CN114853240A - Natural balance ultrahigh concentration multiple and zero discharge control method for circulating cooling water system - Google Patents
Natural balance ultrahigh concentration multiple and zero discharge control method for circulating cooling water system Download PDFInfo
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Abstract
The invention discloses a circulating water system natural balance ultrahigh concentration multiple and zero emission control method. The method comprises the following steps: at the initial stage of operation, continuously adding a high-efficiency scale and corrosion inhibition functional chemical into a circulating cooling water tank to maintain the concentration of the chemical at 100-200mg/L, controlling the concentration to maintain at 50-100mg/L after circulating for 20-30 days, enabling the chemical to reach a heat exchanger along with the circulation of circulating water, filtering part of water and returning the filtered part of water to the circulating cooling water tank; when the sum of the calcium hardness and the total alkalinity in the circulating water exceeds 1200mg/L, adding a high-efficiency micro-foam evaporation pre-precipitation functional chemical into a circulating cooling water pool, wherein the adding concentration is 10-100mg/L, and carrying out micro-foam evaporation pre-precipitation softening treatment; when the turbidity of circulating water is more than or equal to (4-10) NTU or the total iron is more than or equal to (0.5-1) mg/L, adding a chemical with a filtration enhancing function into a circulating cooling water pool, wherein the adding concentration is 0.5-10 mg/L, performing enhanced filtration, directly recycling filtered water into a circulating water system, discharging dirt along with backwash water, performing water-slag separation on the backwash water, returning the separated water to the circulating water system, and discharging separated filter residues outside.
Description
Technical Field
The invention belongs to the technical field of circulating cooling water treatment, and particularly relates to a natural balance ultrahigh concentration multiple and zero emission control method for a circulating cooling water system.
Background
With the shortage of drinkable water resources and increasingly strict environmental regulations, more and more regions and enterprises put forward strict limits on water resource consumption and sewage discharge, and the important strategies of saving water, reducing emission, recycling reclaimed (waste) water and realizing green development become one of more and more enterprises for sustainable development.
For years, the industrial cooling water treatment technology continuously and iteratively progresses in the aspects of increasing the concentration multiple, developing functional chemicals suitable for high-concentration-multiple water treatment, operating processes and the like. In order to ensure good water treatment effect, the concentration multiple of a cooling water system is determined to be different levels from 2-3 times to 4-5 times according to the technical level of functional chemicals developed at different times, in recent years, the concentration multiple of industrial cooling water systems in some industries and regions is increased to nearly 10 times, near zero emission operation is realized, and two problems of 'needing to add acid' and 'incapable of zero emission' still exist. Therefore, there is a need to develop an industrial cooling water treatment technology which does not require acid addition and can realize zero discharge.
Disclosure of Invention
The invention aims to overcome the defects of the high concentration multiple control method of the existing industrial cooling water system and develop a control method which can realize natural balance ultrahigh concentration and zero emission of a circulating cooling water system without adding acid.
The invention is realized by the following technical scheme:
the invention provides a circulating cooling water system natural balance ultrahigh concentration multiple and zero emission control method, which comprises the following steps: at the initial stage of operation of a circulating water system, continuously adding a high-efficiency scale and corrosion inhibition functional chemical at a chemical adding port of a circulating cooling water pool of the circulating cooling water system through a metering pump to ensure that the concentration of the chemical in the circulating water is maintained at 100-200mg/L, controlling the concentration to be maintained at 50-100mg/L after circulating for 20-30 days, enabling the chemical to circularly reach a heat exchanger along with the circulating water, and filtering part of water through a side filter and then returning to the circulating cooling water pool;
when the sum of the calcium hardness and the total alkalinity in the circulating water exceeds 1200mg/L, starting to add a high-efficiency microfoam evaporation pre-precipitation functional chemical into a circulating cooling water tank through a metering pump, continuously adding or impacting adding, wherein the adding concentration is 10-100mg/L, carrying out microfoam evaporation pre-precipitation softening treatment, fully evaporating the circulating water in a cooling tower under the action of the surface activity of the chemical, partially supersaturating a scaling factor in the water due to excessive concentration to crystallize and precipitate, and crystallizing and depositing in an amorphous state in the circulating water tank under the action of lattice distortion of a scale inhibitor; wherein the micro-foam evaporation pre-precipitation functional chemical is 5-10% of acrylic acid-acrylate-propylene sulfonate copolymer; 10-20% of alkyl betaine; the balance of water;
when the turbidity of circulating water is more than or equal to (4-10) NTU or the total iron is more than or equal to (0.5-1) mg/L, adding a chemical with an enhanced filtering function at the position of a circulating cooling water pool close to a water feeding port by a metering pump according to the amount of side filtering water, wherein the adding concentration is 0.5-10 mg/L, performing enhanced filtering on a side filter of the circulating cooling water system after the chemical with the enhanced filtering function is fully combined with dirt in water, directly recycling filtered water to the circulating water system, discharging the dirt along with backwash water of the side filter, feeding the backwash water into a filter pressing device for water-slag separation, returning the separated water to the circulating water system, and discharging the separated filter residues outside, thereby avoiding the replacement discharge operation when the total iron and the turbidity exceed the standard and the material leakage in the traditional operation, and realizing the zero discharge of the water; wherein the chemical with the enhanced filtering function comprises the following components in percentage by weight, 5-10% of sodium polyacrylate; 5-10% of polyacrylic acid; 10-15% of alkyl glycoside; 5-10% of sodium alginate; the balance of water.
The efficient corrosion and scale inhibition chemical comprises the following components in percentage by weight: 10-40% of polyepoxysuccinic acid; 1-5% of tracing type scale inhibition and dispersion agent; 10-20% of organic carboxylic acid; 0.5 to 2 percent of zinc salt; 1-10% of imidazolines; 0.1-1% of azole; the balance of water.
Further preferably, the polyepoxysuccinic acid in the high-efficiency corrosion and scale inhibition chemical is preferably a commercially available liquid preparation, the solid content of the polyepoxysuccinic acid is 40%, and the molecular formula of the polyepoxysuccinic acid is HO (C) 4 H 2 O 5 M 2 ) n H, the polymerization degree n is an integer of 6-20;
the tracing type scale inhibition and dispersion agent is preferably one or a mixture of two of polyacrylic acid (salt) containing fluorescent groups and hydrolyzed polymales in any proportion;
the organic carboxylic acid is preferably one or a mixture of more of tartaric acid, citric acid, lauric acid and benzoic acid in any proportion;
the zinc salt is preferably zinc chloride or zinc sulfate;
the imidazoline is 2-imidazoline, 3-imidazoline and 4-imidazoline;
the azole is preferably triazole, benzotriazole or mercaptobenzotriazole.
The above-mentioned enhanced filtering function typeIn the chemical product, the molecular formula of the sodium polyacrylate is (C) 3 H 3 NaO 2 ) n, the molecular weight is preferably 80-210 ten thousand;
the molecular formula of the polyacrylic acid is (C) 3 H 4 O 2 ) n, the molecular weight is preferably 2-3 ten thousand;
the alkyl glycoside is a commercially available liquid preparation, the solid content is 50%, and the polymerization degree n is 1.1-3.
Compared with the traditional high concentration multiple operation control technology, the invention has the following advantages:
the method avoids the infinite increase of hardness and alkalinity of the circulating water system in the operation of ultrahigh concentration multiple or zero discharge and the acid addition operation for controlling water quality, solves the problem of serious corrosion and scaling of the system caused by supercritical high salt content in the natural balance operation of the industrial cooling water system in the operation of ultrahigh concentration multiple and zero discharge and the recycling of water in high salt, and ensures the good corrosion and scale inhibition effect of the industrial cooling water system. Meanwhile, the technical problem that the crystallization products, the enriched iron ions, suspended matters, colloids and the like cannot be discharged out of the system is solved, and the circulating water system can realize ultra-high concentration times or zero emission operation.
Compared with the prior art, the method has the following beneficial effects:
1) and a natural balance treatment operation process is adopted, so that the acidification operation is avoided, the safety of operators and a circulating water system is greatly improved, and the risk is reduced.
2) And a zero-emission operation process is adopted, so that the consumption of fresh water is reduced, the sewage discharge is avoided, and the environmental hazard is reduced.
3) And the environment-friendly water treatment chemicals are adopted, so that the secondary pollution of the water treatment chemicals to the environment is avoided, and the harm to the environment is reduced.
4) The limit of the circulating water to the water quality is reduced, and the range of the recyclable reclaimed water is enlarged.
The method is suitable for circulating cooling water systems of petrifaction, chemical engineering, metallurgy, electric power and the like.
Drawings
FIG. 1 is a schematic diagram of the process flow of the natural balance ultrahigh concentration multiple and zero emission control method of the circulating cooling water system.
In the figure: 1 is a circulating cooling water pool, 2 is a cooling tower, 3 is a heat exchanger, 4 is a side filter, and 5 is filter pressing equipment
Detailed Description
The technical solution of the present invention is further described below with reference to the following embodiments and accompanying drawings.
As shown in fig. 1, a schematic process flow diagram of the natural balance ultrahigh concentration multiple and zero emission control method of the circulating cooling water system of the invention is shown, the natural balance ultrahigh concentration multiple and zero emission control method of the invention comprises the following steps: at the initial stage of operation of a circulating water system, continuously adding a high-efficiency scale and corrosion inhibition functional chemical at a chemical adding port of a circulating cooling water pool 1 of the circulating cooling water system through a metering pump to ensure that the concentration of the chemical in the circulating water is maintained at 100-200mg/L, controlling the concentration to be maintained at 50-100mg/L after circulating for 20-30 days, circularly reaching a heat exchanger 3 along with the circulating water, and returning part of water to the circulating cooling water pool 1 after being filtered by a side filter 4;
when the sum of the calcium hardness and the total alkalinity in the circulating water exceeds 1200mg/L, starting to add a high-efficiency micro-foam evaporation pre-precipitation functional chemical into the circulating cold water tank 1 through a metering pump, continuously adding or impacting adding, wherein the adding concentration is 10-100mg/L, carrying out micro-foam evaporation pre-precipitation softening treatment, fully evaporating the circulating water in a cooling tower 2 under the action of the surface activity of the chemical, crystallizing and precipitating the scaling factors in the water due to local supersaturation caused by over concentration, and crystallizing and precipitating the scaling factors in an amorphous state in the circulating water tank under the action of lattice distortion of the scale inhibitor;
when the turbidity of circulating water is more than or equal to (4-10) NTU or the total iron is more than or equal to (0.5-1) mg/L, adding a chemical with a filtration enhancing function at the position 4, close to a water feeding port, of a circulating cooling water pool by a metering pump according to the amount of side filtration water, wherein the adding concentration is 0.5-10 mg/L, after the chemical with the filtration enhancing function is fully combined with dirt in water, performing enhanced filtration on a side filter of the circulating cooling water system, directly recycling the filtered water to the circulating water system, discharging the dirt along with backwash water of the side filter, feeding the backwash water into a filter pressing device 5 for water-slag separation, returning the separated water to the circulating water system, and discharging the separated water, so that the replacement discharge operation during the standard exceeding of the total iron and the turbidity and the material leakage in the traditional operation is avoided, and the zero discharge of the water is realized.
Example 1
A natural balance ultrahigh concentration multiple and zero discharge control method is applied to a circulating cooling water system of a certain steel mill, high-efficiency corrosion and scale inhibition functional chemicals are continuously added at the initial stage of normal operation of the system, the proportion is 40% of polyepoxysuccinic acid, 5% of tracing scale inhibition dispersing agent, 10% of citric acid, 1% of zinc sulfate, 3% of 4-imidazoline, 0.5% of benzotriazole, and the balance of water, the adding amount is 200mg/L, and the adding amount can be reduced to 100mg/L after the system operates for 30 days; polyepoxysuccinic acid as commercial liquid preparation with solid content of 40% and molecular expression of HO (C) 4 H 2 O 5 M 2 ) nH, the polymerization degree n is an integer of 6-20.
When the sum of the calcium hardness and the total alkalinity in the circulating water reaches 1200mg/L, high-efficiency microfoam evaporation pre-precipitation functional chemicals are added, and the proportion is 10 percent of acrylic acid-acrylate-propylene sulfonate copolymer; 15% of alkyl betaine; the balance of water, the dosage is 10 mg/L; the acrylic acid-acrylic ester-propylene sulfonate copolymer and the alkyl betaine are both commercially available liquid preparations, and the solid content is 30 percent;
when the turbidity in the circulating water is more than or equal to 4NTU or the total iron is more than or equal to 0.5mg/L, adding a chemical with the function of strengthening the filtration at the water outlet of the circulating water, wherein the mixture ratio of the sodium polyacrylate is 10 percent, the polyacrylic acid is 5 percent and the alkyl glycoside is 10 percent; 10% of sodium alginate; the balance of water, the dosage is 10 mg/L; wherein the molecular formula of the sodium polyacrylate is (C) 3 H 3 NaO 2 ) n, molecular weight 80-150 ten thousand; polyacrylic acid has the molecular formula of (C) 3 H 4 O 2 ) n, molecular weight 2-2.5 ten thousand; the alkyl glycoside is a commercially available liquid preparation with a solids content of 50%.
The upper limit of calcium hardness and alkalinity in the daily industrial cooling water is not controlled, and the upper limit of salt content is not controlled; cl - Less than or equal to 2500mg/L and far higher than the national design specification Cl - The limit value of less than or equal to 700 mg/L.
Corrosion and scale inhibiting effectAnd (4) fruit: the corrosion rate of the carbon steel is 0.011-0.016mm/a, and the corrosion rates of the copper and the stainless steel are 0.0003-0.0007mm/a, which are greatly superior to the national design specifications that the corrosion rate of the carbon steel is less than or equal to 0.075mm/a, and the corrosion rates of the copper and the stainless steel are less than or equal to 0.005 mm/a. Fouling resistance 0.12X 10 -4 -0.16×10 -4 m 2 K/w, dirt thermal resistance far superior to national design specifications is less than or equal to 3.44 multiplied by 10 -4 m 2 The requirement of k/w; the dirt adhesion rate is 1.4-1.7mcm, which is far superior to the management index that the dirt adhesion rate of a common user is less than or equal to 15.0 mcm.
The discharge-free effect after the reinforced filtration is as follows: the turbidity of the circulating water is 1.3-3.5NTU, the total iron is 0.2-0.5mg/L, the concentration multiple is increased from 5 times to 9-11 times, and the water discharge is reduced by 40% compared with the water discharge in the same period in the previous year.
Example 2
A natural balance ultrahigh concentration multiple and zero discharge control method is applied to a circulating cooling water system of a certain petrochemical plant, high-efficiency corrosion and scale inhibition functional chemicals are continuously added within 30 days before the initial stage of normal operation of the system, the ratio is 20% of polyepoxysuccinic acid, 2% of tracing scale inhibition dispersant, 10% of tartaric acid, 2% of zinc chloride, 5% of 4-imidazoline, 1% of mercaptobenzotriazole and the balance of water, the adding amount is 120mg/L, and the adding amount is reduced to 60mg/L after the system operates for 30 days;
when the sum of the calcium hardness and the total alkalinity in the circulating water reaches 1200mg/L, high-efficiency microfoam evaporation pre-precipitation functional chemicals are added, and the proportion is 8 percent of acrylic acid-acrylate-propylene sulfonate copolymer; 10% of alkyl betaine; the balance of water, the dosage is 100 mg/L; the acrylic acid-acrylic ester-propylene sulfonate copolymer and the alkyl betaine are both commercially available liquid preparations, and the solid content is 30 percent;
when the turbidity in the circulating water is more than or equal to 10NTU or the total iron is more than or equal to 1mg/L, adding a chemical with a filtration enhancing function at the water outlet of the circulating water, wherein the adding amount is 2mg/L, and the mixture ratio is 10% of sodium polyacrylate, 10% of polyacrylic acid, 15% of alkyl glycoside, 5% of sodium alginate and the balance of water; wherein the molecular formula of the sodium polyacrylate is (C) 3 H 3 NaO 2 ) n, molecular weight 150-210 ten thousand; polyacrylic acid has the molecular formula of (C) 3 H 4 O 2 ) n, molecular weight 2.5 kaleidoscope-3 ten thousand;
the upper limit of calcium hardness and alkalinity in the daily industrial cooling water is not controlled, and the upper limit of salt content is not controlled; 1810 + 2234mg/L which is far higher than the limit value of the national design standard Cl-less than or equal to 700 mg/L.
The corrosion and scale inhibition effect is as follows: the corrosion rate of the carbon steel is 0.013-0.029mm/a, and the corrosion rates of the copper and the stainless steel are 0.0005-0.0008mm/a, which are greatly superior to the national design specifications of the requirements that the corrosion rate of the carbon steel is less than or equal to 0.075mm/a, and the corrosion rates of the copper and the stainless steel are less than or equal to 0.005 mm/a. Fouling resistance 0.12X 10 -4 -0.18×10 -4 m 2 K/w, far superior to the requirement of national design specification that the fouling thermal resistance is less than or equal to 3.44 multiplied by 10 < -4 > m2 k/w; the dirt adhesion rate is 1.1-1.8mcm, which is far superior to the management index that the dirt adhesion rate of a common user is less than or equal to 15.0 mcm.
The discharge-free effect after the strengthening filtration is as follows: circulating water turbidity is 0.8-1.5NTU, total iron is 0.1-0.3mg/L, concentration times are increased from original 5-7 times to 13-15 times, no forced pollution discharge is realized, and the emission reduction water amount is more than 60% compared with the emission reduction water amount in the same period in the previous year.
Claims (5)
1. A circulating cooling water system natural balance ultrahigh concentration multiple and zero emission control method is characterized in that: the method comprises the following steps:
at the initial stage of the operation of the circulating cooling water system, the concentration of the high-efficiency scale and corrosion inhibition functional chemical is maintained at 100-;
when the sum of the calcium hardness and the total alkalinity in the circulating water exceeds 1200mg/L, starting to add a high-efficiency microfoam evaporation pre-precipitation functional chemical to maintain the concentration of the chemical to be 10-100mg/L, carrying out microfoam evaporation pre-precipitation softening treatment, leading the circulating cooling water to be fully evaporated in a cooling tower through the surface activity of the chemical, leading the scaling factors in the water to locally reach supersaturation due to excessive concentration and crystallize and precipitate, and crystallizing and depositing in an amorphous state in a circulating cooling water tank under the lattice distortion action of the scale inhibitor; wherein the micro-foam evaporation pre-precipitation functional chemical is 5-10% of acrylic acid-acrylate-propylene sulfonate copolymer; 10-20% of alkyl betaine; the balance of water;
when the turbidity of circulating water is more than or equal to (4-10) NTU or the total iron is more than or equal to (0.5-1) mg/L, starting to add the chemical with the enhanced filtering function, wherein the adding concentration is 0.5-10 mg/L, when the chemical with the enhanced filtering function is fully combined with dirt in water, performing enhanced filtering on a side filter of the circulating cooling water system, directly reusing the filtered water in the circulating cooling water system, discharging the dirt along with backwash water of the side filter, feeding the backwash water into a filter pressing device for water-slag separation, returning the separated water to the circulating cooling water system, and discharging the separated filter residue; the chemical with the enhanced filtering function comprises the following components, by weight, 5-10% of sodium polyacrylate; 5-10% of polyacrylic acid; 10-15% of alkyl glycoside; 5-10% of sodium alginate; the balance of water.
2. The method according to claim 1, wherein the high-efficiency scale and corrosion inhibition functional chemical comprises the following components in percentage by weight: 10-40% of polyepoxysuccinic acid; 1-5% of tracing type scale inhibition and dispersion agent; 10-20% of organic carboxylic acid; 0.5 to 2 percent of zinc salt; 1-10% of imidazolines; 0.1-1% of azole; the balance of water.
3. The method as claimed in claim 1, wherein the chemical with high performance scale and corrosion inhibition function is a liquid preparation with a solid content of 40% and a molecular formula of HO (C) 4 H 2 O 5 M 2 ) nH, wherein the polymerization degree n is an integer of 6-20;
the tracing type scale-inhibiting dispersant is one or a mixture of two of polyacrylic acid (salt) containing fluorescent groups and hydrolyzed polymales in any proportion;
the organic carboxylic acid is one or a mixture of more of tartaric acid, citric acid, lauric acid and benzoic acid;
the zinc salt is zinc chloride or zinc sulfate;
the imidazoline is 2-imidazoline, 3-imidazoline and 4-imidazoline;
the azole is triazole, benzotriazole or mercaptobenzotriazole.
4. The method of claim 1, wherein the acrylic acid-acrylate sulfonate copolymer and the alkyl betaine are liquid formulations.
5. The method of claim 1, wherein the chemical with enhanced filtration function is characterized in that the sodium polyacrylate has a molecular weight of 80-210 ten thousand; the molecular weight of the polyacrylic acid is 2-3 ten thousand; the alkyl glycoside is a liquid preparation with the polymerization degree n of 1.1-3.
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| CN202210420354.6A CN114853240B (en) | 2022-04-21 | 2022-04-21 | Natural balance ultra-high concentration multiple and zero emission control method for circulating cooling water system |
| PCT/CN2023/072493 WO2023202175A1 (en) | 2022-04-21 | 2023-01-17 | Naturally balanced ultra-high concentration multiple and zero emission control method for circulating cooling water system |
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| CN202210420354.6A CN114853240B (en) | 2022-04-21 | 2022-04-21 | Natural balance ultra-high concentration multiple and zero emission control method for circulating cooling water system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023202175A1 (en) * | 2022-04-21 | 2023-10-26 | 天津正达科技有限责任公司 | Naturally balanced ultra-high concentration multiple and zero emission control method for circulating cooling water system |
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| CN118616695B (en) * | 2024-08-12 | 2024-10-11 | 贵州贵铝新材料股份有限公司 | Automatic control system of circulating cooling water for aluminum alloy processing |
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| WO2023202175A1 (en) | 2023-10-26 |
| CN114853240B (en) | 2023-08-01 |
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