CN102050526B - Low-phosphorous high concentration cyele circulating water treatment process - Google Patents
Low-phosphorous high concentration cyele circulating water treatment process Download PDFInfo
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- CN102050526B CN102050526B CN2010105491923A CN201010549192A CN102050526B CN 102050526 B CN102050526 B CN 102050526B CN 2010105491923 A CN2010105491923 A CN 2010105491923A CN 201010549192 A CN201010549192 A CN 201010549192A CN 102050526 B CN102050526 B CN 102050526B
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Abstract
The invention relates to a low-phosphorous high concentration cyele circulating water treatment process. The process is characterized in that: 1) a preparation method of a low-phosphorous corrosion inhibition antisludging agent comprises the following steps: adding polyepoxysuccinic acid, benzotriazole, acrylic acid/2-methyl-2-acrylamide propanesulfonic acid/maleic anhydride/2-hydroxyl-2-phosphoryl acetic acid quadripolymer, trisodium citrate, nitrilotriacetic acid, ethylene diamine tetra acetic acid, zinc sulphate and the balance of water; and controlling the reaction temperature to be 40-70 DEG C and controlling the pressure to be 0.1MPa, thus light yellow or colourless low-phosphorous (the concentration of PO4<3-> is less than 1mg/L) corrosion inhibition antisludging agent is obtained; and 2) the low-phosphorous high concentration cyele circulating water treatment process comprise the following steps: applying the low-phosphorous (the concentration of PO4<3-> is less than 1mg/L) corrosion inhibition antisludging agent to a river water, lake water or underground water system with the characteristic of ultra low hardness and corrosive water quality; controlling the drug concentration of replenishing water to be 20-30mg/L; and causing the circulating water to stably flow at high concentration cyele of 5-8 times.
Description
Technical field
The invention belongs to the recirculated cooling water processing technology field, be specifically related to a kind of low-phosphorous (PO
4 3-＜1mg/L) high concentration multiple circulating water treatment process method.Comprising a kind of low-phosphorous (PO
4 3-＜1mg/L) corrosion inhibiting and descaling agent the preparation method and be applied to the High Concentration Circulating Cooling Water system water treatment process of industrial cooling circulating water system.
Background technology
Present stage; Enterprise's industrial circulating cooling water treatment process method adopts phosphorous higher acrylic copolymer, vinylformic acid sulfonic acid analog copolymer, phosphine carboxylic acid copolymer etc. as the circulating water treatment medicament mostly both at home and abroad; Cycles of concentration is mostly about 3～5 times; Water utilization rate is whole to also have very big room for promotion, and phosphorus content is higher in the water treatment, has caused the pollution of environment.Along with the progress of society and the enhancing of people's environmental consciousness, the exploitation of low-phosphorus corrosion and scale inhibitor more and more receives people's attention with application.Organophosphorus acid type corrosion inhibiting and descaling agent with at present both at home and abroad commonly used is an example, and the phosphorus discharging will cause the nutrient laden in waters on every side and possibly cause " red tide ".In some countries such as America and Europe, Japan, the measure of taboo phosphorus has been proposed, require phosphorus (with PO like Germany
4 3-Meter) discharging≤3mg/L.
High Concentration Circulating Cooling Water treatment process method is meant that the cycles of concentration of recirculated cooling water reaches 5 times and above water treatment process method.
The research of international relevant High Concentration Circulating Cooling Water treatment process method is comparatively advanced; Just proposed through improving the imagination that cycles of concentration reaches water coolant " zero release " beginning of the eighties as far back as twentieth century; But all handle, add methods such as s.t. or make up water be softening through the recirculated water bypass is softening; Promote cycles of concentration, reach recirculated water nearly " zero release ".For example: the recirculated cooling water of eight thermal power plants of Germany is handled, and all comes with lime softening---the processing mode of Scale inhibitors, and its cycles of concentration reaches 3～6, and major part is 4, and is respond well; The recirculated cooling water that the 4 X 660MW basses of Australia Nan Weiershizhou are held moral power plant to handle with by-pass flow; The lake water in the very high upright Dare lake of saltiness is taken from this factory water source; Handle through by-pass flow again through lime treatment earlier; Recirculated water by-pass flow treatment facility---press quantity of circulating water 3% as the by-pass flow treatment capacity, adopt and fall alkali device and reverse osmosis unit, make this factory reach the wastewater zero discharge level; The recirculated cooling water of U.S. thermal power plant is handled the softening or other filter dosing of main employing and is handled, and how its cycles of concentration only in Western United States thermal power plant adopts the Combined Processing of lime softening other filter desalination 3～3.5, and its cycles of concentration can be above 10.
The research of the domestic treatment of cooling water of the relevant industrial in recent years process method of China also has bigger development, and is used for engineering construction, but the circulation multiple of water coolant is lower than the advanced foreign technology relevance ratio.Crane coal heat power plant brings up to 5.5 with the cycles of concentration of recirculated water from 2.5 through adopting softening processing of double flow weak acid and recirculated water to add the anti-incrustation corrosion inhibitor processing.Inner Mongol Da Late power plant is through adding s.t. and use phosphorous higher corrosion inhibiting and descaling agent to be applied in the circulating water treatment to recirculated water, with circulating water system move multiplying power by before 3 times bring up to present about 5.
Therefore exploitation is at low-phosphorous (PO
4 3-＜1mg/L) high concentration multiple (8 times) water treatment process method of steady running becomes the development trend of industrial cycle water treatment under the medicament condition.
Summary of the invention
The present invention is a kind of low-phosphorous high concentration multiple circulating water treatment process method; It is characterized in that:
1) preparation method of low-phosphorus corrosion and scale inhibitor:
Described low-phosphorus corrosion and scale inhibitor contains poly-epoxy succinic acid 10～40%, benzotriazole 0.2～3%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 15～30%, trisodium citrate 2～14%, NTA 2～14%, YD 30 2～14%, the zinc sulfate 1～10% of weight percent, and surplus is a water;
Concrete preparation process is following: with poly-epoxy succinic acid, benzotriazole, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 40～70 ℃, and control pressure is 0.1Mpa; Add trisodium citrate, NTA, YD 30; Stir, add zinc sulfate, water again, keep 40～70 ℃; Stir to dissolving fully, obtain faint yellow or colourless low-phosphorous (PO
4 3-＜1mg/L) corrosion inhibiting and descaling agent;
2) low-phosphorous high concentration multiple circulating water treatment technology:
The low-phosphorus corrosion and scale inhibitor of preparation is applied to the recirculating cooling water system water technology of industrial cooling circulating water system; Described low-phosphorous PO
4 3-＜1mg/L corrosion inhibiting and descaling agent is applied to the water system of rivers water or lake, underground water super-low-hardness corrodibility water quality characteristics; Through in moisturizing, adding low-phosphorus corrosion and scale inhibitor, adding consistency is 20～30mg/L in the moisturizing; Make recirculated water in 5～8 times of following steady runnings of high concentration multiple; On-the-spot corrosion inhibiting and descaling agent dosage is through total phosphorus control; Its beneficial effect is:
The recirculated water cycles of concentration is controlled at 5～8 times; Total phosphorus is with PO
4 3-Meter is controlled at 0.8～3.0mg/L; The corrosion rate of recirculated water medium carbon steel lacing film and test tube less than 0.075mm/a, stainless corrosion rate less than the corrosion rate of 0.005mm/a, copper alloy less than 0.005mm/a, adhere to speed less than 15mg/cm
2The moon, fouling resistance value are less than 3.44 * 10
-4m
2K/W, heterotrophic bacterium number are less than 1 * 10
5Individual/mL.
According to treatment process method of the present invention, it is further characterized in that:
The preparation method of low-phosphorus corrosion and scale inhibitor:
Described low-phosphorous PO
4 3-＜1mg/L corrosion inhibiting and descaling agent contains poly-epoxy succinic acid 15～30%, benzotriazole 0.3～1.5%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 20～30%, trisodium citrate 2～6%, NTA 2～6%, YD 30 2～6%, the zinc sulfate 1～5% of weight percent, and surplus is a water;
Concrete preparation process is following: with poly-epoxy succinic acid, benzotriazole, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 50～60 ℃, and control pressure is 0.1Mpa; Add trisodium citrate, NTA, YD 30; Stir, add zinc sulfate, water again, keep 50～60 ℃; Stir to dissolving fully, obtain faint yellow or colourless low-phosphorous PO
4 3-＜1mg/L corrosion inhibiting and descaling agent.
Embodiment
Embodiment 1,
Material by following weight percent prepares corrosion inhibiting and descaling agent:
With poly-epoxy succinic acid 30%, benzotriazole 0.2%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 20% places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 50～60 ℃, and control pressure is 0.1Mpa; Add trisodium citrate 3%, NTA 4%, YD 30 6%; Stir, add zinc sulfate 2%, water 34.8% again, keep 50～60 ℃; Stir to dissolving fully, obtain flaxen low-phosphorous (PO
4 3-＜1mg/L) corrosion inhibiting and descaling agent.
Embodiment 2,
Material by following weight percent prepares corrosion inhibiting and descaling agent:
With poly-epoxy succinic acid 25%, benzotriazole 0.5%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 25% places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 50～60 ℃, and control pressure is 0.1Mpa; Add trisodium citrate 4%, NTA 4%, YD 30 4%; Stir, add zinc sulfate 3%, water 34.5% again, keep 50～60 ℃; Stir to dissolving fully, obtain flaxen low-phosphorous (PO
4 3-＜1mg/L) corrosion inhibiting and descaling agent.
Embodiment 3,
Material by following weight percent prepares corrosion inhibiting and descaling agent:
With poly-epoxy succinic acid 20%, benzotriazole 1.0%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 30% places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 50～60 ℃, and control pressure is 0.1Mpa; Add trisodium citrate 6%, NTA 6%, YD 30 3%; Stir, add zinc sulfate 4%, water 30% again, keep 50～60 ℃; Stir to dissolving fully, obtain flaxen low-phosphorous (PO
4 3-＜1mg/L) corrosion inhibiting and descaling agent.
Embodiment 4,
According to low-phosphorous (PO of the present invention
4 3-＜1mg/L) high concentration multiple circulating water treatment process method is characterized in that at low-phosphorous (PO
4 3-＜1mg/L) condition is to realize the steady running of recirculated cooling water high concentration multiple.Low-phosphorous (PO of the present invention
4 3-＜1mg/L) corrosion inhibiting and descaling agent can be applicable to the water system of super-low-hardness corrodibility water quality characteristics such as the Song Hua River and the Zhujiang River.When the recirculated cooling water cycles of concentration was controlled at 6 times, to add concentration be 30mg/L to low-phosphorus corrosion and scale inhibitor in the moisturizing, and total phosphorus is (with PO in the recirculated water
4 3-Meter) is controlled at 2.0～3.0mg/L.The corrosion rate of recirculated water medium carbon steel lacing film and test tube less than 0.075mm/a, stainless corrosion rate less than the corrosion rate of 0.005mm/a, copper alloy less than 0.005mm/a, adhere to speed less than 15mg/cm
2The moon, fouling resistance value are less than 3.44 * 10
-4m
2K/W, heterotrophic bacterium number are less than 1 * 10
5Individual/mL.
Embodiment 5,
According to low-phosphorous (PO of the present invention
4 3-＜1mg/L) high concentration multiple circulating water treatment process method is characterized in that at low-phosphorous (PO
4 3-＜1mg/L) condition is to realize the steady running of recirculated cooling water high concentration multiple.Low-phosphorous (PO of the present invention
4 3-＜1mg/L) corrosion inhibiting and descaling agent can be applicable to the water system of super-low-hardness corrodibility water quality characteristics such as the Song Hua River and the Zhujiang River.When the recirculated cooling water cycles of concentration was controlled at 7 times, to add concentration be 25mg/L to low-phosphorus corrosion and scale inhibitor in the moisturizing, and total phosphorus is (with PO in the recirculated water
4 3-Meter) is controlled at 1.0～2.0mg/L.The corrosion rate of recirculated water medium carbon steel lacing film and test tube less than 0.075mm/a, stainless corrosion rate less than the corrosion rate of 0.005mm/a, copper alloy less than 0.005mm/a, adhere to speed less than 15mg/cm
2The moon, fouling resistance value are less than 3.44 * 10
-4m
2K/W, heterotrophic bacterium number are less than 1 * 10
5Individual/mL.
Embodiment 6,
According to low-phosphorous (PO of the present invention
4 3-＜1mg/L) high concentration multiple circulating water treatment process method is characterized in that at low-phosphorous (PO
4 3-＜1mg/L) condition is to realize the steady running of recirculated cooling water high concentration multiple.Low-phosphorous (PO of the present invention
4 3-＜1mg/L) corrosion inhibiting and descaling agent can be applicable to the water system of super-low-hardness corrodibility water quality characteristics such as the Song Hua River and the Zhujiang River.When the recirculated cooling water cycles of concentration was controlled at 8 times, to add concentration be 20mg/L to low-phosphorus corrosion and scale inhibitor in the moisturizing, and total phosphorus is (with PO in the recirculated water
4 3-Meter) is controlled at 0.8～1.0mg/L.The corrosion rate of recirculated water medium carbon steel lacing film and test tube less than 0.075mm/a, stainless corrosion rate less than the corrosion rate of 0.005mm/a, copper alloy less than 0.005mm/a, adhere to speed less than 15mg/cm
2The moon, fouling resistance value are less than 3.44 * 10
-4m
2K/W, heterotrophic bacterium number are less than 1 * 10
5Individual/mL.
Claims (2)
1. low-phosphorous high concentration multiple circulating water treatment process method is characterized in that:
1) preparation method of low-phosphorus corrosion and scale inhibitor:
Described low-phosphorus corrosion and scale inhibitor contains poly-epoxy succinic acid 10～40%, benzotriazole 0.2～3%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 15～30%, trisodium citrate 2～14%, NTA 2～14%, YD 30 2～14%, the zinc sulfate 1～10% of weight percent, and surplus is a water;
Concrete preparation process is following: with poly-epoxy succinic acid, benzotriazole, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 40～70 ℃, and control pressure is 0.1Mpa; Add trisodium citrate, NTA, YD 30; Stir, add zinc sulfate, water again, keep 40～70 ℃; Stir to dissolving fully, obtain faint yellow or colourless low-phosphorus corrosion and scale inhibitor;
2) low-phosphorous high concentration multiple circulating water treatment technology:
The low-phosphorus corrosion and scale inhibitor of preparation is applied to the recirculating cooling water system water technology of industrial cooling circulating water system; Described low-phosphorus corrosion and scale inhibitor is applied to the water system of rivers water or lake, underground water super-low-hardness corrodibility water quality characteristics; Through in moisturizing, adding the low-phosphorus corrosion and scale inhibitor of preparation, adding consistency is 20～30mg/L in the moisturizing; Make recirculated water in 5～8 times of following steady runnings of high concentration multiple; On-the-spot corrosion inhibiting and descaling agent dosage is through total phosphorus control; Its beneficial effect is:
The recirculated water cycles of concentration is controlled at 5～8 times; Total phosphorus is with PO
4 3-Meter is controlled at 0.8～3.0mg/L; The corrosion rate of recirculated water medium carbon steel lacing film and test tube less than 0.075mm/a, stainless corrosion rate less than the corrosion rate of 0.005mm/a, copper alloy less than 0.005mm/a, adhere to speed less than 15mg/cm
2The moon, fouling resistance value are less than 3.44 * 10
-4m
2K/W, heterotrophic bacterium number are less than 1 * 10
5Individual/mL.
2. according to the described treatment process method of claim 1, it is characterized in that:
The preparation method of low-phosphorus corrosion and scale inhibitor:
Described low-phosphorus corrosion and scale inhibitor contains poly-epoxy succinic acid 15～30%, benzotriazole 0.3～1.5%, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer 20～30%, trisodium citrate 2～6%, NTA 2～6%, YD 30 2～6%, the zinc sulfate 1～5% of weight percent, and surplus is a water;
Concrete preparation process is following: with poly-epoxy succinic acid, benzotriazole, vinylformic acid/2-methyl-2-acrylamido propanesulfonic acid/MALEIC ANHYDRIDE/2-hydroxyl-2-phosphine acyl acetic acid tetrapolymer places airtight or pressurized vessel; Under the agitation condition, the condition and range of control reaction temperature is 50～60 ℃, and control pressure is 0.1Mpa; Add trisodium citrate, NTA, YD 30; Stir, add zinc sulfate, water again, keep 50～60 ℃; Stir to dissolving fully, obtain faint yellow or colourless low-phosphorus corrosion and scale inhibitor.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557279A (en) * | 2011-12-19 | 2012-07-11 | 中国海洋石油总公司 | High-concentration-multiple circulating water treatment method for desalinated sea water |
| CN104925968B (en) * | 2015-07-07 | 2017-03-01 | 西南石油大学 | A kind of salt tolerant high-temperature-resistant scale inhibitor and preparation method thereof |
| CN110872542A (en) * | 2018-08-30 | 2020-03-10 | 铁岭市龙首精细化工有限公司 | Heat exchanger cleaning agent |
| CN114853240B (en) * | 2022-04-21 | 2023-08-01 | 天津正达科技有限责任公司 | Natural balance ultra-high concentration multiple and zero emission control method for circulating cooling water system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6126859A (en) * | 1998-11-20 | 2000-10-03 | Betzdearborn Inc. | Method and composition for corrosion and deposition inhibition in aqueous systems |
| CN1931745A (en) * | 2006-10-12 | 2007-03-21 | 同济大学 | Low phosphate green composite corrosion and scale inhibitor for treating circular cooling water and its usage |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6126859A (en) * | 1998-11-20 | 2000-10-03 | Betzdearborn Inc. | Method and composition for corrosion and deposition inhibition in aqueous systems |
| CN1931745A (en) * | 2006-10-12 | 2007-03-21 | 同济大学 | Low phosphate green composite corrosion and scale inhibitor for treating circular cooling water and its usage |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Tianjin Chemical Research & Design Institute Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. |
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Effective date of registration: 20191122 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee after: TIANJIN ZHENGDA SCIENCE & TECHNOLOGY CO.,LTD. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. |
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