CN116768378A - Hydrophilic environment-friendly multifunctional scale inhibitor and preparation method and application thereof - Google Patents
Hydrophilic environment-friendly multifunctional scale inhibitor and preparation method and application thereof Download PDFInfo
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical group FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 46
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 46
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920001897 terpolymer Polymers 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 32
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000005764 inhibitory process Effects 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- DGTOAFBVEDTEBA-UHFFFAOYSA-N sodium;prop-1-ene Chemical compound [Na+].[CH2-]C=C DGTOAFBVEDTEBA-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 26
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 21
- 229940047670 sodium acrylate Drugs 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 229920000805 Polyaspartic acid Polymers 0.000 description 11
- 108010064470 polyaspartate Proteins 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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 2
- 238000005452 bending Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001677188 Coccus viridis Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a hydrophilic environment-friendly multifunctional scale inhibitor, a preparation method and application thereof, wherein the scale inhibitor is a composite copolymer formed by grafting polysuccinimide and terpolymer; wherein the terpolymer is itaconic acid/acrylamide/sodium allylsulfonate copolymer, and the mass ratio of polysuccinimide to the terpolymer is (1-2): (2-4). The composite copolymer grafted by polysuccinimide and itaconic acid/acrylamide/sodium allylsulfonate terpolymer has three groups of carboxyl, amido and sulfonic acid, so that the scale inhibitor is environment-friendly, has good scale inhibition performance and shows excellent scale inhibition effects on different scales.
Description
Technical Field
The invention belongs to the technical field of polymer macromolecules and water treatment, and particularly relates to a hydrophilic environment-friendly multifunctional scale inhibitor, a preparation method and application thereof.
Background
In the development process of the oil field, fluid flows out of the oil and gas reservoir through the oil and gas layer, and finally reaches the gathering and transporting system on the ground through the shaft and the well head, and scale forming ions in stratum water are influenced by the change of the oil and gas water balance state, the pressure, the temperature change and the like, so that inorganic salt scale is deposited to generate scale. In the development process of oil and gas fields, the scaling problem is a serious problem, and especially as the development of the oil and gas fields is in depth, the scaling problem is more prominent, and the development cost is also increasing.
Oilfield scale is of two general categories: firstly carbonic acidSalt scale, caCO 3 Most commonly; second, sulfate scale, caSO 4 、BaSO 4 Especially common. Carbonate scale is easier to prevent and treat, and can be cleaned by inorganic acid, but the equipment is corroded in the cleaning process. Because of small solubility product, compact structure and high hardness, sulfate scale is difficult to remove by the traditional pickling chemical method, and the oilfield can only adopt a production stopping and pipe changing or physical removing means, thereby seriously affecting the oilfield production.
Currently, the most widely used and effective method for scale control in oil fields is to add chemical scale inhibitors. As water treatment technology continues to evolve, the "green scale inhibitors" have become the direction of development for industrial water treatment agents in the 21 st century, and commercial scale inhibitors for carbonate and sulfate scale formation are typically polymers such as poly (acrylic acid), polymaleic acid, polyaspartic acid, polyphosphates, and the like. Some scale inhibitors have the problem that the single functional group has no outstanding inhibition performance. In addition, the main flow of scale inhibitor is mainly a phosphorus formula, and excessive discharge of phosphorus-containing substances can cause eutrophication of water body to bring harm to the environment. With the improvement of environmental protection consciousness, the country has started to implement and control the emission standard of various harmful chemical substances related to the environment, so the development of green multifunctional scale inhibitors has become urgent. Polyaspartic Acid (PASP) is a polyamino acid polymer substance with carboxylic acid side chains, and has functions of biodegradation, chelation, dispersion and the like. The polyaspartic acid is easy to adsorb or combine with metal ions due to the molecular structure characteristics of the polyaspartic acid, has the function of preventing scale, and can be used for preventing CaCO in water treatment 3 And CaSO 4 Scale formation. In addition, the copolymer scale inhibitor has been receiving a great deal of attention because it has a plurality of functional groups, shows a strong complexing effect and excellent dispersion characteristics of macromolecules, and can show excellent properties for different types of scale. The low-phosphorus or phosphorus-free efficient copolymer scale inhibitor is used for replacing the traditional phosphorus single-functional group scale inhibitor, and gradually becomes a trend of development of the water treatment industry, so that the development of the green multifunctional scale inhibitor is significant.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrophilic environment-friendly multifunctional scale inhibitor, and a preparation method and application thereof. The multifunctional scale inhibitor provided by the invention is environment-friendly, has good scale inhibition performance and has excellent scale inhibition effect on different scales.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a hydrophilic environment-friendly multifunctional scale inhibitor, which is a composite copolymer formed by grafting polysuccinimide and a terpolymer; wherein the terpolymer is itaconic acid/acrylamide/sodium allylsulfonate copolymer, and the mass ratio of polysuccinimide to the terpolymer is (1-2): (2-4).
Preferably, the number average molecular weight of the composite copolymer is 15000 to 19000.
Preferably, the terpolymer is the polymerization product of the monomers itaconic acid, the monomers acrylamide and the monomer sodium allylsulfonate; the mole ratio of the monomer itaconic acid, the monomer acrylamide and the monomer sodium allylsulfonate is (0.5-1): 2: (1-1.5).
In a second aspect, the invention provides a preparation method of the hydrophilic environment-friendly multifunctional scale inhibitor, which comprises the following steps:
s1, mixing polysuccinimide and a terpolymer, adding an alkali solution to control the pH value to be 9-10, and carrying out grafting reaction under the heating condition;
s2, after the reaction is finished, regulating the pH value to be neutral, and obtaining the multifunctional scale inhibitor.
Preferably, in step S1, the preparation method of the terpolymer comprises the following steps:
respectively preparing itaconic acid solution, sodium allylsulfonate/acrylamide mixed solution and initiator solution;
and heating the itaconic acid solution to 75-80 ℃, adding the sodium allylsulfonate/acrylamide mixed solution and the initiator solution into the itaconic acid solution, and reacting for 2-4 hours at 85-95 ℃ to obtain the terpolymer.
Preferably, in the step S1, the mass percentage of polysuccinimide is 10-20%, the mass percentage of terpolymer is 20-40%, and the balance is deionized water and alkali solution.
Preferably, in step S1, the alkali solution comprises sodium hydroxide solution, the heating temperature is 40-60 ℃, and the reaction time is 8-24 h.
Preferably, in the step S2, after the pH is regulated to be neutral, solid is separated out from the product solution by absolute ethyl alcohol, and the hydrophilic environment-friendly multifunctional scale inhibitor is obtained through filtration, washing and vacuum drying.
In a third aspect, the invention provides an application of the hydrophilic environment-friendly multifunctional scale inhibitor in scale inhibition of water bodies, and particularly in water treatment in the oilfield development process.
Preferably, when the hydrophilic environment-friendly multifunctional scale inhibitor provided by the invention is used for water scale inhibition, the concentration of the scale inhibitor is 10-30 mg/L.
The beneficial effects of the invention are as follows:
the composite copolymer grafted by polysuccinimide and itaconic acid/acrylamide/sodium allylsulfonate terpolymer simultaneously has three groups, namely carboxyl, amido and sulfonic acid, wherein the carboxyl is the most main group for inhibiting calcium scale formation, the sulfonic acid group has stronger capability of inducing lattice distortion, and the amido improves the solubility of the scale inhibitor through forming hydrogen bonds, so that the scale inhibitor has good dispersion performance, metal adsorption capacity and scale inhibition performance.
The invention develops the scale inhibitor with excellent performance and meeting the green chemical development planning from the aspect of sustainable development, and the provided scale inhibitor does not contain phosphorus in the molecule, so that the nutrition of water is reduced, the good biodegradability of the water is ensured, and the environment-friendly and degradable requirements are met.
The invention effectively solves the problem of CaCO caused by the conventional medicament 3 、CaSO 4 、BaSO 4 The scale inhibition performance of the scale is lack of broad spectrum.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the following description will briefly explain the drawings of the embodiments.
FIG. 1 is an infrared spectrum of an IA-AM-SAS terpolymer prepared in example 2 of the present invention;
FIG. 2 is an infrared spectrum of the PASP- (IA-AM-SAS) copolymer prepared in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The embodiment of the invention provides a hydrophilic environment-friendly multifunctional scale inhibitor, which is a composite copolymer formed by grafting polysuccinimide and a terpolymer; wherein the terpolymer is itaconic acid/acrylamide/sodium allylsulfonate copolymer. The structure of the composite copolymer is shown as the following formula (I) or formula (II):
in some embodiments, the mass ratio of polysuccinimide to terpolymer is (1-2): (2 to 4), preferably (1.5 to 2): (3-4), more preferably 1.5:3.
In some embodiments, the terpolymer is a polymerized product of the copolymerization of the monomer itaconic acid, the monomer acrylamide, and the monomer sodium allylsulfonate.
In some preferred embodiments, the terpolymer has the following general structural formula:
wherein m, q, z represent the moles of monomeric itaconic acid, monomeric acrylamide and monomeric sodium allylsulfonate, respectively, and m: q: z= (0.5 to 1): 2: (1-1.5).
In some embodiments, the preparation method of the hydrophilic environment-friendly multifunctional scale inhibitor provided by the invention comprises the following steps:
s1, weighing 10-20% of polysuccinimide, 20-40% of terpolymer and the balance of sodium hydroxide alkali solution and deionized water according to mass percentage, wherein the sum of the mass percentages of the components is 100%. Mixing polysuccinimide and terpolymer, adding alkali solution to control pH to 9-10, and reacting at 40-60 deg.c for 8-24 hr;
s2, after the reaction is finished, regulating the pH value to be neutral, separating out solid from the product solution by using absolute ethyl alcohol, and obtaining the hydrophilic environment-friendly multifunctional scale inhibitor through filtration, washing and vacuum drying.
The Polysuccinimide (PSI) which is an intermediate for synthesizing Polyaspartic Acid (PASP) has high reactivity, and the itaconic acid/acrylamide/sodium allylsulfonate terpolymer and PSI are subjected to ring opening reaction modification, so that functional groups such as carboxyl, sulfonic acid group and the like are introduced to PASP molecular chains. The specific reaction process is as follows:
the olefin monomers all contain carbon-carbon double bonds, and when polymerization occurs, the carbon-carbon double bonds of itaconic acid, acrylamide and sodium allylsulfonate are broken, and then chain polymerization is performed. In some embodiments, in step S1, the terpolymer is obtained from a copolymerization of itaconic acid, sodium allylsulfonate, acrylamide in the presence of an initiator. The reaction formula is as follows:
the method specifically comprises the following steps:
respectively preparing itaconic acid solution, sodium allylsulfonate/acrylamide mixed solution and initiator solution;
and heating the itaconic acid solution to 75-80 ℃, adding the sodium allylsulfonate/acrylamide mixed solution and the initiator solution into the itaconic acid solution, and reacting for 2-4 hours at 85-95 ℃ to obtain the terpolymer.
In some embodiments, the initiator may be a conventional initiator known in the art of high molecular polymerization, including but not limited to ammonium persulfate. The amount of the initiator is 8-12% of the total mass of itaconic acid, sodium allylsulfonate and acrylamide monomers.
In order to make the implementation objects, technical solutions and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be described in more detail below with reference to the accompanying drawings of the present invention.
Example 1
A preparation method of a hydrophilic environment-friendly multifunctional scale inhibitor comprises the following steps:
s1, preparing itaconic acid/acrylamide/sodium allylsulfonate (IA-AM-SAS) terpolymer
Putting itaconic acid and deionized water into a four-neck round bottom flask provided with a thermometer, a condensation reflux device and a stirrer, starting the stirrer to stir uniformly, and heating to 55-60 ℃ until the itaconic acid is completely dissolved, wherein the mass volume ratio of the itaconic acid to the deionized water is 1:3; mixing sodium acrylate and acrylamide with deionized water, stirring and dissolving at normal temperature to obtain sodium acrylate/acrylamide mixed solution, and transferring to a constant pressure funnel. Wherein the mass-volume ratio of the total mass of sodium acrylate/acrylamide to deionized water is 1:2; ammonium persulfate is dissolved in deionized water and is moved to a constant pressure funnel, so that ammonium persulfate solution with the mass concentration of 30% is obtained. Wherein the mole ratio of itaconic acid to acrylamide to sodium acrylate monomer is 0.5:2:1, and ammonium persulfate is 8% of the total mass of itaconic acid to sodium acrylate to acrylamide monomer; and (3) heating the system in the round-bottom flask to 80 ℃, then dropwise adding a sodium acrylate/acrylamide mixed solution, simultaneously dropwise adding an ammonium persulfate solution into the system, heating to 85 ℃ after the dropwise adding is completed for 1h, and reacting for 2h to obtain an itaconic acid/acrylamide/sodium acrylate (IA-AM-SAS) copolymer solution. The copolymer solution was cooled and weighed, and then unreacted monomers were removed through a 2000Da dialysis membrane, and freeze-dried for 48 hours to obtain a purified polymer product (IA-AM-SAS). The terpolymer IA-AM-SAS had a number average molecular weight of 3056 as determined by gel permeation chromatography.
S2, preparing PASP- (IA-AM-SAS) copolymer scale inhibitor
Weighing the following components in percentage by mass: 10% of polysuccinimide, 20% of IA-AM-SAS copolymer, the balance of deionized water and sodium hydroxide solution (15%), wherein the sum of the mass percentages of the components is 100%.
Dissolving IA-AM-SAS in sodium hydroxide solution for standby; taking polysuccinimide in a four-neck flask, and adding deionized water to obtain polysuccinimide suspension; dropwise adding a sodium hydroxide solution of IA-AM-SAS into the polysuccinimide suspension under stirring to react, continuously adjusting the pH value of a reaction system to 9-10 by using a NaOH solution with the mass fraction of 15% in the reaction process, and reacting for 8 hours at 60 ℃; after the reaction was completed, the pH of the mixture was adjusted to 7.+ -. 0.5 with HCl (15%) solution. Adding the obtained neutral mixed solution into four times volume of absolute ethyl alcohol, filtering to separate out sticky pale yellow precipitate, washing with absolute ethyl alcohol for several times to obtain sticky brown yellow paste, and drying in a vacuum drying oven at 60 ℃ to obtain the polyaspartic acid graft copolymer PASP- (IA-AM-SAS). The number average molecular weight of the polymer product was measured to be about 15000.
Example 2
A preparation method of a hydrophilic environment-friendly multifunctional scale inhibitor comprises the following steps:
s1, preparing itaconic acid/acrylamide/sodium allylsulfonate terpolymer
Putting itaconic acid and deionized water into a four-neck round bottom flask provided with a thermometer, a condensation reflux device and a stirrer, starting the stirrer to stir uniformly, and heating to 55-60 ℃ until the itaconic acid is completely dissolved, wherein the mass volume ratio of the itaconic acid to the deionized water is 1:3; mixing sodium acrylate and acrylamide with deionized water, stirring and dissolving at normal temperature to obtain sodium acrylate/acrylamide mixed solution, and transferring to a constant pressure funnel. Wherein the mass-volume ratio of the total mass of sodium acrylate/acrylamide to deionized water is 1:2; ammonium persulfate is dissolved in deionized water and is moved to a constant pressure funnel, so that ammonium persulfate solution with the mass concentration of 30% is obtained. Wherein the mole ratio of itaconic acid to acrylamide to sodium acrylate monomer is 0.5:2:1.5, and ammonium persulfate is 10% of the total mass of itaconic acid to sodium acrylate to acrylamide monomer; and (3) heating the system in the round-bottom flask to 80 ℃, then dropwise adding a sodium acrylate/acrylamide mixed solution, simultaneously dropwise adding an ammonium persulfate solution into the system, heating to 90 ℃ after the dropwise adding is completed for 1h, and reacting for 3h to obtain an itaconic acid/acrylamide/sodium acrylate (IA-AM-SAS) copolymer solution. The copolymer solution was cooled and weighed, and then unreacted monomers were removed through a 2000Da dialysis membrane, and freeze-dried for 48 hours to obtain a purified polymer product (IA-AM-SAS). The terpolymer IA-AM-SAS had a number average molecular weight of 4378 as determined by gel permeation chromatography.
S2, preparing PASP- (IA-AM-SAS) copolymer scale inhibitor
Weighing the following components in percentage by mass: 15% of polysuccinimide, 30% of IA-AM-SAS copolymer, the balance of deionized water and sodium hydroxide solution (15%), wherein the sum of the mass percentages of the components is 100%.
Dissolving IA-AM-SAS in sodium hydroxide solution for standby; taking polysuccinimide in a four-neck flask, and adding deionized water to obtain polysuccinimide suspension. Dropwise adding sodium hydroxide solution of IA-AM-SAS into the polysuccinimide suspension under stirring to react, continuously adjusting the pH value of a reaction system to 9-10 by using NaOH solution in the reaction process, and reacting for 16h at 50 ℃; after the reaction was completed, the pH of the mixture was adjusted to 7.+ -. 0.5 with HCl (15%) solution. Adding the obtained neutral mixed solution into four times volume of absolute ethyl alcohol, filtering to separate out sticky pale yellow precipitate, washing with absolute ethyl alcohol for several times to obtain sticky brown yellow paste, and drying in a vacuum drying oven at 60 ℃ to obtain the polyaspartic acid graft copolymer PASP- (IA-AM-SAS). The number average molecular weight of the polymer product was measured to be about 19000.
FIG. 1 is an infrared spectrum of an IA-AM-SAS terpolymer prepared in the present example, as can be seen from the graph in FIG. 1, 3439.5cm -1 Is characterized by an absorption peak of 2938.6cm due to stretching vibration of N-H bond of unassociated amide group -1 Stretching vibration absorption peak of methylene，2360.7cm -1 Is the absorption peak of-OH in carboxyl of copolymer, 1663.5cm -1 Is provided with a telescopic vibration absorption peak of a carbonyl group of 1403.6cm -1 Is an alpha-methylene absorption peak in carboxylic acid, 1198.4cm -1 Is an asymmetric absorption peak of sulfonic acid group S=O bond, 1040.8cm -1 Is the symmetrical absorption peak of the sulfonic acid group S=O bond, 782cm -1 Is the expansion vibration peak of S-O bond, 612.6cm -1 Is C-S stretching absorption vibration peak. In addition, is combined with 1620-1640cm -1 The absorption peak signal without C=C bond indicates that the monomer has copolymerization reaction, which proves that the IA-AM-SAS terpolymer is successfully prepared, and the copolymer molecule contains functional groups such as carboxylic acid group, amide group, sulfonic acid group and the like, thus having scale inhibition activity.
FIG. 2 is an infrared spectrum of the PASP- (IA-AM-SAS) copolymer prepared in the present example, as can be seen from the graph in FIG. 2, 1165cm for PSI -1 And 1214cm -1 Is the stretching vibration peak of the C-C bond; 1797. 1716cm -1 Characteristic peaks of c=o appear at both sites, which result from coupling of two adjacent c=o s separated by N. 3496. 1396cm -1 The N-H bond vibration absorption peak and the C-N vibration absorption peak in-CONH are respectively 2954cm -1 The characteristic peak of the methine group shows that the PSI has a five-membered ring imide unit structure.
Whereas for PASP- (IA-AM-SAS), 3424cm -1 Is the N-H telescopic vibration absorption peak of amide group, 2940cm -1 Is a stretching vibration absorption peak of methylene, 1666cm -1 The peak at the position is the absorption peak of C=O in carboxyl, 1594cm -1 The strong peak at the position is the absorption peak of C=O in the amide group, 1402cm -1 The peak intensity was increased over PSI as a C-N bending vibration peak in the amide, indicating successful PSI ring opening. 1197cm -1 Is an asymmetric absorption peak of sulfonic acid group S=O bond, 1045cm -1 Is the symmetrical absorption peak of the sulfonic acid group S=O bond, 780cm -1 Is the expansion vibration peak of the S-O bond, 610cm -1 Is C-S telescopic absorption vibration peak of 529cm -1 The peak at this point is the N-H out-of-plane rocking bending vibration peak. These all illustrate PSI ring opening and reaction with IA-AM-SAS, successfully accessing IA-AM-SAS into PSI to form PASP- (IA-AM-SAS) copolymer.
Example 3
A preparation method of a hydrophilic environment-friendly multifunctional scale inhibitor comprises the following steps:
s1, preparing itaconic acid/acrylamide/sodium allylsulfonate terpolymer
Putting itaconic acid and deionized water into a four-neck round bottom flask provided with a thermometer, a condensation reflux device and a stirrer, starting the stirrer to stir uniformly, and heating to 55-60 ℃ until the itaconic acid is completely dissolved, wherein the mass volume ratio of the itaconic acid to the deionized water is 1:3; mixing sodium acrylate and acrylamide with deionized water, stirring and dissolving at normal temperature to obtain sodium acrylate/acrylamide mixed solution, and transferring to a constant pressure funnel. Wherein the mass-volume ratio of the total mass of sodium acrylate/acrylamide to deionized water is 1:2; ammonium persulfate is dissolved in deionized water and is moved to a constant pressure funnel, so that ammonium persulfate solution with the mass concentration of 30% is obtained. Wherein the mole ratio of itaconic acid to acrylamide to sodium acrylate monomer is 1:2:1.5, and ammonium persulfate is 12% of the total mass of itaconic acid to sodium acrylate to acrylamide monomer; and (3) heating the system in the round-bottom flask to 80 ℃, then dropwise adding a sodium acrylate/acrylamide mixed solution, simultaneously dropwise adding an ammonium persulfate solution into the system, heating to 95 ℃ after the dropwise adding is completed for 1h, and reacting for 4h to obtain an itaconic acid/acrylamide/sodium acrylate (IA-AM-SAS) copolymer solution. The copolymer solution was cooled and weighed, and then unreacted monomers were removed through a 2000Da dialysis membrane, and freeze-dried for 48 hours to obtain a purified polymer product (IA-AM-SAS). The terpolymer IA-AM-SAS had a number average molecular weight of 5257 as determined by gel permeation chromatography.
S2, preparing PASP- (IA-AM-SAS) copolymer scale inhibitor
Weighing the following components in percentage by mass: 20% of polysuccinimide, 40% of IA-AM-SAS copolymer, the balance of deionized water and sodium hydroxide solution (15%), and the sum of the mass percentages of the components is 100%.
Dissolving IA-AM-SAS in sodium hydroxide solution for standby; taking polysuccinimide in a four-neck flask, and adding deionized water to obtain polysuccinimide suspension. Dropwise adding sodium hydroxide solution of IA-AM-SAS into the polysuccinimide suspension under stirring to react, continuously adjusting the pH value of a reaction system to 9-10 by using NaOH solution in the reaction process, and reacting for 24 hours at 40 ℃; after the reaction was completed, the pH of the mixture was adjusted to 7.+ -. 0.5 with HCl (15%) solution. Adding the obtained neutral mixed solution into four times volume of absolute ethyl alcohol, filtering to separate out sticky pale yellow precipitate, washing with absolute ethyl alcohol for several times to obtain sticky brown yellow paste, and drying in a vacuum drying oven at 60 ℃ to obtain the polyaspartic acid graft copolymer PASP- (IA-AM-SAS). The number average molecular weight of the polymer product was found to be about 17000.
Performance test:
in examples 1 to 3, the method for measuring the scale inhibition rate of calcium carbonate, calcium sulfate and barium sulfate was as follows:
accurately weighing 0.50g of scale inhibitor, dissolving with a small amount of deionized water, transferring into a 250mL volumetric flask, and diluting to scale to obtain a scale inhibitor solution.
Calcium carbonate: 200mL of deionized water is taken in a 250mL volumetric flask, and CaCl prepared in advance is added 2 Solution of Ca 2+ The content is 96.00 mg.mL -1 . Three groups of experiments, 1.25mL, 2.50mL and 3.75mL of scale inhibitor solution are respectively and accurately added, the mixture is kept stand for 10min, and then Na prepared in advance is added while shaking 2 CO 3 Solution of CO 3 2- The content is 150.72 mg.mL -1 . Adding deionized water to dilute the mixture to a scale, putting the mixture into a triangular flask with a grinding mouth, putting the triangular flask into a water bath with the temperature of 50+/-1 ℃ for constant temperature for half an hour, and standing the flask for 16 hours.
Calcium sulfate: 150mL deionized water is taken in a 250mL volumetric flask, and CaCl prepared in advance is added 2 Solution of Ca 2+ The content is 3000 mg.mL -1 . Three groups of experiments, 1.25mL, 2.50mL and 3.75mL of scale inhibitor solution are respectively and accurately added, the mixture is kept stand for 10min, and then Na prepared in advance is added while shaking 2 SO 4 Solution to make SO 4 2- The content is 7335 mg.mL -1 . Adding deionized water to dilute the mixture to a scale, putting the mixture into a triangular flask with a grinding mouth, putting the triangular flask into a water bath with the temperature of 50+/-1 ℃ for constant temperature for half an hour, and standing the flask for 24 hours.
Barium sulfate: 200mL deionized water was taken inAdding pre-configured BaCl into a 250mL volumetric flask 2 Solution of Ba 2+ The content is 2.8 mg.mL -1 . Three groups of experiments, 2.50mL and 3.75mL of scale inhibitor solution are accurately added respectively, the mixture is kept stand for 10min, and then Na prepared in advance is added while shaking 2 SO 4 Solution to make SO 4 2- The content is 2.06 mg.mL -1 . Adding deionized water to dilute the mixture to a scale, putting the mixture into a triangular flask with a grinding mouth, putting the triangular flask into a water bath with the temperature of 50+/-1 ℃ for constant temperature for half an hour, and standing the flask for 24 hours.
After the reaction was completed, the solution was cooled to room temperature and filtered with quantitative filter paper. CaCO is put into 3 、CaSO 4 And BaSO 4 Titration with ethylenediamine tetraacetic acid (EDTA) standard solution, respectively, to determine Ca 2+ And Ba (beta) 2+ Is a concentration of (3). The scale inhibition properties are shown in tables 1, 2 and 3.
From tables 1 to 3, it is understood that the scale inhibitors prepared in examples 1 to 3 have different scale inhibiting efficiencies depending on the monomer ratio and the preparation conditions.
TABLE 1 static test of calcium carbonate
As shown in Table 1, the scale inhibitor provided by the invention has good inhibition performance on calcium carbonate, and can achieve 99.6% scale inhibition efficiency at 30mg/L.
TABLE 2 static test of calcium sulfate
As shown in Table 2, the scale inhibitor provided by the invention has good inhibition performance on calcium sulfate, overcomes the defect of the IA-AM-SAS ternary polymer on the scale inhibition performance of the calcium sulfate, and can achieve the scale inhibition efficiency of 95.6% by using 30mg/L of the scale inhibitor.
TABLE 3 static test of barium sulfate
As shown in Table 3, the scale inhibitor provided by the invention also has good inhibition performance on barium sulfate, and the scale inhibition efficiency can reach 90.2% by using 30mg/L of the scale inhibitor.
In conclusion, the scale inhibitor provided by the invention not only does not contain phosphorus and meets the requirements of environmental protection and degradability, but also can inhibit CaCO in water body 3 、CaSO 4 、BaSO 4 Can be applied to complex water systems, and has broad spectrum.
It should be noted that, the foregoing embodiments all belong to the same inventive concept, and the descriptions of the embodiments have emphasis, and where the descriptions of the individual embodiments are not exhaustive, reference may be made to the descriptions of the other embodiments.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The hydrophilic environment-friendly multifunctional scale inhibitor is characterized in that the scale inhibitor is a composite copolymer formed by grafting polysuccinimide and a terpolymer; wherein the terpolymer is itaconic acid/acrylamide/sodium allylsulfonate copolymer, and the mass ratio of polysuccinimide to the terpolymer is (1-2): (2-4).
2. The hydrophilic environmental protection type multifunctional scale inhibitor according to claim 1, wherein the number average molecular weight of the composite copolymer is 15000 to 19000.
3. The hydrophilic environmental protection type multifunctional scale inhibitor according to claim 1, wherein the terpolymer is a polymerization product of monomeric itaconic acid, monomeric acrylamide and monomeric sodium allylsulfonate; the molar ratio of the monomer itaconic acid to the monomer acrylamide to the monomer sodium allylsulfonate is (0.5-1): 2: (1-1.5).
4. A method for preparing a hydrophilic environmental-friendly multifunctional scale inhibitor according to any one of claims 1 to 3, comprising the steps of:
s1, mixing polysuccinimide and a terpolymer, adding an alkali solution to control the pH value to be 9-10, and carrying out grafting reaction under the heating condition;
s2, after the reaction is finished, regulating the pH value to be neutral, and obtaining the hydrophilic environment-friendly multifunctional scale inhibitor.
5. The method for preparing a hydrophilic environmental-friendly multifunctional scale inhibitor according to claim 4, wherein in the step S1, the method for preparing the terpolymer comprises the following steps:
respectively preparing itaconic acid solution, sodium allylsulfonate/acrylamide mixed solution and initiator solution;
and heating the itaconic acid solution to 75-80 ℃, adding an allyl sodium sulfonate/acrylamide mixed solution and an initiator solution into the itaconic acid solution, and reacting for 2-4 hours at 85-95 ℃ to obtain the terpolymer.
6. The method for preparing a hydrophilic environmental-friendly multifunctional scale inhibitor according to claim 4, wherein in the step S1, the usage amount of polysuccinimide is 10-20% by mass, the usage amount of terpolymer is 20-40% by mass, and the balance is deionized water and alkali solution.
7. The method for preparing a hydrophilic environmental-friendly multifunctional scale inhibitor according to claim 4, wherein in the step S1, the alkali solution comprises sodium hydroxide solution, the reaction temperature is 40-60 ℃, and the reaction time is 8-24 h.
8. The method for preparing the hydrophilic environment-friendly multifunctional scale inhibitor according to claim 4, wherein in the step S2, after the pH is adjusted to be neutral, the product solution is further subjected to solid precipitation by absolute ethyl alcohol, and the hydrophilic environment-friendly multifunctional scale inhibitor is obtained through filtration, washing and vacuum drying.
9. Use of a hydrophilic environmental protection type multifunctional scale inhibitor according to any one of claims 1 to 3 in scale inhibition of water bodies.
10. The use according to claim 9, wherein the hydrophilic environmental protection type multifunctional scale inhibitor is used at a concentration of 10 to 30mg/L.
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