CN113121025A - Tracer type bio-based scale inhibitor and preparation method and application thereof - Google Patents
Tracer type bio-based scale inhibitor and preparation method and application thereof Download PDFInfo
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 118
- 239000000700 radioactive tracer Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 229920001661 Chitosan Polymers 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 239000000498 cooling water Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 37
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- 238000010907 mechanical stirring Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 10
- JSJHCJAVSDQFLO-UHFFFAOYSA-N 8-hydroxypyrene-1,3,6-trisulfonic acid;sodium Chemical compound [Na].[Na].[Na].C1=C2C(O)=CC(S(O)(=O)=O)=C(C=C3)C2=C2C3=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 JSJHCJAVSDQFLO-UHFFFAOYSA-N 0.000 claims description 9
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000002329 infrared spectrum Methods 0.000 description 22
- 230000005764 inhibitory process Effects 0.000 description 15
- 239000012467 final product Substances 0.000 description 13
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 125000000542 sulfonic acid group Chemical group 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 229940109262 curcumin Drugs 0.000 description 1
- 235000012754 curcumin Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000012921 fluorescence analysis Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- C02F5/12—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 containing nitrogen
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- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
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- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
A tracing type bio-based scale inhibitor contains bio-based high molecular polymer chitosan, and carboxyl and a fluorescent group are arranged on the polymer chitosan. A preparation method of a tracing type bio-based scale inhibitor comprises the following steps: a: preparing a monomer having a fluorescent group; b: preparing the tracing type bio-based scale inhibitor. The preparation method is adopted for the tracer bio-based scale inhibitor, and the tracer bio-based scale inhibitor is applied to scale inhibitors in industrial circulating cooling water. The preparation process of the trace bio-based scale inhibitor is simple, the reaction conditions are mild, the finally obtained scale inhibitor does not need to be purified from a solvent, and no by-product is generated.
Description
Technical Field
The invention relates to preparation and application of a tracing type bio-based scale inhibitor for industrial circulating cooling water, and belongs to the technical field of water treatment.
Background
The problems frequently encountered in industrial production such as salt production, seawater desalination, petroleum exploitation, comprehensive utilization of salt lake resources and the like are calcium sulfate scale, and the scale layer is continuously thickened, so that the heat transfer efficiency is influenced, the heat energy loss is caused, the yield is reduced, the production cost is increased, and the production period is prolonged. The commonly adopted method is to add chemical scale inhibitor, and the method has the characteristics of small using amount, obvious effect and the like. The Chinese patent 'a composite low-phosphorus corrosion and scale inhibitor and application thereof' with the application number of 201110071299.6 discloses a composite low-phosphorus corrosion and scale inhibitor which has good scale inhibition and corrosion inhibition effects, and is compounded with a commercial fluorescent scale inhibitor to realize online monitoring. The Chinese patent 'a corrosion and scale inhibition control method of a circulating cooling water system and a corrosion and scale inhibitor' with the application number of 201911390945.8 discloses a corrosion and scale inhibitor, which has the advantages that a fluorescent monomer is synthesized on a polymer instead of simple physical mixing, so that the water treatment effect is improved, but the 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid accounts for 10-15%, has larger specific gravity and also has the risk of secondary pollution. Therefore, the synthesis of the effective, reasonable and phosphorus-free green and environment-friendly scale inhibitor for removing the calcium sulfate scale and the application of the scale inhibitor in industrial production has great significance. The Chinese patent 'a green environment-friendly multifunctional high-efficiency corrosion and scale inhibitor' with the application number of 201610995825.0 discloses a green environment-friendly multifunctional high-efficiency corrosion and scale inhibitor which has the advantages of high hardness, high alkalinity, high pH value and the like, and the material is green and environment-friendly, high in action efficiency and low in cost. However, the strong base sodium hydroxide is added in the preparation process, so that the preparation process has safety risk and is not suitable for large-scale production.
In the application of actual circulating cooling water, besides the requirements of excellent scale inhibition performance and no secondary pollution of the scale inhibitor, whether the scale inhibitor can be monitored on line is often required, so that accurate addition and supplement of the medicament are also one of important factors to be considered. To achieveThe requirement of on-line monitoring is often realized by adding a fluorescent substance into the scale inhibitor. For the addition of the fluorescent substance, two ways are divided. The first method is simple physical mixing, and directly compounds the fluorescent substance and the scale inhibitor. Chinese patent No. 201610754089.X discloses a fluorescence-labeled scale inhibitor with better chemical stability, but it is prepared by mixing multiple components in a certain proportion, rather than by chemical reaction to obtain macromolecule with fluorescent group. For on-line monitoring according to the fluorescent group on the scale inhibitor, the method has larger error, and the concentration of the scale inhibitor cannot be accurately presumed, so that the actual application effect is poor. The second method is to introduce a fluorescent group to macromolecules of the scale inhibitor by chemical reaction by adopting chemical modification. The scale inhibitor obtained by the method is more accurate in concentration determination during online monitoring. An amino acid fluorescent tracing scale inhibitor is disclosed in Chinese patent 'an amino acid fluorescent tracing scale inhibitor, a preparation method and an application' with application number 201910343995.4, which is prepared by taking curcumin, citric acid and amino acid as main raw materials and carrying out high-temperature reaction. The material does not contain phosphorus, is easy to biodegrade, has lower preparation cost and better calcium sulfate resistance. However, the preparation process needs continuous temperature rise, the whole reaction process is about 30 hours, and the temperature is as high as 200oAnd C, the preparation process is relatively complicated, and large-scale production is not easy to realize. Therefore, a brand new tracing type bio-based scale inhibitor which has good scale inhibition effect, does not cause secondary pollution, is simple and safe to operate and can realize online monitoring is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a trace type bio-based scale inhibitor.
In order to realize the purpose of the invention, the following technical scheme is adopted: a tracing type bio-based scale inhibitor contains bio-based high molecular polymer chitosan, and carboxyl and a fluorescent group are arranged on the polymer chitosan.
A preparation method of a tracing type bio-based scale inhibitor, wherein the tracing type bio-based scale inhibitor contains bio-based high molecular polymer chitosan, and the polymer chitosan has carboxyl and a fluorescent group, comprises the following steps:
a: preparing a monomer having a fluorescent group;
b: preparing the tracing type bio-based scale inhibitor.
Further, the method comprises the following steps of; the method specifically comprises the following steps:
a: preparation of monomers with fluorescent groups:
a1: under the condition of mechanical stirring, 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-neck flask, and then triethylamine solution is added;
a2: under the heating condition of water bath, dripping glycidyl methacrylate into a four-neck flask by using a dropping funnel, and continuously heating for reaction after dripping is finished;
a3: after the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a monomer with a fluorescent group;
b: preparing a tracer type bio-based scale inhibitor;
b1: adding chitosan into hydrochloric acid solution, adding the chitosan into a four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring, and stirring and heating;
b2: respectively adding potassium persulfate, acrylic acid and the monomer with the fluorescent group obtained in the step A3 into water to be dissolved to obtain respective aqueous solutions;
b3: and B2, respectively placing the acrylic acid aqueous solution and the aqueous solution of the monomer with the fluorescent group obtained in the step B into a dropping funnel to ensure the air tightness of the dropping funnel, adding a potassium persulfate solution after introducing nitrogen into a reaction bottle in the reaction bottle, continuing introducing nitrogen after finishing adding, subsequently heating, dropwise adding two aqueous solutions of the acrylic acid aqueous solution and the aqueous solution of the monomer with the fluorescent group, and continuing to react after finishing adding, thus obtaining the tracer bio-based scale inhibitor.
Further, the method comprises the following steps of; in the step A, the mass ratio of the trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate to methanol is 1: (0.1-2): (0.1-2): (1000-; the mechanical stirring speed is 300 r/min; the water bath heating temperature is 40-70 deg.CoC; the reaction time is 4-12 h.
Further, the method comprises the following steps of; in the step B, the mass ratio of chitosan to hydrochloric acid to water is 1: (1-5): (50-200); the mass ratio of the potassium persulfate to the water is 1: 40; the mass ratio of acrylic acid to water is 1: 3; the mass ratio of the monomer with the fluorescent group to the water is 1: 20; the mass ratio of the chitosan to the potassium persulfate to the acrylic acid to the monomer with the fluorescent group is 1: (0.1-0.5): (2-10): (0.2-1); heating at 40-70 deg.CoC; the reaction time is 2-6 h; the magnetic stirring speed is 120 r/min; the dropping speed of the monomer solution was 5 mL/min.
The application of the tracing type bio-based scale inhibitor adopts the tracing type bio-based scale inhibitor, and the tracing type bio-based scale inhibitor adopts the preparation method and is applied to the scale inhibitor in industrial circulating cooling water.
The invention has the following beneficial effects: (1) the molecular structure of the tracing type bio-based scale inhibitor does not contain phosphorus, and the biomacromolecule chitosan is used as a base material, so that the tracing type bio-based scale inhibitor is easy to biodegrade, cannot cause secondary pollution, and has low raw material price and wide source; (2) the trace type bio-based scale inhibitor has excellent calcium sulfate resistance, and can still maintain higher scale inhibition efficiency under the conditions of high hardness, high alkalinity, high temperature and the like; (3) the tracing type bio-based scale inhibitor of the invention introduces fluorescent groups onto materials through polymerization reaction, has lower detection limit for on-line monitoring, and thus realizes accurate feeding; (4) the preparation process of the trace bio-based scale inhibitor is simple, the reaction conditions are mild, the finally obtained scale inhibitor does not need to be purified from a solvent, and no by-product is generated.
Drawings
Fig. 1 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in example 1.
Fig. 2 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in example 2.
Fig. 3 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in example 3.
Fig. 4 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in example 4.
Fig. 5 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in example 5.
Fig. 6 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in example 6.
Fig. 7 is an infrared spectrum of the bio-based scale inhibitor synthesized in comparative example 1.
FIG. 8 is a graph showing the scale inhibition performance of the scale inhibitors of examples 1 to 6 and comparative example 1 against calcium sulfate scale.
FIG. 9 is a linear relationship graph between the concentration of the tracer bio-based scale inhibitor and the fluorescence intensity obtained in example 1.
Detailed Description
In order to more fully explain the implementation of the present invention, the implementation examples of the present invention are provided, which are merely illustrative of the present invention and do not limit the scope of the present invention.
Example 1
Under the condition of mechanical stirring (the rotation speed of the mechanical stirring is 300 r/min), 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-mouth flask, and then triethylamine solution is added. Finally heating in water bath (heating temperature is 40 DEG)oC) Slowly dripping glycidyl methacrylate (trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate and methanol in a mass ratio of 1: 1: 2: 3000) after the dropwise addition was completed, the heating reaction was continued (reaction time: 8 hours). After the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a final product monomer with a fluorescent group;
weighing a certain amount of chitosan, adding the chitosan into a hydrochloric acid solution (the mass ratio of the chitosan to the hydrochloric acid to the water is 1: 4: 100), adding the chitosan into a 500 mL four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring (the magnetic stirring speed is 120 r/min), and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40) is measured outAcrylic acid (acrylic acid and water at a mass ratio of 1: 3) and the monomer having a fluorescent group obtained in the above step (the monomer having a fluorescent group and water at a mass ratio of 1: 20) were respectively added to water to be dissolved to obtain an aqueous solution. Setting up an experimental device, respectively placing the aqueous solutions of the two monomers in a dropping funnel to ensure the air tightness of the device, introducing nitrogen into a reaction bottle, firstly adding a potassium persulfate solution, and continuously introducing nitrogen after the addition. Then the temperature is raised (heating temperature is 50℃)oC) The two aqueous monomer solutions were slowly added dropwise (the rate of addition of the aqueous monomer solution was 5 mL/min), and after the addition was complete, the reaction was continued (reaction time: 3 hours). After the reaction is finished, the final product of the tracing type bio-based scale inhibitor (the mass ratio of the chitosan, the potassium persulfate, the acrylic acid and the monomer with the fluorescent group is 1: 0.1: 10: 0.5) can be obtained.
As a result:
fig. 1 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in this example. As seen from FIG. 1, in the infrared spectrum of the tracer bio-based scale inhibitor, the infrared spectrum is at about 1043, 1646 and 3432cm-1Characteristic peaks are shown, namely stretching vibration peaks of sulfonic acid groups, amino groups and hydroxyl groups respectively, and the successful synthesis of the tracer bio-based scale inhibitor is indicated.
Example 2
Under the condition of mechanical stirring (the rotation speed of the mechanical stirring is 300 r/min), 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-mouth flask, and then triethylamine solution is added. Finally heating in water bath at 50 deg.CoC) Slowly dripping glycidyl methacrylate (trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate and methanol in a mass ratio of 1: 0.1: 0.5: 2000) after the dropwise addition was completed, the heating reaction was continued (reaction time: 6 hours). After the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a final product monomer with a fluorescent group;
weighing a certain amount of chitosan, adding into hydrochloric acid solution (the mass ratio of chitosan, hydrochloric acid and water is 1: 2: 80)Under the condition of magnetic stirring (the rotating speed of the magnetic stirring is 120 r/min), when the chitosan is completely dissolved, adding the chitosan into a 500 mL four-neck flask, and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40), acrylic acid (the mass ratio of acrylic acid to water is 1: 3) and the monomer with a fluorescent group (the mass ratio of the monomer with a fluorescent group to water is 1: 20) obtained in the above step are measured and added to water respectively to be dissolved to obtain an aqueous solution. Setting up an experimental device, respectively placing the aqueous solutions of the two monomers in a dropping funnel to ensure the air tightness of the device, introducing nitrogen into a reaction bottle of a reaction bottle, firstly adding a potassium persulfate solution, and continuously introducing nitrogen after the addition. Then the temperature is raised (heating temperature is 60℃)oC) The two aqueous monomer solutions were slowly added dropwise (the rate of addition of the aqueous monomer solution was 5 mL/min), and after the addition was complete, the reaction was continued (reaction time: 6 hours). After the reaction is finished, the final product of the tracing type bio-based scale inhibitor (the mass ratio of the chitosan, the potassium persulfate, the acrylic acid and the monomer with the fluorescent group is 1: 0.3: 2: 0.6) can be obtained.
As a result:
fig. 2 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in this example. As seen from FIG. 2, in the infrared spectrum of the tracer bio-based scale inhibitor, at about 606, 1636 and 3459cm-1Characteristic peaks are shown, namely stretching vibration peaks of sulfonic acid groups, amino groups and hydroxyl groups respectively, and the successful synthesis of the tracer bio-based scale inhibitor is indicated.
Example 3
Under the condition of mechanical stirring (the rotation speed of the mechanical stirring is 300 r/min), 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-mouth flask, and then triethylamine solution is added. Finally heating in water bath (heating temperature is 70 deg.C)oC) Slowly dripping glycidyl methacrylate (trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate and methanol in a mass ratio of 1: 2: 0.1: 2000) after the dropwise addition was completed, the heating reaction was continued (reaction time: 10 hours). After the reaction was completed, the solution was poured into a flask, and the solvent was added using a rotary evaporatorExtracting methanol to obtain a final product of the monomer with the fluorescent group;
weighing a certain amount of chitosan, adding the chitosan into a hydrochloric acid solution (the mass ratio of the chitosan to the hydrochloric acid to the water is 1: 3: 150), adding the chitosan into a 500 mL four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring (the magnetic stirring speed is 120 r/min), and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40), acrylic acid (the mass ratio of acrylic acid to water is 1: 3) and the monomer with a fluorescent group (the mass ratio of the monomer with a fluorescent group to water is 1: 20) obtained in the above step are measured and added to water respectively to be dissolved to obtain an aqueous solution. Setting up an experimental device, respectively placing the aqueous solutions of the two monomers in a dropping funnel to ensure the air tightness of the device, introducing nitrogen into a reaction bottle of a reaction bottle, firstly adding a potassium persulfate solution, and continuously introducing nitrogen after the addition. Then the temperature was raised (heating temperature 40)oC) The two aqueous monomer solutions were slowly added dropwise (the rate of addition of the aqueous monomer solution was 5 mL/min), and after the addition was completed, the reaction was continued (the reaction time was 5 hours). After the reaction is finished, the final product of the tracing type bio-based scale inhibitor (the mass ratio of the chitosan, the potassium persulfate, the acrylic acid and the monomer with the fluorescent group is 1: 0.2: 7: 0.2) can be obtained.
As a result:
fig. 3 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in this example. As seen from FIG. 3, in the infrared spectrum of the tracer bio-based scale inhibitor, at about 624, 1646 and 3423 cm-1Characteristic peaks are shown, namely stretching vibration peaks of sulfonic acid groups, amino groups and hydroxyl groups respectively, and the successful synthesis of the tracer bio-based scale inhibitor is indicated.
Example 4
Under the condition of mechanical stirring (the rotation speed of the mechanical stirring is 300 r/min), 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-mouth flask, and then triethylamine solution is added. Finally heating in water bath at 50 deg.CoC) Slowly dripping glycidyl methacrylate (8-hydroxy-1, 3, 6-pyrene trisulfonic acid trisodium and triethylamine) into a four-neck flask by using a dropping funnelAnd the mass ratio of the glycidyl methacrylate to the methanol is 1: 0.5: 1: 5000) after the dropwise addition was completed, the heating reaction was continued (reaction time: 4 hours). After the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a final product monomer with a fluorescent group;
weighing a certain amount of chitosan, adding the chitosan into a hydrochloric acid solution (the mass ratio of the chitosan to the hydrochloric acid to the water is 1: 5: 200), adding the chitosan into a 500 mL four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring (the magnetic stirring speed is 120 r/min), and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40), acrylic acid (the mass ratio of acrylic acid to water is 1: 3) and the monomer with a fluorescent group (the mass ratio of the monomer with a fluorescent group to water is 1: 20) obtained in the above step are measured and added to water respectively to be dissolved to obtain an aqueous solution. Setting up an experimental device, respectively placing the aqueous solutions of the two monomers in a dropping funnel to ensure the air tightness of the device, introducing nitrogen into a reaction bottle of a reaction bottle, firstly adding a potassium persulfate solution, and continuously introducing nitrogen after the addition. Then the temperature was raised (heating temperature 70 deg.C)oC) The two aqueous monomer solutions were slowly added dropwise (the rate of addition of the aqueous monomer solution was 5 mL/min), and after the addition was complete, the reaction was continued (reaction time: 2 hours). After the reaction is finished, the final product of the tracing type bio-based scale inhibitor (the mass ratio of the chitosan, the potassium persulfate, the acrylic acid and the monomer with the fluorescent group is 1: 0.5: 8: 0.8) can be obtained.
As a result:
fig. 4 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in this example. From FIG. 4, it can be seen that in the infrared spectrum of the tracer bio-based scale inhibitor, the infrared spectrum is at about 798, 1636 and 3469 cm-1Characteristic peaks are shown, namely stretching vibration peaks of sulfonic acid groups, amino groups and hydroxyl groups respectively, and the successful synthesis of the tracer bio-based scale inhibitor is indicated.
Example 5
Under the condition of mechanical stirring (the rotating speed of the mechanical stirring is 300 r/min), 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-mouth flask, and then addedTriethylamine solution was added. Finally heating in water bath (heating temperature is 60 deg.C)oC) Slowly dripping glycidyl methacrylate (trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate and methanol in a mass ratio of 1: 0.8: 1.5: 4000) after the dropwise addition was completed, the heating reaction was continued (reaction time 12 hours). After the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a final product monomer with a fluorescent group;
weighing a certain amount of chitosan, adding the chitosan into a hydrochloric acid solution (the mass ratio of the chitosan to the hydrochloric acid to the water is 1: 1: 50), adding the chitosan into a 500 mL four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring (the magnetic stirring speed is 120 r/min), and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40), acrylic acid (the mass ratio of acrylic acid to water is 1: 3) and the monomer with a fluorescent group (the mass ratio of the monomer with a fluorescent group to water is 1: 20) obtained in the above step are measured and added to water respectively to be dissolved to obtain an aqueous solution. Setting up an experimental device, respectively placing the aqueous solutions of the two monomers in a dropping funnel to ensure the air tightness of the device, introducing nitrogen into a reaction bottle of a reaction bottle, firstly adding a potassium persulfate solution, and continuously introducing nitrogen after the addition. Then the temperature is raised (heating temperature is 60℃)oC) The two aqueous monomer solutions were slowly added dropwise (the rate of addition of the aqueous monomer solution was 5 mL/min), and after the addition was completed, the reaction was continued (the reaction time was 5 hours). After the reaction is finished, the final product of the tracing type bio-based scale inhibitor (the mass ratio of the chitosan, the potassium persulfate, the acrylic acid and the monomer with the fluorescent group is 1: 0.4: 4: 1) can be obtained.
As a result:
fig. 5 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in this example. From FIG. 5, it can be seen that the infrared spectra of the trace type bio-based scale inhibitor are at about 679, 1654 and 3350 cm-1Characteristic peaks are shown, namely stretching vibration peaks of sulfonic acid groups, amino groups and hydroxyl groups respectively, and the successful synthesis of the tracer bio-based scale inhibitor is indicated.
Example 6
Under the condition of mechanical stirring (the rotation speed of the mechanical stirring is 300 r/min), 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-mouth flask, and then triethylamine solution is added. Finally heating in water bath (heating temperature is 60 deg.C)oC) Slowly dripping glycidyl methacrylate (trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate and methanol in a mass ratio of 1: 1.5: 1.5: 3000) after the dropwise addition was completed, the heating reaction was continued (reaction time: 8 hours). After the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a final product monomer with a fluorescent group;
weighing a certain amount of chitosan, adding the chitosan into a hydrochloric acid solution (the mass ratio of the chitosan to the hydrochloric acid to the water is 1: 3: 100), adding the chitosan into a 500 mL four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring (the rotating speed of the magnetic stirring is 120 r/min), and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40), acrylic acid (the mass ratio of acrylic acid to water is 1: 3) and the monomer with a fluorescent group (the mass ratio of the monomer with a fluorescent group to water is 1: 20) obtained in the above step are measured and added to water respectively to be dissolved to obtain an aqueous solution. Setting up an experimental device, respectively placing the aqueous solutions of the two monomers in a dropping funnel to ensure the air tightness of the device, introducing nitrogen into a reaction bottle of a reaction bottle, firstly adding a potassium persulfate solution, and continuously introducing nitrogen after the addition. Then the temperature is raised (heating temperature is 60℃)oC) The two aqueous monomer solutions were slowly added dropwise (the rate of addition of the aqueous monomer solution was 5 mL/min), and after the addition was complete, the reaction was continued (reaction time: 3 hours). After the reaction is finished, the final product of the tracing type bio-based scale inhibitor (the mass ratio of the chitosan, the potassium persulfate, the acrylic acid and the monomer with the fluorescent group is 1: 0.2: 6: 0.8) can be obtained.
As a result:
fig. 6 is an infrared spectrum of the tracer bio-based scale inhibitor synthesized in this example. As can be seen from FIG. 6, in the tracer modeThe infrared spectrogram of the substance-based scale inhibitor is about 1043, 1582 and 3432cm-1Characteristic peaks are shown, namely stretching vibration peaks of sulfonic acid groups, amino groups and hydroxyl groups respectively, and the successful synthesis of the tracer bio-based scale inhibitor is indicated.
Example 7
Scale inhibition application of tracer type bio-based scale inhibitor
According to the performance evaluation (SY/T5673-93) of the scale inhibitor for the oil field of the Chinese oil and gas industry standard, the main steps of the calcium sulfate resistance are as follows: preparing the sodium sulfate into 7100mg/LSO4 2-Then adding the tracer bio-based scale inhibitors synthesized in examples 1-6 (final concentrations of 2,4, 6, 8, 10mg/L respectively) with stirring, and then adding CaCl2An aqueous solution containing Ca2+The concentration is 6800mg/L (as CaCO)3The same applies hereinafter), adjusting the pH to 7 with NaOH or HCl solution, and finally placing the flask containing the solution at a temperature of 80 deg.CoAnd C, standing for 6 hours at constant temperature in the water bath kettle. After standing and cooling, taking supernatant in the conical flask, and measuring Ca by EDTA titration2+The results of concentration are shown in FIG. 8.
As can be seen from fig. 8, the trace type bio-based scale inhibitors synthesized in examples 1 to 6 all have certain scale inhibition capability. Among them, the trace type bio-based scale inhibitor synthesized in example 1 has the highest scale inhibition effect under the same conditions.
Example 8
On-line monitoring application of tracing type bio-based scale inhibitor
The tracer type bio-based scale inhibitor is prepared into 1mg/L solution by deionized water, and the solution shows yellow green fluorescence under the irradiation of exciting light. The maximum excitation wavelength is 380nm and the emission wavelength is 438nm through the measurement of a fluorescence spectrophotometer. Deionized water is used for preparing tracer type bio-based scale inhibitor solution with the concentration of 2,4, 6, 8 and 10mg/L, the fixed excitation wavelength is 380nm, and the fluorescence intensity of the solution under 438nm is measured, and the result is shown in figure 9.
Comparative example 1
Weighing a certain amount of chitosan, adding into hydrochloric acid solution (chitosan, hydrochloric acid, water)The mass ratio of (1): 3: 100) under the condition of magnetic stirring (the rotating speed of the magnetic stirring is 120 r/min), when the chitosan is completely dissolved, adding the chitosan into a 500 mL four-neck flask, and stirring and heating. Then, potassium persulfate (the mass ratio of potassium persulfate to water is 1: 40) and acrylic acid (the mass ratio of acrylic acid to water is 1: 3) were measured and dissolved in water to obtain an aqueous solution. Setting up an experimental device, putting the aqueous solution of the monomer into a dropping funnel to ensure the air tightness of the device, adding the potassium persulfate solution after introducing nitrogen into a reaction bottle of the reaction bottle, and continuing introducing the nitrogen after adding the potassium persulfate solution. Then the temperature is raised (heating temperature is 50℃)oC) The aqueous monomer solution was slowly dropped (dropping speed of the aqueous monomer solution was 5 mL/min), and after completion of the dropping, the reaction was continued (reaction time: 4 hours). After the reaction is finished, the final product, namely the bio-based scale inhibitor (the mass ratio of the chitosan to the potassium persulfate to the acrylic acid is 1: 0.2: 6) can be obtained.
As a result:
fig. 7 is an infrared spectrum of the bio-based scale inhibitor synthesized in this comparative example. From FIG. 7, it can be seen that in the infrared spectrum of the bio-based scale inhibitor, it is at about 1636 and 3459cm-1Characteristic peaks are shown, namely stretching vibration peaks of amino and hydroxyl respectively, which means the successful synthesis of the bio-based scale inhibitor.
The scale inhibitor in the example 7 is changed from the tracer type bio-based scale inhibitor synthesized in the examples 1 to 6 into the bio-based scale inhibitor synthesized in the comparative example, and the rest is equal to the example 7, so that the scale inhibition effect graph of the bio-based scale inhibitor synthesized in the comparative example is obtained, and the graph is shown in fig. 8. As can be seen from fig. 8, although comparative example 1 is obtained by binary copolymerization of two materials, namely, acrylic acid and chitosan, it also has a certain scale inhibition effect due to various functional groups (carboxyl, hydroxyl and amino) contained therein. However, compared with examples 1-6, the scale inhibition performance of the compound is better than that of comparative example 1 due to the added sulfonic acid group on the structure. Among them, the scale inhibitor of example 1 has the best scale inhibition performance, which is caused by the largest content of effective functional groups. More functional groups react with calcium ions in the aqueous solution, thereby preventing the formation of a precipitate with the corresponding anionic sulfate radical and preventing the formation of scale. This again shows that in the tracer bio-based scale inhibitors synthesized in examples 1-6, the addition of the fluorescent group not only can play a tracing role, but also the sulfonic acid group thereon plays an important role in the scale inhibition effect.
As shown in FIG. 9, the relative fluorescence intensity of the tracer bio-based scale inhibitor increases with the increase of the concentration of the scale inhibitor, and the scale inhibitor shows a good linear relation, wherein the linear fitting equation is y =14.5x +1.2, and the linear correlation coefficient R is20.99199 can be reached. Based on the fluorescence analysis, the tracing type bio-based scale inhibitor can carry out quantitative analysis through fluorescence, and has wide prospect in practical application.
After the embodiments of the present invention have been described in detail, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and it is intended that all simple modifications, equivalent changes and modifications made to the above embodiments based on the technical spirit of the present invention shall fall within the technical scope of the present invention, and the present invention shall not be limited to the embodiments illustrated in the description.
Claims (6)
1. A trace type bio-based scale inhibitor is characterized in that: the tracing type bio-based scale inhibitor contains bio-based high molecular polymer chitosan, and the polymer chitosan is provided with carboxyl and a fluorescent group.
2. A preparation method of a tracing type bio-based scale inhibitor, wherein the tracing type bio-based scale inhibitor contains bio-based high molecular polymer chitosan, and the polymer chitosan has carboxyl and a fluorescent group, is characterized by comprising the following steps:
a: preparing a monomer having a fluorescent group;
b: preparing the tracing type bio-based scale inhibitor.
3. The preparation method of the trace bio-based scale inhibitor according to claim 2, wherein the method comprises the following steps: the method specifically comprises the following steps:
a: preparation of monomers with fluorescent groups:
a1: under the condition of mechanical stirring, 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid trisodium is dissolved in methanol solution and poured into a four-neck flask, and then triethylamine solution is added;
a2: under the heating condition of water bath, dripping glycidyl methacrylate into a four-neck flask by using a dropping funnel, and continuously heating for reaction after dripping is finished;
a3: after the reaction is finished, pouring the solution into a flask, and extracting the solvent methanol by using a rotary evaporator to obtain a monomer with a fluorescent group;
b: preparing a tracer type bio-based scale inhibitor;
b1: adding chitosan into hydrochloric acid solution, adding the chitosan into a four-neck flask after the chitosan is completely dissolved under the condition of magnetic stirring, and stirring and heating;
b2: respectively adding potassium persulfate, acrylic acid and the monomer with the fluorescent group obtained in the step A3 into water to be dissolved to obtain respective aqueous solutions;
b3: and B2, respectively placing the acrylic acid aqueous solution and the aqueous solution of the monomer with the fluorescent group obtained in the step B into a dropping funnel to ensure the air tightness of the dropping funnel, introducing nitrogen into a reaction bottle, adding a potassium persulfate solution, continuously introducing nitrogen after the addition is finished, subsequently heating, dropwise adding two aqueous solutions of the acrylic acid aqueous solution and the aqueous solution of the monomer with the fluorescent group, and continuously reacting after the dropwise addition is finished to obtain the tracer type bio-based scale inhibitor.
4. The method for preparing the tracer bio-based scale inhibitor according to claim 3, wherein the method comprises the following steps: in the step A, the mass ratio of the trisodium 8-hydroxy-1, 3, 6-pyrenetrisulfonate, triethylamine, glycidyl methacrylate to methanol is 1: (0.1-2): (0.1-2): (1000-; the mechanical stirring speed is 300 r/min; the water bath heating temperature is 40-70 deg.CoC; the reaction time is 4-12 h.
5. The method for preparing the tracer bio-based scale inhibitor according to claim 3, wherein the method comprises the following steps: in the step B, the mass ratio of chitosan to hydrochloric acid to water is 1: (1-5): (50-200); the mass ratio of the potassium persulfate to the water is 1: 40; the mass ratio of acrylic acid to water is 1: 3; the mass ratio of the monomer with the fluorescent group to the water is 1: 20; the mass ratio of the chitosan to the potassium persulfate to the acrylic acid to the monomer with the fluorescent group is 1: (0.1-0.5): (2-10): (0.2-1); heating at 40-70 deg.CoC; the reaction time is 2-6 h; the magnetic stirring speed is 120 r/min; the dropping speed of the monomer solution was 5 mL/min.
6. The use of a trace bio-based scale inhibitor according to any one of claims 1 or 2, wherein the trace bio-based scale inhibitor is prepared by the method according to claim 3 or 4, and the method comprises the following steps: the scale inhibitor is applied to industrial circulating cooling water.
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