CN116639822A - Composition for preparing scale inhibitor, preparation method and application of scale inhibitor - Google Patents
Composition for preparing scale inhibitor, preparation method and application of scale inhibitor Download PDFInfo
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- CN116639822A CN116639822A CN202310776369.0A CN202310776369A CN116639822A CN 116639822 A CN116639822 A CN 116639822A CN 202310776369 A CN202310776369 A CN 202310776369A CN 116639822 A CN116639822 A CN 116639822A
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 239000002904 solvent Substances 0.000 claims abstract description 31
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 21
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims abstract description 21
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 21
- HWCXJKLFOSBVLH-UHFFFAOYSA-N 5-amino-2,4-dioxo-1h-pyrimidine-6-carboxylic acid Chemical compound NC1=C(C(O)=O)NC(=O)NC1=O HWCXJKLFOSBVLH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 19
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 22
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 23
- 230000007797 corrosion Effects 0.000 abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 description 18
- 239000013081 microcrystal Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000498 cooling water Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- -1 so that scaling Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application provides a composition for preparing a scale inhibitor, the scale inhibitor, a preparation method and application thereof, and belongs to the technical field of water treatment, wherein the composition comprises maleic anhydride, acrylic acid, sulfonic acid type anionic monomers, a first functional monomer, a second functional monomer, an initiator and water; the raw materials for preparing the first functional monomer comprise 5-amino orotic acid, a first solvent, pyridine and maleic anhydride; the raw materials for preparing the second functional monomer comprise 1, 2-benzisothiazolin-3-one, ethyl chloroacetate, a second solvent and hydrazine hydrate. The scale inhibitor provided by the application has the advantages of high scale inhibition efficiency, good corrosion inhibition effect and excellent antibacterial performance.
Description
Technical Field
The application relates to the technical field of water treatment, in particular to a composition for preparing a scale inhibitor, the scale inhibitor, a preparation method and application thereof.
Background
With the development of society, industrial water has a higher specific gravity, and particularly plays a role in manufacturing, processing, purifying, cooling, and the like, and is called industrial blood. According to statistics, the proportion of industrial water in China accounts for 35-40% of that in China, wherein the cooling water accounts for more than 80% of that in the industrial water, and water resources can be saved by recycling the cooling water. After the cooling water is recycled for a long time, the pH and temperature of the medium rise due to evaporation and concentration of water, so that scaling, metal corrosion, microorganism breeding and the like of the surface of the pipeline can be caused. Therefore, the circulated cooling water needs to be treated.
The most commonly used treatment method of cooling water is to add a scale inhibitor into the cooling water, however, the existing scale inhibitor has the problems of low scale inhibition efficiency, poor corrosion inhibition effect and poor antibacterial performance, so that the scale inhibitor with high scale inhibition efficiency, good corrosion inhibition effect and excellent antibacterial performance is needed to be provided.
Disclosure of Invention
Aiming at one or more technical problems in the prior art, the application provides a composition for preparing a scale inhibitor, the scale inhibitor, a preparation method and application thereof.
The present application provides in a first aspect a composition for preparing a scale inhibitor, the composition comprising maleic anhydride, acrylic acid, a sulfonic acid-based anionic monomer, a first functional monomer, a second functional monomer, an initiator, and water;
the raw materials for preparing the first functional monomer comprise 5-amino orotic acid, a first solvent, pyridine and maleic anhydride;
the raw materials for preparing the second functional monomer comprise 1, 2-benzisothiazolin-3-one, ethyl chloroacetate, a second solvent and hydrazine hydrate.
Preferably, the composition comprises, by weight, 100 to 120 parts of maleic anhydride, 70 to 90 parts of acrylic acid, 20 to 30 parts of sulfonic acid type anionic monomers, 15 to 30 parts of first functional monomers, 15 to 30 parts of second functional monomers, 0.2 to 0.4 part of initiator and 550 to 650 parts of water.
Preferably, the molar ratio of the 5-amino orotic acid, the maleic anhydride and the pyridine is 1 (1.2-1.5): 1.1-1.3;
the mass ratio of the 5-amino orotic acid to the first solvent is (1-1.3): 15.
Preferably, the molar ratio of the hydrazine in the 1, 2-benzisothiazolin-3-one, the ethyl chloroacetate and the hydrazine hydrate is 1 (1.1-1.3): 1.1-1.3;
the mass ratio of the 1, 2-benzisothiazolin-3-one to the second solvent is (1-1.3): 10.
Preferably, the sulfonic acid type anionic monomer is at least one of allylsulfonic acid and vinylsulfonic acid;
the initiator is azo initiator, and the azo initiator is one or more of azo diisobutylamidine hydrochloride, azo diiso Ding Mi hydrochloride, azo diisoheptonitrile and azo diisobutyronitrile, preferably azo diisobutylamidine hydrochloride;
the first solvent is dichloromethane;
the second solvent is ethanol; and/or
The hydrazine content of the hydrazine hydrate is 85%.
In a second aspect, the present application provides a scale inhibitor, the scale inhibitor comprising a composition according to the first aspect as a starting material for its preparation.
The present application provides in a third aspect a method for producing the scale inhibitor according to the second aspect, the method comprising the steps of:
s1, fully mixing maleic anhydride, acrylic acid, sulfonic acid type anionic monomers and water, and regulating the pH value to 5.5-6.5 to obtain a blend;
s2, adding a first functional monomer and a second functional monomer into the blend, uniformly mixing, carrying out first nitrogen introducing and deoxidization, heating to 45-50 ℃ under a protective atmosphere, and adding an initiator to initiate polymerization reaction to obtain the scale inhibitor.
Preferably, the preparation method of the first functional monomer comprises the following steps: mixing 5-amino orotic acid with a first solvent, deoxidizing by second nitrogen introduction, adding pyridine for activation treatment, then adding maleic anhydride, and recrystallizing through a first reaction to obtain the first functional monomer;
preferably, the second nitrogen introducing and deoxidizing time is 30-40 min;
preferably, the temperature of the activation treatment is 20-30 ℃ and the time is 2-3 h;
preferably, the first reaction is carried out under the protection of nitrogen, the reaction temperature is 40-50 ℃ and the reaction time is 2-5 h.
Preferably, the preparation method of the second functional monomer comprises the following steps: and (3) uniformly mixing 1, 2-benzisothiazolin-3-one, ethyl chloroacetate and a second solvent at normal temperature, then adding hydrazine hydrate, performing a second reaction until precipitation is not increased, and filtering to obtain a second functional monomer.
The present application provides in a third aspect the use of a scale inhibitor according to the second aspect in water treatment.
Compared with the prior art, the application has at least the following beneficial effects:
the acrylic acid and maleic anhydride copolymer in the composition can be dissociated into negative ions in the aqueous solution, when the negative ions collide with calcium carbonate microcrystals in the aqueous solution, physical adsorption and chemical adsorption are carried out, so that an electricity taking layer is formed on the surfaces of the calcium carbonate microcrystals, when the calcium carbonate microcrystals are adsorbed by the polymer negative ions, the calcium carbonate microcrystals have the same charge, electrostatic repulsion between the charged calcium carbonate microcrystals can prevent the collision between the calcium carbonate microcrystals from forming large crystals, the calcium carbonate microcrystals are kept in a very small particle state, the contact area of the crystals and water is increased, and therefore the dissolution performance of the crystals is improved. In addition, electrostatic repulsive force between charged calcium carbonate microcrystals can prevent collision between the charged calcium carbonate microcrystals and a metal heat transfer surface, reduce the number of crystal nucleus capable of forming a scale layer and effectively inhibit the formation of the scale layer.
The first functional monomer is prepared from the raw materials of 5-amino orotic acid, the solvent, pyridine and maleic anhydride, and hetero atoms in a molecular structure can be well adsorbed on the surface of carbon steel to form a layer of anti-corrosion film, so that the reaction of interfacial ions can be effectively prevented, aggregation of scale forming crystal nuclei on the surface of a pipeline is inhibited, and the corrosion inhibition performance of a polymer is improved.
The second functional monomer is prepared from 1, 2-benzisothiazolin-3-one, ethyl chloroacetate, a second solvent and hydrazine hydrate, wherein the 1, 2-benzisothiazolin-3-one (isothiazolinone compound) has higher algae killing and bacteria inhibiting biological activity, and the hydrazine acyl is introduced into the structure by reacting with the ethyl chloroacetate and the hydrazine hydrate, so that the bactericidal activity and the bacteria inhibiting performance of the second functional monomer can be further improved, and the polymer has more excellent bacteria inhibiting performance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the embodiments described below will be clearly and completely described in conjunction with the technical solutions of the embodiments of the present application, and it is apparent that the described embodiments are some, but not all, embodiments of the present application, and all other embodiments obtained by persons of ordinary skill in the art without making any inventive effort based on the embodiments of the present application are within the scope of protection of the present application.
The present application provides in a first aspect a composition for preparing a scale inhibitor, the composition comprising maleic anhydride, acrylic acid, a sulfonic acid-based anionic monomer, a first functional monomer, a second functional monomer, an initiator, and water;
the raw materials for preparing the first functional monomer comprise 5-amino orotic acid, a first solvent, pyridine and maleic anhydride;
the raw materials for preparing the second functional monomer comprise 1, 2-benzisothiazolin-3-one, ethyl chloroacetate, a second solvent and hydrazine hydrate.
The acrylic acid and maleic anhydride copolymer in the composition can be dissociated into negative ions in the aqueous solution, when the negative ions collide with calcium carbonate microcrystals in the aqueous solution, physical adsorption and chemical adsorption are carried out, so that an electricity taking layer is formed on the surfaces of the calcium carbonate microcrystals, when the calcium carbonate microcrystals are adsorbed by the polymer negative ions, the calcium carbonate microcrystals have the same charge, electrostatic repulsion between the charged calcium carbonate microcrystals can prevent the collision between the calcium carbonate microcrystals from forming large crystals, the calcium carbonate microcrystals are kept in a very small particle state, the contact area of the crystals and water is increased, and therefore the dissolution performance of the crystals is improved. In addition, electrostatic repulsive force between charged calcium carbonate microcrystals can prevent collision between the charged calcium carbonate microcrystals and a metal heat transfer surface, reduce the number of crystal nucleus capable of forming a scale layer and effectively inhibit the formation of the scale layer.
The first functional monomer is prepared from the raw materials of 5-amino orotic acid, the solvent, pyridine and maleic anhydride, and hetero atoms in a molecular structure can be well adsorbed on the surface of carbon steel to form a layer of anti-corrosion film, so that the reaction of interfacial ions can be effectively prevented, aggregation of scale forming crystal nuclei on the surface of a pipeline is inhibited, and the corrosion inhibition performance of a polymer is improved.
The second functional monomer is prepared from 1, 2-benzisothiazolin-3-one, ethyl chloroacetate, a second solvent and hydrazine hydrate, wherein the 1, 2-benzisothiazolin-3-one (isothiazolinone compound) has higher algae killing and bacteria inhibiting biological activity, and the hydrazine acyl is introduced into the structure by reacting with the ethyl chloroacetate and the hydrazine hydrate, so that the bactericidal activity and the bacteria inhibiting performance of the second functional monomer can be further improved, and the polymer has more excellent bacteria inhibiting performance.
According to some preferred embodiments, the composition comprises 100-120 parts (e.g., may be 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts, 106 parts, 107 parts, 108 parts, 109 parts, 110 parts, 111 parts, 112 parts, 113 parts, 114 parts, 115 parts, 116 parts, 117 parts, 118 parts, 119 parts or 120 parts) of maleic anhydride, 70-90 parts (e.g., may be 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts or 90 parts), 20-30 parts (e.g., may be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts) of sulfonic acid type anionic monomers, 15-30 parts (e.g., 15 to 30 parts (for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts), 15 to 30 parts of a second functional monomer (for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts), 0.2 to 0.4 part (for example, 0.2 parts, 0.3 parts or 0.4 part) of an initiator, and 550 to 650 parts (for example, 550 parts, 555 parts, 560 parts, 565 parts, 570 parts, 575 parts, 580 parts, 585 parts, 590 parts, 635 parts, 600 parts, 605 parts, 610 parts, 615 parts, 620 parts, 625 parts, 630 parts, 640 parts, 645 parts or 650 parts) of water; the application controls the dosage of each component in the composition within the range, thus ensuring that the prepared scale inhibitor has excellent scale inhibition performance, corrosion inhibition performance and antibacterial performance.
According to some preferred embodiments, the molar ratio of 5-amino orotic acid, maleic anhydride and pyridine is 1 (1.2-1.5): 1.1-1.3;
the mass ratio of 5-amino orotic acid to the first solvent is (1-1.3): 15 (for example, may be 1:15, 1.1:15, 1.2:15 or 1.3:15).
According to some preferred embodiments, the molar ratio of hydrazine in 1, 2-benzisothiazolin-3-one, ethyl chloroacetate and hydrazine hydrate is 1 (1.1-1.3): 1.1-1.3;
the mass ratio of the 1, 2-benzisothiazolin-3-one to the second solvent is (1-1.3): 10 (e.g., may be 1:10, 1.1:10, 1.2:10, or 1.3:10).
According to some preferred embodiments, the sulfonic acid-based anionic monomer is at least one of allylsulfonic acid, vinylsulfonic acid; the stability of the polymer under the condition of high mineralization can be effectively improved by selecting the sulfonic acid type anionic monomer.
The initiator is azo initiator, and the azo initiator is one or more of azo diisobutylamidine hydrochloride, azo diiso Ding Mi hydrochloride, azo diisoheptonitrile and azo diisobutyronitrile, preferably azo diisobutylamidine hydrochloride;
the first solvent is dichloromethane;
the second solvent is ethanol; and/or
The hydrazine content of the hydrazine hydrate is 85%.
The hydrazine content of hydrazine hydrate was 85%, which means that the mass fraction of hydrazine was 85%.
In a second aspect, the present application provides a scale inhibitor, the scale inhibitor comprising a composition according to the first aspect as a starting material for its preparation.
The scale inhibitor provided by the application simultaneously comprises acrylic acid and maleic anhydride which can generate copolymer with excellent scale inhibition performance, a first functional monomer with excellent corrosion inhibition effect and a second functional monomer with excellent sterilization and bacteriostasis effect, so that the scale inhibitor has high scale inhibition efficiency, good corrosion inhibition effect and excellent sterilization and bacteriostasis performance, and can meet the requirements of cooling water treatment.
The present application provides in a third aspect a method for producing the scale inhibitor according to the second aspect, the method comprising the steps of:
s1, fully mixing maleic anhydride, acrylic acid, sulfonic acid type anionic monomers and water, and adjusting the pH to 5.5-6.5 (for example, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4 or 6.5) to obtain a blend;
s2, adding a first functional monomer and a second functional monomer into the blend, uniformly mixing, carrying out first nitrogen ventilation and deoxidation, heating to 45-50 ℃ under a protective atmosphere (for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃ or 50 ℃), and adding an initiator to initiate polymerization reaction to obtain the scale inhibitor.
According to some preferred embodiments, the method for preparing the first functional monomer includes: mixing 5-amino orotic acid with a first solvent, deoxidizing by second nitrogen introduction, adding pyridine for activation treatment, then adding maleic anhydride, and recrystallizing through a first reaction to obtain the first functional monomer;
preferably, the second nitrogen-introducing deoxidizing time is 30-40 min (for example, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min or 40 min);
preferably, the temperature of the activation treatment is 20 to 30 ℃ (for example, may be 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃) and the time is 2 to 3 hours (for example, may be 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours);
preferably, the first reaction is carried out under nitrogen protection at a temperature of 40-50 ℃ (e.g., may be 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, or 50 ℃) for a time of 2-5 hours (e.g., may be 2 hours, 2.2 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.8 hours, or 5 hours).
The reaction formula for preparing the first functional monomer is as follows:
in some embodiments of the application, after mixing 5-amino orotic acid with the first solvent, removing oxygen for 30-40 min (for example, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min or 40 min), adding pyridine under nitrogen protection, activating at 20-30deg.C (for example, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C or 30 deg.C) for 2-3 h (for example, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3 h), adding maleic anhydride, and at 40-50deg.C (for example, the first functional monomer may be obtained by subjecting the mixture to a reaction for 2 to 5 hours (for example, 2 hours, 2.2 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.8 hours or 5 hours) at 40℃to 45 ℃ (for example, 40℃41℃42℃43℃44℃or 45 ℃) after recrystallization with acetone and suction filtration, and then drying the mixture for 2 to 4 hours (for example, 2 hours, 2.2 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.8 hours, 3.2 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.8 hours or 4 hours).
According to the application, pyridine is adopted to activate 5-amino orotic acid, then the activated 5-amino orotic acid reacts with maleic anhydride to introduce double bonds capable of carrying out addition polymerization on carbon and carbon, and hetero atoms are introduced into polymer molecules through polymerization reaction, so that the hetero atoms can be well adsorbed on the surface of carbon steel to form a layer of anti-corrosion film, the reaction of interfacial ions is effectively prevented, the aggregation of scale-forming crystal nuclei on the surface of a pipeline is inhibited, and the corrosion inhibition performance of the polymer is further improved.
According to some preferred embodiments, the method for preparing the second functional monomer comprises: and (3) uniformly mixing 1, 2-benzisothiazolin-3-one, ethyl chloroacetate and a second solvent at normal temperature, then adding hydrazine hydrate, performing a second reaction until precipitation is not increased, and filtering to obtain a second functional monomer.
The reaction formula for preparing the second functional monomer is as follows:
in some specific embodiments of the application, 1, 2-benzisothiazolin-3-one, ethyl chloroacetate and ethanol are mixed uniformly at normal temperature, hydrazine hydrate with the hydrazine content of 85% is added dropwise, and the mixture is stirred until precipitation is not increased, and a second functional monomer is obtained through suction filtration, ethanol washing and drying.
According to the application, by adopting the reaction of 1, 2-benzisothiazolin-3-one (isothiazolinone compound), ethyl chloroacetate and hydrazine hydrate, the bactericidal activity and antibacterial performance of the second functional monomer are improved by further introducing a hydrazino group on the basis of the isothiazolinone compound.
The present application provides in a third aspect the use of a scale inhibitor according to the second aspect in water treatment.
In industrial production, an open-type circulating cooling water system is mainly adopted at present, and the method is characterized by energy conservation and environmental protection, and the cooling water can be recycled. After the cooling water is recycled for a long time, the pH and temperature of the medium rise due to evaporation and concentration of water, so that scaling, metal corrosion, microorganism breeding and the like on the surface of the pipeline can be necessarily caused. The formation of scale deposits will lead to a decrease in the heat exchange efficiency of the cooling system, blockage of the pipes, increased initial investment and maintenance costs; corrosion will cause damage and deterioration of production equipment and even serious safety accidents; microorganisms under the action of dissolved oxygen in water can accelerate corrosion of equipment. In order to improve the cooling efficiency of water, increase the recycling frequency of water and reduce the corrosion and damage of the water to equipment, the circulating water needs to be treated. The scale inhibitor provided by the application has the advantages of high scale inhibition efficiency, good corrosion inhibition effect and excellent antibacterial performance, can effectively solve the problems of easy occurrence of scale formation on the surface of a pipeline, metal corrosion, microorganism breeding and the like of cooling water, and meets the requirements of cooling water treatment.
In order to more clearly illustrate the technical scheme and advantages of the present application, the present application will be further described below with reference to examples.
The test method of corrosion inhibition rate, scale inhibition rate and relative bacteriostasis rate of the application refers to the following standard:
corrosion inhibition (%): SY/T5273-2000-3 normal pressure static corrosion rate and corrosion inhibition rate test method.
Scale inhibition (%): a method for measuring the scale inhibition rate of SY/T5673-2020-8.
Relative inhibition (%): SY/T5890-93-6 bactericide performance evaluation method.
Example 1
Preparation of the first functional monomer:
17g of 5-amino orotic acid and 250g of methylene dichloride are sequentially added into a reactor, nitrogen is introduced to remove oxygen for 30min, 9.5g of pyridine is added, and the mixture is activated for 3h at 30 ℃; 13g of maleic anhydride is added, and the mixture reacts for 5 hours at the constant temperature of 45 ℃ under the protection of nitrogen; recrystallizing with acetone, suction filtering, and drying at 45deg.C for 4 hr to obtain the first functional monomer.
Example 2
Preparation of the second functional monomer:
60g of ethanol, 15g of 1, 2-benzisothiazolin-3-one and 14g of ethyl chloroacetate are sequentially added into a reactor, and after being stirred uniformly, 7g of 85% hydrazine hydrate is added, and stirring is carried out at normal temperature until precipitation is not increased, and the second functional monomer is obtained after suction filtration, washing and drying.
The first functional monomer of the following examples and comparative examples of the present application was prepared by the method of example 1, and the second functional monomer was prepared by the method of example 2.
Example 3
S1, adding 110g of maleic anhydride, 80g of acrylic acid, 25g of allylsulfonic acid and deionized water into a reactor, mixing, adjusting the pH of the mixed solution to 6.5 by using granular alkali, and uniformly stirring and mixing to obtain a blend;
s2, adding 20g of a first functional monomer and 20g of a second functional monomer into the blend, stirring and mixing uniformly, blowing nitrogen to deoxidize for 30min, heating to 50 ℃ under the protection of nitrogen, and adding 0.3g of azodiisobutylamidine hydrochloride to initiate polymerization for 4h to obtain the scale inhibitor.
Example 4
S1, adding 100g of maleic anhydride, 90g of acrylic acid, 30g of allylsulfonic acid and deionized water into a reactor, mixing, adjusting the pH of the mixed solution to 5.5 by using granular alkali, and uniformly stirring and mixing to obtain a blend;
s2, adding 25g of a first functional monomer and 20g of a second functional monomer into the blend, stirring and mixing uniformly, blowing nitrogen to deoxidize for 30min, heating to 50 ℃ under the protection of nitrogen, and adding 0.3g of azodiisobutylamidine hydrochloride to initiate polymerization for 4h to obtain the scale inhibitor.
Example 5
S1, adding 120g of maleic anhydride, 75g of acrylic acid, 30g of allylsulfonic acid and deionized water into a reactor, mixing, adjusting the pH of the mixed solution to 6 by using granular alkali, and uniformly stirring and mixing to obtain a blend;
s2, adding 20g of a first functional monomer and 25g of a second functional monomer into the blend, stirring and mixing uniformly, blowing nitrogen to deoxidize for 30min, heating to 50 ℃ under the protection of nitrogen, and adding 0.3g of azodiisobutylamidine hydrochloride to initiate polymerization for 4h to obtain the scale inhibitor.
Comparative example 1
Comparative example 1 is substantially the same as example 3 except that: the first functional monomer was not added.
Comparative example 2
Comparative example 1 is substantially the same as example 3 except that: the mass of the first functional monomer was 50g.
Comparative example 3
Comparative example 3 is substantially the same as example 3 except that: no second functional monomer was added.
Comparative example 4
Comparative example 4 is substantially the same as example 3 except that: the mass of the second functional monomer was 50g.
Comparative example 5
Comparative example 5 is substantially the same as example 3 except that: the first functional monomer and the second functional monomer are not added.
Comparative example 6
Comparative example 6 is substantially the same as example 3 except that: the first functional monomer is replaced with 5-amino orotic acid.
Comparative example 7
Comparative example 7 is substantially the same as example 3 except that: the second functional monomer is replaced by 1, 2-benzisothiazolin-3-one.
TABLE 1 Performance data of the scale inhibitor prepared in examples and comparative examples
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A composition for preparing a scale inhibitor, which is characterized by comprising maleic anhydride, acrylic acid, sulfonic acid type anionic monomers, a first functional monomer, a second functional monomer, an initiator and water;
the raw materials for preparing the first functional monomer comprise 5-amino orotic acid, a first solvent, pyridine and maleic anhydride;
the raw materials for preparing the second functional monomer comprise 1, 2-benzisothiazolin-3-one, ethyl chloroacetate, a second solvent and hydrazine hydrate.
2. The composition according to claim 1, wherein the composition comprises, in parts by weight, 100 to 120 parts of maleic anhydride, 70 to 90 parts of acrylic acid, 20 to 30 parts of sulfonic acid type anionic monomer, 15 to 30 parts of first functional monomer, 15 to 30 parts of second functional monomer, 0.2 to 0.4 part of initiator, and 550 to 650 parts of water.
3. The composition according to claim 1, wherein the molar ratio of 5-amino orotic acid, maleic anhydride and pyridine is 1 (1.2-1.5): 1.1-1.3;
the mass ratio of the 5-amino orotic acid to the first solvent is (1-1.3): 15.
4. The composition according to claim 1, wherein the molar ratio of hydrazine in 1, 2-benzisothiazolin-3-one, ethyl chloroacetate and hydrazine hydrate is 1 (1.1-1.3): 1.1-1.3;
the mass ratio of the 1, 2-benzisothiazolin-3-one to the second solvent is (1-1.3): 10.
5. The composition according to claim 1, wherein the sulfonic acid type anionic monomer is at least one of allylsulfonic acid and vinylsulfonic acid;
the initiator is azo initiator, and the azo initiator is one or more of azo diisobutylamidine hydrochloride, azo diiso Ding Mi hydrochloride, azo diisoheptonitrile and azo diisobutyronitrile, preferably azo diisobutylamidine hydrochloride;
the first solvent is dichloromethane;
the second solvent is ethanol; and/or
The hydrazine content of the hydrazine hydrate is 85%.
6. A scale inhibitor, characterized in that the raw material for preparing the scale inhibitor comprises the composition according to any one of claims 1 to 5.
7. A method of preparing according to claim 6, comprising the steps of:
s1, fully mixing maleic anhydride, acrylic acid, sulfonic acid type anionic monomers and water, and regulating the pH value to 5.5-6.5 to obtain a blend;
s2, adding a first functional monomer and a second functional monomer into the blend, uniformly mixing, carrying out first nitrogen introducing and deoxidization, heating to 45-50 ℃ under a protective atmosphere, and adding an initiator to initiate polymerization reaction to obtain the scale inhibitor.
8. The method of preparing according to claim 7, wherein the method of preparing the first functional monomer comprises: mixing 5-amino orotic acid with a first solvent, deoxidizing by second nitrogen introduction, adding pyridine for activation treatment, then adding maleic anhydride, and recrystallizing through a first reaction to obtain the first functional monomer;
preferably, the second nitrogen introducing and deoxidizing time is 30-40 min;
preferably, the temperature of the activation treatment is 20-30 ℃ and the time is 2-3 h;
preferably, the first reaction is carried out under the protection of nitrogen, the reaction temperature is 40-50 ℃ and the reaction time is 2-5 h.
9. The method of preparing according to claim 7, wherein the method of preparing the second functional monomer comprises: and (3) uniformly mixing 1, 2-benzisothiazolin-3-one, ethyl chloroacetate and a second solvent at normal temperature, then adding hydrazine hydrate, performing a second reaction until precipitation is not increased, and filtering to obtain a second functional monomer.
10. Use of the scale inhibitor of claim 6 in water treatment.
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