CN106830378A - A kind of buck scale preventative and its preparation and filler test method - Google Patents

Abstract

The invention discloses a gray water scale inhibitor and its preparation, screening and testing methods. The gray water scale inhibitor is prepared from the following raw materials in weight percentage: 2%-10% of hydroxyethylidene diphosphonic acid, 2‑Phosphonic acid butane‑1,2,4‑tricarboxylic acid 10%‑15%, maleic acid‑acrylic acid copolymer 20%‑30%, hydrolyzed polymaleic anhydride 10%‑20%, acrylic acid‑acrylic acid hydroxyl Propyl ester copolymer 5%-10%, phosphonocarboxylic acid copolymer 5%-15%, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer 5%-10%, and the balance is pure water. The gray water scale inhibitor prepared by the invention has calcium resistance, pH resistance and high temperature resistance, has good corrosion and scale inhibition performance, and has good scale and scale inhibition effects, and is suitable for gray water with high temperature, high alkali and high temperature. The water quality characteristics of the pH value are especially suitable for the ash removal system of the power plant; the gray water scale inhibitor screened and tested by the gray water scale inhibitor screening test method of the present invention has reached the expected corrosion and scale inhibition effect, which improves the hydraulic ash removal work efficiency.

Description

A kind of gray water scale inhibitor and its preparation and screening test method

technical field

The invention belongs to a scale inhibitor and its preparation and screening test method, in particular to a gray water scale inhibitor and its preparation and screening test method.

Background technique

At present, China's electric power is still dominated by coal-fired power generation structure, so the problem of fly ash treatment is very prominent, there are two main treatment methods, one is dry ash removal, which is often used in water-scarce areas; the other is Use hydraulic ash removal method to discharge to ash storage yard for storage. It is a relatively economical method to send ash and slag to the ash yard by hydraulic ash removal system, which is also the main method of ash removal in China at present. However, when using hydraulic ash removal, due to the action of the scaling factor Ca ²⁺ contained in the gray water and CO ₃ ^2- in the water, CaCO ₃ is deposited on the inner wall of the ash washing tube, and as the running time increases, the inner wall of the ash washing tube becomes scaled It will become more and more serious. If it is not treated, it will reduce the amount of ash discharge and increase the power consumption of ash transportation. In severe cases, it will cause difficulties in ash discharge and directly threaten the normal operation of power production. There are many measures for anti-scaling on the inner wall of the ash flushing pipe, such as furnace smoke treatment, acid pH adjustment method, high-frequency electric field method, pipe method, and scale inhibitor addition method. The gray pipe anti-scaling technology has been greatly developed, and the method of adding anti-scaling agent is a commonly used method at present. However, due to the special water quality requirements of gray water, the Ca ²⁺ ion and pH value of gray water are much higher than those of general industrial water. ~300℃, while the calcium resistance, pH resistance and high temperature resistance of gray water scale inhibitors have certain limitations. There will be a problem of lowering. How to prepare a gray water scale inhibitor and quickly and simply screen and test the gray water scale inhibitor formula with good scale inhibition performance under the actual gray water temperature and scale formation conditions, so that the added gray water scale inhibitor can meet expectations It is a problem that needs to be solved to avoid the phenomenon that the scale inhibition rate of the added gray water scale inhibitor is reduced under the actual gray water temperature scaling condition and affects the hydraulic ash removal.

Contents of the invention

The technical problem to be solved by the present invention is to provide a gray water scale inhibitor and a preparation method thereof. The gray water scale inhibitor prepared by the invention can have calcium resistance, pH resistance and high temperature resistance, and can have good corrosion and scale inhibition performance at the same time, and can be especially suitable for the ash removal system of power plants. Another technical problem to be solved by the present invention is: provide the screening test method of this kind of gray water scale inhibitor, the screening test method using this gray water scale inhibitor can not only quickly and simply simulate the actual scaling conditions at gray water temperature The gray water scale inhibitor with good scale inhibition performance is screened and tested, so that the added gray water scale inhibitor can achieve the expected corrosion and scale inhibition effect; it can also avoid the gray water scale inhibitor added in gray water. Under the actual scaling conditions of temperature, the scale inhibition rate decreases and the effect of hydraulic ash removal is affected, which can improve the efficiency of hydraulic ash removal.

The technical scheme that the present invention solves the problems of the technologies described above is:

A gray water scale inhibitor, characterized in that: it is configured from the following raw materials in weight percentage: 2%-10% of hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid Acid 10%-15%, maleic acid-acrylic acid copolymer 20%-30%, hydrolyzed polymaleic anhydride 10%-20%, acrylic acid-hydroxypropyl acrylate copolymer 5%-10%, phosphonocarboxylic acid copolymer Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer 5%-15%, the balance is pure water;

The content of the active matter of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

The maleic acid-acrylic acid copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer have a solid content of 30%;

The solid content of the hydrolyzed polymaleic anhydride is 40%.

A kind of preparation method of gray water antiscalant is characterized in that, mainly comprises the following steps:

A. Add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above weight percentage ratio, start the mixer and add 2-phosphonic acid butane-1,2,4-tricarboxylic acid with the above weight percentage ratio while stirring. Acrylic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, the rest with pure water filling;

B. Mix the above-mentioned hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-acrylic acid hydroxyl Propyl ester copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and purified water are stirred evenly and filled into plastic barrels for later use.

A kind of screening test method of gray water antiscalant is characterized in that: comprise the steps:

(1) Temperature resistance treatment test of gray water scale inhibitors: Divide 100-120ml of each gray water scale inhibitor of at least 5 kinds of gray water scale inhibitors into two equal parts; divide at least 5 kinds of gray water scale inhibitors A portion of 50-60ml is poured into at least 5 hydrothermal kettles respectively, and at least 5 hydrothermal kettles containing 50-60ml of gray water scale inhibitor are placed in an oven at a temperature of 200-300℃ in turn, and the Heat at least 5 hydrothermal kettles with 50-60ml of gray water scale inhibitors at the same temperature set in the oven for 30min, and then cool down; prepare another 50-60ml of at least 5 kinds of gray water scale inhibitors for use as gray water respectively Scale inhibition rate test without heating at room temperature;

(2) Preparation of scale inhibition rate test solution: add 200-250ml of pure water for tertiary analysis to at least five 500ml volumetric flasks; add calcium chloride standard into at least five 500ml volumetric flasks with a burette Solution, so that the amount of calcium ions is 115-125mg; then add at least 5 gray water scale inhibitors 50ppm-100ppm after heating and cooling in step (1) to the at least 5 500ml volumetric flasks; Add borax buffer solution 20-25ml respectively in the at least 5 500ml volumetric flasks, and add sodium bicarbonate standard solution to the at least 5 500ml volumetric flasks with a burette again, so that the bicarbonate in the at least 5 500ml volumetric flasks The amount of root ions is 355-370 mg respectively;

﹙3﹑Preparation of blank test solution: except that gray water antiscalant is not added, the steps are the same as (2);

(4) Scale inhibition rate test: Pour the scale inhibition rate test solution in at least 5 500ml volumetric flasks made in step (2) and the blank test solution made in step (2) into at least 5 scale inhibition rate test solutions respectively. In the conical flask of test solution and one conical flask of blank test solution, put at least 5 conical flasks of scale inhibition rate test solution and one conical flask of blank test solution respectively equipped with scale inhibition rate test solution and blank test solution. Place in a constant temperature water bath at 79-81°C for 10 hours; after cooling, use at least 5 scale inhibition rate test solutions in conical flasks of scale inhibition rate test solutions and a blank test solution in a blank test solution conical flask with Medium-speed quantitative filter paper filtration to obtain scale inhibition rate test solution filtrate and blank test solution filtrate for later use; respectively pipette 20-25ml of the scale inhibition rate test solution filtrate and place them in at least five 250ml conical flasks, pipette the blank test solution Put 20-25ml of the liquid filtrate into a 250ml blank test solution conical flask, and then pour it into at least five 250ml conical flasks and a 250ml blank test solution filtrate conical flask respectively. Add 50-80ml of tertiary analytical pure water, 3-5ml of potassium hydroxide solution with a concentration of 200g/L and 0.1g of calcium carboxylic acid indicator, and titrate with EDTA standard solution until it changes from purple red to bright blue. as the end point;

(5) Chemical screening: According to the mathematical model of scale inhibition performance of water treatment agents, calculate the scale inhibition rate data of at least 5 kinds of gray water scale inhibitors at the same heating temperature, and compare the scale inhibition rate data of at least 5 kinds of gray water scale inhibitors at the same heating temperature. scale rate, and screen out a gray water scale inhibitor with high scale inhibition rate;

The other 50-60ml of the at least 5 kinds of gray water scale inhibitors were used to test the scale inhibition rate of gray water at room temperature without heating. The steps are the same as the above steps (2), (3) and (4); The scale inhibition performance mathematical model calculates the scale inhibition rate data of the at least five kinds of gray water scale inhibitors at room temperature without heating;

The preparation method of the calcium chloride standard solution is as follows: take 16.7g anhydrous calcium chloride and dissolve it in water and settle to a 1000ml volumetric flask;

The preparation method of the sodium bicarbonate standard solution is as follows: 25.2g sodium bicarbonate is dissolved in water and settled in the 1000ml volumetric flask ^; the sodium bicarbonate standard solution is 1ml containing _18.3mg HCO sodium hydrogen solution;

The preparation method of the borax buffer solution is as follows: take 3.8g sodium tetraborate decahydrate and dissolve it in water and settle to the 1000ml volumetric flask;

The calibration method of the calcium chloride standard solution is as follows: pipette 3-5ml calcium chloride standard solution and place it in a 250ml Erlenmeyer flask, then add 50-80ml three-level analytical pure water, 3-5ml potassium hydroxide solution and about 0.1 g calcium carboxylic acid indicator, titrate with EDTA standard solution until the end point is changed from purple red to bright blue;

The calibration method of the sodium bicarbonate standard solution is as follows: pipette 3-5ml sodium bicarbonate standard solution and place it in a 250ml Erlenmeyer flask, add 50-80ml three-level analytical pure water successively, drop 3-5 drops of bromocresol Green-methyl red indicator solution, titrated with hydrochloric acid standard titration solution from light blue to purple is the end point;

The pH of the borax buffer solution is 8.8-9.2, and the concentration is 0.01mol/L.

The inventor believes that:

Hydroxyethylidene diphosphonic acid (HEDP):

Hydroxyethylidene diphosphonic acid is an organophosphorus series scale and corrosion inhibitor, which has good scale and corrosion inhibition performance. Because the CP bond is very strong, it has high chemical stability and thermal stability. It is also difficult to hydrolyze under the condition of pH value; acid and alkali resistance and chlorine oxidation resistance are better than other organic phosphoric acids. The phosphonate in HEDP has a strong chelating ability for Ca ²⁺ and a good inhibitory ability for silica scale, so HEDP has good scale inhibition effect and obvious solubility limit effect. When combined with 2-phosphine Butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide When -2-methylpropanesulfonic acid copolymer is used in combination, it shows ideal scale inhibition effect and has obvious synergistic effect on solubility limit; because it contains (-OH) group, it can be used in combination with POCA to enhance its calcium phosphate anti-scaling effect.

2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA):

PBTCA is an organic phosphonic acid, which contains a phosphonic acid group and three carboxyl groups in its molecule. It is a highly efficient scale inhibitor and can exert a strong scale inhibitor effect even under very harsh conditions; In the case of high hardness and high alkalinity, the scale inhibition performance is better than other organic phosphonates, and the effect of calcium carbonate scale inhibition is very good, especially in the case of low dosage, it is the best effect among low molecular scale inhibitors , and has certain corrosion inhibition properties. And the phosphorus content is low, and the compound use with HEDP can effectively reduce the phosphorus content, meet the current environmental protection requirements of the low-phosphorus scale inhibitor formula, and can reduce the amount of scale inhibitor and reduce the cost.

Maleic acid-acrylic acid copolymer (MA/AA):

It is a low-molecular-weight polyelectrolyte, containing weakly acidic groups of carboxylic acid groups, which has a strong inhibitory effect on carbonate scale and high thermal stability. It can be used under harsh conditions such as high temperature of 300 ° C. It can be used with 2-phosphonic acid The compound of butane-1,2,4-tricarboxylic acid has good compatibility and synergistic effect, and the scale inhibition performance is enhanced under the conditions of high temperature, high hardness and high alkalinity; It has a good inhibitory effect on the formation of scale; it is also used in combination with organic phosphonate HEDP.

Hydrolyzed Polymaleic Anhydride (HPMA):

HPMA is a low molecular weight polyelectrolyte with high chemical and thermal stability. There is a significant solubility limit effect at high temperature and high pH. It still has a good scale inhibition and dispersion effect on carbonates below 300°C, and the scale inhibition time can reach 100h. The main function is the -COOH group, which has a strong chelating ability for Ba ²⁺ , Ca ²⁺ , Mg ²⁺ , Fe ³⁺ , Cu ²⁺ ions, not only for dispersion and aggregation, but also for During the crystallization process of inorganic scale, it can interfere with the normal arrangement of crystal lattice, so as to achieve the purpose of scale inhibition and scale prevention. When compounded with 2-phosphonic acid butane-1,2,4-tricarboxylic acid and maleic acid-acrylic acid copolymer, it has obvious solubility limit effect and enhanced scale and scale inhibition effect at high temperature and high pH.

Acrylic acid-hydroxypropyl acrylate copolymer:

Acrylic acid-hydroxypropyl acrylate copolymer contains -COOH and -OH, and the carboxylic acid group is a weakly acidic group, which has a strong inhibitory effect on carbonate scale. Hydroxyl, as a hydrophilic group, has a certain effect on inhibiting phosphate scale. And it still has good scale inhibition and dispersion effect under relatively high temperature and alkaline conditions, and the synergistic effect of scale inhibition and scale prevention is enhanced when it is used with HPMA.

Phosphonocarboxylic acid copolymer (POCA):

The structure of POCA contains phosphono group, which has corrosion inhibition performance, and contains carboxyl group, ester group and sulfonic acid group, which has scale inhibition and dispersion performance; due to the organic combination of various functional groups, the phosphono carboxyl copolymer has excellent scale inhibition performance, It also has good properties of dispersing iron oxide particles and stabilizing metal ions; at the same time, it also has good corrosion inhibition performance, showing multi-functional characteristics. It has good dispersibility for calcium carbonate and calcium phosphate scale in circulating cooling water, and has a good inhibitory effect on the deposition of barium sulfate, strontium sulfate and silicon scale. The combination of POCA and organic phosphonic acid (such as HEDP, PBTCA) copolymer (such as HPMA, MA/AA) has a synergistic effect on scale inhibition and dispersion performance.

Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer:

Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer has excellent properties of dispersing iron, zinc hydroxide, calcium carbonate and calcium phosphate in alkaline aqueous solution, and has a sulfonic acid group, which is a strong acidic group , can improve the ability of the polymer to resist cationic precipitation, stabilize zinc salt, inhibit the formation of phosphate and have good dispersion ability for iron oxide. Suitable for high temperature, high alkali, high calcium gray water quality, and with 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid- The combination of hydroxypropyl acrylate copolymer and phosphonocarboxylic acid copolymer has a good synergistic effect.

In the present invention, organic phosphoric acid series scale inhibitors HEDP, PBTCA and polycarboxylic acid polymer scale inhibitors HPMA, POCA, acrylic acid-hydroxypropyl acrylate copolymer, etc. are compounded and used, and organic phosphonic acid series scale inhibitors and polycarboxylate Acid series antiscalants are used in combination. Due to the strong stability of phosphoric acid series antiscalants, polycarboxylic acid antiscalants have good water solubility due to their functional groups such as carboxyl, hydroxyl, and sulfonic acid groups in their structure. It forms a stable water-soluble complex with metal ions in water (such as Ca ²⁺ , Mg ²⁺ , etc.), has good dispersion performance on calcium scale and silicon scale, and has a good synergistic effect after compounding. , The dispersion performance of silica scale is enhanced. In addition, the gray water scale inhibitor requires high temperature resistance due to the special water quality of gray water, and the polymer selected in the present invention is suitable for scale inhibition and scale prevention under high temperature conditions.

The beneficial effects of the present invention are: the gray water scale inhibitors prepared by the present invention are compounded with liquid products, the preparation process is simple and easy to produce, and no heat treatment is required; and the present invention is especially suitable for gray water with high temperature, high alkalinity and high pH value According to the water quality characteristics, the formula is screened, and calcium carbonate scale is mainly used, calcium sulfate, calcium phosphate, etc. are supplemented; the gray water scale inhibitor prepared by the present invention has calcium resistance, pH resistance, high temperature resistance, and has good Excellent corrosion and scale inhibition performance, good scale and scale prevention effect, especially suitable for power plant ash removal system. Simultaneously, the present invention sets the temperature resistance test of gray water scale inhibitors, and obtains the data of the scale inhibition rate of different gray water scale inhibitors under the condition of simulating different gray water temperature scaling, and also obtains the scale inhibition rate of gray water scale inhibitors in The data of the scale inhibition rate under the scaling condition of gray water temperature without heating; the present invention can quickly and simply compare the data through the list to select the gray water scale inhibitor with good scale inhibition performance suitable for scaling conditions of different gray water temperature; The gray water scale inhibitor screening test method of the present invention is closer to the actual scaling use conditions of different gray water temperatures, and the gray water scale inhibitor screened and tested by the gray water scale inhibitor screening test method of the present invention has reached the expected corrosion inhibition Anti-scaling effect: avoiding the occurrence of the phenomenon that the anti-scaling rate of the added gray water anti-scaling agent is reduced under the actual scaling condition of the gray water temperature, which affects the effect of hydraulic ash removal, and improves the efficiency of hydraulic ash removal.

detailed description

The present invention will be described in further detail below through specific examples.

Example 1

A gray water scale inhibitor, characterized in that it is configured from the following raw materials in weight percentage: 2% of hydroxyethylidene diphosphonic acid, 14% of 2-phosphonic acid butane-1,2,4-tricarboxylic acid , maleic acid-acrylic acid copolymer 28%, hydrolyzed polymaleic anhydride 16%, acrylic acid-hydroxypropyl acrylate copolymer 5%, phosphonocarboxylic acid copolymer 9%, acrylic acid-2-acrylamide-2-methyl Propanesulfonic acid copolymer 7%, the balance is pure water;

The content of the active matter of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

The maleic acid-acrylic acid copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer have a solid content of 30%;

The solid content of the hydrolyzed polymaleic anhydride is 40%.

A kind of preparation method of gray water antiscalant is characterized in that, mainly comprises the following steps:

A. Add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above weight percentage ratio, start the mixer and add 2-phosphonic acid butane-1,2,4-tricarboxylic acid with the above weight percentage ratio while stirring. Acrylic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, the rest with pure water filling;

B. Mix the above-mentioned hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-acrylic acid hydroxyl Propyl ester copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and purified water are stirred evenly and filled into plastic barrels for later use.

A kind of screening test method of gray water antiscalant is characterized in that: comprise the steps:

(1) Temperature resistance treatment test of gray water scale inhibitor: Five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 ash prepared by the above-mentioned preparation method of gray water scale inhibitor Divide 100ml of each gray water scale inhibitor of water scale inhibitor into two equal parts; divide one part of five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitor Pour 50ml into 5 hydrothermal kettles respectively, and put the 5 hydrothermal kettles containing 50ml of gray water scale inhibitor into the oven at 200℃ for heating for 30min and cool down; mix 5 kinds of GN-2124, The other 50ml of GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitors are used for the scale inhibition rate test of gray water at room temperature without heating;

﹙2﹑Preparation of scale inhibition rate test solution: add 200ml of pure water for tertiary analysis to five 500ml volumetric flasks respectively; The amount of ions is 115 mg; then add 50 ppm of gray water antiscalant after heating and cooling in the step (1) to the five 500ml volumetric flasks; then add borax to the five 500ml volumetric flasks Buffer solution 20ml, add sodium bicarbonate standard solution in described 5 500ml volumetric flasks again respectively with buret, make the amount of bicarbonate ion in described 5 500ml volumetric flasks be respectively 355mg;

﹙3﹑Preparation of blank test solution: except that gray water antiscalant is not added, the steps are the same as (2);

(4) Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks made in step (2) and the blank test solution made in step (2) respectively into 5 scale inhibition rate test solutions In the Erlenmeyer flask and a blank test solution conical flask, put 5 scale inhibition rate test solution conical flasks and a blank test solution conical flask respectively in 79 ℃ in a constant temperature water bath, place it for 10 hours; after cooling, filter the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in one blank test solution conical flask respectively with medium-speed quantitative filter paper to obtain Scale inhibition rate test solution filtrate and blank test solution filtrate are for later use; respectively pipette 20ml of the scale inhibition rate test solution filtrate into five 250ml Erlenmeyer flasks, pipette 20ml of the blank test solution filtrate into one 250ml blank In the conical flask of test solution, add 50ml of third-grade analytical pure water and 3ml of concentration to five conical flasks of 250ml and one conical flask of 250ml blank test solution filtrate respectively. It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

(5) Agent screening: According to the mathematical model of water treatment agent scale inhibition performance

The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η=(ρ ₄ -ρ ₃ )/(0.240-ρ ₃ )×100%...Formula (1)

In the formula (1) ρ ₄ -add the numerical value of the calcium (Ca ²⁺ ) concentration after the test solution test of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ ₃ - the numerical value of calcium (Ca ²⁺ ) concentration after the test solution test without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-the numerical value of calcium (Ca ²⁺ ) concentration in the test solution prepared before the test, the unit is milligrams per milliliter, mg/ml;

The content of calcium ion (Ca ²⁺ ) is in mass concentration ρ, and the value is expressed in mg/ml, calculated according to formula (2);

ρ=V ₁ cM/V...Formula (2)

In the formula (2), V ₁ -the volume of the EDTA standard solution consumed in the titration, in milliliters (ml);

The exact value of the actual concentration of the c-EDTA standard solution, in moles per liter (mol/L);

The numerical value of the calcium chloride standard solution volume that V-takes, unit is milliliter (ml);

M-calcium (Ca ²⁺ ) molar mass value, unit is gram per mole (g/mol), (M=40.08)

Calculate the scale inhibition rate data of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127 and GN-2128 gray water scale inhibitors at the same heating temperature of 200℃, and compare the 5 kinds of GN-2124 and GN-2125 , GN-2126, GN-2127, and GN-2128 gray water scale inhibitors have a high or low scale inhibition rate at the same heating temperature of 200 ° C, and a gray water scale inhibitor with a high scale inhibition rate is selected;

The other 50-60ml of the at least 5 kinds of gray water scale inhibitors were used to test the scale inhibition rate of gray water at room temperature without heating. Content in ): Add 50 ppm of gray water antiscalant after heating and cooling in step (1) to the five 500ml volumetric flasks; Correspondingly add 50ppm of 5 gray water scale inhibitors to be tested for gray water normal temperature scale inhibition rate in step (1) respectively; and calculate the performance of the at least 5 gray water scale inhibitors at room temperature according to the mathematical model of water treatment agent scale inhibition performance Scale inhibition rate data without heating;

The preparation method of the calcium chloride standard solution is as follows: take 16.7g anhydrous calcium chloride and dissolve it in water and settle to a 1000ml volumetric flask;

The preparation method of the sodium bicarbonate standard solution is as follows: 25.2g sodium bicarbonate is dissolved in water and settled in the 1000ml volumetric flask ^; the sodium bicarbonate standard solution is 1ml containing _18.3mg HCO sodium hydrogen solution;

The preparation method of the borax buffer solution is as follows: take 3.8g sodium tetraborate decahydrate and dissolve it in water and settle to the 1000ml volumetric flask;

The calibration method of the calcium chloride standard solution is as follows: pipette 3ml calcium chloride standard solution and place it in a 250ml Erlenmeyer flask, add 50ml third grade analytically pure water, 3ml potassium hydroxide solution and about 0.1g calcium carboxylic acid indicator successively , Titrate with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

The calibration method of the sodium bicarbonate standard solution is as follows: pipette 3ml of sodium bicarbonate standard solution and place it in a 250ml Erlenmeyer flask, add 50ml of tertiary analytical pure water successively, add 3 drops of bromocresol green-methyl red to indicate solution, titration with hydrochloric acid standard titration solution from light blue to purple is the end point;

The pH of the borax buffer solution is 8.8, and the concentration is 0.01mol/L.

Example 2

A gray water scale inhibitor, characterized in that: it is configured from the following raw materials in weight percentage: 4% of hydroxyethylidene diphosphonic acid, 10% of 2-phosphonic acid butane-1,2,4-tricarboxylic acid , maleic acid-acrylic acid copolymer 30%, hydrolyzed polymaleic anhydride 14%, acrylic acid-hydroxypropyl acrylate copolymer 8%, phosphonocarboxylic acid copolymer 6%, acrylic acid-2-acrylamide-2-methyl Propanesulfonic acid copolymer 10%, the balance is pure water;

The content of the active matter of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

The maleic acid-acrylic acid copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer have a solid content of 30%;

The solid content of the hydrolyzed polymaleic anhydride is 40%.

A kind of preparation method of gray water antiscalant is characterized in that, mainly comprises the following steps:

A. Add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above weight percentage ratio, start the mixer and add the above weight percentage ratio of 2-phosphonic acid butane-1,2,4-tricarboxylic acid while stirring , maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, balance Make up with purified water;

B. Mix the above-mentioned hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-acrylic acid hydroxyl Propyl ester copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and purified water are stirred evenly and filled into plastic barrels for later use.

A kind of screening test method of gray water antiscalant is characterized in that: comprise the steps:

(1) Temperature resistance treatment test of gray water scale inhibitor: Five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 ash prepared by the above-mentioned preparation method of gray water scale inhibitor Divide 110ml of each gray water scale inhibitor of the water scale inhibitor into two equal parts; divide one part of the five kinds of gray water scale inhibitors GN-2124, GN-2125, GN-2126, GN-2127, and GN-2128 Pour 55ml into 5 hydrothermal kettles correspondingly, put the 5 hydrothermal kettles containing 55ml of gray water scale inhibitor in turn into an oven at 230°C for heating for 30min, then cool down; mix 5 kinds of GN-2124, The other 55ml of GN-2125, GN-2126, GN-2127, and GN-2128 gray water scale inhibitors are to be used for the scale inhibition rate test of gray water at room temperature without heating;

﹙2﹑Preparation of scale inhibition rate test solution: add 225ml of pure water for tertiary analysis to five 500ml volumetric flasks respectively; The amount of ions is 120mg; then add 75ppm of 5 gray water antiscalants after heating and cooling in step (1) to the five 500ml volumetric flasks; then add borax to the five 500ml volumetric flasks Buffer solution 25ml, add sodium bicarbonate standard solution respectively in described 5 500ml volumetric flasks again with buret, make the amount of bicarbonate ion in described 5 500ml volumetric flasks be respectively 360mg;

﹙3﹑Preparation of blank test solution: except that gray water antiscalant agent is not added, the steps are the same as (2);

(4) Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks made in step (2) and the blank test solution made in step (2) respectively into 5 scale inhibition rate test solutions In the conical flask and one blank test solution conical flask, put 5 scale inhibition rate test solution conical flasks and a blank test solution conical flask respectively in 80 ℃ in a constant temperature water bath, place it for 10 hours; after cooling, filter the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in one blank test solution conical flask respectively with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are used for later use; respectively pipette 25ml of the scale inhibition rate test solution filtrate into five 250ml conical flasks, and pipette 25ml of the blank test solution filtrate into one 250ml blank In the test solution conical flask, add 60ml third-grade analytical pure water and 4ml concentration It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

(5) Agent screening: According to the mathematical model of water treatment agent scale inhibition performance

The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η=(ρ ₄ -ρ ₃ )/(0.240-ρ ₃ )×100%...Formula (1)

In the formula (1) ρ ₄ -add the numerical value of the calcium (Ca ²⁺ ) concentration after the test solution test of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ ₃ - the numerical value of calcium (Ca ²⁺ ) concentration after the test solution test without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-the numerical value of calcium (Ca ²⁺ ) concentration in the test solution prepared before the test, the unit is milligrams per milliliter, mg/ml;

The content of calcium ion (Ca ²⁺ ) is in mass concentration ρ, and the value is expressed in mg/ml, calculated according to formula (2);

ρ=V ₁ cM/V...Formula (2)

In the formula (2), V ₁ -the volume of the EDTA standard solution consumed in the titration, in milliliters (ml);

The exact value of the actual concentration of the c-EDTA standard solution, in moles per liter (mol/L);

The numerical value of the calcium chloride standard solution volume that V-takes, unit is milliliter (ml);

M-calcium (Ca ²⁺ ) molar mass value, unit is gram per mole (g/mol), (M=40.08)

Calculate the scale inhibition rate data of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127 and GN-2128 gray water scale inhibitors at the same heating temperature of 230℃, and compare the 5 kinds of GN-2124 and GN-2125 , GN-2126, GN-2127, and GN-2128 gray water scale inhibitors have high or low scale inhibition rates at the same heating temperature of 230°C, and a gray water scale inhibitor with high scale inhibition rate is selected;

The other 55ml of the at least 5 kinds of gray water scale inhibitors were used to test the scale inhibition rate of gray water at room temperature without heating. Contents: Add 75ppm of 5 gray water antiscalants after heating and cooling in step (1) to the five 500ml volumetric flasks; Add 75ppm of 5 gray water scale inhibitors to be tested for gray water normal temperature scale inhibition rate in step (1) respectively; and calculate the at least 5 gray water scale inhibitors at room temperature without heating according to the mathematical model of water treatment agent scale inhibition performance Scale inhibition rate data under the state;

The preparation method of the calcium chloride standard solution is as follows: take 16.7g anhydrous calcium chloride and dissolve it in water and settle to a 1000ml volumetric flask;

The preparation method of the sodium bicarbonate standard solution is as follows: 25.2g sodium bicarbonate is dissolved in water and settled in the 1000ml volumetric flask ^; the sodium bicarbonate standard solution is 1ml containing _18.3mg HCO sodium hydrogen solution;

The preparation method of the borax buffer solution is as follows: take 3.8g sodium tetraborate decahydrate and dissolve it in water and settle to the 1000ml volumetric flask;

The calibration method of the calcium chloride standard solution is as follows: pipette 4ml calcium chloride standard solution and place it in a 250ml Erlenmeyer flask, add 60ml third-grade analytical pure water, 4ml potassium hydroxide solution and about 0.1g calcium carboxylic acid indicator successively , Titrate with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

The calibration method of the sodium bicarbonate standard solution is as follows: pipette 4ml of sodium bicarbonate standard solution and place it in a 250ml Erlenmeyer flask, add 60ml of tertiary analytical pure water successively, add 4 drops of bromocresol green-methyl red to indicate solution, titration with hydrochloric acid standard titration solution from light blue to purple is the end point;

The pH of the borax buffer solution is 9.0, and the concentration is 0.01mol/L.

Example 3

A gray water scale inhibitor, characterized in that: it is configured from the following raw materials in weight percentage: 6% of hydroxyethylidene diphosphonic acid, 15% of 2-phosphonic acid butane-1,2,4-tricarboxylic acid , maleic acid-acrylic acid copolymer 20%, hydrolyzed polymaleic anhydride 20%, acrylic acid-hydroxypropyl acrylate copolymer 7%, phosphonocarboxylic acid copolymer 7%, acrylic acid-2-acrylamide-2-methyl Propanesulfonic acid copolymer 6%, the balance is pure water;

The content of the active matter of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

The maleic acid-acrylic acid copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer have a solid content of 30%;

The solid content of the hydrolyzed polymaleic anhydride is 40%.

A kind of preparation method of gray water antiscalant is characterized in that, mainly comprises the following steps:

A. Add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above weight percentage ratio, start the mixer and add the above weight percentage ratio of 2-phosphonic acid butane-1,2,4-tricarboxylic acid while stirring , maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, balance Make up with purified water;

B. Mix the above-mentioned hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-acrylic acid hydroxyl Propyl ester copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and purified water are stirred evenly and filled into plastic barrels for later use.

A kind of screening test method of gray water antiscalant is characterized in that: comprise the steps:

(1) Temperature resistance treatment test of gray water scale inhibitor: Five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 ash prepared by the above-mentioned preparation method of gray water scale inhibitor Divide 110ml of each gray water scale inhibitor of the water scale inhibitor into two equal parts; divide one part of the five kinds of gray water scale inhibitors GN-2124, GN-2125, GN-2126, GN-2127, and GN-2128 Pour 55ml into 5 hydrothermal kettles respectively, and put the 5 hydrothermal kettles containing 55ml of gray water scale inhibitor in turn into an oven at 260°C for heating for 30min and then cool down; mix 5 kinds of GN-2124, The other 55ml of GN-2125, GN-2126, GN-2127, and GN-2128 gray water scale inhibitors are to be used for the scale inhibition rate test of gray water at room temperature without heating;

﹙2﹑Preparation of scale inhibition rate test solution: add 225ml of pure water for tertiary analysis to five 500ml volumetric flasks respectively; The amount of ions is 120mg; then add 90ppm of the five gray water scale inhibitors after heating and cooling in step (1) to the five 500ml volumetric flasks; then add borax to the five 500ml volumetric flasks Buffer solution 25ml, add sodium bicarbonate standard solution respectively in described 5 500ml volumetric flasks again with buret, make the amount of bicarbonate ion in described 5 500ml volumetric flasks be respectively 365mg;

﹙3﹑Preparation of blank test solution: except that gray water antiscalant agent is not added, the steps are the same as (2);

(4) Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks made in step (2) and the blank test solution made in step (2) respectively into 5 scale inhibition rate test solutions In the conical flask and one blank test solution conical flask, put 5 scale inhibition rate test solution conical flasks and a blank test solution conical flask respectively in 80 ℃ in a constant temperature water bath, place it for 10 hours; after cooling, filter the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in one blank test solution conical flask respectively with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are used for later use; respectively pipette 25ml of the scale inhibition rate test solution filtrate into five 250ml Erlenmeyer flasks, and pipette 25ml of the blank test solution filtrate into one 250ml blank In the conical flask of the test solution, add 70ml of third-grade analytical pure water and 5ml of concentration It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

(5) Agent screening: According to the mathematical model of water treatment agent scale inhibition performance

The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η=(ρ ₄ -ρ ₃ )/(0.240-ρ ₃ )×100%...Formula (1)

In the formula (1) ρ ₄ -add the numerical value of the calcium (Ca ²⁺ ) concentration after the test solution test of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ ₃ - the numerical value of calcium (Ca ²⁺ ) concentration after the test solution test without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-the numerical value of calcium (Ca ²⁺ ) concentration in the test solution prepared before the test, the unit is milligrams per milliliter, mg/ml;

The content of calcium ion (Ca ²⁺ ) is in mass concentration ρ, and the value is expressed in mg/ml, calculated according to formula (2);

ρ=V ₁ cM/V...Formula (2)

In the formula (2), V ₁ -the volume of the EDTA standard solution consumed in the titration, in milliliters (ml);

The exact value of the actual concentration of the c-EDTA standard solution, in moles per liter (mol/L);

The numerical value of the calcium chloride standard solution volume that V-takes, unit is milliliter (ml);

M-calcium (Ca ²⁺ ) molar mass value, unit is gram per mole (g/mol), (M=40.08)

Calculate the scale inhibition rate data of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127 and GN-2128 gray water scale inhibitors at the same heating temperature of 260℃, and compare the 5 kinds of GN-2124 and GN-2125 , GN-2126, GN-2127, and GN-2128 gray water scale inhibitors have high or low scale inhibition rates at the same heating temperature of 260°C, and a gray water scale inhibitor with high scale inhibition rate is selected;

The other 55ml of the at least 5 kinds of gray water scale inhibitors were used to test the scale inhibition rate of gray water at room temperature without heating. Contents: Add 90ppm of five gray water antiscalants after heating and cooling in step (1) to the five 500ml volumetric flasks; Add 90ppm of 5 gray water scale inhibitors to be tested for scale inhibition rate of gray water at room temperature in step (1) respectively; and calculate the at least 5 gray water scale inhibitors at room temperature without heating according to the mathematical model of water treatment agent scale inhibition performance The scale inhibition rate data under the state;

The preparation method of the calcium chloride standard solution is as follows: take 16.7g anhydrous calcium chloride and dissolve it in water and settle to a 1000ml volumetric flask;

The preparation method of the sodium bicarbonate standard solution is as follows: 25.2g sodium bicarbonate is dissolved in water and settled in the 1000ml volumetric flask ^; the sodium bicarbonate standard solution is 1ml containing _18.3mg HCO sodium hydrogen solution;

The preparation method of the borax buffer solution is as follows: take 3.8g sodium tetraborate decahydrate and dissolve it in water and settle to the 1000ml volumetric flask;

The calibration method of the calcium chloride standard solution is as follows: pipette 5ml calcium chloride standard solution and place it in a 250ml Erlenmeyer flask, add 70ml third grade analytically pure water, 5ml potassium hydroxide solution and about 0.1g calcium carboxylic acid indicator successively , Titrate with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

The calibration method of the sodium bicarbonate standard solution is as follows: pipette 5ml of sodium bicarbonate standard solution and place it in a 250ml Erlenmeyer flask, add 70ml of tertiary analytical pure water successively, add 5 drops of bromocresol green-methyl red to indicate solution, titration with hydrochloric acid standard titration solution from light blue to purple is the end point;

The pH of the borax buffer solution is 9.1, and the concentration is 0.01mol/L.

Example 4

A gray water scale inhibitor, characterized in that: it is configured from the following raw materials in weight percentage: 10% of hydroxyethylidene diphosphonic acid, 12% of 2-phosphonic acid butane-1,2,4-tricarboxylic acid , maleic acid-acrylic acid copolymer 24%, hydrolyzed polymaleic anhydride 12%, acrylic acid-hydroxypropyl acrylate copolymer 6%, phosphonocarboxylic acid copolymer 10%, acrylic acid-2-acrylamide-2-methyl Propanesulfonic acid copolymer 5%, the balance is pure water;

The content of the active matter of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

The maleic acid-acrylic acid copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer have a solid content of 30%;

The solid content of the hydrolyzed polymaleic anhydride is 40%.

A kind of preparation method of gray water antiscalant is characterized in that, mainly comprises the following steps:

A. Add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above weight percentage ratio, start the mixer and add the above weight percentage ratio of 2-phosphonic acid butane-1,2,4-tricarboxylic acid while stirring , maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, balance Make up with purified water;

B. Mix the above-mentioned hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-acrylic acid hydroxyl Propyl ester copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and purified water are stirred evenly and filled into plastic barrels for later use.

A kind of screening test method of gray water antiscalant is characterized in that: comprise the steps:

(1) Temperature resistance treatment test of gray water scale inhibitor: Five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 ash prepared by the above-mentioned preparation method of gray water scale inhibitor Divide 120ml of each gray water scale inhibitor of water scale inhibitor into two equal parts; divide one part of five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitor Pour 60ml into 5 hydrothermal kettles correspondingly, put the 5 hydrothermal kettles containing 60ml of gray water scale inhibitor in sequence in an oven at 300°C for heating for 30min, then cool down; mix 5 kinds of GN-2124, The other 60ml of GN-2125, GN-2126, GN-2127, and GN-2128 gray water scale inhibitors are to be used for the scale inhibition rate test of gray water at room temperature without heating;

﹙2﹑Preparation of scale inhibition rate test solution: add 250ml of pure water for tertiary analysis to five 500ml volumetric flasks respectively; The amount of ions is 125 mg; then add 100 ppm of the five gray water scale inhibitors after heating and cooling in step (1) to the five 500ml volumetric flasks; then add borax to the five 500ml volumetric flasks Buffer solution 25ml, add sodium bicarbonate standard solution respectively in described 5 500ml volumetric flasks again with buret, make the amount of bicarbonate ion in described 5 500ml volumetric flasks be respectively 370mg;

﹙3﹑Preparation of blank test solution: except that gray water antiscalant agent is not added, the steps are the same as (2);

(4) Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks made in step (2) and the blank test solution made in step (2) respectively into 5 scale inhibition rate test solutions In the Erlenmeyer flask and a blank test solution conical flask, put 5 scale inhibition rate test solution conical flasks and a blank test solution conical flask respectively in 81 ℃ in a constant temperature water bath, place it for 10 hours; after cooling, filter the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in one blank test solution conical flask respectively with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are used for later use; respectively pipette 25ml of the scale inhibition rate test solution filtrate into five 250ml conical flasks, and pipette 25ml of the blank test solution filtrate into one 250ml blank In the conical flask of the test solution, add 80ml of third-grade analytical pure water and 5ml concentration It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

(5) Agent screening: According to the mathematical model of water treatment agent scale inhibition performance

The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η=(ρ ₄ -ρ ₃ )/(0.240-ρ ₃ )×100%...Formula (1)

In the formula (1) ρ ₄ -add the numerical value of the calcium (Ca ²⁺ ) concentration after the test solution test of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ ₃ - the numerical value of calcium (Ca ²⁺ ) concentration after the test solution test without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-the numerical value of calcium (Ca ²⁺ ) concentration in the test solution prepared before the test, the unit is milligrams per milliliter, mg/ml;

The content of calcium ion (Ca ²⁺ ) is in mass concentration ρ, and the value is expressed in mg/ml, calculated according to formula (2);

ρ=V ₁ cM/V...Formula (2)

In the formula (2), V ₁ -the volume of the EDTA standard solution consumed in the titration, in milliliters (ml);

The exact value of the actual concentration of the c-EDTA standard solution, in moles per liter (mol/L);

The numerical value of the calcium chloride standard solution volume that V-takes, unit is milliliter (ml);

M-calcium (Ca ²⁺ ) molar mass value, unit is gram per mole (g/mol), (M=40.08)

Calculate the scale inhibition rate data of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127 and GN-2128 gray water scale inhibitors at the same heating temperature of 300℃, and compare the 5 kinds of GN-2124 and GN-2125 , GN-2126, GN-2127, and GN-2128 gray water scale inhibitors have a high or low scale inhibition rate at the same heating temperature of 300 ° C, and a gray water scale inhibitor with a high scale inhibition rate is selected;

The other 60ml of the at least 5 kinds of gray water scale inhibitors were used to test the scale inhibition rate of gray water at room temperature without heating. Contents: Add 100ppm of five gray water antiscalants after heating and cooling in step (1) to the five 500ml volumetric flasks; Add 100ppm of 5 gray water scale inhibitors to be tested for gray water normal temperature scale inhibition rate in step (1) respectively; and calculate the at least 5 gray water scale inhibitors at room temperature without heating according to the mathematical model of water treatment agent scale inhibition performance Scale inhibition rate data under the state;

The preparation method of the calcium chloride standard solution is as follows: take 16.7g anhydrous calcium chloride and dissolve it in water and settle to a 1000ml volumetric flask;

The preparation method of the sodium bicarbonate standard solution is as follows: 25.2g sodium bicarbonate is dissolved in water and settled in the 1000ml volumetric flask ^; the sodium bicarbonate standard solution is 1ml containing _18.3mg HCO sodium hydrogen solution;

The preparation method of the borax buffer solution is as follows: take 3.8g sodium tetraborate decahydrate and dissolve it in water and settle to the 1000ml volumetric flask;

The calibration method of the calcium chloride standard solution is as follows: pipette 5ml calcium chloride standard solution and place it in a 250ml Erlenmeyer flask, add 80ml third grade analytically pure water, 5ml potassium hydroxide solution and about 0.1g calcium carboxylic acid indicator successively , Titrate with EDTA standard solution until it changes from purple red to bright blue, which is the end point;

The calibration method of the sodium bicarbonate standard solution is as follows: pipette 5ml of sodium bicarbonate standard solution and place it in a 250ml Erlenmeyer flask, add 80ml of third-grade analytical pure water successively, and drop 5 drops of bromocresol green-methyl red to indicate solution, titration with hydrochloric acid standard titration solution from light blue to purple is the end point;

The pH of the borax buffer solution is 9.2, and the concentration is 0.01mol/L.

This table is the test data of the scale inhibition rate of 5 kinds of gray water scale inhibitors calculated by the above 4 examples

Through the above description, those skilled in the art can make various changes and modifications without departing from the technical idea of the present invention, all of which are within the protection scope of the present invention. Matters not covered in the present invention belong to the common knowledge of those skilled in the art.

Claims (5)

1. A gray water scale inhibitor, characterized in that: it is configured from the following raw materials in weight percent: hydroxyethylidene diphosphonic acid 2%-10%, 2-phosphonic acid butane-1,2,4- Tricarboxylic acid 10%-15%, maleic acid-acrylic acid copolymer 20%-30%, hydrolyzed polymaleic anhydride 10%-20%, acrylic acid-hydroxypropyl acrylate copolymer 5%-10%, phosphonocarboxylate Acid copolymer 5%-15%, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer 5%-10%, and the balance is pure water; The content of the active matter of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%; The maleic acid-acrylic acid copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer have a solid content of 30%; The solid content of the hydrolyzed polymaleic anhydride is 40%. 2. the preparation method of a kind of gray water antiscalant as claimed in claim 1 is characterized in that, mainly comprises the following steps: A. Add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above weight percentage ratio, start the mixer and add 2-phosphonic acid butane-1,2,4-tricarboxylic acid with the above weight percentage ratio while stirring. Acrylic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, the rest with pure water filling; B. Mix the above-mentioned hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid-acrylic acid hydroxyl Propyl ester copolymer, phosphonocarboxylic acid copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and purified water are stirred evenly and filled into plastic barrels for later use. 3. the screening test method of the gray water scale inhibitor prepared by the preparation method of a kind of gray water scale inhibitor as claimed in claim 2, is characterized in that: comprise the steps: (1) Temperature resistance treatment test of gray water scale inhibitors: Divide 100-120ml of each gray water scale inhibitor of at least 5 kinds of gray water scale inhibitors into two equal parts; divide at least 5 kinds of gray water scale inhibitors A portion of 50-60ml is poured into at least 5 hydrothermal kettles respectively, and at least 5 hydrothermal kettles containing 50-60ml of gray water scale inhibitor are placed in an oven at a temperature of 200-300℃ in turn, and the Heat at least 5 hydrothermal kettles with 50-60ml of gray water scale inhibitors at the same temperature set in the oven for 30min, and then cool down; prepare another 50-60ml of at least 5 kinds of gray water scale inhibitors for use as gray water respectively Scale inhibition rate test without heating at room temperature; (2) Preparation of scale inhibition rate test solution: add 200-250ml of pure water for tertiary analysis to at least five 500ml volumetric flasks; add calcium chloride standard into at least five 500ml volumetric flasks with a burette Solution, so that the amount of calcium ions is 115-125mg; then add at least 5 gray water scale inhibitors 50ppm-100ppm after heating and cooling in step (1) to the at least 5 500ml volumetric flasks; Add borax buffer solution 20-25ml respectively in the at least 5 500ml volumetric flasks, and add sodium bicarbonate standard solution to the at least 5 500ml volumetric flasks with a burette again, so that the bicarbonate in the at least 5 500ml volumetric flasks The amount of root ions is 355-370 mg respectively; ﹙3﹑Preparation of blank test solution: except that gray water antiscalant agent is not added, the steps are the same as (2); (4) Scale inhibition rate test: Pour the scale inhibition rate test solution in at least 5 500ml volumetric flasks made in step (2) and the blank test solution made in step (2) into at least 5 scale inhibition rate test solutions respectively. In the conical flask of test solution and one conical flask of blank test solution, put at least 5 conical flasks of scale inhibition rate test solution and one conical flask of blank test solution respectively equipped with scale inhibition rate test solution and blank test solution. Place in a constant temperature water bath at 79-81°C for 10 hours; after cooling, use at least 5 scale inhibition rate test solutions in conical flasks of scale inhibition rate test solutions and a blank test solution in a blank test solution conical flask with Medium-speed quantitative filter paper filtration to obtain scale inhibition rate test solution filtrate and blank test solution filtrate for later use; respectively pipette 20-25ml of the scale inhibition rate test solution filtrate and place them in at least five 250ml conical flasks, pipette the blank test solution Put 20-25ml of the liquid filtrate into a 250ml blank test solution conical flask, and then pour it into at least five 250ml conical flasks and a 250ml blank test solution filtrate conical flask respectively. Add 50-80ml of tertiary analytical pure water, 3-5ml of potassium hydroxide solution with a concentration of 200g/L and 0.1g of calcium carboxylic acid indicator, and titrate with EDTA standard solution until it changes from purple red to bright blue. as the end point; (5) Chemical screening: According to the mathematical model of scale inhibition performance of water treatment agents, calculate the scale inhibition rate data of at least 5 kinds of gray water scale inhibitors at the same heating temperature, and compare the scale inhibition rate data of at least 5 kinds of gray water scale inhibitors at the same heating temperature. scale rate, and screen out a gray water scale inhibitor with high scale inhibition rate; The other 50-60ml of the at least 5 kinds of gray water scale inhibitors were used to test the scale inhibition rate of gray water at room temperature without heating. The steps are the same as the above steps (2), (3) and (4); The scale inhibition performance mathematical model calculates the scale inhibition rate data of the at least five kinds of gray water scale inhibitors at room temperature without heating; The preparation method of the calcium chloride standard solution is as follows: take 16.7g anhydrous calcium chloride and dissolve it in water and settle to a 1000ml volumetric flask; The preparation method of the sodium bicarbonate standard solution is as follows: 25.2g sodium bicarbonate is dissolved in water and settled in the 1000ml volumetric flask ^; the sodium bicarbonate standard solution is 1ml containing _18.3mg HCO sodium hydrogen solution; The preparation method of the borax buffer solution is as follows: take 3.8g sodium tetraborate decahydrate and dissolve it in water and settle to the 1000ml volumetric flask; The pH of the borax buffer solution is 8.8-9.2, and the concentration is 0.01mol/L. 4. according to the screening test method of the gray water scale inhibitor prepared by the preparation method of a kind of gray water scale inhibitor described in claim 3 as claimed in claim 2, it is characterized in that: described calcium chloride standard solution calibration method is as follows : Pipette 3-5ml of calcium chloride standard solution into a 250ml Erlenmeyer flask, add 50-80ml of third-grade analytical pure water, 3-5ml of potassium hydroxide solution and about 0.1g of calcium carboxylic acid indicator in sequence, and use EDTA to mark The end point is when the solution is titrated from purple to bright blue. 5. according to the screening test method of the gray water scale inhibitor prepared by the preparation method of a kind of gray water scale inhibitor described in claim 3 as claimed in claim 2, it is characterized in that: described sodium bicarbonate standard solution calibration method is as follows : Pipette 3-5ml of sodium bicarbonate standard solution into a 250ml Erlenmeyer flask, add 50-80ml of tertiary analytical pure water in turn, add 3-5 drops of bromocresol green-methyl red indicator solution, and use hydrochloric acid The titration of the standard titration solution changes from light blue to purple, which is the end point.