WO2015101124A1 - 用于中央空调循环冷却水的无磷缓蚀阻垢剂及其制备方法 - Google Patents

用于中央空调循环冷却水的无磷缓蚀阻垢剂及其制备方法 Download PDF

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WO2015101124A1
WO2015101124A1 PCT/CN2014/092663 CN2014092663W WO2015101124A1 WO 2015101124 A1 WO2015101124 A1 WO 2015101124A1 CN 2014092663 W CN2014092663 W CN 2014092663W WO 2015101124 A1 WO2015101124 A1 WO 2015101124A1
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Prior art keywords
scale inhibitor
corrosion
tourmaline
cooling water
circulating cooling
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PCT/CN2014/092663
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English (en)
French (fr)
Inventor
杨波
李茂东
陈志刚
黄文显
杨麟
林金梅
喻文
李仕平
张辉
杜玉辉
林协东
伍振凌
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广州特种承压设备检测研究院
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Priority to US15/109,282 priority Critical patent/US9714182B2/en
Publication of WO2015101124A1 publication Critical patent/WO2015101124A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/083—Mineral agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/328—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing boron, silicon, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24D—DOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D19/00—Details
    • F24D19/0092—Devices for preventing or removing corrosion, slime or scale
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F23/00—Features relating to the use of intermediate heat-exchange materials, e.g. selection of compositions

Definitions

  • the invention relates to a corrosion and scale inhibitor, belonging to the technical field of circulating cooling water treatment, in particular to a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water and a preparation method thereof.
  • the central air conditioning circulating water system is generally divided into three parts, namely the cooling water system, the chilled water system and the heating water system.
  • circulating cooling water is mostly open, and chilled water and heating water are mostly closed.
  • the open circulating cooling water system the water is in constant contact with the atmosphere, and the dissolved oxygen is increased, which is easy to cause electrochemical corrosion.
  • the continuous evaporation of the cooling water causes the salt content in the circulating water to gradually increase, and the CO 2 in the water escapes to make the CaCO in the water. 3
  • the tendency to scale out on the heat transfer surface increases.
  • the cooling water is in contact with the air, and absorbs a large amount of dust, mud and sand in the air, so that the system sludge is increased.
  • the light in the cooling tower the appropriate temperature, sufficient oxygen and nutrients are beneficial to the growth of bacteria and algae.
  • the concentration of microorganisms and the required nutrient source increase due to circulation concentration, which makes the system slime increase.
  • water for central air conditioning water systems is divided into three categories, namely tap water, demineralized water and deionized water without any treatment.
  • the tap water varies greatly depending on the region.
  • the water hardness in the coastal areas of South China is ⁇ 20mg/L (calculated as CaCO 3 , the same below), the total alkalinity is ⁇ 50mg/L, pH ⁇ 6, which belongs to ultra-low hardness and strong. Corrosive water quality.
  • the demineralized water removes the fouling ions such as Ca 2+ and Mg 2+ , increases the corrosive ions such as Na + and Cl - , and avoids the scaling problem, but increases the corrosion problem.
  • deionized water does not contain fouling ions and corrosive ions, there is dissolved oxygen in the water, and the corrosion process is an initial slow and gradual acceleration process.
  • Chinese patent CN103420495A discloses a preparation method and application of a central air conditioning circulating water scale inhibitor, and a copolymer obtained by polymerizing a certain amount of alkyl glycol ether, maleic anhydride and other monomers copolymerizable.
  • Chinese patent CN1754844A discloses an acidic descaling agent for a central air conditioning circulating water system containing ethylenediaminetetraacetic acid, sodium humate, polyphosphate and water. The main focus of the above two is on scale inhibition, and there is very little corrosion inhibition.
  • Chinese patent CN102718329A discloses a composite corrosion and scale inhibitor for ultra-low hardness circulating cooling water and a preparation method thereof, including an amino group Trimethylidene phosphonic acid, hydroxyethylidene diphosphate, diethylenetriamine pentamethylphosphonic acid, and the like.
  • Chinese patent CN103332797A discloses a circulating cooling water phosphorus-free corrosion and scale inhibitor and an application thereof, which are composed of a non-enzymatic browning reaction product, a phosphorus-free scale inhibitor, a sulfonic acid-containing copolymer, a zinc salt and water.
  • the object of the present invention is to provide a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water, which is simple in preparation method and convenient to use, and the formulated medicament is directly added to the circulating cooling water system during use or diluted with water.
  • the dosing device is added to the circulating cooling water system, and the raw materials for production are easy to purchase, the cost is low, and the effect is remarkable.
  • Another object of the present invention is to provide a method for preparing the above-described phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water.
  • a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water comprises tourmaline, green corrosion and scale inhibitor, and zinc salt.
  • the tourmaline is used in an amount of 5 to 500 g/t (as solids); the green corrosion and scale inhibitor is used in an amount of 5 to 50 g/t (in terms of liquid); 0.2 to 0.8 g/t (based on solids).
  • the phosphorus-free corrosion and scale inhibitor of the present invention comprises magnesium tourmaline, black tourmaline, lithium tourmaline, manganese tourmaline and calcium magnesium tourmaline.
  • the phosphorus-free corrosion and scale inhibitor of the present invention wherein the zinc salt is selected from a mixture of any one or two of zinc sulfate or zinc chloride.
  • the phosphorus-free corrosion and scale inhibitor of the present invention further comprises 0.2 to 2 g/t of benzotriazole (based on solids).
  • the phosphorus-free corrosion and scale inhibitor of the invention is used in an amount of 6 to 16 g/t (in terms of liquid)
  • the concentration ratio of the circulating cooling water of the central air conditioner is 3-12.
  • the present invention also provides a method for preparing a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water, comprising the following steps:
  • step 1) the corrosion and scale inhibitor for the copper-containing equipment is added to the benzotriazole 0.2 to 2 g.
  • the optimum temperature condition is 65 ° C, and the optimum reaction time is 5 hours.
  • the present invention has the following advantages and beneficial effects:
  • the corrosion and scale inhibitor provided by the invention does not contain phosphorus, which can prevent precipitation of calcium phosphate scale and avoid eutrophication of water bodies;
  • the green corrosion and scale inhibitors are non-toxic, such as polyaspartic acid and polyepoxysuccinic acid, which are environmentally friendly products and do not pose any harm to water bodies;
  • Tourmaline polyaspartic acid, polyepoxysuccinic acid, zinc ion, etc. have obvious synergistic effects of corrosion inhibition and scale inhibition, and the effect is remarkable, and the use concentration can be greatly reduced;
  • the utility model relates to a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water, which is composed of tourmaline, green corrosion and scale inhibitor, zinc salt and the like.
  • the tourmaline includes magnesia, black tourmaline, lithium tourmaline, manganese tourmaline, and calcium-magnesium tourmaline.
  • the amount of tourmaline used is from 5 to 500 g/t (based on solids, that is, the amount of solids added per ton of water).
  • the green corrosion and scale inhibitor is selected from any one, two or three of polyaspartic acid, polyepoxysuccinic acid and polymaleic acid.
  • the green corrosion and scale inhibitor is used in an amount of 5 to 50 g/t (based on solids, that is, solid addition per ton of water).
  • the zinc salt is used in an amount of from 0.2 to 0.8 g/t (based on the solid zinc salt, i.e., the amount of solid zinc salt added per ton of water).
  • the zinc salt is selected from any one or a mixture of two of zinc sulfate or zinc chloride.
  • a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water 20 g of polyaspartic acid, 12 g of polyepoxysuccinic acid, and 0.6 g of ZnSO 4 solid are sequentially dissolved in 1000 ml of deionized water. The temperature was raised to 65 ° C, and the above polymer solution was kept warm for 5 hours under stirring, and cooled to obtain a phosphorus-free corrosion and scale inhibitor mother liquid.
  • a phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water 18 g of polyaspartic acid, 12 g of polymaleic acid, and 0.6 g of ZnSO 4 solid are sequentially dissolved in 1000 ml of deionized water. The temperature was raised to 65 ° C, and the above polymer solution was kept warm for 5 hours under stirring, and cooled to obtain a phosphorus-free corrosion and scale inhibitor mother liquid.
  • Phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water 15 g of polyaspartic acid, 10 g of polyepoxysuccinic acid, 10 g of polymaleic acid, 0.6 mg of ZnSO 4 solid, and then dissolved in 1000 ml of deionized In the water. The temperature was raised to 65 ° C, and the above polymer solution was kept warm for 5 hours under stirring, and cooled to obtain a phosphorus-free corrosion and scale inhibitor mother liquid.
  • Phosphorus-free corrosion and scale inhibitor for central air conditioning circulating cooling water green corrosion inhibitor 10a aspartic acid, polyglycolic acid 12g, ZnSO 4 solid 0.6g, benzotriazole 1.8 g was dissolved in 1000 ml of deionized water in that order. The temperature was raised to 65 ° C, and the above polymer solution was kept warm for 5 hours under stirring, and cooled to obtain a phosphorus-free corrosion and scale inhibitor mother liquid.
  • the carbon steel test piece is 20# steel, and the specification is 50 mm ⁇ 25 mm ⁇ 2 mm;
  • the corrosion inhibition performance test is referred to the “National Standard of the People's Republic of China GB/T18175-2000, water treatment corrosion inhibition performance” Determination - Rotating Hanging Method, using a rotating coupon corrosion test for corrosion inhibition performance, temperature 45 ° C, speed 75r / min.
  • the scale inhibition performance test was carried out according to the National Standard of the People's Republic of China GBT/16632-2008, Determination of Scale Inhibition Performance of Water Treatment Agents - Calcium Carbonate Deposition Method.
  • Table 1 shows the corrosion and scale inhibition performance of the examples
  • 1-4 is a mixture of tourmaline, polyaspartic acid, polyepoxysuccinic acid, polymaleic acid and zinc sulfate in different proportions to obtain a multi-component compound having a synergistic effect.
  • the corrosion rate obtained by the coupon corrosion test (Example 1-3 is a carbon steel corrosion test, and Example 4 is a copper alloy corrosion test) can be seen:
  • each composite formula Under the simulated circulating cooling water condition, each composite formula has good corrosion inhibition performance, the corrosion rate is below 0.075mm/a, and the corrosion requirement is lower than the carbon in GB 50050-2007 "Design Code for Industrial Circulating Cooling Water Treatment".
  • the upper limit of corrosion rate of steel equipment is 0.075mm/a (the upper limit of corrosion rate of copper alloy is 0.005mm/a), and the scale inhibition performance also meets the national standard.
  • the corrosion and scale inhibitor provided by the invention has excellent performance, is non-phosphorus, biodegradable, does not lead to eutrophication of water bodies, and has broad application prospect and economic value.
  • the invention provides a simple formula and operation method, which can not only meet the requirements of corrosion and scale inhibition of the circulating cooling water system, but also eliminate the environmental pollution risk caused by the emission of phosphorus in the circulating cooling water system.

Abstract

一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，由电气石、绿色缓蚀阻垢剂、锌盐等组成。其中电气石的用量在５～５００ｇ／ｔ（以固体计），绿色缓蚀阻垢剂的用量在５～５０ｇ／ｔ（以液体计），锌盐的用量在０．２～０．８ｇ／ｔ（以固体计）。电气石包括镁电气石、黑电气石、锂电气石、锰电气石和钙镁电气石等。绿色缓蚀阻垢剂选自聚天冬氨酸、聚环氧琥珀酸和聚马来酸中任意一种、两种或三种。在含铜设备中，加入苯并三唑０．２～２ｇ／ｔ（以固体计），可以有效抑制铜腐蚀。还公开了一种用于中央空调循环冷却水的无磷缓蚀阻垢剂的制备方法。

Description

用于中央空调循环冷却水的无磷缓蚀阻垢剂及其制备方法 技术领域
本发明涉及一种缓蚀阻垢剂，属于循环冷却水处理技术领域，具体涉及一种用于中央空调循环冷却水的无磷缓蚀阻垢剂及其制备方法。
背景技术
中央空调循环水系统一般分为三部分，即冷却水系统、冷冻水系统和采暖水系统。其中循环冷却水多为开放式，冷冻水和采暖水多为封闭式。在开放式循环冷却水系统中，水与大气不断接触，溶解氧增高，容易造成电化学腐蚀；冷却水的不断蒸发使得循环水中含盐量逐渐增加，加上水中CO2逸出，使水中CaCO3在传热面上结垢析出的倾向增加。冷却水和空气接触，吸收了空气中大量的灰尘、泥砂等，使得系统污泥增加。此外，冷却塔内的光照、适宜的温度、充足的氧气和养分都有利于细菌和藻类的生长，微生物的浓度及其所需的营养源因循环浓缩而增加，使得系统粘泥增加，在换热器内沉积之后造成粘泥的危害。
上述产生的腐蚀、水垢和粘泥，三者不是孤立的，是互相联系和相互影响的，如盐垢和污垢往往结合在一起，结垢和粘泥能引起或加重腐蚀。因此，循环冷却水处理的主要任务就是消除或减少结垢、腐蚀及生物粘泥的危害。
一般来说，中央空调水系统的用水分为三类，即未经任何处理的自来水、软化水和去离子水。自来水因地区不同而水质变化较大，在我国华南沿海等地区水质硬度<20mg/L(以CaCO3计，下同)，总碱度<50mg/L，pH≈6，属于超低硬度、强腐蚀性水质。软化水去除了Ca2+、Mg2+等结垢性离子，增加了Na+、Cl-等腐蚀性离子，避免了结垢问题，却加重了腐蚀问题。去离子水虽然不存在结垢性离子和腐蚀性离子，但是水中存在溶解氧，腐蚀过程是一个初始缓慢、逐渐加速的过程。
中国专利CN103420495A公开了中央空调循环水阻垢剂制备方法和应用，选用由一定质量的烷基乙二醇醚、马来酸酐和可共聚的其他单体进行聚合的共聚物。中国专利CN1754844A公开了一种中央空调循环水系统酸性除垢剂，含有乙二胺四乙酸、腐殖酸钠、聚磷酸盐和水。以上两者主要侧重点在阻垢方面，缓蚀方面很少。中国专利CN102718329A公开了超低硬度循环冷却水的复合缓蚀阻垢剂及其制备方法，包括氨基 三甲叉膦酸、羟基乙叉二磷酸、二乙烯三胺五甲叉膦酸等。中国专利CN103332797A公开了一种循环冷却水无磷缓蚀阻垢剂及其应用，由非酶褐变反应产物、无磷阻垢剂、含磺酸基共聚物、锌盐和水组成。以上两者尽管低磷或无磷处理，但是其配方及操作方法复杂，不能有效满足循环冷却水系统对缓蚀、阻垢和杀菌抑菌的全面要求。
发明内容
本发明的目的在于提供一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，其制备方法简单，使用方便，配方药剂在使用过程中直接加入循环冷却水系统或者用水稀释后采用自动加药装置加入循环冷却水系统，生产原材料容易购买，成本低，效果显著。
本发明的另一目的在于提供一种上述用于中央空调循环冷却水的无磷缓蚀阻垢剂的制备方法。
本发明的目的及解决其技术问题是采用以下技术方案来实现的。依据本发明提出的一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，包含电气石、绿色缓蚀阻垢剂、锌盐。其中，所述电气石的用量在5～500g/t(以固体计)；所述绿色缓蚀阻垢剂为的用量在5～50g/t(以液体计)；所述锌盐的用量在0.2～0.8g/t(以固体计)。
本发明的无磷缓蚀阻垢剂，所述电气石包括镁电气石、黑电气石、锂电气石、锰电气石和钙镁电气石等。
本发明的无磷缓蚀阻垢剂，所述锌盐选自硫酸锌或氯化锌中任意一种或两种的混合。
本发明的无磷缓蚀阻垢剂，其还包含0.2～2g/t的苯并三唑(以固体计)。
本发明的无磷缓蚀阻垢剂，所述绿色缓蚀阻垢剂的用量在6～16g/t(以液体计)
本发明的无磷缓蚀阻垢剂，所述中央空调循环冷却水的浓缩倍数为3～12。
另外，本发明还提出了一种用于中央空调循环冷却水的无磷缓蚀阻垢剂的制备方法，包括以下步骤：
1)将聚天冬氨酸、聚环氧琥珀酸和聚马来酸中任意一种、两种或三种的聚合物5～50g溶解于1000ml去离子水当中；加入锌盐0.2～0.8g；
2)升温至55～75℃，在搅拌条件下，上述聚合物溶液保温反应4～6小时，冷却，即得无磷缓蚀阻垢剂母液；
3)在1L中央空调循环冷却水中，先直接投加或者通过可回收电气石加药装置投加电气石6～600mg，随后直接加入上述无磷缓蚀阻垢剂母液1mg。
上述步骤1)中，用于含铜设备的缓蚀阻垢剂加入苯并三唑0.2～2g。
上述步骤2)中，最佳温度条件为65℃，最佳反应时间为5小时。
借由上述技术方案，本发明具有如下优点和有益效果：
1)本发明提供的缓蚀阻垢剂不含磷，既可防止出现磷酸钙垢沉淀，又可以避免出现水体富营养化；
2)不含铬酸盐和亚硝酸盐等有毒配方，使用安全；
3)对锌离子的使用浓度，小于国家要求的排放标准(2mg/L)；
4)绿色缓蚀阻垢剂中聚天冬氨酸和聚环氧琥珀酸等无毒，属于环境友好产品，不存在对水体有危害；
5)电气石、聚天冬氨酸、聚环氧琥珀酸、锌离子等有明显的缓蚀阻垢协同效应，效果显著，并且可以大大降低使用浓度；
6)不含钼酸盐等价格昂贵的缓蚀阻垢剂，物美价廉，无需补钙、补碱、调pH值等，配方简单，便于广泛推广应用。
具体实施方式
一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，由电气石、绿色缓蚀阻垢剂、锌盐等组成。该电气石包括镁电气石、黑电气石、锂电气石、锰电气石和钙镁电气石等。电气石的用量在5～500g/t(以固体计，即每吨水中的固体添加量)。绿色缓蚀阻垢剂选自聚天冬氨酸、聚环氧琥珀酸和聚马来酸中任意一种、两种或三种。绿色缓蚀阻垢剂的用量在5～50g/t(以固体计，即每吨水中的固体添加量)。该锌盐的用量在0.2～0.8g/t(以固体锌盐计，即每吨水中的固体锌盐添加量)。锌盐选自硫酸锌或氯化锌中任意一种或两种的混合。
在含铜设备中，加入苯并三唑0.2～2g/t(以固体计，即每吨水中的固体添加量)，可以有效抑制铜腐蚀。
实施例1
一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，将聚天冬氨酸20g，聚环氧琥珀酸12g，ZnSO4固体0.6g依次溶解于1000ml去离子水当中。升温至65℃，在搅拌条件下，上述聚合物溶液保温反应5小时，冷却，即得无磷缓蚀阻垢剂母液。
在1L中央空调循环冷却水中，先直接投加或者通过可回收电气石加药装置投加电气石100mg，随后直接加入无磷缓蚀阻垢剂母液1mg。电气石可以回收循环使用。
实施例2
一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，将聚天冬氨酸18g，聚马来酸12g，ZnSO4固体0.6g依次溶解于1000ml去离子水当中。升温至65℃，在搅拌条件下，上述聚合物溶液保温反应5小时，冷却，即得无磷缓蚀阻垢剂母液。
在1L中央空调循环冷却水中，先直接投加或者通过可回收电气石加药装置投加电气石100mg，随后直接加入无磷缓蚀阻垢剂母液1mg。电气石可以回收循环使用。
实施例3
一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，将聚天冬氨酸15g，聚环氧琥珀酸10g，聚马来酸10g，ZnSO4固体0.6mg依次溶解于1000ml去离子水当中。升温至65℃，在搅拌条件下，上述聚合物溶液保温反应5小时，冷却，即得无磷缓蚀阻垢剂母液。
在1L中央空调循环冷却水中，先直接投加或者通过可回收电气石加药装置投加电气石120mg，随后直接加入无磷缓蚀阻垢剂母液1mg。电气石可以回收循环使用。
实施例4
一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，将绿色缓蚀阻垢剂聚天冬氨酸15g，聚环氧琥珀酸12g，ZnSO4固体0.6g，苯并三唑1.8g依次溶解于1000ml去离子水当中。升温至65℃，在搅拌条件下，上述聚合物溶液保温反应5小时，冷却，即得无磷缓蚀阻垢剂母液。
在1L中央空调循环冷却水中，先直接投加或者通过可回收电气石加药装置投加电气石120mg，随后直接加入无磷缓蚀阻垢剂母液1mg。电气石可以回收循环使用。
本发明的实施例1-4中，碳钢试片为20#钢，规格50mm×25mm×2mm；缓蚀性能的测试参照《中华人民共和国国家标准GB/T18175-2000，水处理缓蚀性能的测定-旋转挂片法》，采用旋转挂片腐蚀仪进行缓蚀性能实验，温度45℃，转速75r/min。阻垢性能的测试采用《中华人民共和国国家标准GBT/16632-2008，水处理剂阻垢性能的测定-碳酸钙沉积法》。
取广州市某市政供水点水质，pH值6.8，电导率134μs/L，总硬度(以CaCO3计)48mg/L，总碱度(以CaCO3计)22mg/L，氯离子(Cl-)16mg/L。配置浓缩倍数为5的实验用水(水的浓缩倍数可以是3-12)：pH值7.6，总硬度(以CaCO3计)242mg/L，总碱度(以CaCO3计)108mg/L。
表1实施例的缓蚀阻垢性能一览表
Figure PCTCN2014092663-appb-000001
表1的实施例中1-4是将电气石、聚天冬氨酸、聚环氧琥珀酸、聚马来酸和硫酸锌等按不同比例混合，得到具有协同效应的多元复合配方。通过挂片腐蚀实验(实施例1-3为碳钢腐蚀实验，实施例4为铜合金腐蚀实验)得到的腐蚀率可以看出：
在该模拟循环冷却水工况下，各复合配方具有很好的缓蚀性能，腐蚀率均在0.075mm/a以下，腐蚀要求低于GB 50050-2007《工业循环冷却水处理设计规范》中碳钢设备的腐蚀速率上限值0.075mm/a(铜合金腐蚀速率上限值0.005mm/a)，阻垢性能也达到达到国家标准规定。
本发明提供的缓蚀阻垢剂配方性能优异，无磷、可生物降解，不会导致水体富营养化，具有广阔的应用前景和经济价值。
本发明提供了一种简单配方及操作方法，不仅可以满足循环冷却水系统对缓蚀和阻垢的要求，而且可以消除循环冷却水系统因排放磷而造成的环境污染风险。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，故凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。

Claims (9)

  1. 一种用于中央空调循环冷却水的无磷缓蚀阻垢剂，其特征在于其包含：电气石、绿色缓蚀阻垢剂及锌盐；其中，所述绿色缓蚀阻垢剂选自聚天冬氨酸、聚环氧琥珀酸和聚马来酸中任意一种、两种或三种；所述电气石的用量在5～500g/t(以固体计)，所述绿色缓蚀阻垢剂的用量在5～50g/t(以液体计)；所述锌盐的用量在0.2～0.8g/t(以固体计)。
  2. 根据权利要求1所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂，其特征在于：所述电气石包括镁电气石、黑电气石、锂电气石、锰电气石和钙镁电气石等。
  3. 根据权利要求1所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂，其特征在于：所述锌盐选自硫酸锌或氯化锌中任意一种或两种的混合。
  4. 根据权利要求1所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂，其特征在于：其还包含0.2～2g/t的苯并三唑(以固体计)。
  5. 根据权利要求1所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂，其特征在于：所述绿色缓蚀阻垢剂的用量在6～16g/t(以液体计)。
  6. 根据权利要求1所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂，其特征在于：所述中央空调循环冷却水的浓缩倍数为3～12。
  7. 权利要求1-6中任一项所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂的制备方法，其特征在于包括以下步骤：
    1)将聚天冬氨酸、聚环氧琥珀酸和聚马来酸中任意一种、两种或三种的聚合物5～50g溶解于1000ml去离子水当中；加入锌盐0.2～0.8g；
    2)升温至55～75℃，在搅拌条件下，上述聚合物溶液保温反应4～6小时，冷却，即得无磷缓蚀阻垢剂母液；
    3)在1L中央空调循环冷却水中，先直接投加或者通过可回收电气石加药装置投加电气石6～600mg，随后直接加入上述无磷缓蚀阻垢剂母液1mg。
  8. 根据权利要求7所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂的制备方法，其特征在于：步骤1)中，用于含铜设备的缓蚀阻垢剂加入苯并三唑0.2～2g。
  9. 根据权利要求7所述的用于中央空调循环冷却水的无磷缓蚀阻垢剂的制备方法，其特征在于：步骤2)中，最佳温度条件为65℃，最佳反应时间为5小时。
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