CN113583175A - Preparation method of flocculant based on photosensitizer for enhancing visible light initiation - Google Patents
Preparation method of flocculant based on photosensitizer for enhancing visible light initiation Download PDFInfo
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- CN113583175A CN113583175A CN202110898238.0A CN202110898238A CN113583175A CN 113583175 A CN113583175 A CN 113583175A CN 202110898238 A CN202110898238 A CN 202110898238A CN 113583175 A CN113583175 A CN 113583175A
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- flocculant
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- visible light
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- 230000000977 initiatory effect Effects 0.000 title claims abstract description 19
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002708 enhancing effect Effects 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 25
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 238000005189 flocculation Methods 0.000 abstract description 11
- 230000016615 flocculation Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 abstract description 3
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000012663 cationic photopolymerization Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000012682 free radical photopolymerization Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 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 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241000108664 Nitrobacteria Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
本发明公开了一种基于光敏剂强化可见光引发的絮凝剂制备方法，以丙烯酸‑2‑（N,N‑二甲氨基）乙酯（DA）和丙烯酰胺（AM）为原料，尿素为助溶剂，安息香乙醚为光敏性引发剂，4‑异丁基苯基‑4'‑甲基苯基碘六氟磷酸盐为引发剂。将两者依次加入反应瓶中，并加入适当的水，在快速搅拌条件下，三者充分混匀并完全溶解；再加入尿素快速搅拌，最后将安息香乙醚与‑异丁基苯基‑4'‑甲基苯基碘六氟磷酸盐引发剂依次加入；通氮驱氧后并搅拌混匀；最后将反应瓶置与LED灯下反应；反应完毕并经陈化后，对产物进行提取和纯化，即得阳离子絮凝剂。本发明的制备方法操作简便、生产效率高、生成成本较低、稳定性好；所得阳离子絮凝剂溶性好、单体简单、絮凝效果好、功能性强；具有良好的社会效益和经济效益。The invention discloses a preparation method of a flocculant based on enhanced visible light initiation by photosensitizer, which uses acrylic acid-2-(N,N-dimethylamino)ethyl ester (DA) and acrylamide (AM) as raw materials, and urea as a cosolvent , benzoin ether is a photosensitive initiator, and 4-isobutylphenyl-4'-methylphenyl iodide hexafluorophosphate is an initiator. Add the two into the reaction flask in turn, and add appropriate water. Under the condition of rapid stirring, the three are fully mixed and completely dissolved; then urea is added and stirred rapidly, and finally the benzoin ether and -isobutylphenyl-4' are mixed together. -Methyl phenyl iodide hexafluorophosphate initiator is added in sequence; after nitrogen and oxygen drive, stir and mix; finally, the reaction bottle is placed under the LED lamp to react; after the reaction is completed and after aging, the product is extracted and purified , the cationic flocculant is obtained. The preparation method of the invention has the advantages of simple operation, high production efficiency, low production cost and good stability; the obtained cationic flocculant has good solubility, simple monomer, good flocculation effect and strong functionality, and has good social and economic benefits.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a preparation method of a flocculant based on photosensitizer enhanced visible light initiation.
Background
Water is a valuable natural and strategic resource, and plays an indispensable role in urban construction, industrial production, economic development and the well-being and happiness industry of people. Under the large background of water resource shortage, a large amount of municipal sewage and industrial sewage are directly or indirectly discharged into rivers, lakes and seas, so that the fresh water resources are seriously polluted, and the increasingly prominent problems of water resource shortage and pollution thereof are gradually developed to become one of the main obstacles restricting the development of the economic society of China and further improving the living standard of people. The common water treatment technologies mainly comprise methods such as filtration, flocculation, activated carbon adsorption, ion exchange resin, membrane separation, advanced oxidation, an electrochemical method, magnetization treatment, biological immobilization and the like. The flocculation method is the core part of the water treatment process, and is widely adopted due to the advantages of high efficiency, good applicability, low manufacturing cost, convenient use and the like. Free radical polymerization is a main mechanism in the preparation process of the flocculant, the chain growth of the free radical photopolymerization is mainly completed through the double bond addition reaction of acrylate or acrylamide monomers, the monomer types are few, and oxygen has certain inhibition on visible photopolymerization; therefore, free radical polymerization has certain limitations in both initiation efficiency and flocculation effect. It is therefore of great importance to explore other polymerization systems to improve various aspects of flocculant efficiency.
The development of cationic photopolymerization technology was relatively late and was formally proposed in the 80's of the 20 th century. In the cationic initiation process, the cationic initiator photolyzes to form a protonic acid or Lewis acid, which then initiates cationic polymerization. Compared with free radical photopolymerization, cationic photopolymerization systems have more monomers and are insensitive to oxygen inhibition, and once active cations are generated by radiation excitation, the monomers can be initiated to realize cationic polymerization until the monomers are completely converted even if irradiation is stopped. The photosensitizer absorbs visible light, absorbs the visible light to reach an excited state, and generates active cations by electron transfer with the cation initiator. Cationic polymerization is used for flocculant production but is still in the off-going phase. Therefore, the research and development of the flocculant based on the photosensitizer for strengthening the initiation of the visible light has important significance for enriching and developing the visible light polymerization technology.
Chinese patent application No. CN201510129012.9 discloses a preparation method and application of a composite flocculant for treating coking strong brine wastewater, wherein the preparation method of the composite flocculant comprises the following steps: (1) putting matrix chitosan, a photosensitizer benzophenone, a polymerization inhibitor ammonium ferrous sulfate and a catalyst sulfuric acid into an acrylamide aqueous solution to form a mixed solution, filling nitrogen into the mixed solution to remove oxygen in the mixed solution, irradiating the mixed solution by using an ultraviolet lamp, and adjusting the mixed solution to be alkaline by using sodium hydroxide to obtain a chitosan solution grafted with acrylamide; (2) and mixing the prepared chitosan solution grafted with acrylamide with an aluminum-containing compound, an iron-containing compound, polymeric ferric sulfate, polymeric aluminum chloride and a polyamine compound to obtain the composite flocculant. And adding the prepared composite flocculant into the coking concentrated salt wastewater for treatment. The composite flocculant prepared by the invention has the advantages of good stability, small dosage, good flocculation effect, biodegradability, high treatment efficiency and wide pH application range. The flocculant prepared by the method has single pollutant removal type, and the flocculation capability of the flocculant on other pollutants is still under examination.
Chinese patent application No. CN202110368193.6 discloses a sewage treatment flocculant and a preparation method thereof, wherein the flocculant comprises water, acetone, isopropanol, dimethylacetamide, dimethylformamide, alkali lignosulfonate, cationic polyacrylamide, polymerized aluminum sulfate powder, polyvinyl alcohol, bacillus subtilis, nitrobacteria, potassium hydroxide, sodium bicarbonate, carboxymethyl cellulose, N-isopropyl methacrylamide, N-tert-butyl acrylamide and N-isopropyl acrylamide. Compared with the prior art, the flocculant of the invention has the advantages of no secondary pollution, convenient use, strong flocculation capability, good effects of removing oil and suspended matters, no toxicity and no harm, can replace or partially replace the traditional inorganic polymer and synthetic organic polymer flocculant, has wide application range and has popularization and application values. The preparation method has the advantages of excessive monomer types, application of various solvents, inconsistent water solubility and easy secondary pollution to water bodies.
Therefore, it is necessary to develop a cationic flocculant based on photosensitizer-enhanced visible light initiation, which has the advantages of simple monomer, high initiation efficiency, good stability and good flocculation effect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a flocculant based on photosensitizer-enhanced visible light initiation, which has the advantages of low energy consumption, simple process, simple monomers, good water solubility and good product stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
2- (N, N-dimethylamino) ethyl acrylate (DA) and Acrylamide (AM) are used as raw materials, urea is used as a cosolvent, benzoin ethyl ether is used as a photosensitive initiator, and 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate is used as an initiator. Adding the two into a reaction bottle in sequence, adding proper water, and fully mixing and dissolving the three under the condition of rapid stirring; adding urea, stirring quickly, and finally adding benzoin ethyl ether and an isobutyl phenyl-4' -methylphenyl iodohexafluorophosphate initiator in sequence; introducing nitrogen to expel oxygen, and stirring and uniformly mixing; finally, placing the reaction bottle under an LED lamp for reaction; and after the reaction is finished and the product is aged, extracting and purifying the product to obtain the cationic flocculant.
The method specifically comprises the following steps:
1) monomer (b): weighing a certain amount of AM, and placing the AM in pure water to obtain a solution with the concentration of 10-20%; after the mixture is uniformly stirred, a certain amount of DA monomers are weighed in a reaction bottle and uniformly stirred at the temperature of 40-45 ℃, and the concentration of the DA monomers is controlled to be 15-30%.
2) Adding a cosolvent: adding urea with the concentration of 0.01-0.025%, and uniformly stirring until the urea is completely dissolved.
3, adding an initiator: adding photosensitizer benzoin ethyl ether and visible light initiator 4-isobutylphenyl-4 '-methylphenyl iodohexafluorophosphate into a reaction bottle, wherein the concentration of the benzoin ethyl ether in the mixed solution is 0.125% -0.5%, and the concentration of the 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate is 0.2% -0.6%; then nitrogen is introduced to drive out oxygen;
4) visible light illumination and reaction: and finally, placing the mixed solution under a 200-400W visible light lamp for irradiation reaction for 1-2 h. And (4) aging, and then extracting and purifying the product to obtain the flocculant.
Wherein: in the step 1), the concentration of AM is 10-20%, and the concentration of DA monomer is 15-30%. When the AM concentration is less than 10%, the overall polymerization activity of the monomer is not high enough, the polymerization reaction is not completely carried out, and the polymerization product with lower molecular weight is in an apparent form or even in a semifluid state; when the AM concentration is greater than 20%, the functionality of DA in the flocculant is lost, ensuring that it has a certain content. When the DA concentration is less than 15%, the molecular weight and the intrinsic viscosity of the flocculant are too low, so that the initiation efficiency is influenced; when the DA concentration is more than 30%, an excess of DA monomer interferes with the generation of active cations.
And 2) under the condition of appropriate dosage of the cosolvent urea, the generation of hydrogen bonds can be prevented, the crosslinking probability is reduced, and the aim of increasing the product solubility is fulfilled. The urea is uneconomically used in an excessive amount and may affect the flocculation property if the urea acts as a chain transfer agent to lower the intrinsic viscosity of the product.
And 3) the concentration of benzoin ethyl ether in the mixed solution is 0.125-0.5%, and the concentration of the initiator 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate in the mixed solution is 0.2-0.6%. When the adding concentration of benzoin ethyl ether is less than 0.125%, the amount of the photosensitive initiator is too small, and sufficient light energy is difficult to absorb to reach an excited state and generate electron transfer with a cationic initiator, so that the initiation efficiency is influenced; when the adding concentration of benzoin ethyl ether is more than 0.5%, the initiation efficiency is not greatly improved and is not economical. When the adding concentration of the 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate is less than 0.2 percent, less active cations are generated to initiate monomer polymerization when electron transfer occurs, and the initiation efficiency is influenced; when the adding concentration of the 4-isobutylphenyl-4' -methylphenyliodohexafluorophosphate is more than 0.6 percent, the initiation efficiency is not greatly improved and is uneconomical.
In the step 4), the visible light illumination time is 1-2 h, and the power of the LED lamp is 200-400W. Benzoin ethyl ether absorbs enough light energy under the irradiation of visible light to reach an excited state to generate electron transfer with a cation initiator, and active cations are generated. However, when the power of the LED lamp is lower than 200W, the time required for initiating the copolymerization reaction is increased, and the reaction efficiency is reduced; and when the power of the LED lamp is higher than 400W, the molecular weight of the product is not obviously increased, and the energy consumption is increased. When the illumination time is less than 1h, the monomers are not completely copolymerized; and after 2 hours, the molecular weight and the performance of the product cannot be obviously improved, and the energy consumption is larger and uneconomical.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method has the advantages of simple operation, high production efficiency, low production cost and good stability;
2. the cationic flocculant obtained by the invention has good water solubility, simple monomer, good flocculation effect and strong functionality;
3. the invention replaces the traditional free radical polymerization system with cationic polymerization, thereby avoiding the defects of few free radical polymerization monomers, oxygen inhibition and the like, and obtaining certain breakthrough on the initiation performance and flocculation performance of the flocculant. Therefore, the flocculant initiated by the intensified visible light based on the photosensitizer has good social and economic benefits in practical application.
Detailed Description
The present invention will be described in further detail with reference to specific examples, wherein the raw materials used are common commercial products unless otherwise specified.
Example 1:
1) weighing a certain amount of AM, and placing the AM in pure water to obtain a solution with the concentration of 10%; after the mixture is stirred uniformly, a certain amount of DA monomer is weighed in the reaction bottle and is added and stirred uniformly, and the concentration of the DA monomer is controlled to be 15%.
2) Then, 0.01% urea is added and stirred uniformly until the urea is completely dissolved.
3) Adding benzoin ethyl ether with the concentration of 0.125% in the mixed solution into a reaction bottle, adding an initiator with the concentration of 0.2% in the mixed solution, namely 4-isobutylphenyl-4' -methylphenyliodihexafluorophosphate, and then introducing nitrogen and removing oxygen;
4) and finally, placing the mixed solution under a 200W LED visible light lamp for irradiation reaction for 1 h. And (4) aging, and then extracting and purifying the product to obtain the flocculant.
Example 2:
1) weighing a certain amount of AM, and placing the AM in pure water to obtain a solution with the concentration of 15%; after the mixture is stirred uniformly, a certain amount of DA monomer is weighed in the reaction bottle and is added and stirred uniformly, and the concentration of the DA monomer is controlled to be 20%.
2) Then, 0.015% of urea is added and stirred uniformly until the urea is completely dissolved.
3) Adding benzoin ethyl ether with the concentration of 0.2% in the mixed solution into a reaction bottle, adding an initiator with the concentration of 0.3% in the mixed solution, namely 4-isobutylphenyl-4' -methylphenyliodihexafluorophosphate, and then introducing nitrogen and removing oxygen;
4) and finally, placing the mixed solution under a 300W LED visible light lamp for irradiation reaction for 2 h. And (4) aging, and then extracting and purifying the product to obtain the flocculant.
Example 3:
1) weighing a certain amount of AM, and placing the AM in pure water to obtain a solution with the concentration of 20%; after the mixture is stirred uniformly, a certain amount of DA monomer is weighed in the reaction bottle and is added and stirred uniformly, and the concentration of the DA monomer is controlled to be 30%.
2) Then, 0.02% urea was added and stirred until completely dissolved.
3) Adding benzoin ethyl ether with the concentration of 0.3% in the mixed solution into a reaction bottle, adding an initiator with the concentration of 0.4% in the mixed solution, namely 4-isobutylphenyl-4' -methylphenyliodihexafluorophosphate, and then introducing nitrogen and removing oxygen;
4) and finally, placing the mixed solution under a 400W LED visible light lamp for irradiation reaction for 1 h. And (4) aging, and then extracting and purifying the product to obtain the flocculant.
Example 4:
1) weighing a certain amount of AM, and placing the AM in pure water to obtain a solution with the concentration of 15%; after the mixture is stirred uniformly, a certain amount of DA monomer is weighed in the reaction bottle and is added and stirred uniformly, and the concentration of the DA monomer is controlled to be 25%.
2) Then adding urea with the concentration of 0.025 percent, and stirring uniformly until the urea is completely dissolved.
3) Adding benzoin ethyl ether with the concentration of 0.4% in the mixed solution into a reaction bottle, adding an initiator with the concentration of 0.5% in the mixed solution, namely 4-isobutylphenyl-4' -methylphenyliodihexafluorophosphate, and then introducing nitrogen and removing oxygen;
4) and finally, placing the mixed solution under a 300W LED visible light lamp for irradiation reaction for 2 h. And (4) aging, and then extracting and purifying the product to obtain the flocculant.
Example 5:
1) weighing a certain amount of AM, and placing the AM in pure water to obtain a solution with the concentration of 10%; after the mixture is stirred uniformly, a certain amount of DA monomer is weighed in the reaction bottle and is added and stirred uniformly, and the concentration of the DA monomer is controlled to be 20%.
2) Then, 0.02% urea was added and stirred until completely dissolved.
3) Adding benzoin ethyl ether with the concentration of 0.5% in the mixed solution into a reaction bottle, adding an initiator with the concentration of 0.6% in the mixed solution, namely 4-isobutylphenyl-4' -methylphenyliodihexafluorophosphate, and then introducing nitrogen and removing oxygen;
4) and finally, placing the mixed solution under a 200W LED visible light lamp for irradiation reaction for 1 h. And (4) aging, and then extracting and purifying the product to obtain the flocculant.
The intrinsic viscosity and the kaolin removal rate of the organic polymeric flocculants prepared in examples 1 to 5 were measured, and the data are shown in table 1.
TABLE 1 Performance parameters of organic polymeric flocculants
| Product performance | Intrinsic viscosity (dL/g) | Kaolin wastewater removal (%) |
| Example 1 | 11.72 | 96.7 |
| Example 2 | 11.95 | 97.1 |
| Example 3 | 12.23 | 97.5 |
| Example 4 | 12.15 | 97.3 |
| Example 5 | 11.85 | 96.8 |
As can be seen from the above table 1, the flocculant prepared by the method for preparing a flocculant based on photosensitizer enhanced visible light initiation has excellent and stable product performance, good intrinsic viscosity range and good treatment effect on kaolin wastewater. Thus, the method is a practical and excellent method for preparing the organic polymeric flocculant.
Finally, it should be noted that the above-mentioned examples of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (3)
1. A preparation method of a flocculant based on photosensitizer enhanced visible light initiation is characterized in that acrylic acid-2- (N, N-dimethylamino) ethyl ester (DA) and Acrylamide (AM) are used as raw materials, urea is used as a cosolvent, benzoin ethyl ether is used as a photosensitive initiator, 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate is used as an initiator, and a certain amount of AM is weighed and placed in pure water to obtain a solution with the concentration of 10-20%; after stirring uniformly, weighing a certain amount of DA monomer in a reaction bottle, adding and stirring, then adding urea, and stirring uniformly until the DA monomer is completely dissolved; adding photosensitizer benzoin ethyl ether and visible light initiator 4-isobutylphenyl-4 '-methylphenyl iodohexafluorophosphate into a reaction bottle, wherein the concentration of the benzoin ethyl ether in the mixed solution is 0.125% -0.5%, and the concentration of the 4-isobutylphenyl-4' -methylphenyl iodohexafluorophosphate is 0.2% -0.6%; then nitrogen is introduced to drive out oxygen; finally, placing the mixture under a 200-400W LED visible light lamp for irradiation reaction for 1-2 h; and (4) aging, and then extracting and purifying the product to obtain the cationic flocculant.
2. The method for preparing a cationic flocculant according to claim 1, wherein the concentration of urea is 0.01 to 0.025%.
3. The method for preparing the cationic flocculant according to claim 1, wherein the concentration of the DA monomer is 15 to 30%.
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