CN107381843B - Composite water treatment agent suitable for recycling high-chlorine sewage and preparation method thereof - Google Patents
Composite water treatment agent suitable for recycling high-chlorine sewage and preparation method thereof Download PDFInfo
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- CN107381843B CN107381843B CN201710700022.2A CN201710700022A CN107381843B CN 107381843 B CN107381843 B CN 107381843B CN 201710700022 A CN201710700022 A CN 201710700022A CN 107381843 B CN107381843 B CN 107381843B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention provides a composite water treatment agent suitable for recycling high-chlorine sewage, which comprises the following components in parts by weight: 15-25% of 2-hydroxyphosphonoacetic acid, 6-21% of carboxyethylthiosuccinic acid, 1-8% of sodium tetraborate decahydrate, 18-30% of sodium bisulfite, 1-10% of potassium pyrophosphate and the balance of deionized water. Under the condition of water quality of sewage recycling, the agent has the characteristics of high chloride ion applicability, excellent dispersion effect, no deposition in pipelines, oil stain resistance, obvious effect of protecting carbon steel and stainless steel by formed deposition films, low dosage of added materials, environmental protection, excellent scale inhibition performance and the like.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a composite water treatment agent suitable for recycling high-chlorine sewage and a preparation method thereof.
Background
The industrial circulating cooling water system is generally adopted, the recycling rate of industrial water is improved, the recycling rate of circulating water can be improved by taking the recycling of the circulating water and the recycling of sewage as the make-up water of the circulating water system, and more than 90% of fresh water can be saved for the industrial circulating water system by recycling the sewage. The sewage recycling means that the sewage is recycled to a place where the sewage can be used as reclaimed water after being treated and regenerated, so that the sewage is converted into water resources to be utilized. Compared with the new water supplement, the sewage reuse has relatively poor water quality conditions, wherein suspended matters, oil content, calcium hardness, chloride ions and the like are relatively high, and the adding amount of the common organic phosphorus corrosion and scale inhibitor is usually increased by two times in order to inhibit scaling and control corrosion.
The conventional organophosphorus corrosion and scale inhibitor needs to improve the original dosage by 2-3 times to inhibit corrosion and scaling, but when the chloride ion is 1000-2000 mg/L, the chloride ion can cause pitting corrosion on carbon steel and stainless steel pipelines, and when the chloride ion is serious, the pipelines can corrode and perforate. The conventional organophosphorus corrosion and scale inhibitor is difficult to meet even if the concentration is increased, which puts higher requirements on a water treatment agent of circulating water, is suitable for water quality conditions of sewage reuse, has high corrosion and scale inhibition properties, and is suitable for chloride ions of 1000-2000 mg/L.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite water treatment agent suitable for recycling high-chlorine sewage and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite water treatment agent suitable for recycling high-chlorine sewage comprises the following components in parts by weight: 15-25% of 2-hydroxyphosphonoacetic acid, 6-21% of carboxyethylthiosuccinic acid, 1-8% of sodium tetraborate decahydrate, 18-30% of sodium bisulfite, 1-10% of potassium pyrophosphate and the balance of deionized water.
A composite water treatment agent suitable for recycling high-chlorine sewage comprises the following components in parts by weight: 18-22% of 2-hydroxyphosphonoacetic acid, 10-18% of carboxyethylthiosuccinic acid, 3-6% of sodium tetraborate decahydrate, 22-28% of sodium bisulfite, 3-8% of potassium pyrophosphate and the balance of deionized water.
A preparation method of a composite water treatment agent suitable for recycling high-chlorine sewage comprises the following specific steps:
1) firstly, adding sodium tetraborate decahydrate, sodium bisulfite and potassium pyrophosphate into a pressure-bearing reaction kettle A, starting stirring, heating to 210-350 ℃, and continuously stirring for 1-3 hours to mutually fuse and crystallize;
2) injecting deionized water into the other pressure-bearing reaction kettle B, starting heating and stirring to ensure that the temperature reaches 90-110 ℃, and the saturated vapor pressure is 70-143 KPa at the moment to ensure that the deionized water is completely vaporized;
3) when the temperature in the pressure-bearing reaction kettle A is reduced to 100-130 ℃, introducing all vaporized separation steam into the pressure-bearing reaction kettle A, starting stirring and mixing, and then sequentially injecting 2-hydroxyphosphonoacetic acid and carboxyethylsulfosuccinic acid into the pressure-bearing reaction kettle A for not less than 90 min;
4) and (3) observing the solution to be clear and free of impurities, measuring the pH value of the solution to be 2-4, completing fusion, uniformly mixing, keeping the temperature for 1-2 hours, and cooling to room temperature to obtain the composite water treatment agent suitable for recycling the high-chlorine sewage.
Compared with the prior art, the invention has the beneficial effects that:
1) is suitable for the water quality condition of circulating water for sewage reuse, and has excellent corrosion inhibition performance on stainless steel and carbon steel.
2) The water treatment agent has a remarkable corrosion inhibition effect on the stainless steel when the chloride ions are 1000-2000 mg/L and the corrosion inhibition effect is far less than 0.005mm/a, and meets the requirements of industrial circulating cooling water treatment design specifications (GB 50050-2007).
3) The water treatment agent disclosed by the invention has the advantages of excellent dispersion effect, no deposition in a pipeline, small oil stain adsorption loss resistance and excellent scale inhibition performance.
4) The water treatment agent has low cost, is beneficial to environmental protection, the dosage is only 30mg/L-40mg/L, and the agent prepared by the method has stable drug effect and long effective service life.
5) The water treatment agent has good cooperativity, good compatibility among medicaments and excellent corrosion and scale inhibition performance.
Detailed Description
The present invention is described in detail below, but it should be noted that the practice of the present invention is not limited to the following embodiments.
A composite water treatment agent suitable for recycling high-chlorine sewage comprises the following components in parts by weight: 15-25% of 2-hydroxyphosphonoacetic acid, 6-21% of carboxyethylthiosuccinic acid, 1-8% of sodium tetraborate decahydrate, 18-30% of sodium bisulfite, 1-10% of potassium pyrophosphate and the balance of deionized water.
A composite water treatment agent suitable for recycling high-chlorine sewage comprises the following components in parts by weight: 18-22% of 2-hydroxyphosphonoacetic acid, 10-18% of carboxyethylthiosuccinic acid, 3-6% of sodium tetraborate decahydrate, 22-28% of sodium bisulfite, 3-8% of potassium pyrophosphate and the balance of deionized water.
The 2-hydroxyphosphonoacetic acid (HPAA) has the advantages of good chemical stability, difficult hydrolysis, no toxicity, no pollution and the like, has good corrosion inhibition effect on high-hardness water, is stable in film formation, can be used in combination with various water treatment agents, and has a very prominent synergistic effect.
Carboxyethylthiosuccinic acid (CETSA) has various excellent performances such as biodegradability, emulsifying dispersibility, chelation and the like, has better effect of removing sediments of carbon steel, stainless steel pipelines and heat exchangers, can effectively inhibit under-scale corrosion, and is a scale inhibitor with excellent performance.
Sodium bisulfite is a low toxicity compound that possesses both oxygen and chlorine scavenging effects.
The sodium tetraborate decahydrate can play a role in synergy by compounding in the composite water treatment agent.
Potassium pyrophosphate on Ca in hard water2+、Mg2+Has stronger complexing ability, forms softer dirt body and has excellent dirt removing performance.
A preparation method of a composite water treatment agent suitable for recycling high-chlorine sewage comprises the following specific steps:
1) firstly, adding sodium tetraborate decahydrate, sodium bisulfite and potassium pyrophosphate into a pressure-bearing reaction kettle A, starting stirring, heating to 210-350 ℃, and continuously stirring for 1-3 hours to mutually fuse and crystallize;
2) injecting deionized water into the other pressure-bearing reaction kettle B, starting heating and stirring to ensure that the temperature reaches 90-110 ℃, and the saturated vapor pressure is 70-143 KPa at the moment to ensure that the deionized water is completely vaporized;
3) when the temperature in the pressure-bearing reaction kettle A is reduced to 100-130 ℃, introducing all vaporized separation steam into the pressure-bearing reaction kettle A, starting stirring and mixing, and then sequentially injecting 2-hydroxyphosphonoacetic acid and carboxyethylsulfosuccinic acid into the pressure-bearing reaction kettle A for not less than 90 min;
4) and (3) observing the solution to be clear and free of impurities, measuring the pH value of the solution to be 2-4, completing fusion, uniformly mixing, keeping the temperature for 1-2 hours, and cooling to room temperature to obtain the composite water treatment agent suitable for recycling the high-chlorine sewage.
The application method of the composite water treatment agent suitable for recycling the high-chlorine sewage comprises the following steps:
1. the composite water treatment agent for recycling the high-chlorine sewage for the first time needs to be added according to 40mg/L, and needs to be continuously added for 7 days to achieve the best use effect.
2. When the total phosphorus in the circulating water is detected to be maintained at 4mg/L-5mg/L for 7 days continuously, the adding amount is reduced to 30mg/L, and the effect of well protecting carbon steel and stainless steel can be achieved by continuous adding.
The composite water treatment agent prepared by the invention can be used for circulating cooling water systems in the fields of chemical industry, metallurgy, petroleum, electric power and the like for sewage recycling.
The features of the present invention are further illustrated by the following examples.
Example 1:
table 1: water quality of power generation purification ring sewage recycling circulating water system
Under the water quality conditions in the table 1, a rotating coupon corrosion experiment is carried out by adopting a rotating coupon method (GB/T18175-2000) for measuring the corrosion and scale inhibition performance of a water treatment agent, each group of formula is added according to the mass concentration of 40mg/L, the experiment temperature is 45 ℃, the experiment time is 72 hours, and the experiment material is stainless steel or carbon steel. The scale inhibition rate is determined according to the standard of 'determination of scale inhibition performance of water treatment agent-calcium carbonate deposition method' (GB-T16632-. The formula of the composite water treatment agent is as follows: 2-hydroxyphosphonoacetic acid: 22% and carboxyethylthiosuccinic acid: 12%, sodium tetraborate decahydrate: 8%, sodium bisulfite: 26%, potassium pyrophosphate: 3 percent and the balance of deionized water. The corrosion rate of the stainless steel hanging piece is 0.0021mm/a, the corrosion rate of the carbon steel hanging piece is 0.0187mm/a, and the scale inhibition rate of calcium carbonate is 95%.
Example 2:
table 2: water quality of steel-making clean ring sewage recycling circulating water system
Under the water quality conditions in the table 2, a rotating coupon corrosion experiment is carried out by adopting a rotating coupon method (GB/T18175-2000) for measuring the corrosion and scale inhibition performance of a water treatment agent, each group of formula is added according to the mass concentration of 40mg/L, the experiment temperature is 45 ℃, the experiment time is 72 hours, and the experiment material is stainless steel or carbon steel. The scale inhibition rate is determined according to the standard of 'determination of scale inhibition performance of water treatment agent-calcium carbonate deposition method' (GB-T16632-. The formula of the composite water treatment agent is as follows: 2-hydroxyphosphonoacetic acid: 22% and carboxyethylthiosuccinic acid: 18%, sodium tetraborate decahydrate: 5%, sodium bisulfite: 22%, potassium pyrophosphate: 8 percent and the balance of deionized water. The corrosion rate of the stainless steel hanging piece is 0.0019mm/a, the corrosion rate of the carbon steel hanging piece is 0.0211mm/a, and the scale inhibition rate of calcium carbonate is 96%.
Example 3:
table 3: water quality of circulating water system for recycling blast furnace clean ring sewage
Under the water quality conditions in the table 3, a rotating coupon corrosion experiment is carried out by adopting a rotating coupon method (GB/T18175-2000) for measuring the corrosion and scale inhibition performance of a water treatment agent, each group of formula is added according to the mass concentration of 40mg/l, the experiment temperature is 45 ℃, the experiment time is 72 hours, and the experiment material is stainless steel or carbon steel. The scale inhibition rate is determined according to the standard of 'determination of scale inhibition performance of water treatment agent-calcium carbonate deposition method' (GB-T16632-. The formula of the composite water treatment agent is as follows: 2-hydroxyphosphonoacetic acid: 25% and carboxyethylthiosuccinic acid: 15%, sodium tetraborate decahydrate: 5%, sodium bisulfite: 28%, potassium pyrophosphate: 3 percent and the balance of deionized water. The corrosion rate of the stainless steel hanging piece is 0.0038mm/a, the corrosion rate of the carbon steel hanging piece is 0.0597mm/a, and the scale inhibition rate of calcium carbonate is 92%.
Example 4:
the industrial test is carried out on the steel-making sewage recycling circulating water system of a certain steel mill, and the water quality conditions are shown in the table 4.
Table 4: water quality of circulating water system for recycling steelmaking sewage of certain steel mill
Under the water quality conditions of table 4, the compound water treatment agent formula was: 2-hydroxyphosphonoacetic acid: 18% and carboxyethylthiosuccinic acid: 20%, sodium tetraborate decahydrate: 3%, sodium bisulfite: 24%, potassium pyrophosphate: 10 percent and the balance of deionized water. Adding the materials according to the mass concentration of 40mg/L, continuously adding the materials for 7 days, reducing the adding amount to 30mg/L, testing for 1 month, and hanging stainless steel and carbon steel on test pieces. The test results are as follows: the corrosion rate of the stainless steel hanging piece is 0.0035mm/a, the corrosion rate of the carbon steel hanging piece is 0.0431mm/a, the surfaces of stainless steel and carbon steel parts of the maintenance equipment are smooth and clean, no deposited dirt exists, the requirements of industrial circulating cooling water treatment design specifications (GB 50050-2007) are met, and the production requirements are met.
Claims (2)
1. The composite water treatment agent suitable for recycling high-chlorine sewage is characterized by comprising the following components in parts by weight: 15-25% of 2-hydroxyphosphonoacetic acid, 6-21% of carboxyethylthiosuccinic acid, 1-8% of sodium tetraborate decahydrate, 18-30% of sodium bisulfite, 1-10% of potassium pyrophosphate and the balance of deionized water;
the preparation method of the composite water treatment agent suitable for recycling the high-chlorine sewage comprises the following specific steps:
1) firstly, adding sodium tetraborate decahydrate, sodium bisulfite and potassium pyrophosphate into a pressure-bearing reaction kettle A, starting stirring, heating to 210-350 ℃, and continuously stirring for 1-3 hours to mutually fuse and crystallize;
2) injecting deionized water into the other pressure-bearing reaction kettle B, starting heating and stirring to ensure that the temperature reaches 90-110 ℃, and the saturated vapor pressure is 70-143 kPa at the moment to ensure that the deionized water is completely vaporized;
3) when the temperature in the pressure-bearing reaction kettle A is reduced to 100-130 ℃, introducing all vaporized separation steam into the pressure-bearing reaction kettle A, starting stirring and mixing, and then sequentially injecting 2-hydroxyphosphonoacetic acid and carboxyethylsulfosuccinic acid into the pressure-bearing reaction kettle A for not less than 90 min;
4) observing the solution to be clear and free of impurities, measuring the pH value of the solution to be 2-4, completing fusion, uniformly mixing, keeping the temperature for 1-2 hours, and cooling to room temperature to obtain a composite water treatment agent suitable for recycling high-chlorine sewage;
the water treatment agent has a remarkable corrosion inhibition effect on the stainless steel, and the corrosion inhibition effect on the stainless steel is 1000-2000 mg/L and is less than 0.005 mm/a.
2. The composite water treatment agent suitable for recycling high-chlorine sewage according to claim 1, which is characterized by comprising the following components in parts by weight: 18-22% of 2-hydroxyphosphonoacetic acid, 10-18% of carboxyethylthiosuccinic acid, 3-6% of sodium tetraborate decahydrate, 22-28% of sodium bisulfite, 3-8% of potassium pyrophosphate and the balance of deionized water.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176229A (en) * | 1996-09-09 | 1998-03-18 | 中国石油化工总公司 | Compound corrosion-inhibiting antisludging agent used in treating circular cooling water |
| JP2012031448A (en) * | 2010-07-29 | 2012-02-16 | Japan Organo Co Ltd | Water-based metal anticorrosive agent and method for inhibiting corrosion of metal in water system |
| CN102452725A (en) * | 2010-10-20 | 2012-05-16 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor and its application |
| CN105645611A (en) * | 2016-02-03 | 2016-06-08 | 青岛科润生物科技有限公司 | Multifunctional industrial water disposal agent and preparing method thereof |
-
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- 2017-08-16 CN CN201710700022.2A patent/CN107381843B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176229A (en) * | 1996-09-09 | 1998-03-18 | 中国石油化工总公司 | Compound corrosion-inhibiting antisludging agent used in treating circular cooling water |
| JP2012031448A (en) * | 2010-07-29 | 2012-02-16 | Japan Organo Co Ltd | Water-based metal anticorrosive agent and method for inhibiting corrosion of metal in water system |
| CN102452725A (en) * | 2010-10-20 | 2012-05-16 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor and its application |
| CN105645611A (en) * | 2016-02-03 | 2016-06-08 | 青岛科润生物科技有限公司 | Multifunctional industrial water disposal agent and preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 羟乙基硫代丁二酸的合成及其为主螯合剂的新型除垢剂的研究;刘克杰;《中国优秀硕士学位论文全文数据库工程科技I辑》;20080415(第4期);B016-14 * |
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