CN102583792A - Method for preparing composite industrial circulating cooling water scale inhibitor - Google Patents

Abstract

The invention discloses a method for preparing a composite industrial circulating cooling water scale inhibitor. The method is characterized in that the scale inhibitor is composite and comprises the following components in percentage by mass: 35 to 40 percent of polyepoxysuccinic acid, 18 to 25 percent of polyaspartic acid, 15 to 20 percent of acrylic-2-acrylamide-2-methyl propanesulfonic acid, 18 to 28 percent of hydroxyethylidenediphosphonic acid, and the balance of water; and the pH of the scale inhibitor is regulated by using sodium hydroxide. The invention also discloses the method for preparing the composite scale inhibitor. The prepared scale inhibitor has an excellent scale inhibiting effect on CaCO3, Ca3(PO4)2, BaSO4 and SrSO4 scales, and also has inhibition performance, high temperature resistance and controllable molecular weight; and 'three wastes' are not discharged in the whole production process. The method for treating the industrial circulating water, oilfield water and the like is simple in process, low in agent consumption and low in cost, has a good effect, and has good economic benefits and wide social benefits.

Description

A kind of preparation method of composite industrial circulating cooling water scale inhibitor

technical field

The invention belongs to the technical field of chemical industry and relates to a novel water quality stabilizer for circulating water treatment, specifically a stabilizer containing polyepoxysuccinic acid, polyaspartic acid, acrylic acid-2-acrylamide-2-methylpropane The preparation method of the composite scale inhibitor of sulfonic acid and hydroxyethylidene diphosphoric acid.

Background technique

With the rapid development of industrial production, water quality is deteriorating and water consumption is increasing. Since cooling water consumption accounts for 60-70% of industrial water consumption, it is particularly important to save cooling water reasonably. The main way to save cooling water is to increase the recycling rate of cooling water and increase the concentration of cooling water, but this will bring serious corrosion and scaling problems to the cooling water system, and also put forward higher requirements for scale inhibitors. requirements.

As a kind of water treatment agent, antiscalant is widely used in circulating cooling water systems in petroleum, chemical industry, electric power, papermaking, metallurgy, pharmaceutical and other industries. Since the 1960s, water treatment agents have been continuously developed, and most of them are naturally polymerized Lignin, sodium phytate, etc. are used as scale-inhibiting dispersants, and the scale-inhibiting effect is not ideal. The successful development of polyacrylic acid (PAA) and polymaleic acid (PMA) in the early 1970s made a breakthrough in the technology of antiscalant treatment of cooling water, and led to a series of binary, ternary and even antiscalants containing various groups. Development and use of tetrapolymers. At present, the Chinese patent publication application number is 200410066828.3 "A Corrosion and Scale Inhibitor for Industrial Cooling Water System", the application number is 200610137772.5 "A Scale Inhibitor and Its Application in Water Treatment", and the application number is 200710051679.7 "Preparation method of high-efficiency maleic anhydride polymer scale inhibitor", application number 200710022984.3 "A phosphorus-free and environmentally friendly corrosion and scale inhibitor and its preparation method", application number 2007101339925.5 "Allyloxy polyether Anti-scaling agent and preparation method" application number is 200710177189.1 "a corrosion and scale inhibitor for boiler heating network", application number is 200810055017.1 "a corrosion and scale inhibitor for industrial circulating cooling water", application number is 200810123729.2" A quaternary polymer type corrosion and scale inhibitor and its preparation method", etc., the above-mentioned patented technologies all adopt copolymerization. In recent years, with the enhancement of people's awareness of environmental protection, the synthesis of new biodegradable scale inhibitors has gradually attracted the attention of the world, and many environmentally friendly scale inhibitors have come out, among which polyaspartic acid, poly Epoxy succinic acid, at present, the Chinese patent application number is 02111415.3 "preparation method of environmentally friendly scale inhibitor polyaspartic acid" application number is 200410015875.5 "biodegradable corrosion and scale inhibitor polyaspartic acid Preparation method", application number 200610012918.3 "a polyaspartic acid copolymer and its preparation method", application number 200710173243.5 "preparation method of glycine/aspartic acid copolymer used as green scale inhibitor", etc., The scale inhibition effect of aspartic acid scale inhibitor is very good, but the price is relatively expensive, and many enterprises do not use it in order to reduce production costs. Comrades such as Wang Xiange studied "The performance and mechanism of scale inhibition of compound scale inhibitors", Journal of Northeastern University (Natural Science Edition), 2010, 31(6): 909-912, the scale inhibition effect on CaCO ₃ is relatively good, The scale inhibition effect on CaSO ₄ and Fe ₂ O ₃ is relatively poor, and the shelf life of this compound scale inhibitor is very short, and flocculent precipitation occurs within one month; Zhang Yanhe and other comrades studied "aconitic acid-acrylic acid copolymer Research on the synthesis and performance of "Industrial Water Treatment, 2005, 25(2): 48～49, when the addition amount is 15mg/L, the scale inhibition rate reaches 65.71%. After the copolymer is compounded with HEDP and PBTCA, there is Synergistic scale inhibition effect, the scale inhibition rates were 768.0% and 83.91%. Due to the complexity and variability of the water quality of industrial cooling circulating water, a single antiscalant is far from meeting the requirements of industrial water treatment. It is necessary to use several multi-component polymerizations for compounding to introduce more active groups into the compound. Among antiscalants, it gives water treatment agents more and more excellent performance. After investigating the latest research results and experience of compound water treatment agents at home and abroad, the present invention has successfully developed a green and environmentally friendly scale inhibitor suitable for complex water environments through repeated experiments. The scale inhibitor contains -COOH, -SO ₃ H, -OH, -NH ₂ , -PO ₃ and other active groups, a compound scale inhibitor with excellent performance.

Contents of the invention

The object of the present invention is to provide a kind of preparation method of composite industrial circulating cooling water corrosion and scale inhibitor, it is characterized in that, this composite scale inhibitor is made of polyepoxysuccinic acid, polyaspartic acid, acrylic acid-2 -acrylamide-2-methylpropanesulfonic acid, hydroxyethylidene diphosphoric acid, sodium hydroxide and water, wherein each component is by mass percentage: polyepoxysuccinic acid (PESA): 35-40%; polyaspartic acid Acrylic acid (PASP): 18-25%; Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS): 15-20%; Hydroxyethylidene diphosphate (HEDP): 18-28%; The rest is water, with sodium hydroxide to adjust the pH.

A preparation method of composite scale inhibitor, comprising the steps of:

(1) mixing polyepoxysuccinic acid and polyaspartic acid in a mass percentage of 1: 0.5 to 0.7;

(2) Then add 15-20% acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS), 20-25% hydroxyethylidene diphosphoric acid (HEDP), mix well, and add a certain amount deionized water, then stirred and reacted at a constant temperature of 65-70°C for 1.5-2.0 hours, stopped the reaction, cooled to about 50°C, added 50% NaOH solution dropwise to the product, adjusted the pH to nearly neutral, and obtained a light yellow The transparent liquid is the compound antiscalant.

The scale inhibitor prepared by the invention can be widely used in circulating cooling water systems in petroleum, chemical industry, electric power, papermaking, metallurgy, pharmaceutical and other industries to inhibit scaling of cooling water.

The invention has the following advantages: (1) less dosage, low cost, strong scale inhibition ability, excellent scale inhibition effect on calcium, magnesium, barium, strontium and iron scale, good product quality, and a shelf life of more than one year; (2) The thermal stability is good, and the product is biodegradable; (3) The conditions required for the synthesis process are easy to control, the energy consumption is low, the operation is simple, and there is no "three wastes" discharge in the whole production process, which belongs to the clean production process; (4) The antiscalant is in liquid state, opened at the pipe 5 meters before the inlet pipe of cooling water, and pumped into the pipe through the metering pump.

Detailed ways

Example 1

(1) Take 18mL polyepoxysuccinic acid and 10mL polyaspartic acid and place them in a reaction flask, and mix them;

(2) Then add 8mL of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS) and 10mL of hydroxyethylidene diphosphoric acid (HEDP), mix well, add 5mL of deionized water, and stir again React at a constant temperature of 65°C for 2.0 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is a composite scale inhibitor.

Example 2

(1) Take 20mL polyepoxysuccinic acid and 12mL polyaspartic acid and place them in a reaction flask, and mix them;

(2) Then add 10mL of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS) and 12mL of hydroxyethylidene diphosphoric acid (HEDP), mix well, add 5mL of deionized water, and stir again React at a constant temperature of 70°C for 1.5 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is a composite scale inhibitor.

Example 3

(1) Take 15mL polyepoxysuccinic acid and 8mL polyaspartic acid and place them in a reaction flask, and mix them;

(2) Then add 8mL of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS) and 10mL of hydroxyethylidene diphosphoric acid (HEDP), mix well, add 5mL of deionized water, and stir again React at a constant temperature of 65°C for 1.5 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is a composite scale inhibitor.

Example 4

(1) Take 20mL polyepoxysuccinic acid and 10mL polyaspartic acid and place them in the reaction flask, mix well;

(2) Then add 8mL of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS) and 10mL of hydroxyethylidene diphosphoric acid (HEDP), mix well, add 8mL of deionized water, and stir again React at a constant temperature of 70°C for 2.0 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is a composite scale inhibitor.

Example 5

(1) Take 18mL polyepoxysuccinic acid and 12mL polyaspartic acid and place them in a reaction flask, and mix them;

(2) Then add 10mL of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS) and 12mL of hydroxyethylidene diphosphoric acid (HEDP), mix well, add 8mL of deionized water, and stir again React at a constant temperature of 65°C for 1.5 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is a composite scale inhibitor.

Example 6

(1) Take 18mL polyepoxysuccinic acid and 10mL polyaspartic acid and place them in a reaction flask, mix well;

(2) Then add 8 mL of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid (AA/AMPS) and 12 mL of hydroxyethylidene diphosphoric acid (HEDP), mix well, add 5 mL of deionized water, and stir again React at a constant temperature of 70°C for 2.0 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is a composite scale inhibitor.

Example 7

Anti-scaling performance test experiment

Calcium carbonate and calcium phosphate static scale inhibition performance test method is based on GB/T 16632-2008 and GB/T 22626-2008 to measure the scale inhibition performance of scale inhibitors respectively. The experimental conditions for calcium carbonate scale inhibition are: the concentration of Ca ²⁺ is 250mg/L, HCO ₃ ^{-concentration} 250mg/L, pH=7~9, temperature 80℃, time 10h; experimental conditions for calcium phosphate scale inhibition: Ca ²⁺ concentration 250mg/L, PO ₄ ^{3 -} The concentration is 5mg/L, the temperature is 80°C, and the time is 10h. The scale inhibition performance is shown in Table 1; the static scale inhibition performance test method of barium sulfate and strontium sulfate is determined according to the industry standard SY/T5673-93. Scale performance, the experimental conditions for barium sulfate scale inhibition are: Ba ²⁺ concentration is 370mg/L, Sr ²⁺ concentration is 370mg/L, SO ₄ ^2- concentration is 540mg/L, pH=7~9, temperature 70 ℃, the time is 16h, and the scale inhibition performance is shown in Table 1.

The scale inhibition performance of imported scale inhibitors MDC220 and PTP-0100 was tested according to the same test method, and the performance and scale inhibition mechanism of compound scale inhibitors were also tested according to Wang Xiange et al., Journal of Northeastern University (Natural Science Edition) , 2010, 31(6): 909-912, the scale inhibition performance of the composite antiscalant (PESA/PASP/AA/AMPS) prepared in the literature, the results are listed in Table 1.

Table 1 Scale inhibition performance test results

As can be seen from the test results in Table 1, a composite scale inhibitor prepared by the present invention has the best scale inhibition effect on CaCO ₃ , and the scale inhibition rate is above ₉₅ % when the addition amount is 8 mg/L. (PO ₄ ) ₂ , BaSO ₄ and SrSO ₄ also have obvious scale inhibition performance, and the scale inhibition rate is above 80% when the addition amount of the scale inhibitor is 8mg/L. The performance is clearly outperformed by similar products.

How to use: Make the antiscalant product into 10% aqueous solution, and put the antiscalant dose at 5-20mg/L. Determine the specific dosage according to the content of various ions in the water quality, and select the appropriate dosing point according to the needs of the production process.

Claims (5)

1. a preparation method of composite industrial circulating cooling water scale inhibitor, is characterized in that comprising the steps: (1) mixing polyepoxysuccinic acid and polyaspartic acid in a mass percentage of 1: 0.5 to 0.7; (2) Then add 15-20% acrylic acid-2-acrylamide-2-methylpropanesulfonic acid, 20-25% hydroxyethylidene diphosphoric acid, mix well, add a certain amount of deionized water, and then stir React at a constant temperature of 65-70°C for 1.5-2.0 hours, stop the reaction, cool to about 50°C, add 50% NaOH solution dropwise to the product, adjust the pH to near neutral, and obtain a light yellow transparent liquid, which is the compound resistance detergent. 2. The preparation method of a kind of composite industrial circulating cooling water antiscalant according to claim 1 is characterized in that: wherein each component is by mass percentage: polyepoxysuccinic acid: 35-40%; polyaspartic acid Amino acid: 18-25%; Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid: 15-20%; Hydroxyethylidene diphosphoric acid: 18-28%; The rest is water, sodium hydroxide to adjust pH, The sum of the contents of each component is 100%. 3. according to the preparation method described in claim 1 step (2), it is characterized in that reaction temperature is 65～70 ℃. 4. according to the preparation method described in claim 1 step (1), it is characterized in that polyepoxysuccinic acid and polyaspartic acid are between 1: 0.5～0.7 by mass percentage. 5. according to the preparation method described in claim 1 step (2), its characteristic is 45～55 ℃ when the temperature when adjusting pH with NaOH solution after stopping reaction.