CN104891684A - Phosphorus-free composite corrosion and scale inhibitor for bitter circulating water and preparation method thereof - Google Patents
Phosphorus-free composite corrosion and scale inhibitor for bitter circulating water and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a phosphorus-free composite corrosion and scale inhibitor for bitter circulating water and a preparation method thereof, belonging to the technical field of water treatment. The phosphorus-free composite corrosion and scale inhibitor for bitter circulating water is prepared from the following raw materials in percentage by weight: 5-20% of sodium molybdate, 5-20% of urotropine, 10-30% of polyepoxysuccinic acid, 1-5% of azole derivative, 5-20% of hydroxypropyl methacrylate, 5-15% of acrylic acid-acrylate-sulfonate terpolymer, 5-15% of sodium humate, 0.1-1% of fluorescent tracer, 0.5-2% of caustic soda flakes and the balance of deionized water. The phosphorus-free composite corrosion and scale inhibitor for bitter circulating water can not interfere with other water treatment agents, is free of phosphorus, zinc and other components harmful to the environment, and can effectively solve the problems of corrosion and scales in the bitter-based high-salt-content high-pH system. The invention also relates to a simple and convenient preparation method.
Description
Technical field
The present invention relates to a kind of without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water and preparation method thereof, belong to water-treatment technology field.
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.Status, China southeastern coastal areas is important, and shortage of water resources situation is severeer, seriously constrains industrial expansion.And coastland is due near sea, in a lot of surface water and underground water, saltiness is very high, is referred to as " brackish water ".If after being directly used in recirculating cooling water system, very seriously, Water purification work brings very large problem, so utilization ratio is very low at present, causes the significant wastage of water resources for fouling, glutinous mud, particularly etching problem.
Current domestic conventional corrosion inhibiting and descaling agent is all phosphorous formula, and major part is made up of organophosphate and zinc salt etc.First it effectively can not solve the problem such as deposition of zinc salt, scaling corrosion under supersalinity, high pH condition, and particularly high C 1 content water causes carbon steel and stainless etching problem.Simultaneously phosphorous recirculated water is discharged in environment, can make environment waters eutrophication, promotes the growth and breeding of bacterium algae, is formed " red tide ", makes the Coastal environments that already worsen more severe.
Summary of the invention
The object of this invention is to provide a kind of without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water, itself and other water conditioner does not produce interference, the environmentally harmful compositions such as not phosphorous, zinc, it is a kind of environmental type corrosion inhibiting and descaling agent, be specially adapted to the system that southeastern coastal areas brackish water does recirculated cooling water, can effectively solution brackish water time height salinity, the problem of the corrosion and scaling of system under high pH; The invention provides a kind of simple and convenient preparation method simultaneously.
The described without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water, be made up of the raw material of following weight percentage: Sodium orthomolybdate 5 ~ 20%, urotropine 5 ~ 20%, poly-epoxy succinic acid 10 ~ 30%, azole derivative 1 ~ 5%, hydrolytic polymaleic anhydride 5 ~ 20%, acrylic acid-acrylic ester-sulfonate terpolymer 5 ~ 15%, Sodium salts humic acids 5 ~ 15%, fluorescent tracer 0.1 ~ 1%, sheet alkali 0.5 ~ 2%, surplus is deionized water.
Preferably, be made up of the raw material of following weight percentage: Sodium orthomolybdate 10 ~ 15%, urotropine 8 ~ 17%, poly-epoxy succinic acid 15 ~ 27%, azole derivative 2 ~ 5%, hydrolytic polymaleic anhydride 10 ~ 15%, acrylic acid-acrylic ester-sulfonate terpolymer 7 ~ 12%, Sodium salts humic acids 10 ~ 15%, fluorescent tracer 0.2 ~ 0.5%, sheet alkali 1 ~ 2%, surplus is deionized water.
Described Sodium orthomolybdate is Sodium Molybdate Dihydrate.
Described azole derivative is benzotriazole or tolyltriazole.
Described fluorescent tracer is 1,3,6,8-pyrene tetrasulfonic acid sodium.
Described hydrolytic polymaleic anhydride molecular weight is 400 ~ 800.
The preparation method of the described without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water, comprise the following steps: successively poly-epoxy succinic acid, hydrolytic polymaleic anhydride and acrylic acid-acrylic ester-sulfonate terpolymer is added in conversion unit at 20-40 DEG C, Sodium orthomolybdate, Sodium salts humic acids, urotropine and fluorescent tracer is added successively again in whipping process, again the azole derivative and sheet alkali that are dissolved in deionized water are added in conversion unit, leave standstill after stirring, obtain the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water.
In formula of the present invention the character of related component and effect as follows:
Benzotriazole: be white or Bluish white needle crystal, covalent linkage and coordinate bond can be formed with copper atom, mutually replace into key-like polymer, multilayer proofing film is formed on copper surface, the surface of copper is made not produce electrochemical reaction, thus there is fabulous corrosion inhibition, there is good corrosion protection effect too to the metallic substance such as aluminium, steel.In recirculated water, as composite with poly-epoxy succinic acid, vinylformic acid-2-acrylamide-2 methyl propane sulfonic acid multipolymer etc., especially in inclosed recirculated cooling water system, corrosion mitigating effect is best.
Sodium orthomolybdate: be white diamond xln.Sodium orthomolybdate belongs to anodic oxidation membranous type inhibiter, plays slow releasing function at anodic formation one deck ferrous iron-Gao Fe Mo complex oxide passive film, improves corrosion mitigating effect with benzotriazole etc. is composite.
Urotropine: formal name used at school hexamethylenetetramine, molecular formula (CH
2) N
4, white, to light yellow crystalline powder, is polymer, can be adsorbed on metallic surface well, forms layer protecting film, suppresses corrosion of metal.
Acrylic acid-acrylic acid fat-sulfonate terpolymer: there is excellent scale inhibition and dispersion performance, the performance of dissolved salt and suspended particles precipitation in water can be stoped, organophosphorus is outclassed in high temperature scale-inhibiting properties, to calcium carbonate etc., there is excellent restraining effect, all right dispersing iron oxide, there is good synergistic function with various corrosion inhibiting and descaling agent, be specially adapted to the water conditioning of high concentration multiple.
Sodium salts humic acids: molecular formula is C
9h
8nA
2o
4system adopts the natural low magnesium weathered coal of the low calcium of high-quality containing humic acids to refine through chemistry and forms, and it is multi-functional macromolecular compound, containing the active group that hydroxyl, quinonyl, carboxyl etc. are more, there is very large internal surface area, have stronger absorption, exchange, complexing, sequestering power.
Poly-epoxy succinic acid: be a kind of without nitrogen, non-phosphorus organic compound, have scale inhibitor double effects concurrently, biodegradability is got well and is applicable to high-alkali, high rigidity, high temperature, high metal content water system, excellent antiscaling dispersion effect is had under high pH condition, good with chlorine consistency, scale-inhibiting properties does not affect by cl concn, has obvious synergistic function with other composite reagents, is a kind of green Water Treatment Chemicals.
Compared with prior art, the present invention has following beneficial effect:
(1) system component has obvious synergistic function, does not produce interference with other water conditioners;
(2) the environmentally harmful composition such as not phosphorous, zinc in formula, is a kind of environmental type corrosion inhibiting and descaling agent;
(3) the described without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water, be specially adapted to the system that southeastern coastal areas brackish water does recirculated cooling water, can effectively solution brackish water time height salinity, the problem of the corrosion and scaling of system under high pH condition, the corrosion of carbon steel speed indexs such as the erosion rate of carbon steel, copper, stainless steel etc., fouling resistance being all up to state standards require is less than 0.075mm/a, copper and Corrosion of Stainless Steel speed is less than 0.005mm/a, fouling resistance is less than 3.44*10
-4m
2* K/W;
(4) preparation method is simple and convenient, is added in reactor in proportion by each feed composition and stir under normal temperature, and obtained product stability is good.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but it does not limit enforcement of the present invention.
Embodiment 1
Successively poly-epoxy succinic acid, hydrolytic polymaleic anhydride and acrylic acid-acrylic ester-sulfonate terpolymer is added in conversion unit at 20 DEG C, Sodium orthomolybdate, Sodium salts humic acids, urotropine and fluorescent tracer is added successively again in whipping process, again the benzotriazole and sheet alkali that are dissolved in deionized water are added in conversion unit, leave standstill after stirring, obtain the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water.The weight percentage of each raw material is: Sodium orthomolybdate 15%, urotropine 15%, poly-epoxy succinic acid 22%, azole derivative 3%, hydrolytic polymaleic anhydride 13%, acrylic acid-acrylic ester-sodium sulfonate terpolymer 12%, Sodium salts humic acids 5%, 1,3,6,8-pyrene tetrasulfonic acid sodium 0.3%, sheet alkali 1.5%, deionized water 13.2%.
By dynamic analog test, measure the use properties of obtained product.Test method is as follows:
A certain amount of brackish water is injected in dynamic simulation tester, circulates by certain flow, and water temperature is controlled at 40 ± 5 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, quantitatively the indexs such as analysis mensuration total alkalinity, total hardness, pH, chlorion are carried out in regularly sampling, and detect the content of fluorescent tracer in water, to determine dosing, supplementing and water amount of blowdown of adjustment System, continue 240 hours, take out monitoring test piece, calculate erosion rate according to changes in weight.By the monitoring of the discharge of the experiment water of dynamic simulation tester, water-in temperature, outlet temperature, heat medium temperature, calculate fouling resistance data by industrial computer process.Actual data measured: corrosion of carbon steel speed: 0.021mm/a, Corrosion of Stainless Steel speed 0.0009mm/a, copper corrosion speed 0.0011mm/a, fouling resistance 2.85*10
-4m
2* K/W.
Embodiment 2
Successively poly-epoxy succinic acid, hydrolytic polymaleic anhydride and acrylic acid-acrylic ester-sulfonate terpolymer is added in conversion unit at 40 DEG C, Sodium orthomolybdate, Sodium salts humic acids, urotropine and fluorescent tracer is added successively again in whipping process, again the tolyltriazole and sheet alkali that are dissolved in deionized water are added in conversion unit, leave standstill after stirring, obtain the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water.The weight percentage of each raw material is: Sodium orthomolybdate 20%, urotropine 12%, poly-epoxy succinic acid 18%, azole derivative 2%, hydrolytic polymaleic anhydride 10%, acrylic acid-acrylic ester-sodium sulfonate terpolymer 10%, Sodium salts humic acids 8%, 1,3,6,8-pyrene tetrasulfonic acid sodium 0.2%, sheet alkali 1.0%, deionized water 18.8%.
Experimental technique with embodiment 1, actual data measured: corrosion of carbon steel speed: 0.016mm/a, Corrosion of Stainless Steel speed 0.0007mm/a, copper corrosion speed 0.0014mm/a, fouling resistance 2.99*10
-4m
2* K/W.
Embodiment 3
Successively poly-epoxy succinic acid, hydrolytic polymaleic anhydride and acrylic acid-acrylic ester-sulfonate terpolymer is added in conversion unit at 25 DEG C, Sodium orthomolybdate, Sodium salts humic acids, urotropine and fluorescent tracer is added successively again in whipping process, again the benzotriazole and sheet alkali that are dissolved in deionized water are added in conversion unit, leave standstill after stirring, obtain the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water.The weight percentage of each raw material is: Sodium orthomolybdate 8%, urotropine 18%, poly-epoxy succinic acid 25%, azole derivative 2.0%, hydrolytic polymaleic anhydride 5%, acrylic acid-acrylic ester-potassium sulfonate terpolymer 10%, Sodium salts humic acids 15%, 1,3,6,8-pyrene tetrasulfonic acid sodium 0.2%, sheet alkali 1.0%, deionized water 15.8%.
Experimental technique with embodiment 1, actual data measured: corrosion of carbon steel speed: 0.034mm/a, Corrosion of Stainless Steel speed 0.0021mm/a, copper corrosion speed 0.0018mm/a, fouling resistance 2.73*10
-4m
2* K/W.
Known by above data, the described without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water, be specially adapted to the system that southeastern coastal areas brackish water does recirculated cooling water, can effectively solution brackish water time height salinity, the problem of the corrosion and scaling of system under high pH condition, the corrosion of carbon steel speed indexs such as the erosion rate of carbon steel, copper, stainless steel etc., fouling resistance being all up to state standards require is less than 0.075mm/a, copper and Corrosion of Stainless Steel speed is less than 0.005mm/a, fouling resistance is less than 3.44*10
-4m
2* K/W.
Claims (8)
1. the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water, it is characterized in that being made up of the raw material of following weight percentage: Sodium orthomolybdate 5 ~ 20%, urotropine 5 ~ 20%, poly-epoxy succinic acid 10 ~ 30%, azole derivative 1 ~ 5%, hydrolytic polymaleic anhydride 5 ~ 20%, acrylic acid-acrylic ester-sulfonate terpolymer 5 ~ 15%, Sodium salts humic acids 5 ~ 15%, fluorescent tracer 0.2 ~ 0.5%, sheet alkali 0.5 ~ 2%, surplus is deionized water.
2. the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water according to claim 1, it is characterized in that being made up of the raw material of following weight percentage: Sodium orthomolybdate 10 ~ 15%, urotropine 8 ~ 17%, poly-epoxy succinic acid 15 ~ 27%, azole derivative 2 ~ 5%, hydrolytic polymaleic anhydride 10 ~ 15%, acrylic acid-acrylic ester-sulfonate terpolymer 7 ~ 12%, Sodium salts humic acids 10 ~ 15%, fluorescent tracer 0.2 ~ 0.5%, sheet alkali 1 ~ 2%, surplus is deionized water.
3. the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water according to claim 1, is characterized in that: Sodium orthomolybdate is Sodium Molybdate Dihydrate.
4. the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water according to claim 1, is characterized in that: azole derivative is benzotriazole or tolyltriazole.
5. the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water according to claim 1, is characterized in that: fluorescent tracer is 1,3,6,8-pyrene tetrasulfonic acid sodium.
6. the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water according to claim 1, is characterized in that: hydrolytic polymaleic anhydride molecular weight is 400 ~ 800.
7. the arbitrary described preparation method for the without phosphorus composite slow-corrosion scale resistor of brackish water recirculated water of claim 1-6, it is characterized in that comprising the following steps: successively poly-epoxy succinic acid, hydrolytic polymaleic anhydride and acrylic acid-acrylic ester-sulfonate terpolymer is added in conversion unit, Sodium orthomolybdate, Sodium salts humic acids, urotropine and fluorescent tracer is added successively again in stirring, again the azole derivative and sheet alkali that are dissolved in deionized water are added in conversion unit, stir, leave standstill, obtain the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water.
8. the preparation method of the without phosphorus composite slow-corrosion scale resistor for brackish water recirculated water according to claim 7, is characterized in that: added in conversion unit at 20-40 DEG C by poly-epoxy succinic acid, hydrolytic polymaleic anhydride and acrylic acid-acrylic ester-sulfonate terpolymer successively.
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| CN105603436A (en) * | 2015-12-18 | 2016-05-25 | 中国科学院长春应用化学研究所 | Composite corrosion inhibitor and preparation method thereof |
| CN106000112A (en) * | 2016-05-23 | 2016-10-12 | 山东英联化学科技有限公司 | Scale inhibiting-dispersing agent for reverse osmosis membrane and preparation method thereof |
| CN106045071A (en) * | 2016-06-29 | 2016-10-26 | 欣格瑞（山东）环境科技有限公司 | Scale inhibitor for MVR evaporator and preparation method of scale inhibitor |
| CN106757047A (en) * | 2016-11-10 | 2017-05-31 | 武汉钢铁股份有限公司 | A kind of environmentally friendly corrosion inhibitor of sea water |
| CN106745852A (en) * | 2016-12-15 | 2017-05-31 | 钦州市钦南区科学技术情报研究所 | A kind of phosphate-free corrosion inhibition antisludging agent and preparation method thereof |
| CN106809963A (en) * | 2017-03-06 | 2017-06-09 | 王仲贤 | It is without phosphorus without sodium water-treating agent of boiler |
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| CN105603436A (en) * | 2015-12-18 | 2016-05-25 | 中国科学院长春应用化学研究所 | Composite corrosion inhibitor and preparation method thereof |
| CN105603436B (en) * | 2015-12-18 | 2017-11-17 | 中国科学院长春应用化学研究所 | A kind of composite corrosion inhibitor and preparation method thereof |
| CN106000112B (en) * | 2016-05-23 | 2018-11-20 | 山东英联化学科技有限公司 | Dirt dispersion agent and preparation method thereof for reverse osmosis membrane |
| CN106000112A (en) * | 2016-05-23 | 2016-10-12 | 山东英联化学科技有限公司 | Scale inhibiting-dispersing agent for reverse osmosis membrane and preparation method thereof |
| CN106045071A (en) * | 2016-06-29 | 2016-10-26 | 欣格瑞（山东）环境科技有限公司 | Scale inhibitor for MVR evaporator and preparation method of scale inhibitor |
| CN106045071B (en) * | 2016-06-29 | 2019-07-02 | 欣格瑞（山东）环境科技有限公司 | A kind of MVR evaporator antisludging agent and preparation method thereof |
| CN106757047A (en) * | 2016-11-10 | 2017-05-31 | 武汉钢铁股份有限公司 | A kind of environmentally friendly corrosion inhibitor of sea water |
| CN106745852A (en) * | 2016-12-15 | 2017-05-31 | 钦州市钦南区科学技术情报研究所 | A kind of phosphate-free corrosion inhibition antisludging agent and preparation method thereof |
| CN106809963A (en) * | 2017-03-06 | 2017-06-09 | 王仲贤 | It is without phosphorus without sodium water-treating agent of boiler |
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| CN109019883A (en) * | 2018-08-15 | 2018-12-18 | 鞍钢贝克吉利尼水处理有限公司 | Phosphate-free corrosion inhibition antisludging agent and preparation method thereof for Waste Water Reuse technology |
| CN109019883B (en) * | 2018-08-15 | 2022-04-01 | 鞍钢栗田(鞍山)水处理有限公司 | Non-phosphorus corrosion and scale inhibitor for industrial sewage reuse technology and preparation method thereof |
| CN109133387A (en) * | 2018-08-22 | 2019-01-04 | 江苏科利恩净水科技有限公司 | A kind of formula of non-phosphorus scale and corrosion inhibitor and preparation method thereof |
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| 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 |
| CN112047498A (en) * | 2020-07-29 | 2020-12-08 | 深圳市长隆科技有限公司 | Circulating water phosphorus-free corrosion and scale inhibitor and preparation method thereof |
| CN112079450A (en) * | 2020-09-24 | 2020-12-15 | 德蓝水技术股份有限公司 | Fluorescent non-phosphorus scale inhibitor and preparation method thereof |
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