CN106830378B - Preparation and screening test method of grey water scale inhibitor - Google Patents

Preparation and screening test method of grey water scale inhibitor Download PDF

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CN106830378B
CN106830378B CN201710099236.9A CN201710099236A CN106830378B CN 106830378 B CN106830378 B CN 106830378B CN 201710099236 A CN201710099236 A CN 201710099236A CN 106830378 B CN106830378 B CN 106830378B
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段丽菊
张庆龙
要晓丽
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Shandong Huayou Water Processing Technology Co ltd
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

本发明公开了一种灰水阻垢剂的制备和筛选测试方法，所述灰水阻垢剂，由下述重量百分比的原料配置而成：羟基乙叉二膦酸2％‑10％，2‑膦酸丁烷‑1,2,4‑三羧酸10％‑15％，马来酸‑丙烯酸共聚物20％‑30％，水解聚马来酸酐10％‑20％，丙烯酸‑丙烯酸羟丙酯共聚物5％‑10％，膦酰基羧酸共聚物5％‑15％，丙烯酸‑2‑丙烯酰胺‑2‑甲基丙磺酸共聚物5％‑10％，余量为纯净水。本发明制备的灰水阻垢剂具有耐钙性、耐pH性、耐高温性，具有很好的缓蚀阻垢性能，阻垢和防垢效果好，适用于灰水高温、高碱、高pH值的水质特性，特别适用于电厂除灰系统；本发明所筛选测试的灰水阻垢剂达到了预期的缓蚀阻垢效果，提高了水力除灰工作效率。The invention discloses a preparation and screening test method of a grey water scale inhibitor. The grey water scale inhibitor is prepared from the following raw materials in weight percentage: 2%-10% of hydroxyethylidene diphosphonic acid, 2% ‑Butane Phosphonate‑1,2,4‑Tricarboxylic Acid 10%‑15%, Maleic Acid‑Acrylic Copolymer 20%‑30%, Hydrolyzed Polymaleic Anhydride 10%‑20%, Acrylic Acid‑Hydroxypropyl Acrylic Acid Ester copolymer 5%-10%, phosphonocarboxylic acid copolymer 5%-15%, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer 5%-10%, and the balance is purified water. The grey 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 high temperature, high alkali and high temperature grey water. The water quality characteristic of pH value is especially suitable for the ash removal system of the power plant; the gray water scale inhibitor screened and tested by the present invention achieves the expected corrosion and scale inhibition effect, and improves the working efficiency of hydraulic ash removal.

Description

一种灰水阻垢剂的制备和筛选测试方法Preparation and screening test method of a grey water scale inhibitor

技术领域technical field

本发明属于一种阻垢剂的制备和筛选测试方法，特别是属于一种灰水阻垢剂的制备和筛选测试方法。The invention belongs to a preparation and screening test method of a scale inhibitor, in particular to a preparation and screening test method of a grey water scale inhibitor.

背景技术Background technique

目前，中国的电力仍旧是以燃煤为主的发电结构，因此粉煤灰的处理问题很突出，主要有两种处理方式，一是采取干除灰，在缺水地区应用较多；二是采用水力除灰方式排至储灰场存放。利用水力除灰系统将灰和渣送到灰场是比较经济的方法，这也是目前中国主要的一种除灰方式。但是在采用水力除灰时，由于灰水中含有的结垢因子Ca2+与水中CO3 2-作用产生CaCO3沉积在冲灰管内壁上，随着运行时间的增加，冲灰管内壁结垢将越来越严重，如不进行处理，轻则减少排灰量，增加输灰电耗，严重时可造成排灰困难，直接威胁电力生产的正常进行。冲灰管内壁防垢有多种措施，如炉烟处理、加酸调pH法、高频电场法、管材法、投加阻垢剂法等，随着技术进步和生产实际的迫切要求，冲灰管防垢技术有了较大的发展，投加阻垢剂法是目前普遍使用的方法。但是由于灰水的特殊水质要求，灰水的Ca2+离子和pH值都较一般的工业用水高得多，实际使用过程中灰水系统的压力为4.0～8.0MPa，灰水温度一般为150～300℃，而灰水阻垢剂的耐钙性、耐pH性、耐高温性都有一定的限制，部分灰水阻垢剂在灰水实际高pH、不同高温使用条件下阻垢率就会出现降低的问题。如何制备一种灰水阻垢剂并快速、简单的在实际灰水温度成垢条件下筛选测试出阻垢性能好的灰水阻垢剂配方，使所投加的灰水阻垢剂达到预期的缓蚀阻垢效果，避免所投加的灰水阻垢剂在实际灰水温度成垢条件下出现阻垢率降低而影响水力除灰的现象是需要解决的问题。At present, China's electricity is still mainly based on coal-fired power generation. Therefore, the problem of fly ash treatment is very prominent. There are two main treatment methods. One is to use dry ash removal, which is widely used in water-deficient areas; It is discharged to the ash storage yard by hydraulic ash removal method. The use of hydraulic ash removal system to send ash and slag to the ash field is a relatively economical method, which is also the main ash removal method in China at present. However, when hydraulic ash removal is used, CaCO 3 is deposited on the inner wall of the ash flushing pipe due to the action of the scaling factor Ca 2+ contained in the ash water and CO 3 2- in the water. 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 may cause difficulty in ash discharge, which directly threatens the normal operation of power production. There are various measures to prevent scale on the inner wall of the ash flushing pipe, such as furnace smoke treatment, acid addition to pH adjustment, high frequency electric field method, pipe method, adding scale inhibitor method, etc. The anti-scaling technology of ash pipes has been greatly developed, and the method of adding anti-scaling agents is currently a commonly used method. However, due to the special water quality requirements of grey water, the Ca 2+ ions and pH values of grey water are much higher than those of general industrial water. ～300℃, while the calcium resistance, pH resistance and high temperature resistance of the grey water scale inhibitors are limited. There will be a problem of lowering. How to prepare a grey water scale inhibitor and quickly and simply screen and test the grey water scale inhibitor formula with good scale inhibition performance under the actual grey water temperature scaling conditions, so that the added grey 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 decreases under the actual gray water temperature scaling condition and affects the hydraulic ash removal.

发明内容SUMMARY OF THE INVENTION

本发明所要解决的技术问题是：提供一种灰水阻垢剂的制备方法。本发明制备的灰水阻垢剂能具有耐钙性、耐pH性、耐高温性，同时能具有很好的缓蚀阻垢性能，特别能适用于电厂除灰系统。本发明所要解决的另一个技术问题是：提供该种灰水阻垢剂的筛选测试方法，使用该灰水阻垢剂的筛选测试方法不仅能快速、简单的模拟在灰水温度实际成垢条件下筛选测试出阻垢性能好的灰水阻垢剂，使所投加的灰水阻垢剂能达到预期的缓蚀阻垢效果；还能避免所投加的灰水阻垢剂在灰水温度实际成垢条件下出现阻垢率降低而影响水力除灰效果的现象发生，能提高水力除灰工作效率。The technical problem to be solved by the present invention is to provide a preparation method of a grey water scale inhibitor. The grey water scale inhibitor prepared by the invention can have calcium resistance, pH resistance and high temperature resistance, and at the same time has good corrosion and scale inhibition performance, and is especially suitable for power plant ash removal system. Another technical problem to be solved by the present invention is: to provide a screening test method for the grey water scale inhibitor, which can not only quickly and simply simulate the actual scaling conditions at the grey water temperature The grey water scale inhibitor with good scale inhibition performance was screened and tested, so that the added grey water scale inhibitor can achieve the expected corrosion and scale inhibition effect; it can also avoid the added grey water scale inhibitor in the grey water. Under the actual scaling conditions of temperature, the phenomenon that the scale inhibition rate decreases and affects the effect of hydraulic ash removal occurs, which can improve the efficiency of hydraulic ash removal.

本发明解决上述技术问题的技术方案是：The technical scheme that the present invention solves the above-mentioned technical problems is:

一种灰水阻垢剂的制备方法，其特征是：所述灰水阻垢剂由下述重量百分比的原料配置而成：羟基乙叉二膦酸2％-10％，2-膦酸丁烷-1,2,4-三羧酸10％-15％，马来酸-丙烯酸共聚物20％-30％，水解聚马来酸酐10％-20％，丙烯酸-丙烯酸羟丙酯共聚物5％-10％，膦酰基羧酸共聚物5％-15％，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物5％-10％，余量为纯净水；A preparation method of a grey water scale inhibitor, characterized in that: the grey water scale inhibitor is prepared from the following raw materials in weight percentage: 2%-10% of hydroxyethylidene diphosphonic acid, butyl 2-phosphonate Alkane-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%, phosphonocarboxylic acid copolymer 5%-15%, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer 5%-10%, the balance is pure water;

所述羟基乙叉二膦酸和2-膦酸丁烷-1,2,4-三羧酸活性物含量均为50％；The active content of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

所述马来酸-丙烯酸共聚物，丙烯酸-丙烯酸羟丙酯共聚物,膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物固体含量均为30％；The solid content of the maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer are all 30%;

所述水解聚马来酸酐固体含量为40％；The solid content of the hydrolyzed polymaleic anhydride is 40%;

主要包括下述步骤：It mainly includes the following steps:

A、在反应釜中按照上述重量百分比配比加入羟基乙叉二膦酸，开启搅拌机边搅拌边加入上述重量百分比配比的2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物，余量用纯净水补齐；A, add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above-mentioned weight percentage ratio, turn on the stirrer and add the 2-phosphonic acid butane-1,2,4-tricarboxylic acid of the above-mentioned 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 balance is pure water replenishment;

B、在反应釜中将上述羟基乙叉二膦酸，2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物和纯净水搅拌均匀后灌装塑料桶备用。B, in the reactor, 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 pure water are mixed evenly and then filled into plastic bucket for use.

一种灰水阻垢剂的筛选测试方法，其特征是：包括如下步骤：A screening test method for a grey water scale inhibitor, characterized in that it comprises the following steps:

﹙1﹚灰水阻垢剂耐温性处理试验：将至少5种灰水阻垢剂的每种灰水阻垢剂100-120ml分别分成相等的两份；将至少5种灰水阻垢剂的一份50-60ml分别对应倒入至少5个水热釜中，将装有灰水阻垢剂50-60ml的至少5个水热釜依次放入温度为200-300℃烘箱中，装有灰水阻垢剂50-60ml的至少5个水热釜在该烘箱设定的同一温度加热30min，冷却；将至少5种灰水阻垢剂的另一份50-60ml备用分别待做灰水常温不加热阻垢率实验；﹙1﹚Grey water scale inhibitor temperature resistance treatment test: Divide 100-120ml of each grey water scale inhibitor of at least 5 kinds of grey water scale inhibitors into two equal parts; at least 5 kinds of grey 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 with a temperature of 200-300 ° C in turn, and are equipped with At least 5 hydrothermal kettles of 50-60ml of grey water scale inhibitor are heated for 30min at the same temperature set by the oven, and cooled; another 50-60ml of at least 5 kinds of grey water scale inhibitor are separately prepared as grey water. Scale inhibition rate experiment without heating at room temperature;

﹙2﹚阻垢率试液的制备：向至少5个500ml容量瓶中分别加入200-250ml三级分析用纯水；用滴定管分别再向所述至少5个500ml容量瓶中加入氯化钙标准溶液，使钙离子的量为115-125mg；再向所述至少5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的至少5个灰水阻垢剂50ppm-100ppm；再向所述至少5个500ml容量瓶中分别加入硼砂缓冲溶液20-25ml，用滴定管再分别向所述至少5个500ml容量瓶中加入碳酸氢钠标准溶液，使得所述至少5个500ml容量瓶中碳酸氢根离子的量分别为355-370mg；﹙2﹚Preparation of the test solution for scale inhibition rate: add 200-250ml of pure water for tertiary analysis into at least 5 500ml volumetric flasks respectively; add calcium chloride standard to the at least 5 500ml volumetric flasks with a burette solution, so that the amount of calcium ions is 115-125mg; then at least 5 gray water scale inhibitors 50ppm-100ppm after heating and cooling in step {1} are added to the at least 5 500ml volumetric flasks in sequence; Add 20-25ml of borax buffer solution to the at least five 500ml volumetric flasks respectively, and then add sodium bicarbonate standard solution to the at least five 500ml volumetric flasks with a burette, so that the hydrogen carbonate in the at least five 500ml volumetric flasks The amount of root ions is 355-370mg;

﹙3﹚空白试液的制备：除不加灰水阻垢剂外，步骤同(2)；﹙3﹚Preparation of blank test solution: the steps are the same as (2) except that no lime water scale inhibitor is added;

﹙4﹚阻垢率试验：将步骤﹙2﹚制成的至少5个500ml容量瓶中的阻垢率试液和步骤﹙3﹚制成的空白试液分别对应倒入至少5个阻垢率试液锥形瓶内和一个空白试液锥形瓶内，将分别装有阻垢率试液和空白试液的至少5个阻垢率试液锥形瓶和一个空白试液锥形瓶分别放置于79-81℃恒温水浴锅中，放置10h；冷却后将至少5个阻垢率试液锥形瓶中的阻垢率试液和一个空白试液锥形瓶中的空白试液分别用中速定量滤纸过滤得到阻垢率试液滤液和空白试液滤液备用；分别移取所述阻垢率试液滤液20-25ml置于至少5个250ml锥形瓶中，移取所述空白试液滤液20-25ml置于1个250ml空白试液锥形瓶中，再分别依次向装有阻垢率试液滤液的至少5个250ml锥形瓶和1个250ml空白试液滤液锥形瓶中内加入50-80ml三级用分析纯水、3-5ml浓度为200g/L的氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液分别滴定到由紫红色变为亮蓝色即为终点；﹙4﹚Scale inhibition rate test: Pour at least 5 scale inhibition rate test solutions in at least 5 500ml volumetric flasks prepared in step ﹙2﹚ and the blank test solution prepared in step ﹙3﹚ respectively. In the test solution conical flask and one blank test solution conical flask, place at least 5 scale inhibition rate test solution conical flasks and one blank test solution conical flask respectively containing the scale inhibition rate test solution and blank test solution respectively. Place it in a constant temperature water bath at 79-81°C for 10 hours; after cooling, use at least 5 scale inhibition rate test solution in conical flasks and a blank test solution in a blank test solution conical flask respectively. Filter with medium-speed quantitative filter paper to obtain scale inhibition rate test solution filtrate and blank test solution filtrate for use; pipette 20-25ml of the scale inhibition rate test solution filtrate and place them in at least 5 250ml conical flasks, and pipette the blank test solution. Put 20-25ml of the filtrate into a 250ml blank test solution conical flask, and then put them into at least five 250ml conical flasks and one 250ml blank test solution filtrate in turn 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 to bright blue. is the end point;

﹙5﹚药剂筛选：根据水处理剂阻垢性能数学模型分别计算至少5种灰水阻垢剂在同一加热温度下阻垢率数据，比较至少5种灰水阻垢剂在同一加热温度下阻垢率高低，并筛选出阻垢率高的一个灰水阻垢剂；﹙5﹚Reagent screening: Calculate the scale inhibition rate data of at least 5 kinds of gray water scale inhibitors at the same heating temperature according to the mathematical model of the scale inhibition performance of the water treatment agent, and compare the resistance of at least 5 kinds of gray water scale inhibitors at the same heating temperature. The scale rate is high and low, and a gray water scale inhibitor with high scale inhibition rate is screened out;

所述水处理剂阻垢性能数学模型为：The mathematical model of the scale inhibition performance of the water treatment agent is:

以百分率表示的水处理剂阻垢性能按以下式(1)计算The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η＝(ρ4-ρ3)/(0.240-ρ3)×100％....式(1)η=(ρ 4 -ρ 3 )/(0.240-ρ 3 )×100%.... Formula (1)

式(1)中ρ4-加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；In the formula (1), ρ 4 - the value of the calcium (Ca 2+ ) concentration after adding the test solution of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ3-未加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；ρ 3 - the value of calcium (Ca 2+ ) concentration after the test solution without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-试验前配制好的试液中钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；0.240 - the value of calcium (Ca 2+ ) concentration in the test solution prepared before the test, in milligrams per milliliter, mg/ml;

钙离子(Ca2+)的含量以质量浓度ρ计，数值以mg/ml表示，按式(2)计算；The content of calcium ions (Ca 2+ ) is calculated in terms of mass concentration ρ, and the value is expressed in mg/ml, and is calculated according to formula (2);

ρ＝V1cM/V....式(2)ρ=V 1 cM/V.... Formula (2)

式(2)中V1-滴定中消耗EDTA标液的体积，单位为毫升(ml)；In formula (2), the volume of EDTA standard solution consumed in V 1 -titration, the unit is milliliter (ml);

c-EDTA标液的实际浓度准确数值，单位为摩尔每升(mol/L)；The exact value of the actual concentration of c-EDTA standard solution, the unit is mole per liter (mol/L);

V-所取氯化钙标液体积的数值，单位为毫升(ml)；V-the value of the volume of the calcium chloride standard solution taken, in milliliters (ml);

M-钙(Ca2+)摩尔质量的数值，单位为克每摩尔(g/mol)，(M＝40.08)；M-value of the molar mass of calcium (Ca 2+ ), in grams per mole (g/mol), (M=40.08);

所述至少5种灰水阻垢剂的另一份50-60ml分别做灰水常温不加热阻垢率实验的步骤同上述步骤﹙2﹚、﹙3﹚、﹙4﹚；并根据水处理剂阻垢性能数学模型分别计算该至少5种灰水阻垢剂在常温不加热状态下的阻垢率数据；The other 50-60ml of the at least 5 kinds of gray water scale inhibitors are respectively the same as the above steps (2﹚, ﹙3﹚, ﹙4﹚) for the gray water normal temperature non-heating scale inhibition rate experiment; and according to the water treatment agent The scale inhibition performance mathematical model calculates the scale inhibition rate data of the at least 5 kinds of gray water scale inhibitors under normal temperature without heating;

所述氯化钙标液配制方法如下：称取16.7g无水氯化钙溶于水中并定容到1000ml容量瓶中；The preparation method of the calcium chloride standard solution is as follows: Weigh 16.7g of anhydrous calcium chloride and dissolve it in water and set the volume to a 1000ml volumetric flask;

所述碳酸氢钠标液配制方法如下：称取25.2g碳酸氢钠溶于水中并定容到1000ml容量瓶中；所述碳酸氢钠标准溶液即为1ml含18.3mg HCO3 -的碳酸氢钠溶液；The preparation method of the sodium bicarbonate standard solution is as follows: Weigh 25.2g of sodium bicarbonate and dissolve it in water and set the volume to a 1000ml volumetric flask; the sodium bicarbonate standard solution is 1ml of sodium bicarbonate containing 18.3mg HCO 3 - solution;

所述硼砂缓冲溶液配制方法如下：称取3.8g十水四硼酸钠溶于水中并定容到1000ml容量瓶中；The preparation method of the borax buffer solution is as follows: Weigh 3.8g of sodium tetraborate decahydrate, dissolve it in water and set the volume to a 1000ml volumetric flask;

所述氯化钙标液标定方法如下：移取3-5ml氯化钙标液置于250ml锥形瓶中，依次加入50-80ml三级用分析纯水、3-5ml氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液滴定到由紫红色变为亮蓝色即为终点；The calcium chloride standard solution calibration method is as follows: pipette 3-5ml calcium chloride standard solution and place it in a 250ml conical flask, and sequentially add 50-80ml tertiary analytical pure water, 3-5ml potassium hydroxide solution and 0.1 g calcium carboxylic acid indicator, titrated with EDTA standard until it changes from purple to bright blue as the end point;

所述碳酸氢钠标液标定方法如下：移取3-5ml碳酸氢钠标液置于250ml锥形瓶中，依次加入50-80ml三级用分析纯水、滴加3-5滴溴甲酚绿-甲基红指示液，用盐酸标准滴定溶液滴定由浅蓝色变为紫色即为终点；The sodium bicarbonate standard solution calibration method is as follows: pipette 3-5ml sodium bicarbonate standard solution and place it in a 250ml conical flask, sequentially add 50-80ml tertiary analytical pure water, and drop 3-5 drops of bromocresol. Green-methyl red indicator solution, titration with standard hydrochloric acid titration solution from light blue to purple is the end point;

所述硼砂缓冲溶液pH为8.8-9.2，浓度为0.01mol/L。The pH of the borax buffer solution is 8.8-9.2, and the concentration is 0.01 mol/L.

发明人认为：The inventor believes that:

羟基乙叉二膦酸(HEDP)：Hydroxyethylidene diphosphonic acid (HEDP):

羟基乙叉二膦酸是一种有机磷系列的阻垢缓蚀剂，具有良好的阻垢缓蚀性能，由于C-P键很牢固，有较高的化学稳定性和热稳定性，在高温、高pH值条件下也难水解；耐酸碱性、耐氯氧化性能较其它有机磷酸好。HEDP中的膦酸根对Ca2+具有很强的螯合能力，同时对硅垢的抑制能力也很好,因而HEDP具较好的阻垢效果并具明显的溶限效应，当和2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物复配使用时，表现出理想的阻垢效果并具明显的溶限协同效应；由于含(-OH)基团，与POCA复配使用可以增强其磷酸钙垢阻垢效果。Hydroxyethylidene diphosphonic acid is a scale and corrosion inhibitor of organic phosphorus series. It has good scale and corrosion inhibition performance. Due to the strong CP bond, it has high chemical stability and thermal stability. It is also difficult to hydrolyze under pH conditions; acid and alkali resistance and chlorine oxidation resistance are better than other organic phosphoric acids. The phosphonate group in HEDP has a strong chelating ability to Ca 2+ , and also has a good ability to inhibit silica scale, so HEDP has a 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 used in combination with -2-methylpropanesulfonic acid copolymer, it shows ideal scale inhibition effect and has obvious solvent-limiting synergistic effect; due to the (-OH) group, it can enhance its calcium phosphate when used in combination with POCA. Scale-inhibiting effect.

2-膦酸丁烷-1,2,4-三羧酸(PBTCA)：2-Phosphonobutane-1,2,4-tricarboxylic acid (PBTCA):

PBTCA是一种有机膦酸，分子中含有一个膦酸基，还含有三个羧基，是一种高效阻垢剂，即使在很苛刻的条件下也能发挥很强的阻垢作用；在高温、高硬度、高碱度情况下，阻垢性能优于其他有机膦酸盐，阻碳酸钙垢的效果十分优良，尤其是在使用剂量低的情况下，是低分子阻垢剂中效果最好的，并且具有一定的缓蚀性能。且含磷量低，与HEDP复配使用可以有效的降低磷含量，适应目前环保要求的低磷阻垢剂配方，并且能减少阻垢剂的用量降低成本。PBTCA is an organic phosphonic acid, which contains one phosphonic acid group and three carboxyl groups in the molecule. It is a highly efficient scale inhibitor, which can exert a strong antiscale 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 calcium carbonate scale inhibition effect is very good, especially in the case of low dosage, it is the best low molecular scale inhibitor , and has a certain corrosion inhibition performance. 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.

马来酸-丙烯酸共聚物(MA/AA)：Maleic acid-acrylic acid copolymer (MA/AA):

是一种低分子量的聚电解质，含有羧酸基弱酸性基团，对碳酸盐垢的抑制作用很强，热稳定性高，可在300℃高温等恶劣条件下使用，与2-膦酸丁烷-1,2,4-三羧酸复配具有良好的相容性和协同增效作用，在高温、高硬度、高碱度情况下，阻垢性能增强；同时对包括磷酸盐在内的水垢的生成具有良好的抑制作用；还与有机膦酸盐HEDP等复配使用。It is a low-molecular-weight polyelectrolyte containing a weak acid group of carboxylic acid group, which has a strong inhibitory effect on carbonate scale and high thermal stability. It can be used under harsh conditions such as 300 °C high temperature. Butane-1,2,4-tricarboxylic acid compound has good compatibility and synergistic effect, under the condition of high temperature, high hardness and high alkalinity, the scale inhibition performance is enhanced; It has a good inhibitory effect on the formation of scale; it is also used in combination with organic phosphonates such as HEDP.

水解聚马来酸酐(HPMA)：Hydrolyzed Polymaleic Anhydride (HPMA):

HPMA是一种低分子量聚电解质，化学稳定性及热稳定性高。在高温和高pH下有明显的溶限效应。在300℃以下对碳酸盐仍具有良好的阻垢分散效果，阻垢时间可达100h。主要起作用的是-COOH基团，它对Ba2+、Ca2+、Mg2+、Fe3+、Cu2+等离子具有较强的螯合能力，不仅有分散和凝聚作用，还能在无机垢结晶过程中能够干扰晶格的正常排列，从而达到阻垢和防垢的目的。与2-膦酸丁烷-1,2,4-三羧酸、马来酸-丙烯酸共聚物复配在高温和高pH下有明显的溶限效应及阻垢和防垢效果增强。HPMA is a low molecular weight polyelectrolyte with high chemical and thermal stability. There is obvious solubility limit effect at high temperature and high pH. It still has good scale inhibition and dispersion effect on carbonate below 300℃, and the scale inhibition time can reach 100h. The main function is the -COOH group, which has strong chelating ability to Ba 2+ , Ca 2+ , Mg 2+ , Fe 3+ , Cu 2+ plasma, not only dispersing and agglomerating effect, but also in the During the crystallization process of inorganic scale, it can interfere with the normal arrangement of the crystal lattice, so as to achieve the purpose of scale inhibition and scale prevention. Compounding with 2-phosphonic acid butane-1,2,4-tricarboxylic acid and maleic acid-acrylic acid copolymer has obvious solubility limit effect and enhanced scale and anti-scaling effect at high temperature and high pH.

丙烯酸-丙烯酸羟丙酯共聚物：Acrylic-Hydroxypropyl Acrylate Copolymer:

丙烯酸-丙烯酸羟丙酯共聚物含有-COOH和-OH，羧酸基属弱酸性基团，对碳酸盐垢的抑制作用很强。羟基作为亲水基团对抑制磷酸盐垢有一定功效。且在较高温和碱性条件下仍具有良好的阻垢分散作用，与HPMA共用阻垢和防垢协同效应增强。Acrylic acid-hydroxypropyl acrylate copolymer contains -COOH and -OH, and the carboxylic acid group is a weak acid 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 higher temperature and alkaline conditions, and the synergistic effect of scale inhibition and scale prevention is enhanced when used with HPMA.

膦酰基羧酸共聚物(POCA)：Phosphonocarboxylic acid copolymer (POCA):

POCA结构中含有膦酰基，具有缓蚀性能，含有羧基、酯基和磺酸基，具有阻垢分散性能；由于多种官能团的有机结合，使得膦酰基羧基共聚物既具有优异的阻垢性能，又具有良好的分散氧化铁颗粒和稳定金属离子性能；同时还兼有较好的缓蚀性能，呈现出多功能的特点。对循环冷却水中的碳酸钙、磷酸钙垢有很好的分散性能，并且对硫酸钡和硫酸锶及硅垢的沉积有良好的抑制作用。POCA和有机膦酸(如HEDP、PBTCA)共聚物(如HPMA、MA/AA)复配具有阻垢分散性能增效作用。The POCA structure contains phosphono groups, which have corrosion inhibition properties, carboxyl groups, ester groups and sulfonic acid groups, and have scale inhibition and dispersion properties; due to the organic combination of various functional groups, the phosphonocarboxyl copolymers have excellent scale inhibition properties. It also has good properties of dispersing iron oxide particles and stabilizing metal ions; at the same time, it also has good corrosion inhibition properties, showing the characteristics of multi-function. It has good dispersing performance on 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 compounding of POCA and organic phosphonic acid (such as HEDP, PBTCA) copolymer (such as HPMA, MA/AA) has a synergistic effect of scale inhibition and dispersion performance.

丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物：Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer:

丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物具有在碱性水溶液中分散铁、锌氢氧化物和碳酸钙、磷酸钙的优良性能，具有磺酸基团，为强酸性基团，能提高聚合物抗阳离子沉淀的能力，稳定锌盐，抑制磷酸盐形成以及对氧化铁有良好的分散能力。适用于高温、高碱、高钙型的灰水水质，且与2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物复配有良好的协同效应。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. It has a sulfonic acid group and is a strong acid group. , can improve the ability of polymer to resist cationic precipitation, stabilize zinc salt, inhibit the formation of phosphate and have good dispersing ability to iron oxide. It is suitable for high-temperature, high-alkali, and high-calcium gray water quality, and can be combined with 2-phosphonic acid butane-1,2,4-tricarboxylic acid, maleic acid-acrylic acid copolymer, hydrolyzed polymaleic anhydride, acrylic acid- Hydroxypropyl acrylate copolymer and phosphonocarboxylic acid copolymer have good synergistic effect.

本发明将有机磷酸系列阻垢剂HEDP、PBTCA和聚羧酸型聚合物阻垢剂HPMA、POCA、丙烯酸-丙烯酸羟丙酯共聚物等复配使用，有机膦酸系列的阻垢剂和聚羧酸系列阻垢剂复配使用，由于磷酸系列阻垢剂稳定性强，而聚羧酸型阻垢剂因其结构中具有羧基、羟基、磺酸基等官能团，具有很好的水溶性，能与水中金属离子(如Ca2+、Mg2+等)形成稳定的水溶性配合物，对钙垢、硅垢等具有较好的分散性能，复配之后有很好的协同效应，对钙垢、硅垢的分散性能增强。另外灰水阻垢剂由于灰水特殊的水质要求阻垢剂耐高温，本发明选用的聚合物适用于高温条件下的阻垢和防垢。In the invention, organic phosphoric acid series scale inhibitors HEDP, PBTCA and polycarboxylic acid type polymer scale inhibitors HPMA, POCA, acrylic acid-hydroxypropyl acrylate copolymer and the like are used in combination, and organic phosphonic acid series scale inhibitors and polycarboxylate Acid series scale inhibitors are used in combination. Due to the strong stability of phosphoric acid series scale inhibitors, polycarboxylate scale inhibitors have good water solubility due to their structure with functional groups such as carboxyl, hydroxyl, and sulfonic acid groups. It forms stable water-soluble complexes with metal ions (such as Ca 2+ , Mg 2+ , etc.) in water, and has good dispersing properties for calcium scale, silica scale, etc. After compounding, it has a good synergistic effect. , The dispersion performance of silica scale is enhanced. In addition, because the special water quality of gray water requires the scale inhibitor to be resistant to high temperature, the polymer selected in the present invention is suitable for scale inhibition and anti-scaling under high temperature conditions.

本发明有益效果是：本发明制备的灰水阻垢剂均为液体产品复配而成，制备工序简单易生产，不需要加热处理；且本发明特别针对灰水高温、高碱、高pH值的水质特性而筛选配方，以阻碳酸钙垢为主、硫酸钙、磷酸钙等为辅；本发明制备的灰水阻垢剂具有耐钙性、耐pH性、耐高温性，同时具有很好的缓蚀阻垢性能，阻垢和防垢效果好，特别适用于电厂除灰系统。同时本发明设置了灰水阻垢剂耐温性试验，并取得了不同灰水阻垢剂在模拟不同灰水温度成垢条件下的阻垢率的数据，还取得了灰水阻垢剂在不加热灰水温度成垢条件下的阻垢率的数据；本发明可以快速、简单的通过列表进行数据比较筛选出适应不同灰水温度成垢条件的阻垢性能好的灰水阻垢剂；本发明的灰水阻垢剂筛选测试方法更贴近实际的不同灰水温度成垢使用条件，本发明的灰水阻垢剂筛选测试方法所筛选测试的灰水阻垢剂达到了预期的缓蚀阻垢效果；避免了所投加的灰水阻垢剂在灰水温度实际成垢条件下出现阻垢率降低而影响水力除灰效果现象的发生，提高了水力除灰工作效率。The beneficial effects of the present invention are: the grey water scale inhibitor prepared by the present invention is all compounded from liquid products, the preparation process is simple and easy to produce, and does not require heating; According to the water quality characteristics, the formula is screened, mainly calcium carbonate scale inhibitor, calcium sulfate, calcium phosphate, etc. as a supplement; the gray water scale inhibitor prepared by the present invention has calcium resistance, pH resistance, high temperature resistance, and has good It has excellent corrosion and scale inhibition performance, and has good scale and scale inhibition effects, especially suitable for power plant ash removal systems. At the same time, the present invention sets up the temperature resistance test of the grey water scale inhibitor, and obtains the data of the scale inhibition rate of different grey water scale inhibitors under the simulated scaling conditions of different grey water temperatures, and also obtains the grey water scale inhibitor in the The data of the scale inhibition rate under the condition of unheated grey water temperature scaling; the present invention can quickly and simply perform data comparison through a list to screen out a grey water scale inhibitor with good scale inhibition performance that adapts to different grey water temperature scaling conditions; The grey water scale inhibitor screening test method of the present invention is more close to the actual conditions of use of scale formation at different grey water temperatures, and the grey water scale inhibitor screened and tested by the grey water scale inhibitor screening test method of the present invention achieves the expected corrosion inhibition Scale inhibition effect; avoids the phenomenon that the scale inhibition rate of the added gray water scale inhibitor is reduced under the actual scaling condition of the gray water temperature and affects the hydraulic ash removal effect, and improves the hydraulic ash removal work efficiency.

具体实施方式Detailed ways

下面通过具体实施例对本发明作进一步的详细描述。The present invention will be further described in detail below through specific embodiments.

实施例1Example 1

一种灰水阻垢剂的制备方法，其特征是：所述灰水阻垢剂由下述重量百分比的原料配置而成：羟基乙叉二膦酸2％，2-膦酸丁烷-1,2,4-三羧酸14％，马来酸-丙烯酸共聚物28％，水解聚马来酸酐16％，丙烯酸-丙烯酸羟丙酯共聚物5％，膦酰基羧酸共聚物9％，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物7％，余量为纯净水；A preparation method of a grey water scale inhibitor, characterized in that: the grey water scale inhibitor is prepared from the following raw materials in percentage by weight: 2% hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1 ,2,4-tricarboxylic acid 14%, 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-methylpropanesulfonic acid copolymer 7%, the balance is pure water;

所述羟基乙叉二膦酸和2-膦酸丁烷-1,2,4-三羧酸活性物含量均为50％；The active content of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

所述马来酸-丙烯酸共聚物，丙烯酸-丙烯酸羟丙酯共聚物,膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物固体含量均为30％；The solid content of the maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer are all 30%;

所述水解聚马来酸酐固体含量为40％；The solid content of the hydrolyzed polymaleic anhydride is 40%;

主要包括下述步骤：It mainly includes the following steps:

A、在反应釜中按照上述重量百分比配比加入羟基乙叉二膦酸，开启搅拌机边搅拌边加入上述重量百分比配比的2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物，余量用纯净水补齐；A, add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above-mentioned weight percentage ratio, turn on the stirrer and add the 2-phosphonic acid butane-1,2,4-tricarboxylic acid of the above-mentioned 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 balance is pure water replenishment;

B、在反应釜中将上述羟基乙叉二膦酸，2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物和纯净水搅拌均匀后灌装塑料桶备用。B, in the reactor, 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 pure water are mixed evenly and then filled into plastic bucket for use.

一种灰水阻垢剂的筛选测试方法，其特征是：包括如下步骤：A screening test method for a grey water scale inhibitor, characterized in that it comprises the following steps:

﹙1﹚灰水阻垢剂耐温性处理试验：将上述一种灰水阻垢剂的制备方法制备的5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的每种灰水阻垢剂100ml分别分成相等的两份；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的一份50ml分别对应倒入5个的水热釜中，将装有灰水阻垢剂50ml的5个水热釜依次放入温度为200℃烘箱中进行加热30min，冷却；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的另一份50ml备用分别待做灰水常温不加热阻垢率实验；﹙1﹚Temperature resistance treatment test of grey water scale inhibitor: 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water prepared by the above-mentioned preparation method of grey water scale inhibitor 100ml of each grey water scale inhibitor of water scale inhibitor is divided into two equal parts; one part of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water scale inhibitor 50ml were poured into 5 hydrothermal kettles respectively, and 5 hydrothermal kettles containing 50ml of gray water scale inhibitor were sequentially placed in an oven with a temperature of 200°C for heating for 30min and cooling; five kinds of GN-2124, Another 50ml of GN-2125, GN-2126, GN-2127, and GN-2128 gray water scale inhibitors are to be used for the gray water scale inhibition test at room temperature without heating;

﹙2﹚阻垢率试液的制备：向5个500ml容量瓶中分别加入200ml三级分析用纯水；用滴定管分别再向所述5个500ml容量瓶中加入氯化钙标准溶液，使钙离子的量为115mg；再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂50ppm；再向所述5个500ml容量瓶中分别加入硼砂缓冲溶液20ml，用滴定管再分别向所述5个500ml容量瓶中加入碳酸氢钠标准溶液，使得所述5个500ml容量瓶中碳酸氢根离子的量分别为355mg；﹙2﹚Preparation of the test solution for scale inhibition rate: add 200ml of pure water for tertiary analysis into five 500ml volumetric flasks respectively; The amount of ions is 115mg; then add 50 ppm of gray water scale inhibitor after heating and cooling in step (1) correspondingly to the five 500ml volumetric flasks; then add borax to the five 500ml volumetric flasks respectively 20ml of buffer solution, add sodium bicarbonate standard solution to the five 500ml volumetric flasks with a burette, so that the amount of bicarbonate ions in the five 500ml volumetric flasks is respectively 355mg;

﹙3﹚空白试液的制备：除不加灰水阻垢剂外，步骤同(2)；﹙3﹚Preparation of blank test solution: the steps are the same as (2) except that no lime water scale inhibitor is added;

﹙4﹚阻垢率试验：将步骤﹙2﹚制成的5个500ml容量瓶中的阻垢率试液和步骤﹙3﹚制成的空白试液分别对应倒入5个阻垢率试液锥形瓶内和一个空白试液锥形瓶内，将分别装有阻垢率试液和空白试液的5个阻垢率试液锥形瓶和一个空白试液锥形瓶分别放置于79℃恒温水浴锅中，放置10h；冷却后将5个阻垢率试液锥形瓶中的阻垢率试液和一个空白试液锥形瓶中的空白试液分别用中速定量滤纸过滤得到阻垢率试液滤液和空白试液滤液备用；分别移取所述阻垢率试液滤液20ml置于5个250ml锥形瓶中，移取所述空白试液滤液20ml置于1个250ml空白试液锥形瓶中，再分别依次向装有阻垢率试液滤液的5个250ml锥形瓶和1个250ml空白试液滤液锥形瓶中内加入50ml三级用分析纯水、3ml浓度为200g/L的氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液分别滴定到由紫红色变为亮蓝色即为终点；﹙4﹚Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks prepared in step ﹙2﹚ and the blank test solution prepared in step ﹙3﹚ into 5 scale inhibition rate test solutions respectively. In the conical flask and a blank test solution conical flask, place 5 scale inhibition rate test solution conical flasks and a blank test solution conical flask respectively in 79 ℃ constant temperature water bath, placed for 10h; after cooling, the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in a blank test solution conical flask were respectively filtered with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are for use; pipette 20ml of the scale inhibition rate test solution filtrate and place them in five 250ml conical flasks, pipette 20ml of the blank test solution filtrate and place them in one 250ml blank In the conical flask of the test solution, 50ml of tertiary analytical pure water and 3ml of concentration of It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until the end point is changed from purple red to bright blue;

﹙5﹚药剂筛选：根据水处理剂阻垢性能数学模型即﹙5﹚Reagent screening: According to the mathematical model of the scale inhibition performance of the water treatment agent, the

以百分率表示的水处理剂阻垢性能按以下式(1)计算The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η＝(ρ4-ρ3)/(0.240-ρ3)×100％....式(1)η=(ρ 4 -ρ 3 )/(0.240-ρ 3 )×100%.... Formula (1)

式(1)中ρ4-加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；In the formula (1), ρ 4 - the value of the calcium (Ca 2+ ) concentration after adding the test solution of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ3-未加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；ρ 3 - the value of calcium (Ca 2+ ) concentration after the test solution without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-试验前配制好的试液中钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；0.240 - the value of calcium (Ca 2+ ) concentration in the test solution prepared before the test, in milligrams per milliliter, mg/ml;

钙离子(Ca2+)的含量以质量浓度ρ计，数值以mg/ml表示，按式(2)计算；The content of calcium ions (Ca 2+ ) is calculated in terms of mass concentration ρ, and the value is expressed in mg/ml, and is calculated according to formula (2);

ρ＝V1cM/V....式(2)ρ=V 1 cM/V.... Formula (2)

式(2)中V1-滴定中消耗EDTA标液的体积，单位为毫升(ml)；In formula (2), the volume of EDTA standard solution consumed in V 1 -titration, the unit is milliliter (ml);

c-EDTA标液的实际浓度准确数值，单位为摩尔每升(mol/L)；The exact value of the actual concentration of c-EDTA standard solution, the unit is mole per liter (mol/L);

V-所取氯化钙标液体积的数值，单位为毫升(ml)；V-the value of the volume of the calcium chloride standard solution taken, in milliliters (ml);

M-钙(Ca2+)摩尔质量的数值，单位为克每摩尔(g/mol)，(M＝40.08)M - Numerical value of the molar mass of calcium (Ca 2+ ) in grams per mole (g/mol), (M=40.08)

分别计算5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一200℃加热温度下阻垢率数据，比较5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一200℃加热温度下阻垢率高低，并筛选出阻垢率高的一个灰水阻垢剂；Calculate the scale inhibition rate data of five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitors at the same heating temperature of 200℃, and compare the five kinds of GN-2124, GN-2125 , GN-2126, GN-2127, GN-2128 gray water scale inhibitor at the same 200 ℃ heating temperature, and screen out a gray water scale inhibitor with high scale inhibition rate;

所述至少5种灰水阻垢剂的另一份50-60ml分别做灰水常温不加热阻垢率实验的步骤同上述步骤﹙2﹚、﹙3﹚、﹙4﹚，并将步骤﹙2﹚中的内容：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂50ppm；更换为：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚分别待做灰水常温阻垢率实验的5个灰水阻垢剂50ppm；并根据水处理剂阻垢性能数学模型分别计算该至少5种灰水阻垢剂在常温不加热状态下的阻垢率数据；The other 50-60ml of the at least 5 kinds of gray water scale inhibitors are respectively used in the gray water normal temperature non-heating scale inhibition rate experiments. Contents in ﹚: Then add the 50 ppm of gray water scale inhibitor in step ﹙1﹚ after heating and cooling to the 5 500ml volumetric flasks in sequence; replace with: then add to the 5 500ml volumetric flasks in sequence Correspondingly adding step (1), 50 ppm of 5 grey water scale inhibitors to be tested for the scale inhibition rate of grey water at room temperature respectively; Scale inhibition rate data without heating;

所述氯化钙标液配制方法如下：称取16.7g无水氯化钙溶于水中并定容到1000ml容量瓶中；The preparation method of the calcium chloride standard solution is as follows: Weigh 16.7g of anhydrous calcium chloride and dissolve it in water and set the volume to a 1000ml volumetric flask;

所述碳酸氢钠标液配制方法如下：称取25.2g碳酸氢钠溶于水中并定容到1000ml容量瓶中；所述碳酸氢钠标准溶液即为1ml含18.3mg HCO3 -的碳酸氢钠溶液；The preparation method of the sodium bicarbonate standard solution is as follows: Weigh 25.2g of sodium bicarbonate and dissolve it in water and set the volume to a 1000ml volumetric flask; the sodium bicarbonate standard solution is 1ml of sodium bicarbonate containing 18.3mg HCO 3 - solution;

所述硼砂缓冲溶液配制方法如下：称取3.8g十水四硼酸钠溶于水中并定容到1000ml容量瓶中；The preparation method of the borax buffer solution is as follows: Weigh 3.8g of sodium tetraborate decahydrate, dissolve it in water and set the volume to a 1000ml volumetric flask;

所述氯化钙标液标定方法如下：移取3ml氯化钙标液置于250ml锥形瓶中，依次加入50ml三级用分析纯水、3ml氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液滴定到由紫红色变为亮蓝色即为终点；The calibration method of the calcium chloride standard solution is as follows: pipette 3ml of the calcium chloride standard solution and place it in a 250ml conical flask, and sequentially add 50ml of tertiary analytical pure water, 3ml of potassium hydroxide solution and 0.1g of calcium carboxylic acid indicator , titrated with EDTA standard until it changes from purple to bright blue as the end point;

所述碳酸氢钠标液标定方法如下：移取3ml碳酸氢钠标液置于250ml锥形瓶中，依次加入50ml三级用分析纯水、滴加3滴溴甲酚绿-甲基红指示液，用盐酸标准滴定溶液滴定由浅蓝色变为紫色即为终点；The sodium bicarbonate standard solution calibration method is as follows: pipette 3ml sodium bicarbonate standard solution and place it in a 250ml conical flask, sequentially add 50ml tertiary analytical pure water, drop 3 drops of bromocresol green-methyl red indicator The end point is titrated from light blue to purple with standard hydrochloric acid titration solution;

所述硼砂缓冲溶液pH为8.8，浓度为0.01mol/L。The pH of the borax buffer solution is 8.8, and the concentration is 0.01 mol/L.

实施例2Example 2

一种灰水阻垢剂的制备方法，其特征是：所述灰水阻垢剂由下述重量百分比的原料配置而成：羟基乙叉二膦酸4％，2-膦酸丁烷-1,2,4-三羧酸10％，马来酸-丙烯酸共聚物30％，水解聚马来酸酐14％，丙烯酸-丙烯酸羟丙酯共聚物8％，膦酰基羧酸共聚物6％，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物10％，余量为纯净水；A preparation method of a grey water scale inhibitor, characterized in that: the grey water scale inhibitor is prepared from the following raw materials by weight percentage: 4% of hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1 ,2,4-tricarboxylic acid 10%, 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-methylpropanesulfonic acid copolymer 10%, the balance is pure water;

所述羟基乙叉二膦酸和2-膦酸丁烷-1,2,4-三羧酸活性物含量均为50％；The active content of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

所述马来酸-丙烯酸共聚物，丙烯酸-丙烯酸羟丙酯共聚物,膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物固体含量均为30％；The solid content of the maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer are all 30%;

所述水解聚马来酸酐固体含量为40％；The solid content of the hydrolyzed polymaleic anhydride is 40%;

主要包括下述步骤：It mainly includes the following steps:

A、在反应釜中按照上述的重量百分比配比加入羟基乙叉二膦酸，开启搅拌机边搅拌边加入上述的重量百分比配比的2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物，余量用纯净水补齐；A, in the reaction kettle, add hydroxyethylidene diphosphonic acid according to the above-mentioned weight percentage ratio, open the stirrer and add the 2-phosphonic acid butane-1,2,4-tricarboxylic acid of the above-mentioned weight percentage ratio 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、在反应釜中将上述羟基乙叉二膦酸，2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物和纯净水搅拌均匀后灌装塑料桶备用。B, in the reactor, 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 pure water are mixed evenly and then filled into plastic bucket for use.

一种灰水阻垢剂的筛选测试方法，其特征是：包括如下步骤：A screening test method for a grey water scale inhibitor, characterized in that it comprises the following steps:

﹙1﹚灰水阻垢剂耐温性处理试验：将上述一种灰水阻垢剂的制备方法制备的5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的每种灰水阻垢剂110ml分别分成相等的两份；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的一份55ml分别对应倒入5个的水热釜中，将装有灰水阻垢剂55ml的5个水热釜依次放入温度为230℃烘箱中进行加热30min，冷却；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的另一份55ml备用分别待做灰水常温不加热阻垢率实验；﹙1﹚Temperature resistance treatment test of grey water scale inhibitor: 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water prepared by the above-mentioned preparation method of grey water scale inhibitor 110ml of each grey water scale inhibitor of water scale inhibitor is divided into two equal parts; one part of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water scale inhibitor 55ml were poured into 5 hydrothermal kettles correspondingly, and 5 hydrothermal kettles containing 55ml of gray water scale inhibitor were sequentially placed in an oven with a temperature of 230°C for heating for 30min and cooling; five kinds of GN-2124, Another 55ml of GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitor is to be used for the gray water scale inhibition rate experiment at room temperature without heating;

﹙2﹚阻垢率试液的制备：向5个500ml容量瓶中分别加入225ml三级分析用纯水；用滴定管分别再向所述5个500ml容量瓶中加入氯化钙标准溶液，使钙离子的量为120mg；再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂75ppm；再向所述5个500ml容量瓶中分别加入硼砂缓冲溶液25ml，用滴定管再分别向所述5个500ml容量瓶中加入碳酸氢钠标准溶液，使得所述5个500ml容量瓶中碳酸氢根离子的量分别为360mg；﹙2﹚Preparation of the test solution for scale inhibition rate: add 225ml of pure water for tertiary analysis into five 500ml volumetric flasks respectively; The amount of ions is 120mg; then add 5 pieces of gray water scale inhibitor 75ppm corresponding to step (1) after heating and cooling into the 5 500ml volumetric flasks in turn; then add borax to the 5 500ml volumetric flasks respectively 25ml of buffer solution, add sodium bicarbonate standard solution to the five 500ml volumetric flasks with a burette, so that the amount of bicarbonate ions in the five 500ml volumetric flasks is respectively 360mg;

﹙3﹚空白试液的制备：除不加灰水阻垢剂药剂外，步骤同(2)；﹙3﹚Preparation of blank test solution: The steps are the same as (2) except that no lime water scale inhibitor is added;

﹙4﹚阻垢率试验：将步骤﹙2﹚制成的5个500ml容量瓶中的阻垢率试液和步骤﹙3﹚制成的空白试液分别对应倒入5个阻垢率试液锥形瓶内和一个空白试液锥形瓶内，将分别装有阻垢率试液和空白试液的5个阻垢率试液锥形瓶和一个空白试液锥形瓶分别放置于80℃恒温水浴锅中，放置10h；冷却后将5个阻垢率试液锥形瓶中的阻垢率试液和一个空白试液锥形瓶中的空白试液分别用中速定量滤纸过滤得到阻垢率试液滤液和空白试液滤液备用；分别移取所述阻垢率试液滤液25ml置于5个250ml锥形瓶中，移取所述空白试液滤液25ml置于1个250ml空白试液锥形瓶中，再分别依次向装有阻垢率试液滤液的5个250ml锥形瓶和1个250ml空白试液滤液锥形瓶中内加入60ml三级用分析纯水、4ml浓度为200g/L的氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液分别滴定到由紫红色变为亮蓝色即为终点；﹙4﹚Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks prepared in step ﹙2﹚ and the blank test solution prepared in step ﹙3﹚ into 5 scale inhibition rate test solutions respectively. In the conical flask and one blank test solution conical flask, place 5 scale inhibition rate test solution conical flasks and one blank test solution conical flask with scale inhibition rate test solution and blank test solution respectively in 80 ℃ constant temperature water bath, placed for 10h; after cooling, the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in a blank test solution conical flask were respectively filtered with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are for use; pipette 25ml of the scale inhibition rate test solution filtrate and place them in five 250ml conical flasks, pipette 25ml of the blank test solution filtrate and place them in one 250ml blank In the test solution conical flask, add 60ml tertiary analytical pure water and 4ml concentration to five 250ml conical flasks and one 250ml blank test solution filtrate containing the scale inhibition rate test solution filtrate in turn. It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until the end point is changed from purple red to bright blue;

﹙5﹚药剂筛选：根据水处理剂阻垢性能数学模型即﹙5﹚Reagent screening: According to the mathematical model of the scale inhibition performance of the water treatment agent, the

以百分率表示的水处理剂阻垢性能按以下式(1)计算The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η＝(ρ4-ρ3)/(0.240-ρ3)×100％....式(1)η=(ρ 4 -ρ 3 )/(0.240-ρ 3 )×100%.... Formula (1)

式(1)中ρ4-加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；In the formula (1), ρ 4 - the value of the calcium (Ca 2+ ) concentration after adding the test solution of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ3-未加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；ρ 3 - the value of calcium (Ca 2+ ) concentration after the test solution without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-试验前配制好的试液中钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；0.240 - the value of calcium (Ca 2+ ) concentration in the test solution prepared before the test, in milligrams per milliliter, mg/ml;

钙离子(Ca2+)的含量以质量浓度ρ计，数值以mg/ml表示，按式(2)计算；The content of calcium ions (Ca 2+ ) is calculated in terms of mass concentration ρ, and the value is expressed in mg/ml, and is calculated according to formula (2);

ρ＝V1cM/V....式(2)ρ=V 1 cM/V.... Formula (2)

式(2)中V1-滴定中消耗EDTA标液的体积，单位为毫升(ml)；In formula (2), the volume of EDTA standard solution consumed in V 1 -titration, the unit is milliliter (ml);

c-EDTA标液的实际浓度准确数值，单位为摩尔每升(mol/L)；The exact value of the actual concentration of c-EDTA standard solution, the unit is mole per liter (mol/L);

V-所取氯化钙标液体积的数值，单位为毫升(ml)；V-the value of the volume of the calcium chloride standard solution taken, in milliliters (ml);

M-钙(Ca2+)摩尔质量的数值，单位为克每摩尔(g/mol)，(M＝40.08)M - Numerical value of the molar mass of calcium (Ca 2+ ) in grams per mole (g/mol), (M=40.08)

分别计算5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一230℃加热温度下阻垢率数据，比较5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一230℃加热温度下阻垢率高低，并筛选出阻垢率高的一个灰水阻垢剂；Calculate the scale inhibition rate data of five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitors at the same heating temperature of 230℃, and compare the five kinds of GN-2124, GN-2125 , GN-2126, GN-2127, GN-2128 gray water scale inhibitor at the same 230 ℃ heating temperature, and screen out a gray water scale inhibitor with high scale inhibition rate;

所述至少5种灰水阻垢剂的另一份55ml分别做灰水常温不加热阻垢率实验的步骤同上述步骤﹙2﹚、﹙3﹚、﹙4﹚，并将步骤﹙2﹚中的内容：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂75ppm；更换为：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚分别待做灰水常温阻垢率实验的5个灰水阻垢剂75ppm；并根据水处理剂阻垢性能数学模型分别计算该至少5种灰水阻垢剂在常温不加热状态下的阻垢率数据；The other 55ml of the at least 5 kinds of gray water scale inhibitors are respectively used in the gray water normal temperature unheated scale inhibition rate experiments. Contents: Add 5 pieces of gray water scale inhibitor 75ppm after heating and cooling in step (1) correspondingly to the 5 500ml volumetric flasks in turn; replace with: then add the 5 pieces of 500ml volumetric flasks correspondingly in turn Step ﹙1﹚5 gray water scale inhibitors 75ppm to be used for the gray water scale inhibition rate experiment at room temperature respectively; and according to the mathematical model of the scale inhibition performance of the water treatment agent, calculate the at least 5 kinds of gray water scale inhibitors at room temperature without heating Scale inhibition rate data under state;

所述氯化钙标液配制方法如下：称取16.7g无水氯化钙溶于水中并定容到1000ml容量瓶中；The preparation method of the calcium chloride standard solution is as follows: Weigh 16.7g of anhydrous calcium chloride and dissolve it in water and set the volume to a 1000ml volumetric flask;

所述碳酸氢钠标液配制方法如下：称取25.2g碳酸氢钠溶于水中并定容到1000ml容量瓶中；所述碳酸氢钠标准溶液即为1ml含18.3mg HCO3 -的碳酸氢钠溶液；The preparation method of the sodium bicarbonate standard solution is as follows: Weigh 25.2g of sodium bicarbonate and dissolve it in water and set the volume to a 1000ml volumetric flask; the sodium bicarbonate standard solution is 1ml of sodium bicarbonate containing 18.3mg HCO 3 - solution;

所述硼砂缓冲溶液配制方法如下：称取3.8g十水四硼酸钠溶于水中并定容到1000ml容量瓶中；The preparation method of the borax buffer solution is as follows: Weigh 3.8g of sodium tetraborate decahydrate, dissolve it in water and set the volume to a 1000ml volumetric flask;

所述氯化钙标液标定方法如下：移取4ml氯化钙标液置于250ml锥形瓶中，依次加入60ml三级用分析纯水、4ml氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液滴定到由紫红色变为亮蓝色即为终点；The calcium chloride standard solution calibration method is as follows: pipette 4ml of calcium chloride standard solution and place it in a 250ml conical flask, add 60ml of tertiary analytical pure water, 4ml of potassium hydroxide solution and 0.1g of calcium carboxylic acid indicator in turn. , titrated with EDTA standard until it changes from purple to bright blue as the end point;

所述碳酸氢钠标液标定方法如下：移取4ml碳酸氢钠标液置于250ml锥形瓶中，依次加入60ml三级用分析纯水、滴加4滴溴甲酚绿-甲基红指示液，用盐酸标准滴定溶液滴定由浅蓝色变为紫色即为终点；The sodium bicarbonate standard solution calibration method is as follows: pipette 4ml sodium bicarbonate standard solution and place it in a 250ml conical flask, sequentially add 60ml third-grade analytical pure water, drop 4 drops of bromocresol green-methyl red indicator The end point is titrated from light blue to purple with standard hydrochloric acid titration solution;

所述硼砂缓冲溶液pH为9.0，浓度为0.01mol/L。The pH of the borax buffer solution is 9.0, and the concentration is 0.01 mol/L.

实施例3Example 3

一种灰水阻垢剂的制备方法，其特征是：所述灰水阻垢剂由下述重量百分比的原料配置而成：羟基乙叉二膦酸6％，2-膦酸丁烷-1,2,4-三羧酸15％，马来酸-丙烯酸共聚物20％，水解聚马来酸酐20％，丙烯酸-丙烯酸羟丙酯共聚物7％，膦酰基羧酸共聚物7％，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物6％，余量为纯净水；A preparation method of a grey water scale inhibitor, characterized in that: the grey water scale inhibitor is prepared from the following raw materials by weight percentage: 6% of hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1 ,2,4-tricarboxylic acid 15%, 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-methylpropanesulfonic acid copolymer 6%, the balance is pure water;

所述羟基乙叉二膦酸和2-膦酸丁烷-1,2,4-三羧酸活性物含量均为50％；The active content of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

所述马来酸-丙烯酸共聚物，丙烯酸-丙烯酸羟丙酯共聚物,膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物固体含量均为30％；The solid content of the maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer are all 30%;

所述水解聚马来酸酐固体含量为40％；The solid content of the hydrolyzed polymaleic anhydride is 40%;

主要包括下述步骤：It mainly includes the following steps:

A、在反应釜中按照上述的重量百分比配比加入羟基乙叉二膦酸，开启搅拌机边搅拌边加入上述的重量百分比配比的2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物，余量用纯净水补齐；A, in the reaction kettle, add hydroxyethylidene diphosphonic acid according to the above-mentioned weight percentage ratio, open the stirrer and add the 2-phosphonic acid butane-1,2,4-tricarboxylic acid of the above-mentioned weight percentage ratio 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、在反应釜中将上述羟基乙叉二膦酸，2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物和纯净水搅拌均匀后灌装塑料桶备用。B, in the reactor, 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 pure water are mixed evenly and then filled into plastic bucket for use.

一种灰水阻垢剂的筛选测试方法，其特征是：包括如下步骤：A screening test method for a grey water scale inhibitor, characterized in that it comprises the following steps:

﹙1﹚灰水阻垢剂耐温性处理试验：将上述一种灰水阻垢剂的制备方法制备的5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的每种灰水阻垢剂110ml分别分成相等的两份；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的一份55ml分别对应倒入5个的水热釜中，将装有灰水阻垢剂55ml的5个水热釜依次放入温度为260℃烘箱中进行加热30min，冷却；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的另一份55ml备用分别待做灰水常温不加热阻垢率实验；﹙1﹚Temperature resistance treatment test of grey water scale inhibitor: 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water prepared by the above-mentioned preparation method of grey water scale inhibitor 110ml of each grey water scale inhibitor of water scale inhibitor is divided into two equal parts; one part of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water scale inhibitor 55ml were poured into 5 hydrothermal kettles respectively, and 5 hydrothermal kettles containing 55ml of grey water scale inhibitor were sequentially placed in an oven with a temperature of 260°C for heating for 30min and cooling; 5 kinds of GN-2124, Another 55ml of GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitor is to be used for the gray water scale inhibition rate experiment at room temperature without heating;

﹙2﹚阻垢率试液的制备：向5个500ml容量瓶中分别加入225ml三级分析用纯水；用滴定管分别再向所述5个500ml容量瓶中加入氯化钙标准溶液，使钙离子的量为120mg；再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂90ppm；再向所述5个500ml容量瓶中分别加入硼砂缓冲溶液25ml，用滴定管再分别向所述5个500ml容量瓶中加入碳酸氢钠标准溶液，使得所述5个500ml容量瓶中碳酸氢根离子的量分别为365mg；﹙2﹚Preparation of the test solution for scale inhibition rate: add 225ml of pure water for tertiary analysis into five 500ml volumetric flasks respectively; The amount of ions is 120mg; then add the 5 gray water scale inhibitor 90ppm corresponding to step (1) after heating and cooling into the 5 500ml volumetric flasks in turn; then add borax to the 5 500ml volumetric flasks respectively 25ml of buffer solution, add sodium bicarbonate standard solution to the five 500ml volumetric flasks with a burette, so that the amount of bicarbonate ions in the five 500ml volumetric flasks is respectively 365mg;

﹙3﹚空白试液的制备：除不加灰水阻垢剂药剂外，步骤同(2)；﹙3﹚Preparation of blank test solution: The steps are the same as (2) except that no lime water scale inhibitor is added;

﹙4﹚阻垢率试验：将步骤﹙2﹚制成的5个500ml容量瓶中的阻垢率试液和步骤﹙3﹚制成的空白试液分别对应倒入5个阻垢率试液锥形瓶内和一个空白试液锥形瓶内，将分别装有阻垢率试液和空白试液的5个阻垢率试液锥形瓶和一个空白试液锥形瓶分别放置于80℃恒温水浴锅中，放置10h；冷却后将5个阻垢率试液锥形瓶中的阻垢率试液和一个空白试液锥形瓶中的空白试液分别用中速定量滤纸过滤得到阻垢率试液滤液和空白试液滤液备用；分别移取所述阻垢率试液滤液25ml置于5个250ml锥形瓶中，移取所述空白试液滤液25ml置于1个250ml空白试液锥形瓶中，再分别依次向装有阻垢率试液滤液的5个250ml锥形瓶和1个250ml空白试液滤液锥形瓶中内加入70ml三级用分析纯水、5ml浓度为200g/L的氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液分别滴定到由紫红色变为亮蓝色即为终点；﹙4﹚Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks prepared in step ﹙2﹚ and the blank test solution prepared in step ﹙3﹚ into 5 scale inhibition rate test solutions respectively. In the conical flask and one blank test solution conical flask, place 5 scale inhibition rate test solution conical flasks and one blank test solution conical flask with scale inhibition rate test solution and blank test solution respectively in 80 ℃ constant temperature water bath, placed for 10h; after cooling, the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in a blank test solution conical flask were respectively filtered with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are for use; pipette 25ml of the scale inhibition rate test solution filtrate and place them in five 250ml conical flasks, pipette 25ml of the blank test solution filtrate and place them in one 250ml blank In the conical flask of the test solution, 70ml of tertiary analytical pure water and 5ml of concentration of It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until the end point is changed from purple red to bright blue;

﹙5﹚药剂筛选：根据水处理剂阻垢性能数学模型即﹙5﹚Reagent screening: According to the mathematical model of the scale inhibition performance of the water treatment agent, the

以百分率表示的水处理剂阻垢性能按以下式(1)计算The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η＝(ρ4-ρ3)/(0.240-ρ3)×100％....式(1)η=(ρ 4 -ρ 3 )/(0.240-ρ 3 )×100%.... Formula (1)

式(1)中ρ4-加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；In the formula (1), ρ 4 - the value of the calcium (Ca 2+ ) concentration after adding the test solution of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ3-未加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；ρ 3 - the value of calcium (Ca 2+ ) concentration after the test solution without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-试验前配制好的试液中钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；0.240 - the value of calcium (Ca 2+ ) concentration in the test solution prepared before the test, in milligrams per milliliter, mg/ml;

钙离子(Ca2+)的含量以质量浓度ρ计，数值以mg/ml表示，按式(2)计算；The content of calcium ions (Ca 2+ ) is calculated in terms of mass concentration ρ, and the value is expressed in mg/ml, and is calculated according to formula (2);

ρ＝V1cM/V....式(2)ρ=V 1 cM/V.... Formula (2)

式(2)中V1-滴定中消耗EDTA标液的体积，单位为毫升(ml)；In formula (2), the volume of EDTA standard solution consumed in V 1 -titration, the unit is milliliter (ml);

c-EDTA标液的实际浓度准确数值，单位为摩尔每升(mol/L)；The exact value of the actual concentration of c-EDTA standard solution, the unit is mole per liter (mol/L);

V-所取氯化钙标液体积的数值，单位为毫升(ml)；V-the value of the volume of the calcium chloride standard solution taken, in milliliters (ml);

M-钙(Ca2+)摩尔质量的数值，单位为克每摩尔(g/mol)，(M＝40.08)M - Numerical value of the molar mass of calcium (Ca 2+ ) in grams per mole (g/mol), (M=40.08)

分别计算5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一260℃加热温度下阻垢率数据，比较5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一260℃加热温度下阻垢率高低，并筛选出阻垢率高的一个灰水阻垢剂；Calculate the scale inhibition rate data of five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitors at the same heating temperature of 260℃, and compare the five kinds of GN-2124, GN-2125 , GN-2126, GN-2127, GN-2128 gray water scale inhibitor at the same 260 ℃ heating temperature, the scale inhibition rate is high, and screened out a gray water scale inhibitor with high scale inhibition rate;

所述至少5种灰水阻垢剂的另一份55ml分别做灰水常温不加热阻垢率实验的步骤同上述步骤﹙2﹚、﹙3﹚、﹙4﹚，并将步骤﹙2﹚中的内容：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂90ppm；更换为：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚分别待做灰水常温阻垢率实验的5个灰水阻垢剂90ppm；并根据水处理剂阻垢性能数学模型分别计算该至少5种灰水阻垢剂在常温不加热状态下的阻垢率数据；The other 55ml of the at least 5 kinds of gray water scale inhibitors are respectively used in the gray water normal temperature unheated scale inhibition rate experiments. Contents: Add 5 pieces of gray water scale inhibitor 90ppm after heating and cooling in step (1) correspondingly to the 5 500ml volumetric flasks in turn; replace with: then add the 5 pieces of 500ml volumetric flasks correspondingly in turn Step ﹙1﹚ Add 5 grey water scale inhibitors 90 ppm to be used in the grey water normal temperature scale inhibition rate experiment respectively; and calculate the at least 5 kinds of grey water scale inhibitors at room temperature without heating according to the mathematical model of the scale inhibition performance of the water treatment agent. Scale inhibition rate data under state;

所述氯化钙标液配制方法如下：称取16.7g无水氯化钙溶于水中并定容到1000ml容量瓶中；The preparation method of the calcium chloride standard solution is as follows: Weigh 16.7g of anhydrous calcium chloride and dissolve it in water and set the volume to a 1000ml volumetric flask;

所述碳酸氢钠标液配制方法如下：称取25.2g碳酸氢钠溶于水中并定容到1000ml容量瓶中；所述碳酸氢钠标准溶液即为1ml含18.3mg HCO3 -的碳酸氢钠溶液；The preparation method of the sodium bicarbonate standard solution is as follows: Weigh 25.2g of sodium bicarbonate and dissolve it in water and set the volume to a 1000ml volumetric flask; the sodium bicarbonate standard solution is 1ml of sodium bicarbonate containing 18.3mg HCO 3 - solution;

所述硼砂缓冲溶液配制方法如下：称取3.8g十水四硼酸钠溶于水中并定容到1000ml容量瓶中；The preparation method of the borax buffer solution is as follows: Weigh 3.8g of sodium tetraborate decahydrate, dissolve it in water and set the volume to a 1000ml volumetric flask;

所述氯化钙标液标定方法如下：移取5ml氯化钙标液置于250ml锥形瓶中，依次加入70ml三级用分析纯水、5ml氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液滴定到由紫红色变为亮蓝色即为终点；The calcium chloride standard solution calibration method is as follows: pipette 5ml of calcium chloride standard solution and place it in a 250ml conical flask, add 70ml of tertiary analytical pure water, 5ml of potassium hydroxide solution and 0.1g of calcium carboxylic acid indicator in turn. , titrated with EDTA standard until it changes from purple to bright blue as the end point;

所述碳酸氢钠标液标定方法如下：移取5ml碳酸氢钠标液置于250ml锥形瓶中，依次加入70ml三级用分析纯水、滴加5滴溴甲酚绿-甲基红指示液，用盐酸标准滴定溶液滴定由浅蓝色变为紫色即为终点；The sodium bicarbonate standard solution calibration method is as follows: pipette 5ml sodium bicarbonate standard solution and place it in a 250ml conical flask, sequentially add 70ml tertiary analytical pure water, drop 5 drops of bromocresol green-methyl red indicator The end point is titrated from light blue to purple with standard hydrochloric acid titration solution;

所述硼砂缓冲溶液pH为9.1，浓度为0.01mol/L。The pH of the borax buffer solution is 9.1, and the concentration is 0.01 mol/L.

实施例4Example 4

一种灰水阻垢剂的制备方法，其特征是：所述灰水阻垢剂由下述重量百分比的原料配置而成：羟基乙叉二膦酸10％，2-膦酸丁烷-1,2,4-三羧酸12％，马来酸-丙烯酸共聚物24％，水解聚马来酸酐12％，丙烯酸-丙烯酸羟丙酯共聚物6％，膦酰基羧酸共聚物10％，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物5％，余量为纯净水；A preparation method of a grey water scale inhibitor, characterized in that: the grey water scale inhibitor is prepared from the following raw materials by weight percentage: 10% of hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1 ,2,4-tricarboxylic acid 12%, 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-methylpropanesulfonic acid copolymer 5%, the balance is pure water;

所述羟基乙叉二膦酸和2-膦酸丁烷-1,2,4-三羧酸活性物含量均为50％；The active content of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%;

所述马来酸-丙烯酸共聚物，丙烯酸-丙烯酸羟丙酯共聚物,膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物固体含量均为30％；The solid content of the maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer are all 30%;

所述水解聚马来酸酐固体含量为40％；The solid content of the hydrolyzed polymaleic anhydride is 40%;

主要包括下述步骤：It mainly includes the following steps:

A、在反应釜中按照上述的重量百分比配比加入羟基乙叉二膦酸，开启搅拌机边搅拌边加入上述的重量百分比配比的2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物，余量用纯净水补齐；A, in the reaction kettle, add hydroxyethylidene diphosphonic acid according to the above-mentioned weight percent proportioning, turn on the stirrer and add the 2-phosphonic acid butane-1,2,4-tricarboxylic acid of the above-mentioned weight percent proportioning 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、在反应釜中将上述羟基乙叉二膦酸，2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物和纯净水搅拌均匀后灌装塑料桶备用。B, in the reactor, 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 pure water are mixed evenly and then filled into plastic bucket for use.

一种灰水阻垢剂的筛选测试方法，其特征是：包括如下步骤：A screening test method for a grey water scale inhibitor, characterized in that it comprises the following steps:

﹙1﹚灰水阻垢剂耐温性处理试验：将上述一种灰水阻垢剂的制备方法制备的5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的每种灰水阻垢剂120ml分别分成相等的两份；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的一份60ml分别对应倒入5个的水热釜中，将装有灰水阻垢剂60ml的5个水热釜依次放入温度为300℃烘箱中进行加热30min，冷却；将5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂的另一份60ml备用分别待做灰水常温不加热阻垢率实验；﹙1﹚Temperature resistance treatment test of grey water scale inhibitor: 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water prepared by the above-mentioned preparation method of grey water scale inhibitor 120ml of each grey water scale inhibitor of water scale inhibitor is divided into two equal parts; one part of 5 kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 grey water scale inhibitors 60ml were poured into 5 hydrothermal kettles respectively, and 5 hydrothermal kettles containing 60ml of gray water scale inhibitor were placed in an oven with a temperature of 300°C for heating for 30min and cooling; 5 kinds of GN-2124, Another 60ml of GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitor is to be used for the gray water scale inhibition rate experiment at room temperature without heating;

﹙2﹚阻垢率试液的制备：向5个500ml容量瓶中分别加入250ml三级分析用纯水；用滴定管分别再向所述5个500ml容量瓶中加入氯化钙标准溶液，使钙离子的量为125mg；再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂100ppm；再向所述5个500ml容量瓶中分别加入硼砂缓冲溶液25ml，用滴定管再分别向所述5个500ml容量瓶中加入碳酸氢钠标准溶液，使得所述5个500ml容量瓶中碳酸氢根离子的量分别为370mg；﹙2﹚Preparation of the test solution for scale inhibition rate: add 250ml of pure water for tertiary analysis into five 500ml volumetric flasks respectively; The amount of ions is 125mg; then add 100ppm of 5 gray water antiscalants after heating and cooling in step (1) to the 5 500ml volumetric flasks in turn; then add borax to the 5 500ml volumetric flasks respectively 25ml of buffer solution, add sodium bicarbonate standard solution to the five 500ml volumetric flasks with a burette, so that the amount of bicarbonate ions in the five 500ml volumetric flasks is respectively 370mg;

﹙3﹚空白试液的制备：除不加灰水阻垢剂药剂外，步骤同(2)；﹙3﹚Preparation of blank test solution: The steps are the same as (2) except that no lime water scale inhibitor is added;

﹙4﹚阻垢率试验：将步骤﹙2﹚制成的5个500ml容量瓶中的阻垢率试液和步骤﹙3﹚制成的空白试液分别对应倒入5个阻垢率试液锥形瓶内和一个空白试液锥形瓶内，将分别装有阻垢率试液和空白试液的5个阻垢率试液锥形瓶和一个空白试液锥形瓶分别放置于81℃恒温水浴锅中，放置10h；冷却后将5个阻垢率试液锥形瓶中的阻垢率试液和一个空白试液锥形瓶中的空白试液分别用中速定量滤纸过滤得到阻垢率试液滤液和空白试液滤液备用；分别移取所述阻垢率试液滤液25ml置于5个250ml锥形瓶中，移取所述空白试液滤液25ml置于1个250ml空白试液锥形瓶中，再分别依次向装有阻垢率试液滤液的5个250ml锥形瓶和1个250ml空白试液滤液锥形瓶中内加入80ml三级用分析纯水、5ml浓度为200g/L的氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液分别滴定到由紫红色变为亮蓝色即为终点；﹙4﹚Scale inhibition rate test: Pour the scale inhibition rate test solution in five 500ml volumetric flasks prepared in step ﹙2﹚ and the blank test solution prepared in step ﹙3﹚ into 5 scale inhibition rate test solutions respectively. In the conical flask and one blank test solution conical flask, place 5 scale inhibition rate test solution conical flasks and one blank test solution conical flask with scale inhibition rate test solution and blank test solution respectively in 81. ℃ constant temperature water bath, placed for 10h; after cooling, the scale inhibition rate test solution in five conical flasks of scale inhibition rate test solution and the blank test solution in a blank test solution conical flask were respectively filtered with medium-speed quantitative filter paper to obtain The scale inhibition rate test solution filtrate and the blank test solution filtrate are for use; pipette 25ml of the scale inhibition rate test solution filtrate and place them in five 250ml conical flasks, pipette 25ml of the blank test solution filtrate and place them in one 250ml blank In the conical flask of the test solution, 80ml of tertiary analytical pure water and 5ml of concentration of It is 200g/L potassium hydroxide solution and 0.1g calcium carboxylic acid indicator, respectively titrated with EDTA standard solution until the end point is changed from purple red to bright blue;

﹙5﹚药剂筛选：根据水处理剂阻垢性能数学模型即﹙5﹚Reagent screening: According to the mathematical model of the scale inhibition performance of the water treatment agent, the

以百分率表示的水处理剂阻垢性能按以下式(1)计算The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1)

η＝(ρ4-ρ3)/(0.240-ρ3)×100％....式(1)η=(ρ 4 -ρ 3 )/(0.240-ρ 3 )×100%.... Formula (1)

式(1)中ρ4-加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；In the formula (1), ρ 4 - the value of the calcium (Ca 2+ ) concentration after adding the test solution of the water treatment agent, the unit is milligram per milliliter, mg/ml;

ρ3-未加入水处理药剂的试液试验后的钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；ρ 3 - the value of calcium (Ca 2+ ) concentration after the test solution without adding water treatment agent, the unit is milligram per milliliter, mg/ml;

0.240-试验前配制好的试液中钙(Ca2+)浓度的数值，单位为毫克每毫升，mg/ml；0.240 - the value of calcium (Ca 2+ ) concentration in the test solution prepared before the test, in milligrams per milliliter, mg/ml;

钙离子(Ca2+)的含量以质量浓度ρ计，数值以mg/ml表示，按式(2)计算；The content of calcium ions (Ca 2+ ) is calculated in terms of mass concentration ρ, and the value is expressed in mg/ml, and is calculated according to formula (2);

ρ＝V1cM/V....式(2)ρ=V 1 cM/V.... Formula (2)

式(2)中V1-滴定中消耗EDTA标液的体积，单位为毫升(ml)；In formula (2), the volume of EDTA standard solution consumed in V 1 -titration, the unit is milliliter (ml);

c-EDTA标液的实际浓度准确数值，单位为摩尔每升(mol/L)；The exact value of the actual concentration of c-EDTA standard solution, the unit is mole per liter (mol/L);

V-所取氯化钙标液体积的数值，单位为毫升(ml)；V-the value of the volume of the calcium chloride standard solution taken, in milliliters (ml);

M-钙(Ca2+)摩尔质量的数值，单位为克每摩尔(g/mol)，(M＝40.08)M - Numerical value of the molar mass of calcium (Ca 2+ ) in grams per mole (g/mol), (M=40.08)

分别计算5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一300℃加热温度下阻垢率数据，比较5种GN-2124、GN-2125、GN-2126、GN-2127、GN-2128灰水阻垢剂在同一300℃加热温度下阻垢率高低，并筛选出阻垢率高的一个灰水阻垢剂；Calculate the scale inhibition rate data of five kinds of GN-2124, GN-2125, GN-2126, GN-2127, GN-2128 gray water scale inhibitors at the same heating temperature of 300℃, and compare the five kinds of GN-2124, GN-2125 , GN-2126, GN-2127, GN-2128 gray water scale inhibitor at the same 300 ℃ heating temperature, the scale inhibition rate is high, and screened out a gray water scale inhibitor with high scale inhibition rate;

所述至少5种灰水阻垢剂的另一份60ml分别做灰水常温不加热阻垢率实验的步骤同上述步骤﹙2﹚、﹙3﹚、﹙4﹚，并将步骤﹙2﹚中的内容：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚加热冷却后的5个灰水阻垢剂100ppm；更换为：再向所述5个500ml容量瓶中依次相对应加入步骤﹙1﹚分别待做灰水常温阻垢率实验的5个灰水阻垢剂100ppm；并根据水处理剂阻垢性能数学模型分别计算该至少5种灰水阻垢剂在常温不加热状态下阻垢率数据；The other 60ml of the at least 5 kinds of grey water scale inhibitors are respectively used in the grey water normal temperature unheated scale inhibition rate experiment. Contents: Add 5 pieces of gray water scale inhibitor 100ppm after heating and cooling in step (1) to the 5 500ml volumetric flasks in sequence; replace with: then add to the 5 500ml volumetric flasks in sequence correspondingly Step ﹙1﹚ Add 100 ppm of 5 grey water scale inhibitors to be used for the grey water scale inhibition rate experiment at room temperature respectively; and calculate the at least 5 kinds of grey water scale inhibitors without heating at room temperature according to the mathematical model of the scale inhibition performance of the water treatment agent. Scale inhibition rate data under state;

所述氯化钙标液配制方法如下：称取16.7g无水氯化钙溶于水中并定容到1000ml容量瓶中；The preparation method of the calcium chloride standard solution is as follows: Weigh 16.7g of anhydrous calcium chloride and dissolve it in water and set the volume to a 1000ml volumetric flask;

所述碳酸氢钠标液配制方法如下：称取25.2g碳酸氢钠溶于水中并定容到1000ml容量瓶中；所述碳酸氢钠标准溶液即为1ml含18.3mg HCO3 -的碳酸氢钠溶液；The preparation method of the sodium bicarbonate standard solution is as follows: Weigh 25.2g of sodium bicarbonate and dissolve it in water and set the volume to a 1000ml volumetric flask; the sodium bicarbonate standard solution is 1ml of sodium bicarbonate containing 18.3mg HCO 3 - solution;

所述硼砂缓冲溶液配制方法如下：称取3.8g十水四硼酸钠溶于水中并定容到1000ml容量瓶中；The preparation method of the borax buffer solution is as follows: Weigh 3.8g of sodium tetraborate decahydrate, dissolve it in water and set the volume to a 1000ml volumetric flask;

所述氯化钙标液标定方法如下：移取5ml氯化钙标液置于250ml锥形瓶中，依次加入80ml三级用分析纯水、5ml氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液滴定到由紫红色变为亮蓝色即为终点；The calcium chloride standard solution calibration method is as follows: pipette 5ml of calcium chloride standard solution and place it in a 250ml conical flask, add 80ml of tertiary analytical pure water, 5ml of potassium hydroxide solution and 0.1g of calcium carboxylic acid indicator in turn. , titrated with EDTA standard until it changes from purple to bright blue as the end point;

所述碳酸氢钠标液标定方法如下：移取5ml碳酸氢钠标液置于250ml锥形瓶中，依次加入80ml三级用分析纯水、滴加5滴溴甲酚绿-甲基红指示液，用盐酸标准滴定溶液滴定由浅蓝色变为紫色即为终点；The sodium bicarbonate standard solution calibration method is as follows: pipette 5ml sodium bicarbonate standard solution and place it in a 250ml conical flask, sequentially add 80ml third-grade analytical pure water, drop 5 drops of bromocresol green-methyl red indicator The end point is titrated from light blue to purple with standard hydrochloric acid titration solution;

所述硼砂缓冲溶液pH为9.2，浓度为0.01mol/L。The pH of the borax buffer solution is 9.2, and the concentration is 0.01 mol/L.

本表是上述4个实施例所计算出的5种灰水阻垢剂阻垢率试验数据This table is the test data of the scale inhibition rate of 5 kinds of grey water scale inhibitors calculated by the above 4 examples

Figure GDA0002635060210000161
Figure GDA0002635060210000161

Figure GDA0002635060210000171
Figure GDA0002635060210000171

Figure GDA0002635060210000181
Figure GDA0002635060210000181

通过上述的说明内容，本领域技术人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改都在本发明的保护范围之内。本发明的未尽事宜，属于本领域技术人员的公知常识。Based on 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 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 (2)

1.一种灰水阻垢剂的制备方法，其特征是：所述灰水阻垢剂由下述重量百分比的原料配置而成：羟基乙叉二膦酸2％-10％，2-膦酸丁烷-1,2,4-三羧酸10％-15％，马来酸-丙烯酸共聚物20％-30％，水解聚马来酸酐10％-20％，丙烯酸-丙烯酸羟丙酯共聚物5％-10％，膦酰基羧酸共聚物5％-15％，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物5％-10％，余量为纯净水；1. a preparation method of grey water scale inhibitor, it is characterized in that: described grey water scale inhibitor is configured by the following raw material by weight percentage: hydroxyethylidene diphosphonic acid 2%-10%, 2-phosphine 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% of organic matter, 5%-15% of phosphonocarboxylic acid copolymer, 5%-10% of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, and the balance is pure water; 所述羟基乙叉二膦酸和2-膦酸丁烷-1,2,4-三羧酸活性物含量均为50％；The active content of the hydroxyethylidene diphosphonic acid and 2-phosphonic acid butane-1,2,4-tricarboxylic acid is both 50%; 所述马来酸-丙烯酸共聚物，丙烯酸-丙烯酸羟丙酯共聚物,膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物固体含量均为30％；The solid content of the maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, phosphonocarboxylic acid copolymer, and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer are all 30%; 所述水解聚马来酸酐固体含量为40％；The solid content of the hydrolyzed polymaleic anhydride is 40%; 主要包括下述步骤：It mainly includes the following steps: A、在反应釜中按照上述重量百分比配比加入羟基乙叉二膦酸，开启搅拌机边搅拌边加入上述重量百分比配比的2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物，余量用纯净水补齐；A, add hydroxyethylidene diphosphonic acid in the reaction kettle according to the above-mentioned weight percentage ratio, turn on the stirrer and add the 2-phosphonic acid butane-1,2,4-tricarboxylic acid of the above-mentioned 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 balance is pure water replenishment; B、在反应釜中将上述羟基乙叉二膦酸，2-膦酸丁烷-1,2,4-三羧酸，马来酸-丙烯酸共聚物，水解聚马来酸酐，丙烯酸-丙烯酸羟丙酯共聚物，膦酰基羧酸共聚物，丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物和纯净水搅拌均匀后灌装塑料桶备用。B, in the reactor, 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 pure water are mixed evenly and then filled into plastic bucket for use. 2.如权利要求1所述一种灰水阻垢剂的制备方法制备的灰水阻垢剂的筛选测试方法，其特征是：包括如下步骤：2. the screening test method of the grey water scale inhibitor prepared by the preparation method of a kind of grey water scale inhibitor as claimed in claim 1, is characterized in that: comprise the steps: (1﹚灰水阻垢剂耐温性处理试验：将至少5种灰水阻垢剂的每种灰水阻垢剂100-120ml分别分成相等的两份；将至少5种灰水阻垢剂的一份50-60ml分别对应倒入至少5个水热釜中，将装有灰水阻垢剂50-60ml的至少5个水热釜依次放入温度为200-300℃烘箱中，装有灰水阻垢剂50-60ml的至少5个水热釜在该烘箱设定的同一温度加热30min，冷却；将至少5种灰水阻垢剂的另一份50-60ml备用分别待做灰水常温不加热阻垢率实验；(1﹚Grey water scale inhibitor temperature resistance treatment test: divide 100-120ml of each grey water scale inhibitor of at least 5 kinds of grey water scale inhibitors into two equal parts; at least 5 kinds of grey water scale inhibitors are divided into two equal parts; 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 with a temperature of 200-300 ° C in turn, and are equipped with At least 5 hydrothermal kettles of 50-60ml of grey water scale inhibitor are heated for 30min at the same temperature set by the oven, and cooled; another 50-60ml of at least 5 kinds of grey water scale inhibitor are separately prepared as grey water. Scale inhibition rate experiment without heating at room temperature; (2﹚阻垢率试液的制备：向至少5个500ml容量瓶中分别加入200-250ml三级分析用纯水；用滴定管分别再向所述至少5个500ml容量瓶中加入氯化钙标准溶液，使钙离子的量为115-125mg；再向所述至少5个500ml容量瓶中依次相对应加入步骤(1﹚加热冷却后的至少5个灰水阻垢剂50ppm-100ppm；再向所述至少5个500ml容量瓶中分别加入硼砂缓冲溶液20-25ml，用滴定管再分别向所述至少5个500ml容量瓶中加入碳酸氢钠标准溶液，使得所述至少5个500ml容量瓶中碳酸氢根离子的量分别为355-370mg；(2) Preparation of test solution for scale inhibition rate: add 200-250ml of pure water for tertiary analysis to at least five 500ml volumetric flasks respectively; use a burette to add calcium chloride standard to the at least five 500ml volumetric flasks respectively solution, so that the amount of calcium ions is 115-125mg; then add step (1) to the at least 5 500ml volumetric flasks in turn correspondingly to add at least 5 gray water scale inhibitors 50ppm-100ppm after heating and cooling; Add 20-25ml of borax buffer solution to the at least five 500ml volumetric flasks respectively, and then add sodium bicarbonate standard solution to the at least five 500ml volumetric flasks with a burette, so that the hydrogen carbonate in the at least five 500ml volumetric flasks The amount of root ions is 355-370mg; (3﹚空白试液的制备：除不加灰水阻垢剂药剂外，步骤同(2)；(3) Preparation of blank test solution: the steps are the same as (2) except that no grey water scale inhibitor is added; (4﹚阻垢率试验：将步骤(2﹚制成的至少5个500ml容量瓶中的阻垢率试液和步骤(3﹚制成的空白试液分别对应倒入至少5个阻垢率试液锥形瓶内和一个空白试液锥形瓶内，将分别装有阻垢率试液和空白试液的至少5个阻垢率试液锥形瓶和一个空白试液锥形瓶分别放置于79-81℃恒温水浴锅中，放置10h；冷却后将至少5个阻垢率试液锥形瓶中的阻垢率试液和一个空白试液锥形瓶中的空白试液分别用中速定量滤纸过滤得到阻垢率试液滤液和空白试液滤液备用；分别移取所述阻垢率试液滤液20-25ml置于至少5个250ml锥形瓶中，移取所述空白试液滤液20-25ml置于1个250ml空白试液锥形瓶中，再分别依次向装有阻垢率试液滤液的至少5个250ml锥形瓶和1个250ml空白试液滤液锥形瓶中内加入50-80ml三级用分析纯水、3-5ml浓度为200g/L的氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液分别滴定到由紫红色变为亮蓝色即为终点；(4﹚Scaling inhibition rate test: Pour at least 5 scale inhibition rate test solutions in at least 5 500ml volumetric flasks prepared in step (2﹚ and the blank test solution prepared in step (3﹚) respectively. In the test solution conical flask and one blank test solution conical flask, place at least 5 scale inhibition rate test solution conical flasks and one blank test solution conical flask respectively with scale inhibition rate test solution and blank test solution respectively. Place it in a constant temperature water bath at 79-81°C for 10 hours; after cooling, use at least 5 scale inhibition rate test solution in conical flasks and a blank test solution in a blank test solution conical flask respectively. Filter with medium-speed quantitative filter paper to obtain scale inhibition rate test solution filtrate and blank test solution filtrate for use; pipette 20-25ml of the scale inhibition rate test solution filtrate and place them in at least 5 250ml conical flasks, and pipette the blank test solution. Put 20-25ml of the filtrate into a 250ml blank test solution conical flask, and then put them into at least five 250ml conical flasks and one 250ml blank test solution filtrate in turn 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 to bright blue. is the end point; (5﹚药剂筛选：根据水处理剂阻垢性能数学模型分别计算至少5种灰水阻垢剂在同一加热温度下阻垢率数据，比较至少5种灰水阻垢剂在同一加热温度下阻垢率高低，并筛选出阻垢率高的一个灰水阻垢剂；(5) Reagent screening: Calculate the scale inhibition rate data of at least 5 kinds of gray water scale inhibitors at the same heating temperature according to the mathematical model of the scale inhibition performance of the water treatment agent, and compare the resistance of at least 5 kinds of gray water scale inhibitors at the same heating temperature. The scale rate is high and low, and a gray water scale inhibitor with high scale inhibition rate is screened out; 所述至少5种灰水阻垢剂的另一份50-60ml分别做灰水常温不加热阻垢率实验的步骤同上述步骤(2﹚、(3﹚、(4﹚；并根据水处理剂阻垢性能数学模型分别计算该至少5种灰水阻垢剂在常温不加热状态下的阻垢率数据；The other 50-60ml of the at least 5 kinds of gray water scale inhibitors are respectively the same as the above steps (2﹚, (3﹚, (4﹚; and according to the water treatment agent) The scale inhibition performance mathematical model calculates the scale inhibition rate data of the at least 5 kinds of gray water scale inhibitors under normal temperature without heating; 所述水处理剂阻垢性能数学模型为：The mathematical model of the scale inhibition performance of the water treatment agent is: 以百分率表示的水处理剂阻垢性能按以下式(1)计算The scale inhibition performance of the water treatment agent expressed in percentage is calculated according to the following formula (1) η＝(ρ4-ρ3)/(0.240-ρ3)×100％ 式(1)η=(ρ 4 -ρ 3 )/(0.240-ρ 3 )×100% Equation (1) 式(1)中ρ4为加入水处理药剂的试液试验后的Ca2+浓度的数值，单位为毫克每毫升；In the formula (1), ρ 4 is the numerical value of the Ca concentration after adding the test solution of the water treatment agent, and the unit is milligrams per milliliter; ρ3为未加入水处理药剂的试液试验后的Ca2+浓度的数值，单位为毫克每毫升；ρ 3 is the numerical value of Ca 2+ concentration after the test solution without adding water treatment agent, the unit is milligram per milliliter; 0.240为试验前配制好的试液中Ca2+浓度的数值，单位为毫克每毫升；0.240 is the value of Ca 2+ concentration in the test solution prepared before the test, in milligrams per milliliter; Ca2+的含量以质量浓度ρ计，数值以mg/ml表示，按式(2)计算；The content of Ca 2+ is calculated in terms of mass concentration ρ, and the value is expressed in mg/ml, and is calculated according to formula (2); ρ＝V1cM/V 式(2)ρ=V 1 cM/V Formula (2) 式(2)中V1为滴定中消耗EDTA标液的体积，单位为毫升；In formula (2), V 1 is the volume of EDTA standard solution consumed in the titration, and the unit is milliliter; c为EDTA标液的实际浓度准确数值，单位为摩尔每升；c is the exact value of the actual concentration of the EDTA standard solution, in moles per liter; V为所取氯化钙标液体积的数值，单位为毫升；V is the value of the volume of the calcium chloride standard solution taken, in milliliters; M为Ca2+摩尔质量的数值，单位为克每摩尔，M＝40.08；M is the value of the molar mass of Ca 2+ , in grams per mole, M=40.08; 所述氯化钙标液配制方法如下：称取16.7g无水氯化钙溶于水中并定容到1000ml容量瓶中；The preparation method of the calcium chloride standard solution is as follows: Weigh 16.7g of anhydrous calcium chloride and dissolve it in water and set the volume to a 1000ml volumetric flask; 所述碳酸氢钠标液配制方法如下：称取25.2g碳酸氢钠溶于水中并定容到1000ml容量瓶中；所述碳酸氢钠标准溶液即为1ml含18.3mg HCO3 -的碳酸氢钠溶液；The preparation method of the sodium bicarbonate standard solution is as follows: Weigh 25.2g of sodium bicarbonate and dissolve it in water and set the volume to a 1000ml volumetric flask; the sodium bicarbonate standard solution is 1ml of sodium bicarbonate containing 18.3mg HCO 3 - solution; 所述硼砂缓冲溶液配制方法如下：称取3.8g十水四硼酸钠溶于水中并定容到1000ml容量瓶中；The preparation method of the borax buffer solution is as follows: Weigh 3.8g of sodium tetraborate decahydrate, dissolve it in water and set the volume to a 1000ml volumetric flask; 所述硼砂缓冲溶液pH为8.8-9.2，浓度为0.01mol/L；The pH of the borax buffer solution is 8.8-9.2, and the concentration is 0.01 mol/L; 所述氯化钙标液标定方法如下：移取3-5ml氯化钙标液置于250ml锥形瓶中，依次加入50-80ml三级用分析纯水、3-5ml氢氧化钾溶液和0.1g钙羧酸指示剂，用EDTA标液滴定到由紫红色变为亮蓝色即为终点；The calcium chloride standard solution calibration method is as follows: pipette 3-5ml calcium chloride standard solution and place it in a 250ml conical flask, and sequentially add 50-80ml tertiary analytical pure water, 3-5ml potassium hydroxide solution and 0.1 g calcium carboxylic acid indicator, titrated with EDTA standard until it changes from purple to bright blue as the end point; 所述碳酸氢钠标液标定方法如下：移取3-5ml碳酸氢钠标液置于250ml锥形瓶中，依次加入50-80ml三级用分析纯水、滴加3-5滴溴甲酚绿-甲基红指示液，用盐酸标准滴定溶液滴定由浅蓝色变为紫色即为终点。The sodium bicarbonate standard solution calibration method is as follows: pipette 3-5ml sodium bicarbonate standard solution and place it in a 250ml conical flask, sequentially add 50-80ml tertiary analytical pure water, and drop 3-5 drops of bromocresol. Green-methyl red indicator solution, titration with standard hydrochloric acid titration solution from light blue to purple is the end point.
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