CN116462802B - Environment-friendly scale inhibition dispersing agent and preparation method thereof - Google Patents

Environment-friendly scale inhibition dispersing agent and preparation method thereof Download PDF

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CN116462802B
CN116462802B CN202310720433.3A CN202310720433A CN116462802B CN 116462802 B CN116462802 B CN 116462802B CN 202310720433 A CN202310720433 A CN 202310720433A CN 116462802 B CN116462802 B CN 116462802B
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maleic acid
mass
cmc
scale inhibition
mass ratio
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CN116462802A (en
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刘展
闫美芳
李娜
刘振法
张利辉
高玉华
李海花
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Hebei Sangwote Water Treatment Co ltd
Energy Research Institute of Hebei Academy of Sciences
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Hebei Sangwote Water Treatment Co ltd
Energy Research Institute of Hebei Academy of Sciences
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The invention relates to a green environment-friendly scale inhibition and dispersion agent and a preparation method thereof, wherein the environment-friendly scale inhibition and dispersion agent is prepared by copolymerizing sodium carboxymethyl cellulose, itaconic acid and maleic acid, the mass ratio of the sodium carboxymethyl cellulose, the itaconic acid and the maleic acid is 1:1:2-3, and the sodium carboxymethyl cellulose/itaconic acid/maleic acid polymer provided by the invention has excellent scale inhibition performance and ferric oxide dispersion performance, is low in cost, greatly promotes polymerization of monomers by an initiator and a chain transfer agent, is simple to prepare, can greatly reduce industrial cost, and reduces treatment cost of industrial circulating water.

Description

Environment-friendly scale inhibition dispersing agent and preparation method thereof
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an environment-friendly scale inhibition dispersing agent and a preparation method thereof.
Background
Currently, research on environmental-friendly water treatment agents at home and abroad is mainly performed on Polyaspartic Acid (PASP) and polyepoxysuccinic acid (PESA). PASP has no phosphorus, no toxicity, biodegradability, chelating function and scale inhibiting effect, but PASP molecules contain nitrogen element, so that water eutrophication is easy to cause after long-term use, and water environment is damaged. The PESA has the characteristics of no phosphorus, no nitrogen and biodegradability, has double functions of scale and corrosion inhibition, and is an environment-friendly scale inhibitor with great development prospect. However, the PESA has little effect on calcium phosphate and iron oxide dispersion due to the main carboxyl functional group in the molecular structure, and the application is greatly limited, and the usage amount is large when the PESA is applied to water with high hardness and high alkalinity. Based on the above drawbacks, there is a need to find new water treatment agents.
Sodium carboxymethyl cellulose (CMC-Na for short) is the most widely used cellulose type in the world today. Is a cellulose derivative having a glucose polymerization degree of 100 to 2000 and has a relative molecular mass of 242.16. White fibrous or granular powder. Used as a thickener in the food industry, as a pharmaceutical carrier in the pharmaceutical industry, as a binder, anti-redeposition agent in the daily chemical industry. Protective colloids used as sizing agents and printing pastes in the printing and dyeing industry, and the like. Can be used as the component of oil extraction fracturing fluid in petrochemical industry.
The subject team starts to research on the use of sodium carboxymethyl cellulose for polymerization of scale inhibition dispersing agents in 2020, and declares Chinese patent CN113651436A, and discloses a technical scheme of copolymerization of sodium carboxymethyl cellulose and itaconic acid, which has good scale inhibition performance and ferric oxide dispersion performance, and can not pollute the water environment after long-term use. Although some findings are made, the study on sodium carboxymethyl cellulose has been continued, and attempts have been made to find scale inhibition dispersants with more ideal properties.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provide an environment-friendly scale inhibition dispersing agent with excellent performance, and simultaneously provide a preparation method and scale inhibition application thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme:
in order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
subject 1
The invention provides an environment-friendly scale inhibition and dispersion agent which is prepared by copolymerizing sodium carboxymethyl cellulose, itaconic acid and maleic acid, wherein the mass ratio of the sodium carboxymethyl cellulose to the itaconic acid to the maleic acid is 1:1:2-3.
As some preferred embodiments of the present invention, the mass ratio of sodium carboxymethyl cellulose, itaconic acid and maleic acid is 1:1:2 or 1:1:3.
Subject matter II
The invention provides a preparation method of an environment-friendly scale inhibition dispersing agent, which is characterized by comprising the following steps:
s1, adding sodium carboxymethylcellulose into distilled water, stirring and dissolving, introducing nitrogen, and heating to 80-90 ℃; sequentially adding isopropanol and ammonium ceric nitrate, stirring for a period of time, dropwise adding a maleic acid aqueous solution, and polymerizing at constant temperature for a period of time after the dropwise adding is finished;
s2, sequentially adding itaconic acid and maleic acid, introducing nitrogen, adding isopropanol and ammonium cerium nitrate, polymerizing for a period of time, and cooling to room temperature to obtain a brown yellow transparent liquid, namely a polymer aqueous solution;
the mass ratio of the maleic acid added in the step S1 to the maleic acid added in the step S2 is 1:2-2:1.
As some preferred embodiments of the invention, the addition amount of the ceric ammonium nitrate in the step S1 is 5-10% of the total mass of the S1 raw material; the addition amount of the ammonium cerium nitrate in the step S2 is 5-10% of the total mass of the S2 raw material.
As some preferred embodiments of the invention, the addition amount of the isopropanol in the step S1 is 10-15% of the total mass of the S1 raw material; and in the step S2, the addition amount of the isopropanol is 10-15% of the total mass of the S2 raw material.
As some preferred embodiments of the present invention, step S1 is to add sodium carboxymethyl cellulose into distilled water of 10 times mass, stir and dissolve, and the mass percentage of the maleic acid aqueous solution in step S1 is 10%.
As some preferred embodiments of the present invention, the polymerization time in the step S1 is 1h, and the polymerization time in the step S2 is 3-5 h.
As some preferred embodiments of the present invention, the dropping time of the maleic acid in the step S1 is 1h.
Subject III
The invention also provides application of the scale inhibition and dispersion agent in the technical subject one as a water treatment agent in industrial circulating cooling water.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
1. the sodium carboxymethyl cellulose/itaconic acid/maleic acid polymer (CMC-Na/IA/MA) provided by the invention has excellent scale inhibition performance and ferric oxide dispersion performance.
2. The CMC-Na/IA/MA ternary polymer provided by the invention has the advantages that the scale inhibition performance and the dispersion performance are obviously improved through monomer selection and proportion adjustment, and the CMC-Na/IA/MA ternary polymer has a synergistic effect.
3. The CMC-Na/IA/MA ternary polymer provided by the invention has low cost, the initiator and the chain transfer agent greatly promote the polymerization of monomers, the preparation method has high polymerization degree, the industrial cost can be greatly reduced, and the treatment cost of industrial circulating water is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
Example 1
The environment-friendly scale inhibition and dispersion agent is prepared by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 10% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, sequentially adding isopropanol which is 10 percent of the total mass of IA and MA in the S2 step and ammonium cerium nitrate with the mass ratio of 5 percent, introducing nitrogen, continuously preserving heat for reaction for 3 hours at 90 ℃, and cooling to room temperature to obtain a brown yellow transparent liquid, namely the polymer (CMC-Na/IA/MA) aqueous solution.
Example 2
The environment-friendly scale inhibition and dispersion agent is prepared by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:2, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 85 ℃ in a water bath, sequentially adding isopropanol with the mass 15% of the total mass of the raw materials in S1 and cerium ammonium nitrate with the mass 8%, introducing nitrogen, stirring for 15min, dropwise adding 10% of MA aqueous solution into a reaction system by adopting a syringe pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 85℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, then sequentially adding isopropanol which is 15 percent of the total mass of IA and MA in S2 and ammonium cerium nitrate with the mass ratio of 8 percent, introducing nitrogen, continuously preserving heat for reaction for 4 hours at the temperature of 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid, namely the polymer (CMC-Na/IA/MA) aqueous solution.
Example 3
The environment-friendly scale inhibition and dispersion agent is prepared by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:2, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 80 ℃ in a water bath, sequentially adding isopropanol with the mass 12% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 80℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, sequentially adding isopropanol accounting for 12% of the total mass of IA and MA in S2 and 10% of cerous ammonium nitrate, introducing nitrogen, carrying out heat preservation reaction on the solution at 80 ℃ for 4 hours, and cooling to room temperature to obtain a brown yellow transparent liquid, namely a polymer (CMC-Na/IA/MA) aqueous solution.
Example 4
The environment-friendly scale inhibition and dispersion agent is prepared by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 80 ℃ in a water bath, sequentially adding isopropanol with the mass 15% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min, and setting dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 80℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:2 into an S1 system at the same time, sequentially adding isopropanol which is 15 percent of the total mass of IA and MA in S2 and ammonium cerium nitrate with the mass ratio of 10 percent, introducing nitrogen, carrying out heat preservation reaction on the solution at 80 ℃ for 5 hours, and cooling to room temperature to obtain brown yellow transparent liquid, namely the polymer (CMC-Na/IA/MA) aqueous solution.
Example 5
The environment-friendly scale inhibition and dispersion agent is prepared by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 12% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, sequentially adding isopropanol accounting for 12% of the total mass of IA and MA in S2 and cerium ammonium nitrate accounting for 5%, introducing nitrogen, continuously preserving heat for reaction for 3 hours at 90 ℃, and cooling to room temperature to obtain a brown yellow transparent liquid, namely a polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 1
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
S1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 5% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, then sequentially adding isopropanol which is 5 percent of the total mass of IA and MA in S2 and cerium ammonium nitrate with the mass ratio of 5 percent, introducing nitrogen, continuously preserving heat for reaction for 3 hours at 90 ℃, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 2
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:3, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 80 ℃ in a water bath, sequentially adding isopropanol with the mass 15% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min, and setting dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 80℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: and (3) adding the IA with the same mass as CMC-Na into the S1 system, sequentially adding the isopropanol with the mass of 15% and the cerium ammonium nitrate with the mass of 10% which are equivalent to the IA in the S2, introducing nitrogen, continuously preserving the heat of the solution at 80 ℃ for reaction for 5 hours, and cooling to room temperature to obtain transparent liquid, namely the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 3
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:2, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 70 ℃ in a water bath, sequentially adding isopropanol with the mass 15% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 70℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA with the mass ratio of CMC-Na to S1 at the same time, sequentially adding isopropanol which is 15% of the total mass of IA and MA in S2 and ammonium cerium nitrate which is 8%, introducing nitrogen, continuously preserving heat for reaction for 4 hours at 70 ℃, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 4
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 10% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, then sequentially adding isopropanol which is 10 percent of the total mass of IA and MA in S2 and cerium ammonium nitrate with the mass ratio of 5 percent, introducing nitrogen, continuously preserving heat for reaction for 1h at 90 ℃, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 5
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:2, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 80 ℃ in a water bath, sequentially adding isopropanol with the mass 12% of the total mass of the raw materials in S1 and cerium ammonium nitrate with the mass 10%, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting a syringe pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 80℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, sequentially adding isopropanol accounting for 12% of the total mass of IA and MA in S2 and 10% of ammonium cerium nitrate, continuously preserving heat at 80 ℃ for reaction for 4 hours, and cooling to room temperature to obtain transparent liquid, namely a polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 6
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 80 ℃ in a water bath, sequentially adding isopropanol with the mass 15% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 80℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:2 into an S1 system simultaneously, then sequentially adding isopropanol which is 15 percent of the total mass of IA and MA in S2 and ceric ammonium nitrate with the mass ratio of 2 percent, introducing nitrogen, continuously preserving heat for reaction for 5 hours at 80 ℃, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 7
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 12% of the total mass of the raw materials in S1 and ammonium persulfate with the mass 5%, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system by adopting a syringe pump after 15min, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system at the same time, sequentially adding isopropanol which is 12 percent of the total mass of IA and MA in S2 and ammonium persulfate which is 5 percent of the total mass of IA and MA, introducing nitrogen, continuously preserving heat for reaction for 3 hours at 90 ℃, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 8
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and acrylamide, wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the acrylamide is 1:1:3.
The preparation method comprises the following steps:
s1: CMC-Na and acrylamide with the mass ratio of 1:2 are weighed according to the amount, CMC-Na is added into a flask, deionized water with the mass 10 times that of CMC-Na is added into a system, the mixture is stirred and dissolved at normal temperature, the water bath of the system is heated to 80 ℃, isopropanol with the mass 12% of the total mass of the raw materials in S1 and cerium ammonium nitrate with the mass 10% of the total mass of the raw materials in S1 are sequentially added, nitrogen is introduced, 10% of acrylamide aqueous solution is dripped into a reaction system by adopting an injection pump after 15min, and the dripping speed is set, so that the dripping is completed within 1h. The solution was reacted at 80℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: and (3) simultaneously adding IA and acrylamide in a mass ratio of 1:1 into an S1 system, sequentially adding isopropanol accounting for 12% of the total mass of the IA and the acrylamide in S2 and 10% of ceric ammonium nitrate, introducing nitrogen, continuously preserving heat for reaction for 2 hours at 80 ℃, and cooling to room temperature to obtain transparent liquid, namely the polymer aqueous solution.
Comparative example 9
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:3.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:2, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 85 ℃ in a water bath, sequentially adding isopropanol with the mass 15% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 85℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA and MA with the mass ratio of 1:1 into an S1 system simultaneously, then sequentially adding isopropanol which is 15 percent of the total mass of IA and MA in S2 and ammonium cerium nitrate with the mass ratio of 8 percent, introducing nitrogen, continuously preserving heat for reaction for 2 hours at the temperature of 85 ℃, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 10
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:1.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 10% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA equivalent to CMC-Na into S1 system, adding 10% isopropyl alcohol and 5% ceric ammonium nitrate, introducing nitrogen, keeping the solution at 90 deg.C for reaction for 3h, cooling to room temperature to obtain transparent liquid, which is polymer (CMC-Na/IA/MA) water solution.
Comparative example 11
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:2:1.
The preparation method comprises the following steps:
s1: weighing CMC-Na and MA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 10% of the total mass of the raw materials in S1 and cerium ammonium nitrate, introducing nitrogen, dropwise adding 10% of MA aqueous solution into a reaction system after 15min by adopting an injection pump, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding IA which is 2 times of CMC-Na into S1 system, adding 10% isopropyl alcohol and 5% ceric ammonium nitrate into the system, charging nitrogen, keeping the solution at 90 ℃ for reaction for 3 hours, cooling to room temperature, obtaining transparent liquid, namely polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 12
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
The preparation method comprises the following steps:
weighing CMC-Na, IA and MA with the mass ratio of 1:1:2, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in water bath, adding IA and MA, sequentially adding isopropanol with the mass 12% of the total mass of the raw materials in S1 and 5% of ceric ammonium nitrate, introducing nitrogen, carrying out heat preservation reaction on the solution at 90 ℃ for 3 hours, and cooling to room temperature to obtain transparent liquid, namely the polymer (CMC-Na/IA/MA) aqueous solution.
Comparative example 13
A scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose (CMC-Na), itaconic Acid (IA) and Maleic Acid (MA), wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid to the maleic acid is 1:1:2.
The preparation method comprises the following steps:
s1: weighing CMC-Na and IA with the mass ratio of 1:1, adding CMC-Na into a flask, adding deionized water with the mass 10 times that of CMC-Na into a system, stirring and dissolving at normal temperature, heating the system to 90 ℃ in a water bath, sequentially adding isopropanol with the mass 12% of the total mass of the raw materials in S1 and cerium ammonium nitrate with the mass 5%, introducing nitrogen, beginning to dropwise add 10% of IA aqueous solution into a reaction system by adopting an injection pump after 15min, and setting the dropwise adding speed to finish dropwise adding within 1h. The solution was reacted at 90℃for 1 hour with heat preservation to complete the first stage polymerization.
S2: adding MA which is equivalent to 2 times of CMC-Na mass into an S1 system, sequentially adding isopropyl alcohol which is equivalent to 12% of MA mass and cerium ammonium nitrate which is equivalent to 5% of MA mass, introducing nitrogen, continuously preserving heat at 90 ℃ for reaction for 4 hours, and cooling to room temperature to obtain transparent liquid which is the polymer (CMC-Na/IA/MA) aqueous solution.
Test examples
The polymers obtained in examples and comparative examples were evaluated for scale inhibition property and dispersibility, respectively.
(1) Determination of the Scale inhibition Properties of calcium carbonate
The experiment uses formulated water and non-evaporative concentration to determine CaCO resistance 3 Performance, ca 2+ HCO (hydrogen cyanide) and HCO (hydrogen cyanide) 3 - The concentration is 600mg/L and 1200mg/L (CaCO) 3 Metering), adding a certain amount of water treatment agent into 500ml of water sample, putting the water sample into a constant-temperature water bath kettle with the temperature of 80 ℃, and standing for 10 hours at constant temperature. Then cooling to room temperature, collecting supernatant, and measuring Ca therein by EDTA method 2+ And (3) performing a blank test on the concentration, and calculating the scale inhibition rate according to a formula (1).
(1)
Wherein:C 0 to heat Ca in the solution after the experiment without adding the scale inhibition and dispersing agent 2+ Content, mg/L;
C 1 to heat Ca in the solution after the experiment when adding the scale inhibition and dispersing agent 2+ Content, mg/L;
C 2 ca for experimental water without adding scale inhibition and dispersing agent and heating 2+ Content, mg/L.
(2) Determination of calcium phosphate scale inhibition Properties
The experiment adopts the preparation water and uses non-evaporation concentration to measure the Ca resistance 3 (PO 4 ) 2 Performance, ca 2+ The concentration is 250mg/L (CaCO) 3 Meter), PO 4 3- A certain amount of water treatment agent is added into 500ml of water sample with the concentration of 150mg/L, the pH value of the solution is 9 (regulated by sodium tetraborate), and the water sample is put into a constant-temperature water bath kettle with the temperature of 80 ℃ and kept stand for 10 hours at constant temperature. Cooling to room temperature, collecting supernatant, and measuring PO therein with visible spectrophotometer 4 3- Content, blank experiments were performed at the same time. The calculation of the scale inhibition rate is shown in a formula (2).
(2)
Wherein: c (C) 0 To heat PO in the post-test solution without adding scale inhibiting dispersant 4 3- Content, mg/L;
C 1 to heat PO in the post-experiment solution when adding the scale inhibiting dispersant 4 3- Content, mg/L;
C 2 for PO without adding scale inhibition dispersing agent and without heating 4 3- Content, mg/L.
(3) Dispersing Fe 2 O 3 Measurement of Properties
Preparing the following experimental water sample, ca, by using analytically pure anhydrous calcium chloride and ferrous ammonium sulfate as reagents 2+ The concentration is 150mg/L (CaCO) 3 Meter), fe 2+ Adding a certain amount of water treatment agent into 500ml water sample with concentration of L0mg/L, adjusting pH to 9 (regulated by sodium tetraborate), stirring for 15min, and adding into water samplePlacing in a constant temperature water bath at 50deg.C for 5h, cooling to room temperature, collecting upper layer solution, measuring light transmittance T with a visible spectrophotometer at 450nm, and dispersing with smaller light transmittance (with distilled water as reference and 100%).
The measurement results are shown in Table 1.
TABLE 1
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1. The preparation method of the green environment-friendly scale inhibition dispersing agent is characterized in that the green environment-friendly scale inhibition dispersing agent is prepared by copolymerizing sodium carboxymethyl cellulose, itaconic acid and maleic acid, and the mass ratio of the sodium carboxymethyl cellulose to the itaconic acid to the maleic acid is 1:1:2-3, and specifically comprises the following steps:
s1: adding sodium carboxymethylcellulose into distilled water, stirring and dissolving, introducing nitrogen, and heating to 80-90 ℃; sequentially adding isopropanol and ammonium ceric nitrate, stirring, dropwise adding a maleic acid aqueous solution, and polymerizing for a period of time at constant temperature after the dropwise adding is finished;
s2: sequentially adding itaconic acid and maleic acid, introducing nitrogen, adding isopropanol and ammonium cerium nitrate, polymerizing for a period of time, and cooling to room temperature to obtain a brown transparent liquid, namely a polymer aqueous solution;
the mass ratio of the maleic acid added in the step S1 to the maleic acid added in the step S2 is 1:2-2:1;
the addition amount of the ammonium cerium nitrate in the step S1 is 5-10% of the total mass of the S1 raw material;
the polymerization time in the step S1 is 1h, and the polymerization time in the step S2 is 3-5 h;
the addition amount of the isopropanol in the step S1 is 10-15% of the total mass of the S1 raw material;
the addition amount of the ammonium cerium nitrate in the step S2 is 5-10% of the total mass of the S2 raw material;
and in the step S2, the addition amount of the isopropanol is 10-15% of the total mass of the S2 raw material.
2. The preparation method of the environment-friendly scale inhibition and dispersion agent according to claim 1, wherein in the step S1, sodium carboxymethyl cellulose is added into distilled water with the mass of 10 times and stirred for dissolution, and the mass percentage of the maleic acid aqueous solution in the step S1 is 10%.
3. The method for preparing the environment-friendly scale inhibition and dispersion agent according to claim 1, wherein the dripping time of the maleic acid in the step S1 is 1h.
4. The preparation method of the environment-friendly scale inhibition and dispersion agent according to claim 1, wherein the mass ratio of the sodium carboxymethyl cellulose to the itaconic acid to the maleic acid is 1:1:2 or 1:1:3.
5. Use of the green and environment-friendly scale inhibition and dispersion agent prepared by the method according to any one of claims 1-4 as a water treatment agent in industrial circulating cooling water.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728103A (en) * 1970-06-22 1973-04-17 Mo Textilny I Method of removing metal values from solution
JP5901831B1 (en) * 2015-11-20 2016-04-13 伯東株式会社 Method for producing scale inhibitor and method for preventing scale
CN111040077A (en) * 2019-12-31 2020-04-21 广东巴德富新材料有限公司 Modified itaconic acid and maleic acid copolymer, preparation method and application thereof
CN113651436A (en) * 2021-08-25 2021-11-16 河北省科学院能源研究所 Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080020961A1 (en) * 2006-07-21 2008-01-24 Rodrigues Klin A Low Molecular Weight Graft Copolymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728103A (en) * 1970-06-22 1973-04-17 Mo Textilny I Method of removing metal values from solution
JP5901831B1 (en) * 2015-11-20 2016-04-13 伯東株式会社 Method for producing scale inhibitor and method for preventing scale
CN111040077A (en) * 2019-12-31 2020-04-21 广东巴德富新材料有限公司 Modified itaconic acid and maleic acid copolymer, preparation method and application thereof
CN113651436A (en) * 2021-08-25 2021-11-16 河北省科学院能源研究所 Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Improving Application Performance of in situ Polymerization and Crosslinking System of Maleic Acid/Itaconic Acid for Cotton Fabric;Zhangmi Huang;《Fibers and Polymers》;281-288 *

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