CN103395897A - Non-phosphorus environmentally-friendly water treatment agent and preparation method thereof - Google Patents
Non-phosphorus environmentally-friendly water treatment agent and preparation method thereof Download PDFInfo
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- CN103395897A CN103395897A CN2013103736690A CN201310373669A CN103395897A CN 103395897 A CN103395897 A CN 103395897A CN 2013103736690 A CN2013103736690 A CN 2013103736690A CN 201310373669 A CN201310373669 A CN 201310373669A CN 103395897 A CN103395897 A CN 103395897A
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- maleic anhydride
- natural high
- high moleculer
- moleculer eompound
- water treatment
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011574 phosphorus Substances 0.000 title abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 26
- 238000006277 sulfonation reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 241001597008 Nomeidae Species 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000008234 soft water Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 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 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 235000019357 lignosulphonate Nutrition 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- HFDCVHDLKUZMDI-UHFFFAOYSA-N sulfuric acid titanium Chemical compound [Ti].OS(O)(=O)=O HFDCVHDLKUZMDI-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 3
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 239000002455 scale inhibitor Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZMYKITJYWFYRFJ-UHFFFAOYSA-N 4-oxo-4-(2-phenylethylamino)butanoic acid Chemical compound OC(=O)CCC(=O)NCCC1=CC=CC=C1 ZMYKITJYWFYRFJ-UHFFFAOYSA-N 0.000 description 1
- 102100035024 Carboxypeptidase B Human genes 0.000 description 1
- 241001677188 Coccus viridis Species 0.000 description 1
- 101000946524 Homo sapiens Carboxypeptidase B Proteins 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
The invention discloses a non-phosphorus environmentally-friendly water treatment agent and a preparation method thereof. The method comprises the following steps: performing grafting reaction on a natural high-molecular compound and maleic anhydride to obtain a maleic anhydride grafted natural high-molecular compound; performing copolymerization on the maleic anhydride grafted natural high-molecular compound and an acrylic acid monomer to obtain a copolymer; modifying the copolymer. The agent disclosed by the invention is green and pollution-free in synthetic process, and the product obtained is applied to a water treatment system and can be used as a corrosion and scale inhibitor to replace a conventional phosphorus containing agent. The agent disclosed by the invention is more excellent in performance and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to water treatment field, relate in particular to a kind of Phosphateless environmentally friendly water treatment agent and synthetic method thereof.
Background technology
At present, the processing of recirculated cooling water, mainly take chemical treatment as main, need to be added appropriate chemical treatment medicine and control the harm such as the corrosion and scaling of water coolant feedwater equipment and water-transmission line, bacterium algae, glutinous mud in recirculated cooling water.It is water treatment agent that the present recirculating cooling water system of China mainly adopts organophosphorus, they have excellent inhibition, scale-inhibiting properties, consumption is few, low price, but its a large amount of water quality nutrition accumulations that cause that use, impel the problem of the numerous life of a large amount of bacterium algae can not be ignored, so eco-friendly without phosphorus type water treatment agent becomes the focus of lot of domestic and foreign water treatment enterprise and research institution's research.
Without phosphorus water treatment corrosion inhibitors is the Focal point and difficult point of recirculated cooling water non-phosphorus scale and corrosion inhibitor formula.Generally speaking, the corrosion-mitigation scale-inhibition agent prescription is comprised of scale inhibition dispersed component and inhibition component two portions.Without phosphorus water treating corrosion and scale inhibitor of less types, and have the defect of self, its application be restricted, at present except the minority kinds such as molybdate, zinc salt, Sunmorl N 60S also with the composite use of phosphorus family corrosion inhibitor, basically being eliminated of other, the example of successful Application seldom.
" green scale corrosion inhibitor " of developing without phosphorus type must become the developing direction of industrial circulating cooling water treatment agent medicament.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiencies in the prior art, and water treatment agent and the novel preparation method thereof of a kind of excellent performance and Phosphateless environmentally friendly is provided.
Particular content of the present invention is: a kind of Phosphateless environmentally friendly water treatment agent is made by the preparation method who comprises following reactions steps: the copolyreaction that the graft reaction of natural high moleculer eompound and maleic anhydride obtains maleic anhydride graft natural high moleculer eompound, maleic anhydride graft natural high moleculer eompound and acrylic monomer obtains multipolymer.
Further, above-mentioned water treatment agent, also comprise in its preparation method the copolyreaction gained multipolymer of maleic anhydride graft natural high moleculer eompound and acrylic monomer is carried out the modification step, obtain water treatment agent.
The present invention also provides a kind of preparation method of novel non-phosphate environment-protective water treatment agent, the copolyreaction that the graft reaction that comprises natural high moleculer eompound and maleic anhydride obtains maleic anhydride graft natural high moleculer eompound process, maleic anhydride graft natural high moleculer eompound and acrylic monomer obtains the water treatment agent process, wherein
The graft reaction step of natural high moleculer eompound and maleic anhydride:
(1) take the soft water of counting by weight 400-600 part and join in stainless steel cauldron, stir; (2) will take the natural high moleculer eompound of counting by weight 100-300 part and join in aforesaid reaction vessel, and heat up and make its dissolving; (3) the powdery solid maleic anhydride that will count by weight 40-80 part at the uniform velocity joins in reactor; (4) add in the process of maleic anhydride powder, constantly drip the pH value in sodium hydroxide solution control reactor.(5) powder add complete after, be warming up to 10 ℃-80 ℃, continue reaction 1-4 hour, below the interior material pH value to 8 of sour conditioned reaction still, obtain product maleic anhydride graft natural high moleculer eompound;
Wherein also comprise in above-mentioned steps (3) and add the catalyst sulfuric acid titanium of counting by weight 2-6 part simultaneously in reactor; Wherein above-mentioned natural high moleculer eompound is a kind of in xylogen and modification derivant, Mierocrystalline cellulose and modification derivant thereof, starch and modification derivant thereof, and wherein the lignin modification derivative is selected from a kind of in sulfonated lignin, aminated lignin, alkylation xylogen, oxidative lignin; Cellulose modified derivative is selected from a kind of in etherified cellulose, esterified cellulose; The starch conversion derivative is selected from a kind of in modified starch, dextran.In above-mentioned natural high moleculer eompound and maleic anhydride graft reaction process, the pH value that drips in step (4) in sodium hydroxide solution control reactor is between 6-10.
The copolyreaction process of maleic anhydride graft natural high moleculer eompound and acrylic monomer comprises: the catalyzer that (1) will count 1-7 part by weight adds in the reactor of product maleic anhydride graft natural high moleculer eompound place, after intensification is dissolved catalyzer fully; (2) acrylic monomer of take initiator solution, counting by weight 60-100 part is added dropwise to reactor.(3) above-mentioned material dropping complete after, be warming up to 60 ℃-100 ℃, continue reaction 1-4 hour, obtain copolymer products, i.e. water treatment agent A; Step in wherein copolyreaction process (1) used catalyst is inorganic molysite, and wherein said inorganic molysite comprises a kind of in ferrous ammonium sulphate, ferrous sulfate, iron protochloride, iron(ic) chloride, ferric sulfate; Acrylic monomer in step (2) comprises one or more in vinylformic acid, methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate; Above-mentioned selected initiator solution is commercially available prod, can be selected from one or more in azo, peroxide, redox class initiator.
In addition, above-mentioned water treatment agent synthetic method, also comprise copolymer products---the modification step of water treatment agent A, wherein the modification step comprises: (1) obtains the copolyreaction gained copolymer products of maleic anhydride graft natural high moleculer eompound and acrylic monomer the thick product of brown after underpressure distillation; (2) control temperature 5-50 ℃, drip the vitriol oil in above-mentioned product, interval time the assaying reaction thing acid number, and calculate sulfonation degree,, when product reaches predetermined sulfonation degree, finish sulfonation reaction; (3) use again in sodium hydroxide solution and the excessive vitriol oil, obtain the water treatment agent B after modification; Wherein said predetermined sulfonation degree should be controlled in 20～50%.
The water treatment agent that obtains by the inventive method, can guarantee fully carrying out of each step reaction by accurate control synthesis condition, gained water treatment agent slowly-releasing scale-inhibiting properties is due to the ortho-water treatment agent of the existing method preparation in market at present, and whole building-up process green non-pollution, product is the non-phosphate environment-friendly type water treatment agent, can be used as inhibiter and be applied in water treatment system, excellent performance, be suitable for large-scale commercial production.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is further elaborated.
Embodiment 1
The graft reaction step of natural high moleculer eompound and maleic anhydride:
(1), to adding the soft water of 450g in churned mechanically 1L laboratory reaction still, stir (2) and add 150g, xylogen, rising temperature for dissolving under whipped state; (3) control temperature-stable at 30 ℃, add 4g titanium sulfate and powdery maleic anhydride 60g in reactor, drip simultaneously sodium hydroxide and control pH between 7-9; (4) after maleic anhydride adds, temperature is raised to 35 ℃, strengthens reaction 2 hours. below the material pH to 8 in hydrochloric acid conditioned reaction still, obtain product maleic anhydride graft natural high moleculer eompound.
The copolyreaction process of maleic anhydride graft natural high moleculer eompound and acrylic monomer:
(5) add the 1.1g ferrous sulfate to aforesaid reaction vessel, heat up it is dissolved fully, and drip 70g methyl acrylate and 80g initiator solution (i.e. 20% ammonium persulfate aqueous solution) uniformly in reactor, be controlled in 2 hours and all add.
(6) after material dropping finishes, temperature is controlled at 90 ℃ and continues reaction 2 hours, obtains copolymer products, i.e. water treatment agent A.
Be the modification step of water treatment agent A to copolymer products:
(7) the product underpressure distillation in step (6) is extremely steamed without moisture; (8) drip the vitriol oil in reactor, control temperature at 20 ℃, after 1.5 hours, vitriol oil add-on is 20g, and the product sulfonation degree reaches 30%, finishes sulfonation reaction; (9) to dripping in reactor in sodium hydroxide and the excessive vitriol oil, more than transferring PH to 2, discharging, obtain the water treatment agent B after modification.
Embodiment 2
The graft reaction step of natural high moleculer eompound and maleic anhydride:
(1), to adding the soft water of 500g in churned mechanically 1L laboratory reaction still, stir (2) and add 200g treated starch, rising temperature for dissolving under whipped state; (3) control temperature-stable at 30 ℃, add 4g titanium sulfate and powdery maleic anhydride 100g in reactor, drip simultaneously sodium hydroxide and control pH between 7-9; (4) after maleic anhydride adds, temperature is raised to 40 ℃, strengthens reaction 2 hours, below the material pH to 8 in sulfuric acid conditioned reaction still, obtains product maleic anhydride graft natural high moleculer eompound.
The copolyreaction process of maleic anhydride graft natural high moleculer eompound and acrylic monomer:
(5) add the 1.1g ferrous sulfate to aforesaid reaction vessel, heat up it is dissolved fully, and drip 80g vinylformic acid and 100g initiator solution (i.e. 10% the V-50 aqueous solution) uniformly in reactor, be controlled in 2 hours and all add.
(6) after material dropping finishes, temperature is controlled at 90 ℃ and continues reaction 2 hours, obtains copolymer products, i.e. water treatment agent A.
Be the modification step of water treatment agent A to copolymer products:
(7) the product underpressure distillation in step (6) is extremely steamed without moisture; (8) drip the vitriol oil in reactor, control temperature at 20 ℃, after 1.5 hours, vitriol oil add-on is 20g, and the product sulfonation degree reaches 25%, finishes sulfonation reaction; (9) to dripping in reactor in sodium hydroxide and the excessive vitriol oil, more than transferring PH to 2, discharging, obtain the water treatment agent B after modification.
Embodiment 3
The graft reaction step of natural high moleculer eompound and maleic anhydride:
(1), to adding the soft water of 450g in churned mechanically 1L four-hole boiling flask, stir (2) and add 180g oligose, rising temperature for dissolving under whipped state; (3) control temperature-stable at 30 ℃, add 4g titanium sulfate and powdery maleic anhydride 75g in reactor, drip simultaneously sodium hydroxide and control pH between 7-9; (4) after maleic anhydride adds, temperature is raised to 40 ℃, strengthens reaction 2 hours, below the material pH to 8 in hydrochloric acid conditioned reaction still, obtains product maleic anhydride graft natural high moleculer eompound.
The copolyreaction process of maleic anhydride graft natural high moleculer eompound and acrylic monomer:
(5) add the 1.1g ferrous sulfate to aforesaid reaction vessel, intensification is dissolved it fully, and drip 55g methacrylic acid, 20g methyl acrylate and 80g initiator solution (the 10% tertbutyl peroxide aqueous solution) uniformly in reactor, be controlled in 2 hours and all add.
(6) after material dropping finishes, temperature is controlled at 90 ℃ and continues reaction 2 hours, obtains copolymer products, i.e. water treatment agent A.
Be the modification step of water treatment agent A to copolymer products:
(7) the product underpressure distillation in step (6) is extremely steamed without moisture; (8) drip the vitriol oil in reactor, control temperature at 20 ℃, after 1.5 hours, vitriol oil add-on is 20g, and the product sulfonation degree reaches 45%, finishes sulfonation reaction; (9) to dripping in reactor in sodium hydroxide and the excessive vitriol oil, more than transferring PH to 2, discharging, obtain the water treatment agent B after modification.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
The product performance test
1. evaluation of antisludging performance--tosca method
In the present invention, the phosphate-free corrosion inhibition antisludging agent before and after processing through the 3rd step sulfonation modifying is done the static-state scale inhibition experiment, and to contrast commercially available traditional phosphorus be corrosion inhibiting and descaling agent and conventional phosphate-free corrosion inhibition antisludging agent (PESA, poly-epoxy succinic acid; PASP: poly aspartic acid), result following (experimental technique is with reference to GB/T16632-2008):
The CaCO of the different chemical feeding quantities of table 1
3The dirt scale inhibition performance
As can be seen from Table 1, the novel non-phosphate environment-protective water treatment agent of the present invention's preparation is better than commercially available traditional phosphorus aspect scale-inhibiting properties be corrosion inhibiting and descaling agent and conventional phosphate-free corrosion inhibition antisludging agent product, and through the scale-inhibiting properties of modification procedure after product, be significantly improved.
2. corrosion inhibition evaluation--rotary hanging plate etching test
Respectively take Songhua River System, ChangJiang River, Yellow River System, northwest quality of groundwater as foundation, having contrasted product of the present invention and commercially available traditional phosphorus is the corrosion inhibition of corrosion inhibiting and descaling agent and conventional phosphate-free corrosion inhibition antisludging agent product, test method is with reference to GB/T18175-2000,45 ℃ of experimental temperatures, experimental period 144 hours; Lacing film adopts A3 II shaped steel sheet, every group parallel two.
Table 2 inhibition experiment water quality:
Table 3 inhibition experimental result:
As can be seen from Table 3, the novel non-phosphate environment-protective water treatment agent of the present invention preparation is better than traditional phosphorous medicament and commercially available without phosphorus pharmaceutical products aspect corrosion inhibition, for the water quality in different basins, good corrosion mitigating effect is arranged.
Claims (10)
1. Phosphateless environmentally friendly water treatment agent, it is characterized in that being made by the preparation method who comprises following reactions steps: the copolyreaction that the graft reaction of natural high moleculer eompound and maleic anhydride obtains maleic anhydride graft natural high moleculer eompound, maleic anhydride graft natural high moleculer eompound and acrylic monomer obtains multipolymer.
2. water treatment agent as claimed in claim 1, is characterized in that in the preparation method also comprising the modification step to the gained multipolymer.
3. the preparation method of a Phosphateless environmentally friendly water treatment agent, it is characterized by to have adopted and comprise following synthetic reaction process: the copolyreaction that the graft reaction of natural high moleculer eompound and maleic anhydride obtains maleic anhydride graft natural high moleculer eompound, maleic anhydride graft natural high moleculer eompound and acrylic monomer obtains multipolymer, be water treatment agent A, wherein
Natural high moleculer eompound and maleic anhydride graft reaction process comprise: (1) takes the soft water of counting by weight 400-600 part and joins in stainless steel cauldron, stirs; (2) will take the natural high moleculer eompound of counting by weight 100-300 part and join in aforesaid reaction vessel, and heat up and make its dissolving; (3) the powdery solid maleic anhydride that will count by weight 40-80 part at the uniform velocity joins in reactor; (4) add in the process of maleic anhydride powder, constantly drip the pH value in sodium hydroxide solution control reactor; (5) powder add complete after, be warming up to 10 ℃-80 ℃, continue reaction 1-4 hour, below the interior material pH value to 8 of sour conditioned reaction still, obtain product maleic anhydride graft natural high moleculer eompound;
Wherein also comprise in above-mentioned steps (3) and add the catalyst sulfuric acid titanium of counting by weight 2-6 part simultaneously in reactor;
The copolyreaction process of maleic anhydride graft natural high moleculer eompound and acrylic monomer comprises: the catalyzer that (1) will count 1-7 part by weight adds in the reactor of product maleic anhydride graft natural high moleculer eompound place, heats up catalyzer is dissolved fully; (2) acrylic monomer of take initiator solution, counting by weight 60-100 part is added dropwise to reactor.(3) above-mentioned material dropping complete after, be warming up to 60 ℃-100 ℃, continue reaction 1-4 hour, obtain multipolymer, i.e. water treatment agent A.
4. synthetic method according to claim 3, it is characterized in that in described natural high moleculer eompound and maleic anhydride graft reaction process, described natural high moleculer eompound is a kind of in xylogen and modification derivant, Mierocrystalline cellulose and modification derivant thereof, starch and modification derivant thereof, and wherein the lignin modification derivative is selected from a kind of in sulfonated lignin, aminated lignin, alkylation xylogen, oxidative lignin; Cellulose modified derivative is selected from a kind of in etherified cellulose, esterified cellulose; The starch conversion derivative is selected from a kind of in modified starch, dextran.
5. synthetic method according to claim 3, is characterized in that wherein in natural high moleculer eompound and maleic anhydride graft reaction process, and dripping the pH value that sodium hydroxide solution controls in reactor in step (4) is between 6-10.
6. synthetic method according to claim 3, it is characterized in that in described maleic anhydride graft natural high moleculer eompound and acrylic monomer polymerization process, the acrylic monomer in step (2) comprises one or more in vinylformic acid, methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate.
7. synthetic method according to claim 3, it is characterized in that in described maleic anhydride graft natural high moleculer eompound and acrylic monomer polymerization process, the initiator solution described in step (2) is one or more in azo, peroxide, redox class initiator.
8. synthetic method according to claim 3, it is characterized in that in described maleic anhydride graft natural high moleculer eompound and acrylic monomer polymerization process, its step (1) used catalyst is inorganic molysite, and wherein said inorganic molysite comprises a kind of in ferrous ammonium sulphate, ferrous sulfate, iron protochloride, iron(ic) chloride, ferric sulfate.
9. as synthetic method as described in claim 3-8 any one, characterized by further comprising the modification step of water treatment agent, wherein the modification step comprises: (1) obtains the copolyreaction gained multipolymer of maleic anhydride graft natural high moleculer eompound and acrylic monomer the thick product of brown after underpressure distillation; (2) control temperature 5-50 ℃, drip the vitriol oil in above-mentioned product, interval time the assaying reaction thing acid number, and calculate sulfonation degree,, when product reaches predetermined sulfonation degree, finish sulfonation reaction; (3) use again in sodium hydroxide solution and the excessive vitriol oil, obtain the water treatment agent B after modification.
10. synthetic method according to claim 9, is characterized in that in described modification step, and the predetermined sulfonation degree of the described multipolymer of step (2) should be controlled in 20～50%.
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| CN103964589A (en) * | 2014-04-24 | 2014-08-06 | 宋晶冰 | Preparation method for novel non-phosphorus corrosion inhibitor applied to circulating water system |
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| CN106145396A (en) * | 2016-08-09 | 2016-11-23 | 丁玉琴 | A kind of preparation method of Phosphateless environmentally friendly dirt dispersion agent |
| CN107244752A (en) * | 2017-06-09 | 2017-10-13 | 武汉理工大学 | A kind of efficient and environment-friendly type anti-incrustation corrosion inhibitor and its preparation |
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| CN108439618A (en) * | 2018-03-14 | 2018-08-24 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | A kind of coal gasification buck scale preventative and preparation method thereof |
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