Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof

文档序号：1840910 发布日期：2021-11-16 浏览：17次中文

阅读说明：本技术 一种无磷非氮型阻垢分散剂及其制备方法和应用 (Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof ) 是由刘展刘振法张利辉闫美芳李海花高玉华于 2021-08-25 设计创作，主要内容包括：本发明涉及一种无磷非氮型阻垢分散剂及其制备方法和应用,所述聚合物由羧甲基纤维素钠和衣康酸进行共聚所得,所述羧甲基纤维素钠和衣康酸的质量比为1:2,本发明以羧甲基纤维素钠和衣康酸为单体,通过硫酸铵作为引发剂,异丙醇作为链转移剂,聚合而成,得到的聚合物具有良好的阻垢性能和分散氧化铁的性能。(The invention relates to a non-phosphorus non-nitrogen type scale inhibition and dispersion agent and a preparation method and application thereof, wherein a polymer is obtained by copolymerizing sodium carboxymethylcellulose and itaconic acid, the mass ratio of the sodium carboxymethylcellulose to the itaconic acid is 1:2, the polymer is polymerized by taking the sodium carboxymethylcellulose and the itaconic acid as monomers, taking ammonium sulfate as an initiator and taking isopropanol as a chain transfer agent, and the obtained polymer has good scale inhibition performance and ferric oxide dispersion performance.)

1. The non-phosphorus non-nitrogen scale inhibition and dispersion agent is characterized by being prepared by copolymerizing sodium carboxymethylcellulose and itaconic acid, wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid is 1:1.5-1: 2.5.

2. The phosphorus-free non-nitrogen scale inhibiting and dispersing agent of claim 1, wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid is 1:2.

3. The preparation method of the phosphorus-free non-nitrogen scale inhibiting and dispersing agent of claim 1, which is characterized by comprising the following steps:

(1) adding sodium carboxymethylcellulose into distilled water, stirring for dissolving, introducing nitrogen, and heating to 75-90 ℃;

(2) adding isopropanol, adding ammonium persulfate, stirring for a period of time, dropwise adding itaconic acid for 0.5-1.5h, polymerizing at constant temperature for a period of time after the dropwise adding is finished, and cooling to room temperature to obtain brown yellow transparent liquid, namely a polymer (CMC/IA) aqueous solution.

4. The preparation method of the phosphorus-free non-nitrogen scale inhibiting and dispersing agent according to claim 3, wherein the addition amount of ammonium persulfate in the step (2) is 5-15% of the total mass of the raw materials.

5. The preparation method of the phosphorus-free non-nitrogen scale inhibiting and dispersing agent according to claim 3, wherein the addition amount of the isopropanol in the step (2) is 5-12% of the total mass of the raw materials.

6. The preparation method of the phosphorus-free non-nitrogen scale inhibiting and dispersing agent according to claim 3, wherein the polymerization time in the step (2) is 3-5 hours.

7. The preparation method of the phosphorus-free non-nitrogen scale inhibiting and dispersing agent according to claim 3, wherein the dropping time in the step (2) is 1 hour, and the polymerization time is 4 hours.

8. The method for preparing the phosphorus-free non-nitrogen scale inhibiting and dispersing agent according to claim 3, wherein the heating temperature in the step (1) is 85 ℃.

9. The use of the phosphorus-free non-nitrogen scale inhibiting and dispersing agent of claim 1 as a water treatment agent in industrial circulating cooling water.

Technical Field

The invention belongs to the technical field of water treatment, and particularly relates to a phosphorus-free non-nitrogen scale inhibition and dispersion agent and a preparation method and application thereof.

Background

With the restriction of phosphorus and nitrogen-containing wastewater discharge and the strategic requirements of sustainable development at home and abroad, the development of environment-friendly scale inhibitors and water treatment processes has become a key research point at home and abroad. At present, the researches on environment-friendly water treatment agents at home and abroad are mainly Polyaspartic Acid (PASP) and polyepoxysuccinic acid (PESA). PASP is phosphorus-free, non-toxic and biodegradable, and has a chelating function and a scale inhibition effect, but the PASP molecules contain nitrogen elements, so that water eutrophication is easily caused after long-term use, and the water environment is damaged. The PESA has the characteristics of no phosphorus, no nitrogen and biodegradability, has double functions of scale inhibition and corrosion inhibition, and is an environment-friendly scale inhibitor with great development prospect. However, since the molecular structure of PESA is mainly carboxyl functional group, it has little effect on calcium phosphate inhibition and iron oxide dispersion, its application is greatly limited, and it is used in a large amount when applied to water with high hardness and high alkalinity. In view of the above-mentioned drawbacks, there is a need to find new water treatment agents.

Sodium carboxymethylcellulose (CMC-Na for short) is the cellulose with the widest application range and the largest dosage in the world at present. The cellulose derivative has a glucose polymerization degree of 100-2000 and a relative molecular mass of 242.16. White fibrous or granular powder. Can be used as thickener in food industry, drug carrier in medical industry, and adhesive and anti-redeposition agent in 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.

At present, chitin and sodium carboxymethylcellulose are reported to be used as functional surface materials, polyacrylonitrile is used as a base membrane supporting layer, epichlorohydrin and glycerol triglycidyl ether are used as cross-linking agents, chitin/sodium carboxymethylcellulose-epichlorohydrin cross-linked and blended composite nanofiltration membrane is prepared, advanced treatment experiments of the nanofiltration membrane on water in textile printing and dyeing wastewater are studied, and results show that the removal rates of dissolved total phosphorus, aniline and CODCr can respectively reach 79.59%, 29.24% and 88.06%. The CODCr content of the outlet water of the nanofiltration membrane is less than or equal to 15 mg.L < -1 >, and reaches the first-level discharge standard according to the ground water environment quality standard GB 3838-88. However, no research and report about the application of the sodium carboxymethylcellulose and the itaconic acid in the scale inhibition water treatment agent are available at present.

Disclosure of Invention

The invention aims to overcome the defects in the prior art, provides a phosphorus-free non-nitrogen scale inhibition and dispersion agent, and also provides a preparation method and scale inhibition application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

subject of the technology 1

The invention provides a non-phosphorus non-nitrogen scale inhibition and dispersion agent, which is obtained by copolymerizing sodium carboxymethylcellulose and itaconic acid, wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid is 1:1.5-1: 2.5.

As some preferred embodiments of the present invention, the mass ratio of the sodium carboxymethylcellulose to the itaconic acid is 1:2.

Subject matter two

The invention provides a preparation method of a phosphorus-free non-nitrogen scale inhibition and dispersion agent, which comprises the following steps:

(1) adding sodium carboxymethylcellulose into distilled water, stirring and dissolving, introducing nitrogen, and heating to 75-90 ℃;

(2) adding isopropanol, then adding ammonium persulfate, stirring for a period of time, dropwise adding itaconic acid for 0.5-1.5h, after finishing dropwise adding, polymerizing at constant temperature for a period of time, and cooling to room temperature to obtain a brown yellow transparent liquid, namely a polymer (CMC/IA) aqueous solution.

As some preferred embodiments of the invention, the adding amount of the ammonium persulfate in the step (2) is 4-8% of the total mass of the raw materials.

As some preferred embodiments of the invention, the adding amount of the isopropanol in the step (2) is 8-12% of the total mass of the raw materials.

As some preferred embodiments of the present invention, the polymerization time in the step (2) is 3 to 5 hours.

As some preferred embodiments of the present invention, the dropping time in the step (2) is 1h, and the polymerization time is 4 h.

As some preferred embodiments of the present invention, the heating temperature in the step (1) is 85 ℃.

Subject three

The invention also provides the application of the polymer as a water treatment agent in industrial circulating cooling water.

As some preferred embodiments of the present invention, the water treatment agent is a scale inhibitor or a dispersant.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

1. the sodium carboxymethylcellulose and itaconic acid polymer provided by the invention has good scale inhibition performance and ferric oxide dispersion performance.

2. The sodium carboxymethylcellulose and the itaconic acid polymer provided by the invention are phosphorus-free and nitrogen-free, and can not cause pollution to water environment after long-term use.

3. The sodium carboxymethyl cellulose and itaconic acid polymer provided by the invention have low cost, can greatly reduce the industrial cost, and reduce the treatment cost of industrial circulating water.

4. The preparation method provided by the invention has the advantages of mild conditions and high polymerization conversion rate, and is beneficial to industrial large-scale production.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail and fully with reference to the following embodiments.

Example 1

A non-phosphorus non-nitrogen scale inhibition and dispersion agent is obtained by copolymerizing sodium carboxymethylcellulose and itaconic acid, wherein the mass ratio of the sodium carboxymethylcellulose to the itaconic acid is 1:2.

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 5% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 4h at 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid which is the aqueous solution of the polymer (CMC/IA).

Example 2

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 8% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 5h at 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid which is the aqueous solution of the polymer (CMC/IA).

Example 3

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 12% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 10min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 3h at 75 ℃, and cooling to room temperature to obtain brown yellow transparent liquid which is the aqueous solution of the polymer (CMC/IA).

Example 4

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol accounting for 12% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate accounting for 8% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 4h at 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid, namely a polymer (CMC/IA) aqueous solution.

Example 5

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol accounting for 12% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate accounting for 15% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 5h at 90 ℃, and cooling to room temperature to obtain brown yellow transparent liquid, namely a polymer (CMC/IA) aqueous solution.

Comparative example 1

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium ceric nitrate which is 5% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system, wherein the dropwise adding time is 1h, continuing to perform heat preservation reaction at 85 ℃ for 4h, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 2

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium ceric nitrate which is 5% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system, wherein the dropwise adding time is 1h, continuing to perform heat preservation reaction at 85 ℃ for 2h, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 3

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 65 ℃ in a water bath, adding isopropanol which is 15% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium ceric nitrate which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system, wherein the dropwise adding time is 1h, continuing to perform heat preservation reaction at 65 ℃ for 4h, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 4

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 5% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 2% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 4h at 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 5

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 7% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for 15min, dropwise adding the itaconic acid into the reaction system for 1h, continuing to perform heat preservation reaction for 4h at 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 6

A non-phosphorus non-nitrogen scale inhibition and dispersion agent is prepared by the following method:

weighing sodium carboxymethylcellulose, adding into a flask, adding deionized water to normal temperature, stirring and dissolving. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10 percent of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 10 percent of the total mass of the sodium carboxymethylcellulose and the itaconic acid, continuing the heat preservation reaction for 4 hours at the temperature of 85 ℃, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 7

A non-phosphorus non-nitrogen scale inhibition and dispersion agent is prepared by the following method:

weighing itaconic acid according to the weight, adding the itaconic acid into a flask, adding deionized water to the temperature of normal temperature, stirring and dissolving. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10 percent of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 15 percent of the total mass of the sodium carboxymethylcellulose and the itaconic acid, continuing to perform heat preservation reaction for 4 hours at the temperature of 85 ℃, and cooling to room temperature to obtain colorless transparent liquid.

Comparative example 8

The mixture is prepared by mixing sodium carboxymethylcellulose and itaconic acid according to the mass ratio of 1:2.

Comparative example 9

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 5% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for a period of time, dropwise adding the itaconic acid into the reaction system, wherein the dropwise adding time is 0.5h, continuing to perform heat preservation reaction at 85 ℃ for 6h, and cooling to room temperature to obtain brown yellow transparent liquid.

Comparative example 10

It is prepared by the following method:

weighing sodium carboxymethylcellulose according to the weight, adding the sodium carboxymethylcellulose into a flask, adding deionized water to the flask, stirring the mixture to dissolve the sodium carboxymethylcellulose at normal temperature. Introducing nitrogen, heating to 85 ℃ in a water bath, adding isopropanol which is 10% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, then adding ammonium persulfate which is 5% of the total mass of the sodium carboxymethylcellulose and the itaconic acid, stirring for a period of time, dropwise adding the itaconic acid into the reaction system, wherein the dropwise adding time is 1.5h, continuing to perform heat preservation reaction at 85 ℃ for 2h, and cooling to room temperature to obtain brown yellow transparent liquid.

Test examples

The polymers obtained in examples and comparative examples were evaluated for scale inhibition performance and dispersion performance, respectively.

(1) Determination of calcium carbonate Scale inhibition Properties

The experiment adopts the preparation of water and uses non-evaporative concentration to determine the resistance CaCO₃Property, Ca²⁺And HCO₃ ^-The concentrations are 600mg/L and 1200mg/L (as CaCO)₃Metering), adding a certain amount of water treatment agent into 500ml of water sample, putting the water treatment agent into a water bath kettle with the constant temperature of 80 ℃, and standing for 10 hours at the constant temperature. Cooling to room temperature, collecting supernatant, and measuring Ca content by EDTA method²⁺And (5) carrying out a blank test at the same time. The scale inhibition rate is calculated according to the formula (1).

In the formula: c₀Heating Ca in the solution after the experiment when the scale inhibition dispersant is not added²⁺Content, mg/L;

C₁heating Ca in the solution after the experiment when adding the scale inhibition dispersant²⁺Content, mg/L;

C₂ca of experimental water without adding scale-inhibiting dispersant and heating²⁺Content, mg/L.

(2) Measurement of calcium phosphate Scale inhibition Properties

The experiment adopts the preparation of water and uses non-evaporative concentration to determine the Ca resistance₃(PO₄)₂Property, Ca²⁺The concentration is 250mg/L (as CaCO)₃Meter), PO₄ ^3-The concentration is 150mg/L, a certain amount of water treatment agent is added into 500ml of water sample, the pH value of the solution is 9 (adjusted by sodium tetraborate), and the solution is placed into a water bath kettle with the constant temperature of 80 ℃ and kept stand for 10 hours at the constant temperature. Cooling to room temperature, collecting supernatant, and measuring PO with visible spectrophotometer₄ ^3-And (4) carrying out blank experiments simultaneously. The scale inhibition rate is calculated according to the formula (2).

In the formula: c₀Heating PO in the solution after the experiment when no scale inhibiting dispersant is added₄ ^3-Content, mg/L;

C₁heating PO in the solution after the experiment when adding the scale inhibition dispersant₄ ^3-Content, mg/L;

C₂PO of experimental water without adding scale-inhibiting dispersant and heating₄ ^3-Content, mg/L.

(3) Dispersing Fe₂O₃Determination of Properties

Analytically pure anhydrous calcium chloride and ferrous ammonium sulfate are used as reagents to prepare an experimental water sample Ca²⁺The concentration is 150mg/L (as CaCO)₃Meter), Fe²⁺The concentration is L0mg/L, a certain amount of water treatment agent is added into 500ml of water sample, the pH value of the solution is 9 (adjusted by sodium tetraborate), after strong stirring for 15min, the solution is placed in a constant temperature water bath at 50 ℃ for 5h, after cooling to room temperature, the upper layer solution is taken, a visible spectrophotometer is used for measuring the light transmittance T of the solution under 450nm, the smaller the light transmittance is, the better the dispersion effect is (the light transmittance is 100 percent by taking distilled water as a reference).

The results are shown in Table 1.

TABLE 1

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

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Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof

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