to obtain the hyperbranched polyglycidyl glycerol.
As a preferred embodiment of the present invention, the method for preparing the Diol-HPEI polymer comprises the following steps,
b1: diluting an aqueous Hyperbranched Polyethyleneimine (HPEI) solution with deionized water to a solid concentration of 10 wt% at room temperature, and purging with argon for 10 minutes;
b2: slowly adding glycidol into a Hyperbranched Polyethyleneimine (HPEI) solution at room temperature, stirring the solution at room temperature for 3 hours after the addition is finished, and heating the solution in a water bath at 60 ℃ for 3 hours;
b3: after the B2 is heated, cooling at room temperature, and dialyzing the cooled solution by using a membrane tube with the MWCO range of 6000-8000 for 3 days for purification;
b4: the purified solution was concentrated by vacuum distillation in a rotary evaporator to obtain a viscous solution, and the concentrated solution was freeze-dried overnight to obtain Diol-HPEI polymer.
An ultrafiltration process for efficiently recovering a boron hyperbranched polymer comprises the following steps:
s1: dissolving the hyperbranched polymer in a solution containing boric acid, and adjusting the pH value;
s2: and after the adjustment is finished, stirring for 50-70 minutes, and then filtering the solution by using an ultrafiltration membrane.
In a preferred embodiment of the present invention, the mass ratio of the hyperbranched polymer to boron is 10:1 to 100: 1.
In a preferable embodiment of the invention, the pH of the solution in S1 is 6.9 to 9.0.
The invention has the following beneficial effects:
the hyperbranched polyhydroxy polymer is synthesized, and the chelating agent enhanced ultrafiltration process method is adopted, so that the hyperbranched polyhydroxy polymer is applied to the high-efficiency recovery of boron in water and is used as a polychelating agent for boron recovery, and the interception efficiency of boron is improved.
Detailed Description
In order that those skilled in the art can better understand the present invention, the following embodiments are provided to further illustrate the present invention.
Example 1
A preparation method of Hyperbranched Polyglycidyl Glycerol (HPG) comprises the following steps,
a1: 1.5mmol of pentaerythritol (THME) and 0.5mmol of NaOCH3Dissolved inIn 100mL of methanol to obtain a mixture;
a2: heating the mixture obtained in A1 to 75 +/-1 ℃, and keeping the temperature for vacuumizing for 4 hours to remove methanol and water and generate sodium alkoxide;
a3: after the sodium alkoxide obtained in A2 is cooled, mixing 1, 4-dioxane with the cooled sodium alkoxide, and carrying out ultrasonic treatment for 20 minutes to obtain a uniform solution;
a4: continuously introducing argon gas into the homogeneous solution obtained in A3 for 10 minutes to remove dissolved oxygen, keeping the solution under an inert atmosphere, stirring the solution and heating to 95 +/-1 ℃, slowly injecting 150mmol of argon-purified glycidol into the solution at the temperature at the speed of 1.8ml/h by an autosampler, keeping the mixture at 95 +/-1 ℃ after completely adding the glycidol solution, continuously stirring for 12 hours, stirring the obtained sediment, dissolving the sediment in methanol and precipitating the sediment in ether, and taking the sediment;
a5: and (3) drying the precipitate product obtained in the step (S4) in vacuum at 80 ℃, re-dissolving the dried product in deionized water, dialyzing for 3 days by using a membrane tube with the MWCO range of 6000-8000 Da, and drying to obtain the hyperbranched polyglycidyl glycerol.
The chemical formula of the synthesis of the hyperbranched polyglycidyl is expressed as follows:
example 2
A method for preparing a Diol-HPEI polymer comprises the following steps,
b1: diluting 20g of an aqueous Hyperbranched Polyethyleneimine (HPEI) solution with deionized water to a solid concentration of 10 wt% at room temperature, and purging with argon for 10 minutes;
b2: slowly adding 40g of glycidol into a Hyperbranched Polyethyleneimine (HPEI) solution within 20 minutes at room temperature, stirring the solution for 3 hours at room temperature after the addition is finished, and heating the solution for 3 hours in a water bath at 60 ℃;
b3: after the B2 is heated, cooling at room temperature, and dialyzing the cooled solution by using a membrane tube with the MWCO range of 6000-8000 for 3 days for purification;
b4: the purified solution was concentrated by vacuum distillation in a rotary evaporator to obtain a viscous solution, and the concentrated solution was freeze-dried overnight to obtain Diol-HPEI polymer.
The chemical formula for Diol-HPEI polymer synthesis is expressed as:
an ultrafiltration process for efficiently recovering a boron hyperbranched polymer comprises the following steps:
s1: dissolving the hyperbranched polymer in a solution containing boric acid, and adjusting the pH value;
s2: and after the adjustment is finished, stirring for 50-70 minutes, and then filtering the solution by using an ultrafiltration membrane.
The products obtained in example 1 and example 2 were used for boric acid filtration;
an ultrafiltration process for efficiently recovering a boron hyperbranched polymer comprises the following steps:
s1: dissolving the hyperbranched polymer in a solution containing boric acid, and adjusting the pH value; wherein the mass ratio of the polymer to boron is fixed to 100:1, pH value is 6.9;
s2: after completion of the adjustment, the mixture was stirred for 60 minutes, and then the solution was filtered with an ultrafiltration membrane.
After the ultrafiltration membrane treatment, analyzing the original solution and the filtrate by using ICP-OES and TOC, and calculating the retention rate of boron and organic matters; the calculation formula is as follows:
the retention rate (R) is obtained by the following formula:
wherein Cp is the solute content of the permeate and Cf is the solute content of the feed solution;
wherein the solute refers to a chelating agent or boric acid.
According to the scheme, the temperature of the boric acid solution is adjusted, and then the rejection rate of boron and organic matters at the temperature is calculated; table 1 was obtained;
| temperature of | Membrane flux (LMH/bar) | Retention rate of chelating agent% | Boric acid retention% | |
| HPG | 25 | 54 | 99.6 | 50.5 |
| HPG | 45 | 68 | 99.6 | 68.0 |
| HPG | 65 | 75 | 99.9 | 89.8 |
| Diol-HPEI | 25 | 48 | 99.8 | 53.9 |
| Diol-HPEI | 45 | 74 | 99.7 | 78.6 |
| Diol-HPEI | 65 | 98 | 99.9 | 94.7 |
Table 1: detection data of hyperbranched polymer processed at different temperatures
From table 1, it can be seen that there is a tendency for the permeation flux to increase with increasing temperature; this is due to the agglomeration of polymer molecules caused by boric acid, which can eliminate pore plugging; the attachment of boron to the polymer chain can also alter the interaction between the polymer and the negatively charged membrane surface, thereby avoiding the formation of a fouling layer on the membrane surface; (ii) a The boron rejection capacity also increases with temperature, which means that high temperatures will effectively promote the chelation process;
however, these two polymers behave differently in terms of boron rejection and flux reduction; the boron rejection rate of the Diol-HPEI solution is far higher than that of the HPG solution; this is mainly due to the differences in their polymer structures; in order to complex effectively with boron, the chelating polymer must satisfy the following conditions: (1) having an inert skeleton; (2) containing an ortho diol consisting of two hydroxyl groups occupying ortho cis positions; (3) providing a proton acceptor group that neutralizes protons during the complexation process; (4) high running capacity with fast dynamics. The main structural difference between these two polymers is the proton acceptor. As proton acceptor groups, tertiary amine groups on the Diol-HPEI branches are clearly superior to ether groups on the HPG chains in terms of their protonating ability. In addition, the high chelating ability of the Diol-HPEI polymer may be due to its large number of hydroxyl groups. Also, the clustering of polymers in the Diol-HPEI solution may be more sensitive to temperature, and thus the flux in the Diol-HPEI solution shows a steeper trend.
In the case of the other process being unchanged, the mass ratio of the polymer to boron was changed to be fixed (i.e., the chelating agent loading amount), and then the detection was performed, and the obtained data is shown in table 2:
| chelating agent loading | Boric acid retention% | |
| HPG | 1 | 59.1 |
| HPG | 10 | 85.6 |
| HPG | 20 | 88.3 |
| HPG | 100 | 89.8 |
| Diol-HPEI | 1 | 68.2 |
| Diol-HPEI | 10 | 89.9 |
| Diol-HPEI | 20 | 93.6 |
| Diol-HPEI | 100 | 94.7 |
Table 2: detection data under different chelating agent loading
The flux of both polymer solutions tended to decrease with increasing polymer loading, meaning that the fouling tendency was more pronounced; as the polymer loading increases, the active sites for chelation also increase, so the boron rejection rate rises a step in the early stage and then slowly increases as the polymer loading increases; when the HPG loading is greater than 20, the rejection does not increase significantly, indicating that higher HPG loadings may not achieve better separation performance; the low boron rejection may be due to the slow rate of chelation reaction between HPG and boron; in contrast, when the load amount of Diol-HPEI is higher than 100, the boron rejection rate can be further increased.
Under the condition that other processes are not changed, the pH values of the polymer and the boron solution are changed, and then the detection is carried out, and the obtained data are shown in the table 3:
table 3: detection data at different pH values
As can be seen from Table 3, the pH is most effective at neutral pH.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (6)
1. A hyperbranched polymer for efficiently recovering boron is characterized in that: the hyperbranched polymer is hyperbranched polyhydroxylated polymer, and the hyperbranched polyhydroxylated polymer is one of hyperbranched polyglycidyl glycerol and Diol-HPEI polymer;
the hyperbranched polyglycidyl is synthesized by anionic ring-opening polymerization of glycidol on pentaerythritol (THME) nuclei, using NaOCH31, 4-dioxane as a catalyst is used as a reaction medium;
the Diol-HPEI polymer is synthesized by grafting glycidol onto Hyperbranched Polyethyleneimine (HPEI) molecules through epoxy amine nucleophilic addition reaction.
2. The hyperbranched polymer for efficiently recovering boron according to claim 1, wherein: the preparation method of the hyperbranched polyglycidyl comprises the following steps,
a1: pentaerythritol (THME) and NaOCH3Dissolving in methanol to obtain a mixture;
a2: heating the mixture obtained from A1 to 75 +/-1 ℃, keeping the temperature, and vacuumizing for 4-5 hours to remove methanol and water and generate sodium alkoxide;
a3: after the sodium alkoxide obtained in A2 is cooled, mixing 1, 4-dioxane with the cooled sodium alkoxide, and carrying out ultrasonic treatment for 20-25 minutes to obtain a uniform solution;
a4: continuously introducing argon gas into the uniform solution obtained from A3 for 10 minutes to remove dissolved oxygen, keeping the solution in an inert atmosphere, stirring the solution, heating to 95 +/-1 ℃, slowly injecting argon-purified glycidol into the solution at the temperature, completely adding the glycidol solution, keeping the mixture at 95 +/-1 ℃, continuously stirring for 12-12.5 hours, dissolving the stirred sediment in methanol, precipitating the sediment in diethyl ether, and taking the sediment;
a5: and (3) drying the precipitate product obtained in the step (S4) in vacuum at 80 ℃, re-dissolving the dried product in deionized water, dialyzing for 3 days by using a membrane tube with the MWCO range of 6000-8000 Da, and drying to obtain the hyperbranched polyglycidyl glycerol.
3. The hyperbranched polymer for efficiently recovering boron according to claim 1, wherein: the preparation method of the Diol-HPEI polymer comprises the following steps,
b1: diluting an aqueous Hyperbranched Polyethyleneimine (HPEI) solution with deionized water to a solid concentration of 10 wt% at room temperature, and purging with argon for 10 minutes;
b2: slowly adding glycidol into a Hyperbranched Polyethyleneimine (HPEI) solution at room temperature, stirring the solution at room temperature for 3 hours after the addition is finished, and heating the solution in a water bath at 60 ℃ for 3 hours;
b3: after the B2 is heated, cooling at room temperature, and dialyzing the cooled solution by using a membrane tube with the MWCO range of 6000-8000 for 3 days for purification;
b4: the purified solution was concentrated by vacuum distillation in a rotary evaporator to obtain a viscous solution, and the concentrated solution was freeze-dried overnight to obtain Diol-HPEI polymer.
4. An ultrafiltration process of the hyperbranched polymer for efficiently recovering boron, which is based on any one of claims 1 to 3, is characterized in that: the method comprises the following steps:
s1: dissolving the hyperbranched polymer in a solution containing boric acid, and adjusting the pH value;
s2: and after the adjustment is finished, stirring for 50-70 minutes, and then filtering the solution by using an ultrafiltration membrane.
5. The ultrafiltration process of hyperbranched polymer for efficient recovery of boron according to claim 4, wherein: the mass ratio of the hyperbranched polymer to boron is 10: 1-100: 1.
6. The ultrafiltration process of hyperbranched polymer for efficient recovery of boron according to claim 4, wherein: the pH value of the solution in the S1 is 6.9-9.0.
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