CN104058511A - Non-phosphorus composite corrosion and scale inhibitor used for circulating water - Google Patents
Non-phosphorus composite corrosion and scale inhibitor used for circulating water Download PDFInfo
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- CN104058511A CN104058511A CN201410264952.4A CN201410264952A CN104058511A CN 104058511 A CN104058511 A CN 104058511A CN 201410264952 A CN201410264952 A CN 201410264952A CN 104058511 A CN104058511 A CN 104058511A
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Abstract
The invention provides a non-phosphor composite corrosion and scale inhibitor used for circulating water. The non-phosphorous composite and scale inhibitor consists of the following components in percentage by weight: 10-15% of polyaspartic acid, 10-20% of polyepoxysuccinic acid, 5-15% of zinc sulfate, 1-2% of imidazole derivatives, 15-25% of acrylic acid-2- acrylamide-2-2 methyl propanesulfonic acid copolymer, 10-20% of sodium gluconate ad the balance of water. Formula components have obvious synergistic effect, do not contain phosphor, so the non-phosphor composite corrosion and scale inhibitor is an environment-friendly corrosion and scale inhibitor, has no pollution on environment after being exhausted, is an environment-friendly type water treating agent, can effectively solve problems such as scale corrosion existing in circulating cooling water, and is especially suitable for a circulating cooling water system which is added with sulfuric acid to improve concentration multiple. The non-phosphor composite corrosion and scale inhibitor disclosed by the invention has very good dispersion effect on dirt such as calcium carbonate, calcium sulfate and barium sulfate, and ensures that corrosion rate of metals such as carbon steel and copper to reach national standards.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of without phosphorus composite slow-corrosion scale resistor.
Background technology
Along with China's industrial expansion, fresh water consumption increases rapidly, and many areas face serious water crisis.In town water, process water accounts for 60 ~ 80% of water consumption, and industrial colling consumption accounts for 70 ~ 80% of whole industrial water consumption.But pertinent data shows the recycling rate of water used by the industries average out to 40 ~ 50% of China.Ten thousand yuan of output value water loss of China's urban industry reach 340 cubic metres, are 10 ~ 20 times of developed country, and water loss is high, and repeating utilization factor is low, are the outstanding problems that China's industrial system water resources is utilized.Adopt process for cleanly preparing, Development of Novel water-saving technology, is to alleviate a light hydropenic major action.Therefore, saving industrial colling, limited water resources is utilized, is the most important thing of industrial circle water conservation.
The cycles of concentration that improves recirculated cooling water is the main path of saving water coolant, but along with cycles of concentration increases, in water coolant, zwitterion concentration increases, the dirt such as calcium carbonate that easily generates indissoluble is attached to heat exchanger surface, affect heat exchange efficiency, harm circulating water system.Current main solution is to add corrosion inhibiting and descaling agent, but single add corrosion inhibiting and descaling agent improve cycles of concentration limited, so the general employing of factory is first to add sulfuric acid to reduce under the condition of basicity in recirculated water, add again corrosion inhibiting and descaling agent, can increase substantially like this recirculated cooling water cycles of concentration, reach the object of energy-saving and emission-reduction.
Most domestic corrosion-mitigation scale-inhibition agent prescription is all phosphorous formula at present, organic phosphoric acid, especially organic multicomponent phosphoric acid and salt thereof, stable chemical performance, ability comparatively high temps and pH value, having significantly features such as " threshold effects " and " synergistic effect ", is a now widely used class water conditioner.But organophosphorus can not effectively suppress calcium phosphate scale, zinc dirt and solve the problems such as iron oxide precipitation, and itself easily forms organic phosphoric acid dirt.Simultaneously due to the eutrophication of phosphorus to environment waters, promote the growth of bacterium algae and form " red tide ", cause the pollution at water source.Add the system of sulfuric acid raising water coolant cycles of concentration, due to SO
4 2-too high levels, and after corrosion inhibiting and descaling agent generation chemical reaction, easily generate the calcium sulfate scale of indissoluble, be attached to heat exchanger surface, affect heat exchange efficiency, become a difficult point of circulating water treatment.
After recirculated water fouling, easily do not cause heat transfer rate high or conduct heat inhomogeneous, the corrosion inhibiting and descaling agent of current domestic use mainly contains molybdate, tungstate, chromic salt etc., the concentration content of these corrosion inhibiting and descaling agents itself is high, and heavy dose also adds can cause very large pollution to environment.
Summary of the invention
The shortcoming of prior art in view of the above, develops the Phosphateless environmentally friendly corrosion inhibiting and descaling agent that is applicable to High Concentration Circulating Cooling Water system, is specially adapted to add the recirculating cooling water system of sulfuric acid.Can resolution system fouling and the problem of corrosion, also can effectively solve and add after sulfuric acid, SO in water coolant
4 2-too high, and the problem of the calcium sulfate scale of generation indissoluble.
For achieving the above object and other relevant objects, the invention provides a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water, each component by following part by weight forms: poly aspartic acid 10-15%, poly-epoxy succinic acid 10-20%, zinc sulfate 5-15%, azole derivative 1-2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5-25%, Sunmorl N 60S 10-20%, all the other compositions are water.
Preferably, described azole derivative is benzotriazole or tolyltriazole.
Preferably, described without phosphorus composite slow-corrosion scale resistor is by each component of following part by weight: poly aspartic acid 12-15%, poly-epoxy succinic acid 10-15%, zinc sulfate 7-15%, benzotriazole 1-2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5-20%, Sunmorl N 60S 10-20%, all the other compositions are water.
Preferably, described zinc sulfate is Zinc Sulphate Heptahydrate.
Preferably, described without phosphorus composite slow-corrosion scale resistor is by each component of following part by weight: poly aspartic acid 13%, poly-epoxy succinic acid 13%, Zinc Sulphate Heptahydrate 10%, benzotriazole 2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid multipolymer 20%, Sunmorl N 60S 20%, water 22%.
A kind of preparation method of the without phosphorus composite slow-corrosion scale resistor for recirculated water, successively by poly aspartic acid, poly-epoxy succinic acid, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, azole derivative adds in conversion unit at 20-40 DEG C of temperature, after stirring, leave standstill and get final product, the weight ratio of each raw material is: poly aspartic acid 10-15%, poly-epoxy succinic acid 10-20%, zinc sulfate 5-15%, azole derivative 1-2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5-25%, Sunmorl N 60S 10-20%, all the other compositions are water.
As mentioned above, a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water of the present invention, there is following beneficial effect: component of the present invention is poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, system component has obvious synergistic function, and system component is not phosphorous, it is environmental protection corrosion inhibiting and descaling agent, environmentally safe after discharge, it is a kind of environmentally friendly water conditioner, can effectively solve the problems such as the fouling corrosion existing in recirculated cooling water, be specially adapted to add the recirculating cooling water system of sulfuric acid raising cycles of concentration.The dirts such as calcium carbonate, calcium sulfate, barium sulfate are had to good dispersion effect, and the inhibition speed of the metal such as carbon steel, copper is up to state standards, the erosion rate of carbon steel metalloid is less than 0.075mm/a, and the erosion rate of copper and copper alloy is less than 0.005mm/a, and scale inhibition performance is more than 98%.In addition, product of the present invention is at normal temperatures each feed composition to be added in reactor and stirred in proportion, and production technique is simple, and component is composite easily, and product stability is good.
Embodiment
By particular specific embodiment explanation embodiments of the present invention, person skilled in the art scholar can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets below.
Specific embodiment 1:
A kind of without phosphorus composite slow-corrosion scale resistor for recirculated water, its preparation method is: successively poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, benzotriazole are added in conversion unit at 25 DEG C of temperature, after stirring, leave standstill and get final product.The weight ratio of each raw material is: poly aspartic acid 13%, poly-epoxy succinic acid 13%, Zinc Sulphate Heptahydrate 10%, benzotriazole 2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid multipolymer 20%, Sunmorl N 60S 20%, water 22%.Test by corrosion-mitigation scale-inhibition, measure the use properties of corrosion inhibiting and descaling agent, test method: a certain amount of water is injected in dynamic testing equipment, circulate by certain flow, and water temperature is controlled to 60 ± 1 DEG C; Control refill flow, make water level in device substantially keep constant, test film is suspended in system, add test medicine, start test.In process of the test, add sulfuric acid to reduce total alkalinity, keep moving under high concentration multiple, quantitatively indexs such as measuring total alkalinity, total hardness, PH, chlorion is analyzed in regularly sampling, supplementing and water amount of blowdown of adjustment System, continue 120 hours, take out monitoring test piece, calculate erosion rate according to changes in weight.The monitoring of the discharge of the experiment water by dynamic simulation tester, water-in temperature, water outlet temperature, heat medium temperature, calculates scale inhibition performance data by industrial computer processing.
Experiment records: corrosion of carbon steel speed: 0.010mm/a, copper corrosion speed 0.0014mm/a, scale inhibition performance 100%.
Specific embodiment 2:
A kind of without phosphorus composite slow-corrosion scale resistor for recirculated water, its preparation method is: successively poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, benzotriazole are added in conversion unit at 20 DEG C of temperature, after stirring, leave standstill and get final product, the weight ratio of each raw material is: poly aspartic acid 10%, poly-epoxy succinic acid 10%, Zinc Sulphate Heptahydrate 5%, benzotriazole 1%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5%, Sunmorl N 60S 20%, water 39%.Test method is with specific embodiment 1.Experiment records: corrosion of carbon steel speed: 0.015mm/a, copper corrosion speed 0.0024mm/a, scale inhibition performance 100%.
Specific embodiment 3:
A kind of without phosphorus composite slow-corrosion scale resistor for recirculated water, its preparation method is: successively by poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, methyl phenylpropyl alcohol triazole adds in conversion unit at 30 DEG C of temperature, after stirring, leave standstill and get final product, the weight ratio of each raw material is: poly aspartic acid 15%, poly-epoxy succinic acid 20%, Zinc Sulphate Heptahydrate 15%, methyl phenylpropyl alcohol triazole 2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid multipolymer 25%, Sunmorl N 60S 10%, water 13%.Test method is with specific embodiment 1.Experiment records: corrosion of carbon steel speed: 0.021mm/a, copper corrosion speed 0.0015mm/a, scale inhibition performance 100%.
The molecular formula of benzotriazole is C
6h
5n
3white or Bluish white needle crystal, can form covalent linkage and coordinate bond with copper atom, mutually replace into key shape polymer, form multilayer proofing film on copper surface, make the surface of copper not produce electrochemical reaction, thereby there is fabulous corrosion inhibition, the metallic substance such as aluminium, steel is had to good corrosion protection effect too.In recirculated water, as composite with poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer etc., especially corrosion mitigating effect the best in inclosed recirculated cooling water system.
Vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer has excellent anticorrosion-antiscaling property, can stop the performance of dissolved salt in water and suspended particles precipitation, aspect high temperature scale-inhibiting properties, outclassing organophosphorus, calcium carbonate etc. is had to excellent restraining effect, all right dispersing iron oxide, can improve the solubleness of zinc, there is good synergy, be specially adapted to the water conditioning of high concentration multiple.
Without phosphorus composite slow-corrosion scale resistor of the present invention, has carried out the trial run of a year by a definite date, opens after interchanger, and heat transfer tube surface forms layer protecting film, occurs without fouling, corrosion.Prove the good anticorrosion-antiscaling effect of without phosphorus composite slow-corrosion scale resistor of the present invention.
In sum, the invention provides a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water, component of the present invention is poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, azole derivative, system component has obvious synergistic function, and system component is not phosphorous, it is environmental protection corrosion inhibiting and descaling agent, environmentally safe after discharge, it is a kind of environmentally friendly water conditioner, can effectively solve the problems such as the fouling corrosion existing in recirculated cooling water, be specially adapted to add the recirculating cooling water system of sulfuric acid raising cycles of concentration.The dirts such as calcium carbonate, calcium sulfate, barium sulfate are had to good dispersion effect, and the inhibition speed of the metal such as carbon steel, copper is up to state standards, the erosion rate of carbon steel metalloid is less than 0.075mm/a, and the erosion rate of copper and copper alloy is less than 0.005mm/a, and scale inhibition performance is more than 98%.In addition, product of the present invention is at normal temperatures each feed composition to be added in reactor and stirred in proportion, and production technique is simple, and component is composite easily, and product stability is good.So the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (6)
1. the without phosphorus composite slow-corrosion scale resistor for recirculated water, it is characterized in that: the each component by following part by weight forms: poly aspartic acid 10-15%, poly-epoxy succinic acid 10-20%, zinc sulfate 5-15%, azole derivative 1-2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5-25%, Sunmorl N 60S 10-20%, all the other compositions are water.
2. a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water according to claim 1, is characterized in that: described azole derivative is benzotriazole or tolyltriazole.
3. a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water according to claim 1 and 2, it is characterized in that: described without phosphorus composite slow-corrosion scale resistor is by each component of following part by weight: poly aspartic acid 12-15%, poly-epoxy succinic acid 10-15%, zinc sulfate 7-15%, benzotriazole 1-2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5-20%, Sunmorl N 60S 10-20%, all the other compositions are water.
4. a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water according to claim 2, is characterized in that: described zinc sulfate is Zinc Sulphate Heptahydrate.
5. a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water according to claim 4, it is characterized in that: described without phosphorus composite slow-corrosion scale resistor is by each component of following part by weight: poly aspartic acid 13%, poly-epoxy succinic acid 13%, Zinc Sulphate Heptahydrate 10%, benzotriazole 2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid multipolymer 20%, Sunmorl N 60S 20%, water 22%.
6. a kind of without phosphorus composite slow-corrosion scale resistor for recirculated water according to claim 4, it is characterized in that: a kind of preparation method of the without phosphorus composite slow-corrosion scale resistor for recirculated water, successively by poly aspartic acid, poly-epoxy succinic acid, vinylformic acid 2-acrylamide-2-2 methyl propane sulfonic acid multipolymer, water, zinc sulfate, Sunmorl N 60S, azole derivative adds in conversion unit at 20-40 DEG C of temperature, after stirring, leave standstill and get final product, the weight ratio of each raw material is: poly aspartic acid 10-15%, poly-epoxy succinic acid 10-20%, zinc sulfate 5-15%, azole derivative 1-2%, vinylformic acid-2-acrylamide-2-2 methyl propane sulfonic acid copolymer 1 5-25%, Sunmorl N 60S 10-20%, all the other compositions are water.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104261575A (en) * | 2014-10-16 | 2015-01-07 | 山东天庆科技发展有限公司 | High-COD special non-phosphorus corrosion and scale inhibitor and preparation method thereof |
| CN104355418A (en) * | 2014-10-24 | 2015-02-18 | 中国海洋石油总公司 | Preparation method of non-phosphorus corrosion and scale inhibitor |
| CN106277377A (en) * | 2016-08-29 | 2017-01-04 | 山东胜伟园林科技有限公司 | A kind of modified antisludging agent and preparation method thereof |
| CN106287899A (en) * | 2016-08-16 | 2017-01-04 | 重庆中节能三峰能源有限公司 | Industrial exhaust heat ground heating system |
| CN106745856A (en) * | 2017-03-27 | 2017-05-31 | 刘雄杰 | A kind of without phosphorus slow-release scale inhibitor |
| CN107777789A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Low-phosphor efficient anti-incrustation corrosion inhibitor for circulating water treatment and preparation method thereof |
| CN108017162A (en) * | 2017-12-06 | 2018-05-11 | 唐山市金沙工贸有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and preparation method thereof |
| CN109264878A (en) * | 2018-11-30 | 2019-01-25 | 攀枝花钢城集团瑞天安全环保有限公司 | Compound phosphate-free corrosion inhibition antisludging agent and preparation method thereof |
| CN109761380A (en) * | 2019-03-04 | 2019-05-17 | 乌鲁木齐市科发展精细化工有限公司 | Research of non-phosphorus scale inhibitor and preparation method thereof containing tracer polymer |
| CN110171882A (en) * | 2019-05-06 | 2019-08-27 | 无锡广源高科技有限公司 | A kind of corrosion-mitigation scale-inhibition agent prescription containing biodegradable quaternary ammonium and its application |
| CN110526423A (en) * | 2019-09-16 | 2019-12-03 | 天津正达科技有限责任公司 | A kind of higher concentration iron recirculated water phosphate-free water treatment agent |
| CN111087100A (en) * | 2019-12-30 | 2020-05-01 | 河北利源环保科技有限公司 | Corrosion and scale inhibition control method for circulating cooling water system and corrosion and scale inhibitor |
| CN111115855A (en) * | 2019-12-14 | 2020-05-08 | 嘉兴沃特泰科环保科技股份有限公司 | Non-phosphorus scale inhibitor for circulating water and preparation method and application thereof |
| CN111439852A (en) * | 2020-05-22 | 2020-07-24 | 德蓝水技术股份有限公司 | Zinc salt corrosion inhibitor and preparation method thereof |
| WO2021243820A1 (en) * | 2020-06-03 | 2021-12-09 | 山东省食品发酵工业研究设计院 | Method for producing highly adaptable green scale inhibitor and composite scale inhibitor thereof |
| CN115571863A (en) * | 2022-10-08 | 2023-01-06 | 广东邦普循环科技有限公司 | Wet-process phosphoric acid scale dissolver and preparation method and application thereof |
| CN116854265A (en) * | 2023-06-27 | 2023-10-10 | 河北省科学院能源研究所 | Preparation method of slow-release type phosphorus-free scale inhibitor for industrial circulating water |
| CN116947224A (en) * | 2023-09-21 | 2023-10-27 | 山东上远环保科技有限公司 | Circulating water treatment agent and preparation method thereof |
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| CN104261575A (en) * | 2014-10-16 | 2015-01-07 | 山东天庆科技发展有限公司 | High-COD special non-phosphorus corrosion and scale inhibitor and preparation method thereof |
| CN104355418A (en) * | 2014-10-24 | 2015-02-18 | 中国海洋石油总公司 | Preparation method of non-phosphorus corrosion and scale inhibitor |
| CN106287899A (en) * | 2016-08-16 | 2017-01-04 | 重庆中节能三峰能源有限公司 | Industrial exhaust heat ground heating system |
| CN106277377A (en) * | 2016-08-29 | 2017-01-04 | 山东胜伟园林科技有限公司 | A kind of modified antisludging agent and preparation method thereof |
| CN107777789A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Low-phosphor efficient anti-incrustation corrosion inhibitor for circulating water treatment and preparation method thereof |
| CN106745856A (en) * | 2017-03-27 | 2017-05-31 | 刘雄杰 | A kind of without phosphorus slow-release scale inhibitor |
| CN108017162A (en) * | 2017-12-06 | 2018-05-11 | 唐山市金沙工贸有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and preparation method thereof |
| CN109264878A (en) * | 2018-11-30 | 2019-01-25 | 攀枝花钢城集团瑞天安全环保有限公司 | Compound phosphate-free corrosion inhibition antisludging agent and preparation method thereof |
| CN109264878B (en) * | 2018-11-30 | 2022-02-22 | 攀枝花钢城集团瑞天安全环保有限公司 | Composite phosphorus-free corrosion and scale inhibitor and preparation method thereof |
| CN109761380A (en) * | 2019-03-04 | 2019-05-17 | 乌鲁木齐市科发展精细化工有限公司 | Research of non-phosphorus scale inhibitor and preparation method thereof containing tracer polymer |
| CN110171882B (en) * | 2019-05-06 | 2021-11-16 | 无锡广源高科技有限公司 | Formula and application of corrosion and scale inhibitor containing degradable quaternary ammonium salt |
| CN110171882A (en) * | 2019-05-06 | 2019-08-27 | 无锡广源高科技有限公司 | A kind of corrosion-mitigation scale-inhibition agent prescription containing biodegradable quaternary ammonium and its application |
| CN110526423A (en) * | 2019-09-16 | 2019-12-03 | 天津正达科技有限责任公司 | A kind of higher concentration iron recirculated water phosphate-free water treatment agent |
| CN111115855A (en) * | 2019-12-14 | 2020-05-08 | 嘉兴沃特泰科环保科技股份有限公司 | Non-phosphorus scale inhibitor for circulating water and preparation method and application thereof |
| CN111087100A (en) * | 2019-12-30 | 2020-05-01 | 河北利源环保科技有限公司 | Corrosion and scale inhibition control method for circulating cooling water system and corrosion and scale inhibitor |
| CN111439852A (en) * | 2020-05-22 | 2020-07-24 | 德蓝水技术股份有限公司 | Zinc salt corrosion inhibitor and preparation method thereof |
| WO2021243820A1 (en) * | 2020-06-03 | 2021-12-09 | 山东省食品发酵工业研究设计院 | Method for producing highly adaptable green scale inhibitor and composite scale inhibitor thereof |
| CN115571863A (en) * | 2022-10-08 | 2023-01-06 | 广东邦普循环科技有限公司 | Wet-process phosphoric acid scale dissolver and preparation method and application thereof |
| CN115571863B (en) * | 2022-10-08 | 2024-02-09 | 广东邦普循环科技有限公司 | Wet phosphoric acid scale-dissolving agent and preparation method and application thereof |
| CN116854265A (en) * | 2023-06-27 | 2023-10-10 | 河北省科学院能源研究所 | Preparation method of slow-release type phosphorus-free scale inhibitor for industrial circulating water |
| CN116947224A (en) * | 2023-09-21 | 2023-10-27 | 山东上远环保科技有限公司 | Circulating water treatment agent and preparation method thereof |
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