A green and environmentally friendly scale inhibitor

Abstract

The present invention relates to a green environmentally friendly scale inhibitor, which is characterized in that the raw material components of the scale inhibitor are respectively as follows: 25% to 30% of betaine aqueous solution, 10% to 20% of hydrolyzed polymaleic anhydride, 10% to 15% of polyepoxysuccinic acid (PESA), 15% to 20% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% to 35% of deionized water in percentage by mass. The scale inhibitor prepared by the present invention has a good inhibitory effect on calcium carbonate scale. It is suitable for water with hardness, and is also a green environmentally friendly scale inhibitor, which can avoid pollution to the environment from the source and meet the requirements of green development of water treatment agents.

Description

Technical Field

[0001] The invention relates to the field of water treatment agents, and in particular to a green and environmentally friendly scale inhibitor. Background Art

[0002] Industrial water is the "blood" of industrial system operation, of which industrial cooling water accounts for more than 70% of industrial water. Scaling is a common problem in the working process of circulating cooling water. Inorganic scale is mostly deposited or adhered to the pipe wall in the form of precipitation. Its production will hinder the normal heat transfer of the pipe, and even damage the equipment in severe cases. Scale inhibitors are widely used due to their convenient dosing and significant effects. They are the most common and effective method for scaling control. The main types of scale inhibitors are phosphonic acid scale inhibitors, carboxylic acid scale inhibitors, natural polymer scale inhibitors, natural modified polymer scale inhibitors and carbon nanoscale inhibitors. In the context of carbon peak, carbon neutrality and green development, environmental protection and low carbon have become the mainstream of green development today. More and more scholars have turned their attention to the preparation and synthesis of natural polymer scale inhibitors and their modifications. Natural green scale inhibitors are mainly plant extracts and their synthetic products. Compared with traditional synthetic scale inhibitors, they have the advantages of being renewable, easy to obtain, low production cost and environmentally friendly. The rich functional groups (including hydroxyl, carboxyl and amino) give it good chelating and dispersing effects, and it has good scale inhibition performance within a certain concentration and temperature range.

[0003] Yu Fu et al. (J. Agric. Food Chem. 2020, 68, 42, 11595–11611) purified betalain from beetroot. Betalain can prevent and treat cardiovascular diseases, showing its great potential as a functional natural pigment. However, due to its good water solubility and the presence of three carboxylic acid groups and two hydroxyl groups in its structure, it has the potential to be a scale inhibitor. These groups can play an important role in inhibiting the growth of sulfate and carbonate crystals. Therefore, it is of far-reaching significance to develop environmentally friendly scale inhibitors around renewable and easily available betalain. Summary of the invention

[0004] The purpose of the present invention is to improve the deficiencies of the prior art and provide a green and environmentally friendly scale inhibitor.

[0005] The technical solution of the present invention is: a green and environmentally friendly scale inhibitor, characterized in that the raw material components of the scale inhibitor are respectively as follows in mass percentage: 25% to 30% of betaine aqueous solution, 10% to 20% of hydrolyzed polymaleic anhydride, 10% to 15% of polyepoxysuccinic acid (PESA), 15% to 20% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% to 35% of deionized water.

[0006] Preferably, the mass ratio of betalain in the betalain aqueous solution to water is 0.2-0.32 g / L; and the betalain is extracted from pitaya peel.

[0007] Preferably, betalain is extracted by the following method, and the specific steps are as follows: wash the pitaya to remove the pulp, cut the peel into small pieces, put it into a material machine and stir it evenly to obtain pitaya peel pulp, pour the stirred pitaya peel pulp into a container, and add deionized water; the volume ratio of the peel pulp to water is 1: (20-21); react in a constant temperature water bath; centrifuge, use a microporous filter membrane to filter out pectin to obtain a crude extract, and the concentration of the crude extract is 4.2-4.8 mg / mL; take a macroporous resin, a crude extract and ethanol and oscillate and analyze on a shaker at a flow rate of 1.5-1.8 mL / min, then put the betalain into a dialysis bag for dialysis, and the dialysis time is 12-13.5 hours; evaporate and remove ethanol by a rotary evaporator, and freeze-dry in a freeze dryer to obtain betalain.

[0008] Preferably, the temperature of the constant temperature water bath is 40-42° C., the reaction time is 1.4-1.5 h, the speed of the centrifuge is 8000-10000 r / min, and the centrifuge time is 15-20 min.

[0009] Preferably, the pore size of the microporous filter membrane is 0.22-0.25 μm; the mass volume ratio of the macroporous resin to the crude extract is 2.5-5 g / mL, and the volume ratio of the crude extract to ethanol is 1:(3-5).

[0010] Preferably, the molecular weight of the dialysis bag is 3500-3600; the macroporous resin is AB-8.

[0011] Preferably, the polyepoxysuccinic acid is purchased from MacLean Reagent Company with a relative molecular weight of 600-800; the hydrolyzed polymaleic anhydride is purchased from MacLean Reagent Company with a relative molecular weight of 500-800; and the acrylic acid-hydroxypropyl acrylate-AMPS terpolymer is purchased from Aladdin Company.

[0012] The present invention provides a method for preparing the green environmentally friendly scale inhibitor, and the specific steps are as follows: adding the following raw material components by mass percentage into a reaction kettle: 25% to 30% of a homemade betalain solution, 10% to 20% of hydrolyzed polymaleic anhydride, 10% to 15% of polyepoxysuccinic acid (PESA), 15% to 20% of acrylic acid-hydroxypropyl acrylate-AMPS ternary polymer, and 30% to 35% of deionized water; mixing and stirring for 30 to 40 minutes to obtain the scale inhibitor.

[0013] Beneficial effects:

[0014] The present invention obtains a green environmentally friendly scale inhibitor by compounding betalain, hydrolyzed maleic anhydride, polyepoxysuccinic acid, and acrylic acid-hydroxypropyl acrylate-AMPS ternary polymer with different mass fractions. The scale inhibitor has carboxyl and hydroxyl functional groups, and can play a good synergistic role after compounding, occupying the main crystal plane of calcium carbonate, inducing lattice distortion, and changing calcium carbonate from calcite to vaterite, thereby playing a good inhibitory effect on calcium carbonate scale. DETAILED DESCRIPTION

[0015] The present invention is described in detail below in conjunction with specific embodiments. The polyepoxysuccinic acid described below was purchased from MacLean Reagent Company, with a relative molecular weight between 600-800; the hydrolyzed polymaleic anhydride was purchased from MacLean Reagent Company, with a relative molecular weight between 500-800; and the acrylic acid-hydroxypropyl acrylate-AMPS terpolymer was purchased from Aladdin Company.

[0016] Example 1: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp. Take the peel pulp volume of 5mL, add the volume of water of 100mL, react in a constant temperature water bath at 40℃ for 1.4h, centrifuge at 8000r / min for 15min, use 0.22μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.2mg / mL; take AB-8 macroporous resin 2.5g, crude extract 1mL, ethanol 6mL, shake and analyze on a shaker at a flow rate of 1.5mL / min, then put betalain into a dialysis bag with a molecular weight of 3500 for dialysis, and the dialysis time is 12h. Ethanol is evaporated and removed by rotary evaporator, and betalain is obtained by freeze drying in a freeze dryer. Betalain is formulated into a 0.2g / L solution.

[0017] The scale inhibitor prepared according to weight percentage is prepared by adding the following raw material components according to weight percentage into the reactor: 25% of homemade betaine solution, 10% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 20% of polyepoxysuccinic acid (relative molecular weight 600), 15% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% of deionized water, and mixing and stirring for 30 minutes to obtain the scale inhibitor.

[0018] Scale inhibition performance test:

[0019] The scale inhibition performance of the scale inhibitor was determined according to the method of "Determination of scale inhibition performance of water treatment agents - calcium carbonate deposition method" GB / T 16632-2019. Place the beaker with the scale inhibitor in a water bath at (80±1)℃ for 8-10h. Dry filter with medium-speed quantitative filter paper while hot. After the filtrate cools, transfer 15mL of the filtrate into a 250mL conical flask, add water to about 80mL, add 5mL of potassium hydroxide solution and about 0.1g of calcium-carboxylic acid indicator. Titrate with disodium ethylenediaminetetraacetic acid standard until the solution changes from purple-red to bright blue, which is the end point. Calculate the mass concentration of calcium ions in the test solution and blank test solution respectively according to formula (1).

[0020] Calcium ions (Ca 2+ ) content is calculated as mass concentration ρ1 according to formula (1):

[0021]

[0022] Where:

[0023] ρ1——Calcium ion (Ca 2+ ) mass concentration, in milligrams per milliliter (mg / mL);

[0024] V1——the volume of disodium ethylenediaminetetraacetic acid standard titration solution consumed in the titration, in milliliters (mL);

[0025] c——The accurate value of the actual concentration of the standard titration solution of disodium ethylenediaminetetraacetate, in moles per liter (mol / L);

[0026] M——Calcium ion (Ca 2+ ) is the numerical value of the molar mass in grams per mole (g / mol) (M = 40.08);

[0027] V——the value of the volume of calcium chloride standard solution, in milliliters (mL) (V=2)

[0028] The scale inhibition performance of the scale inhibitor is expressed in η and the value is expressed in %, which is calculated according to formula (2):

[0029]

[0030] Where:

[0031] ρ2——Calcium ions (Ca 2+ ) is the mass concentration value in milligrams per milliliter (mg / mL);

[0032] ρ1——Calcium ion (Ca) after the blank test solution without water treatment agent added 2+ ) is the mass concentration value in milligrams per milliliter (mg / mL);

[0033] ρ——Calcium ions (Ca 2+ ) is the mass concentration value in milligrams per milliliter (mg / mL);

[0034] The scale inhibition performance test was carried out, and the scale inhibition rate for calcium carbonate was 92.3%;

[0035] Example 2: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp. Take the peel pulp volume of 4mL, add the volume of water of 80mL, react in a constant temperature water bath at 41℃ for 1.4h, centrifuge at 8500r / min for 16min, use 0.22μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.3mg / mL; take AB-8 macroporous resin 2.5g, crude extract 1mL, ethanol 3mL, shake and analyze on a shaker at a flow rate of 1.6mL / min, then put betalain into a dialysis bag with a molecular weight of 3600 for dialysis, and the dialysis time is 13h. Ethanol is evaporated and removed by rotary evaporator, and betalain is obtained by freeze drying in a freeze dryer. Betalain is formulated into a 0.3g / L solution.

[0036] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 25% of homemade betaine solution, 12% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 10% of polyepoxysuccinic acid (relative molecular weight 600), 18% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 35% of deionized water, and mixed and stirred for 35 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 93.4%;

[0037] Example 3: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp. Take the peel pulp volume of 3mL, add the volume of water of 60mL, react in a constant temperature water bath at 40℃ for 1.5h, centrifuge at 9000r / min for 17min, use 0.23μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.4mg / mL; take AB-8 macroporous resin 5g, crude extract 2mL, ethanol 6mL, shake and analyze on a shaker at a flow rate of 1.7mL / min, then put betalain into a dialysis bag with a molecular weight of 3500 for dialysis, and the dialysis time is 12.5h. Ethanol is evaporated and removed by rotary evaporator, and betalain is obtained by freeze drying in a freeze dryer. Betalain is formulated into a 0.28g / L solution.

[0038] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 30% of homemade betaine solution, 10% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 10% of polyepoxysuccinic acid (relative molecular weight 600), 20% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% of deionized water, and mixed and stirred for 40 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 94.5%;

[0039] Example 4: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp, take the peel pulp volume of 4mL, and add the volume of water of 80mL. React in a constant temperature water bath at 42℃ for 1.4h, centrifuge at 9500r / min for 17min, use a 0.22μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.4mg / mL; take AB-8 macroporous resin 2.5g, crude extract 1mL, ethanol 5mL, shake and analyze on a shaker at a flow rate of 1.8mL / min, then put betalain into a dialysis bag with a molecular weight of 3600 for dialysis, and the dialysis time is 12h. Ethanol is evaporated and removed by rotary evaporator, and betalain is obtained by freeze drying in a freeze dryer. Betalain is formulated into a 0.28g / L solution.

[0040] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 30% of homemade betaine solution, 14% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 10% of polyepoxysuccinic acid (relative molecular weight 600), 16% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% of deionized water, and mixed and stirred for 35 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 94.8%;

[0041] Example 5: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp, take the peel pulp volume of 3mL, and add the volume of water of 60mL. React in a constant temperature water bath at 41℃ for 1.4h, centrifuge at 10000r / min for 18min, use a 0.23μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.4mg / mL; take AB-8 macroporous resin 5g, crude extract 2mL, ethanol 6mL, shake and analyze on a shaker at a flow rate of 1.6mL / min, then put betalain into a dialysis bag with a molecular weight of 3500 for dialysis, and the dialysis time is 13h. Ethanol is evaporated and removed by rotary evaporator, and betalain is obtained by freeze drying in a freeze dryer. Betalain is formulated into a 0.28g / L solution.

[0042] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 30% of homemade betaine solution, 11% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 10% of polyepoxysuccinic acid (relative molecular weight 600), 19% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% of deionized water, and mixed and stirred for 30 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 95.4%;

[0043] Example 6: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp. Take the peel pulp volume of 5mL, and add the volume of water of 100mL. React in a constant temperature water bath at 40℃ for 1.5h, centrifuge at 9500r / min for 17min, use a 0.25μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.6mg / mL; AB-8 macroporous resin 2.5g, crude extract 1mL, ethanol 4mL, shake and analyze on a shaker at a flow rate of 1.7mL / min, then put the betacyanin into a dialysis bag with a molecular weight of 3600 for dialysis, and the dialysis time is 12.5h. Ethanol is evaporated and removed by rotary evaporator, and betacyanin is obtained by freeze drying in a freeze dryer. Betacyanin is formulated into a 0.2g / L solution.

[0044] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 25% of homemade betaine solution, 15% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 15% of polyepoxysuccinic acid (relative molecular weight 600), 15% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, 30% of deionized water, and mixed and stirred for 35 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 96.7%;

[0045] Example 7: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp. The volume of the peel pulp is 4mL, and the volume of water added is 80mL. React in a constant temperature water bath at 41°C for 1.4h, centrifuge at 8500r / min for 18min, and use a 0.23μm microporous filter membrane to filter out pectin to obtain a crude extract with a concentration of 4.8mg / mL; take 5g of AB-8 macroporous resin, 2mL of crude extract, and 6mL of ethanol, shake and analyze on a shaker at a flow rate of 1.8mL / min, and then put the betacyanin into a dialysis bag with a molecular weight of 3600 for dialysis, and the dialysis time is 13h. Ethanol is evaporated and removed by rotary evaporator, and betacyanin is obtained by freeze drying in a freeze dryer. Betacyanin is formulated into a 0.2g / L solution.

[0046] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 25% of homemade betaine solution, 18% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 12% of polyepoxysuccinic acid (relative molecular weight 600), 15% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% of deionized water, and mixed and stirred for 40 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 97.1%;

[0047] Example 8: Wash the pitaya to remove the pulp, cut the peel into small pieces, put it into the material machine and stir it evenly to obtain the pitaya peel pulp, take the peel pulp volume of 3mL, and add the volume of water of 60mL. React in a constant temperature water bath at 42℃ for 1.5h, centrifuge at 9500r / min for 19min, use a 0.22μm microporous filter membrane to filter out pectin to obtain a crude extract, the concentration of the crude extract is 4.6mg / mL; take AB-8 macroporous resin 10g, crude extract 2mL, ethanol 8mL, shake and analyze on a shaker at a flow rate of 1.7mL / min, then put the betacyanin into a dialysis bag with a molecular weight of 3600 for dialysis, and the dialysis time is 12.5h. Ethanol is evaporated and removed by rotary evaporator, and betacyanin is obtained by freeze drying in a freeze dryer. Betacyanin is formulated into a 0.28g / L solution.

[0048] The scale inhibitor prepared by weight percentage is added into the reactor in the following raw material components by weight percentage: 30% of homemade betaine solution, 10% of hydrolyzed polymaleic anhydride (relative molecular weight 500), 10% of polyepoxysuccinic acid (relative molecular weight 600), 20% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% of deionized water, and mixed and stirred for 35 minutes to obtain the scale inhibitor. The scale inhibition performance test is the same as that of Example 1, and the scale inhibition rate for calcium carbonate is 98.5%.

Claims

1. A green and environmentally friendly scale inhibitor, characterized in that The raw material components of the scale inhibitor are as follows: 25% to 30% betalain aqueous solution, 10% to 20% hydrolyzed polymaleic anhydride, 10% to 15% polyepoxysuccinic acid, 15% to 20% acrylic acid-hydroxypropyl acrylate-AMPS ternary polymer, and 30% to 35% deionized water in percentage by mass; wherein the mass ratio of betalain in the betalain aqueous solution to the volume ratio of water is 0.2-0.32 g / L; the betalain is extracted from pitaya peel by the following method The extraction method comprises the following specific steps: washing the pitaya to remove the pulp, cutting the peel into small pieces, putting the pieces into a material machine and stirring them evenly to obtain pitaya peel pulp, pouring the stirred pitaya peel pulp into a container, and adding deionized water; the volume ratio of pitaya peel pulp to water is 1:(20-21); reacting in a constant temperature water bath; centrifuging, filtering out pectin with a microporous filter membrane to obtain a crude extract, the concentration of which is 4.2-4.8 mg / mL; taking a macroporous resin, the crude extract and ethanol and oscillating and analyzing them on a shaker at a flow rate of 1.5-1.8 mL / min, and then putting the betacyanin into a dialysis bag for dialysis, and the dialysis time is 12-13.5 h; removing the ethanol by evaporation with a rotary evaporator, and freeze-drying in a freeze dryer to obtain the betacyanin.

2. The green and environmentally friendly scale inhibitor according to claim 1, characterized in that The temperature of the constant temperature water bath is 40-42 o C, reaction time is 1.4-1.5h; centrifugal speed is 8000-10000r / min, and centrifugal time is 15-20min.

3. The green and environmentally friendly scale inhibitor according to claim 1, characterized in that The pore size of the microporous filter membrane is 0.22-0.25 μm; the mass volume ratio of the macroporous resin to the crude extract is 2.5-5 g / mL, and the volume ratio of the crude extract to ethanol is 1:(3-5).

4. The green and environmentally friendly scale inhibitor according to claim 1, characterized in that The molecular weight of the dialysis bag is 3500-3600; the macroporous resin is AB-8.

5. The green and environmentally friendly scale inhibitor according to claim 1, characterized in that The relative molecular weight of the polyepoxysuccinic acid is 600-800; the relative molecular weight of the hydrolyzed polymaleic anhydride is 500-800.

6. A method for preparing the green and environmentally friendly scale inhibitor as claimed in claim 1, characterized in that The specific steps are as follows: adding raw material components in percentage by mass into a reaction kettle: 25% to 30% of a homemade betalain aqueous solution, 10% to 20% of hydrolyzed polymaleic anhydride, 10% to 15% of polyepoxysuccinic acid (PESA), 15% to 20% of acrylic acid-hydroxypropyl acrylate-AMPS terpolymer, and 30% to 35% of deionized water; mixing and stirring for 30 to 40 minutes to obtain a scale inhibitor.

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