WO2018040782A1 - 利用两碱法盐泥制备有机环保融雪剂的方法 - Google Patents

利用两碱法盐泥制备有机环保融雪剂的方法 Download PDF

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WO2018040782A1
WO2018040782A1 PCT/CN2017/093783 CN2017093783W WO2018040782A1 WO 2018040782 A1 WO2018040782 A1 WO 2018040782A1 CN 2017093783 W CN2017093783 W CN 2017093783W WO 2018040782 A1 WO2018040782 A1 WO 2018040782A1
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organic
melting agent
snow melting
parts
environmentally friendly
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PCT/CN2017/093783
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English (en)
French (fr)
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陈留平
徐俊辉
韩俊甜
苏志俊
崔耀星
冷翠婷
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中盐金坛盐化有限责任公司
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Priority to US16/072,885 priority Critical patent/US10308519B2/en
Publication of WO2018040782A1 publication Critical patent/WO2018040782A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C09K3/185—Thawing materials
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the invention belongs to the technical field of environmental protection and solid waste resource utilization, and particularly relates to a method for preparing an organic environmentally friendly snow melting agent by using a two-alkali salt slurry.
  • Snowing in winter is the "big enemy” that hinders traffic.
  • snow melting agent came into being.
  • the snow melting agent was mainly used in airports, highways, railways, urban streets and other places to play the role of snow removal or antifreeze.
  • Chloride salt snow melting agents have been widely used in snow removal and ice removal because of their good snow melting effect and low price. Until now, some countries still use chlorine salt as the main body of snow melting agent, and China is no exception. However, excessive use of chloride salt snow melting agent will lead to a large number of roadside vegetation deaths, roads, bridges, concrete pavements are corroded and damaged, and the snow that has been incorporated into the snow melting agent melts and penetrates into the surface, polluting rivers and groundwater, causing serious damage to the ecological environment. The destruction. Therefore, it is extremely urgent to study new types of snow melting agents to improve the performance of existing snow melting agents.
  • CMA Calcium Magnesium Acetate
  • It is an environmentally friendly chemical developed in the United States in the 1980s to replace the deicing (snow) agent sodium chloride in highways, with sodium chloride.
  • CMA has the advantages of low melting point, biodegradability, low corrosivity to concrete and metal in highway infrastructure, and basically no pollution to soil and water sources.
  • CMA is prepared by reacting glacial acetic acid with dolomite, but the production cost is high, and the price of the product is 30 times that of sodium chloride, which restricts the universal application of CMA.
  • the brine purification process is a key process for the salt industry to improve the purity of refined salt products, reduce the content of impurities in salt, and increase the whiteness of salt products.
  • the chemical components involved in the salt mud produced by the two-alkaline brine purification process include CaCO 3 , Mg(OH) 2 and a small amount of NaCl, CaSO 4 , etc. Due to the large output and complex composition, direct discharge brings environmental pollution. At present, most domestic enterprises deal with salt mud by using it as a waste landfill. At present, research and development of rational salt mud treatment industrial application technology is a common technical problem faced by all domestic salt companies.
  • the invention provides a method for preparing an organic environmentally friendly snow melting agent by using a two-alkali salt mud, which can not only reduce the cost of salt mud treatment, but also fully utilize resources to turn waste into treasure, and greatly reduce the production cost of organic environmental protection snow melting agent.
  • Full advantage The use of trace components in salt mud further enhances the performance of the snow melting agent.
  • the technical scheme adopted by the invention is: reacting the salt mud with the organic acid, filtering the filtrate, concentrating, centrifugal spray drying, granulation to obtain an organic environment-friendly snow melting agent,
  • composition of the two alkali salt slurry is calculated by weight fraction, CaCO 3 85-95 parts, NaCl 0.5-1.5 parts, Mg(OH) 2 8.5- 13.2 parts, CaSO 4 1.5-4.0 parts, Fe(OH) 3 0.5 to 1.5 parts, 0.5 to 1.0 parts of Al(OH) 3 and 0.1 to 2.0 parts of SiO 2 (if the composition or content of the original salt sludge other than silica is different from the above standard, it can be removed by conventional means or Added means to adjust),
  • the organic acid is formic acid, acetic acid, propionic acid, wood acetic acid or other organic waste acid, preferably formic acid, acetic acid or other organic waste acid.
  • the specific operation is that the two alkali salt slurry is dispersed into a slurry in water, and then the organic acid is added dropwise to the slurry under stirring until no bubbles appear in the reaction system.
  • the bubbles generated by the above reaction are carbon dioxide gas, which can be collected and utilized as by-products;
  • the vacuum degree under reduced pressure is 0.06-0.09Mpa
  • the temperature is 70-80 ° C
  • the liquid product obtained after concentration under reduced pressure (including decolorization or non-decolorization) can be directly used as a liquid organic environment-friendly snow melting agent;
  • the solid powder is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 7 mm and an ellipsoidal shape.
  • the invention has the beneficial effects that the organic environment-friendly snow melting agent is prepared by reacting the two alkali salt mud and the organic acid produced in the brine purification process for the first time, fully utilizing the calcium and magnesium ions in the salt mud, and due to the trace ions There is a clear synergistic effect on the ability to melt snow and ice; realize the recycling of solid waste of salt mud, turn waste into treasure and greatly reduce the production cost of organic environmental snow melting agent, and save the processing cost of salt mud, reduce the cost Environmental pollution.
  • the prepared CMA type snow melting agent is an environmentally-friendly chemical recognized on the market. Compared with sodium chloride snow melting agent, CMA has low melting point, biodegradability, and corrosiveness to concrete and metal in highway infrastructure. Small, basically does not cause pollution to the soil and water sources. It is in line with the national guidelines for energy conservation, emission reduction and environmental protection.
  • composition of the two-alkaline salt sludge used in the present example is calculated as parts by weight of CaCO 3 94.5 parts, NaCl 1.2 parts, Mg(OH) 2 9.5 parts, CaSO 4 2.5 parts, Fe(OH) 3 0.7 parts, 0.9 parts of Al(OH) 3 and 2.0 parts of SiO 2 ,
  • the solid powder obtained in the step (2) is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 6 mm and an ellipsoidal shape.
  • composition of the two-alkaline salt slurry used in the present example is calculated as parts by weight of CaCO 3 93 parts, NaCl 0.8 parts, Mg(OH) 2 10 parts, CaSO 4 3.2 parts, Fe(OH) 3 0.85 parts, 0.8 parts of Al(OH) 3 and 0.5 parts of SiO 2 ,
  • the solid powder obtained in the step (2) is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 6 mm and an ellipsoidal shape.
  • a mixture containing 500 g of CaCO 3 and a component of CaCO 3 94.5 parts by weight, 1.2 parts of NaCl, 9.5 parts of Mg(OH) 2 , 2.5 parts of CaSO 4 and 2.0 parts of SiO 2 is added to 500 mL of water. And stirring and dispersing into a slurry at normal temperature (25 ° C), and then adding pure acetic acid to the slurry under stirring until no bubbles appear in the reaction system;
  • the solid powder obtained in the step (2) is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 6 mm and an ellipsoidal shape.
  • (1) containing 500gCaCO 3 and component parts is calculated as CaCO 3 93 parts by weight, NaCl 0.8 parts, Mg (OH) 2 10 parts, CaSO 4 3.2 parts, Fe (OH) 3 0.85 parts, SiO 2 0.5 parts
  • the mixture was added to 500 mL of water and stirred at room temperature (25 ° C) to disperse into a slurry, and then pure formic acid was added dropwise to the slurry under stirring until no bubbles appeared in the reaction system;
  • the solid powder obtained in the step (2) is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 6 mm and an ellipsoidal shape.
  • composition of the two-alkaline salt slurry used in the present embodiment is calculated as parts by weight of CaCO 3 94.5 parts, NaCl 1.2 parts, Mg(OH) 2 9.5 parts, CaSO 4 2.5 parts, Fe(OH) 3 parts, al (OH) 3 4 parts, SiO 2 2.0 parts
  • the solid powder obtained in the step (2) is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 6 mm and an ellipsoidal shape.
  • (1) containing 500gCaCO 3 and component parts is calculated as CaCO 3 93 parts by weight, NaCl 0.8 parts, Mg (OH) 2 10 parts, CaSO 4 3.2 parts, Al (OH) 3 0.8 parts, SiO 2 0.5 parts
  • the mixture was added to 500 mL of water and stirred at room temperature (25 ° C) to disperse into a slurry, and then pure formic acid was added dropwise to the slurry under stirring until no bubbles appeared in the reaction system;
  • the solid powder obtained in the step (2) is granulated by a roll to obtain an organic environment-friendly snow melting agent having a particle size of 4 to 6 mm and an ellipsoidal shape.
  • an etching solution was prepared, and sodium chloride (purity ⁇ 99.9%) was separately added to seven 2000 mL beakers, and Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example
  • the organic environment-friendly snow melting agent product in 4 is prepared as a test solution according to the solute mass fraction of 18.0%;
  • the sample is a rectangular 20-gauge carbon steel sheet (GB/T 699), the size is 5mm ⁇ 2.5mm ⁇ 0.2mm.
  • the sample is wiped off with surface filter oil before the experiment, soaked in acetone and absolute ethanol, and then dried.
  • the samples were wrapped one by one with filter paper and placed in a desiccator for later use. After the experiment, the samples were accurately weighed with the analytical balance and then immersed in the above-mentioned corresponding number of corrosion solutions.
  • the experimental temperature was 40 ° C
  • the test piece line speed was 0.35 m / s
  • no air was introduced during the soaking process, and the air was continuously immersed 48 After the hour, wipe off the surface rust and then pickle, alkali wash, wash with water, remove excess water with absolute ethanol, and then weigh again after drying.
  • the corrosion inhibition rate is determined according to the corrosion reduction, and the corrosion rate is calculated as follows:
  • the corrosion inhibition rate X 2 of each sample was calculated by the corrosion rate measured by the above formula (for specific detection and calculation results, see Table 1):
  • X 0 is the corrosion rate of the prepared sodium chloride corrosion test solution on the test piece, the unit is mm/a;
  • X 1 is the corrosion rate of the test piece prepared by the corrosion test solution prepared in the above-mentioned respective examples and comparative examples, in units of mm/a.
  • the organic environment-friendly snow melting agent of the invention can significantly reduce the corrosion of the standard carbon steel sheet, and the corrosion rate of the sodium chloride to the carbon steel is equivalent to the number of the organic snow melting agent of the invention.
  • the corrosion inhibition effect of the comparative example product was lower than that of the present invention.
  • Example 1 Referring to the test method for the ability to melt snow and ice in the national standard of snow melting salt, the organic environment-friendly snow melting agent in Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 was weighed. 200g of each product, placed in 6 400mL beakers, dissolved in water and transferred to 6 1000mL volumetric flasks, shaken, and set to volume; in each volumetric flask, Example 1, Example 2, Comparative Example 1.
  • the test solutions of the snow melting agent products of Comparative Example 2, Comparative Example 3, and Comparative Example 4 were sequentially labeled as: test solution 1, test solution 2, test solution 3, test solution 4, test solution 5, and test solution. 6;
  • test solution 6 Take six 150mL sample bottles of the same diameter and height, add 100mL water and place them in a low temperature incubator at -10 °C until they are fully frozen; respectively, remove 25mL of the above test solution 1, test solution 2, test solution 3, test Liquid 4, test solution 5, test solution 6, and respectively transferred into 6 50mL beakers, placed in a low temperature incubator at -8 ° C for 12h and then reserved;
  • the spare test solution 1, test solution 2, test solution 3, and test solution 4 The test solution 5 and the test solution 6 are quickly poured into a sample vial containing ice cubes, and then returned to a low temperature incubator at -10 ° C, and the sample vials are taken out at 20 minutes, 40 minutes, and 60 minutes, respectively. Immediately pour the liquid, and quickly weigh the quality of the beaker and the remaining ice.
  • Table 2 The obtained temperature and snow melting capacity data are shown in Table 2:
  • Example 2 Sodium chloride (purity ⁇ 99.9%) and organic environmentally friendly snow melting in Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were respectively added to 7 beakers.
  • the product product was added to the test solution according to the solute mass fraction of 18.0%. 70.0 mL of each test solution was separately taken and tested according to the requirements of SH/T 0090.
  • the BSY-188Z engine coolant freezing point tester was used for testing. The results are shown in Table 3:
  • Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Freezing point / °C -14.3 -19.2 -19.7 -8.3 -8.8 -9.1 -8.6
  • the freezing point of the conventional calcium carbonate magnesium salt snow melting agent is above the sodium chloride snow melting agent, which is one aspect of the performance of this type of snow melting agent is not as good as conventional sodium chloride; In the application, the freezing point of the calcium carboxylate salt-melting agent after doping with the relevant trace components was significantly reduced.

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Abstract

一种利用两碱法盐泥制备有机环保融雪剂的方法，属于环境保护和固体废弃物资源化利用技术领域。该方法包括如下步骤：首先将有机酸与两碱法盐泥在常温下搅拌反应，再将反应体系过滤，将所得滤液减压浓缩、离心喷雾干燥得到固体粉末并造粒，得到有机环保型融雪剂。该方法不仅实现了盐泥固废的循环利用，变废为宝大幅降低有机环保类融雪剂的生产成本，而且由于微量离子的存在对融雪化冰能力有明显的协同提升作用。

Description

[根据细则37.2由ISA制定的发明名称]　利用两碱法盐泥制备有机环保融雪剂的方法 技术领域
本发明属于环境保护和固体废弃物资源化利用技术领域，特别涉及一种利用两碱法盐泥制备有机环保融雪剂的方法。
背景技术
冬季下雪是阻碍交通的“大敌”。二十世纪四、五十年代，随着交通运输的迅速发展，融雪剂应运而生，融雪剂主要用于机场、公路、铁路、城市街道等地方，起到除雪或防冻作用。
氯盐类融雪剂因其融雪效果好、价格便宜，一直被广泛地应用于道路的除雪化冰，直到现在，一些国家仍以氯盐作为融雪剂的主体，我国也不例外。然而，过度使用氯盐融雪剂会导致路旁植被大量死亡，公路、桥梁、混凝土路面受到腐蚀破坏，被掺进了融雪剂的雪融化后渗入地表，污染江河、地下水，对生态环境造成了严重的破坏。所以研究新型的融雪剂，改善现有融雪剂的性能迫在眉睫。
20世纪80年代末90年代初，国外开始研究乙酸盐融雪剂，醋酸钙镁盐的出现使之有了突破性的改变。醋酸钙镁盐(CMA)为醋酸钙和醋酸镁的混合物，是20世纪80年代美国为代替高速公路的除冰(雪)剂氯化钠而开发的一种环保型化学品，与氯化钠相比较，CMA具有熔点低、可生物降解、对公路基础设施中的混凝土与金属的腐蚀性小、基本上对土壤和水源不造成污染等优点。通常，CMA是由冰醋酸与白云石反应制得，但此生产成本高，其产品价格为氯化钠的30倍，制约了CMA的普遍应用。
卤水净化工艺是制盐行业提高精制盐产品纯度，降低盐中杂质含量，提高盐产品白度的一个关键过程。两碱法卤水净化工艺所产生的盐泥中所涉及的化学成分包括CaCO3、Mg(OH)2以及少量NaCl、CaSO4等，由于产出量大，成分复杂，直接排放带来环境污染。目前，国内大多数企业对盐泥的处理方法是将其作为废物填埋。目前研究开发合理的盐泥处理工业化应用技术，是国内所有制盐企业共同面临的技术难题。
发明内容
本发明提供了一种利用两碱法盐泥制备有机环保融雪剂的方法，不仅能够省去降低盐泥处理费用，还可以充分利用资源变废为宝，大幅降低有机环保类融雪剂的生产成本，充分利 用盐泥中的微量成分进一步提高融雪剂的使用性能。
本发明采用的技术方案为：将盐泥和有机酸反应，过滤后滤液经过浓缩、离心喷雾干燥、造粒后得到有机环保型融雪剂，
具体步骤为：
(1)将有机酸与两碱法盐泥在常温(25℃)下搅拌反应，
其中，两碱法盐泥的组成按重量份数计算为，CaCO3 85～95份、NaCl 0.5～1.5份、Mg(OH)28.5～13.2份、CaSO4 1.5～4.0份、Fe(OH)3 0.5～1.5份、Al(OH)3 0.5～1.0份、SiO2 0.1～2.0份(如原始盐泥中除二氧化硅外的组分或含量与上述标准有出入，可通过常规的去除或添加的手段加以调整)，
有机酸为甲酸、乙酸、丙酸、木醋酸或其他有机废酸，优选为甲酸、乙酸或其他有机废酸，
具体操作为，将两碱法盐泥在水中分散为浆料，再于搅拌状态下向该浆料中滴加有机酸直至反应体系没有气泡出现，
上述反应产生的气泡为二氧化碳气体，可作为副产物收集利用；
(2)对步骤(1)得到的反应体系过滤，将所得滤液减压浓缩并离心喷雾干燥得到固体粉末，
减压浓缩时的真空度为0.06～0.09Mpa，温度为70～80℃，减压浓缩后得到的液态产物(包括脱色或不脱色)可直接作为液态有机环保型融雪剂；
(3)将步骤(2)中得到的固体粉末造粒，得到有机环保型融雪剂，
对固体粉末对辊造粒得到颗粒大小为4～7mm、形状为椭球型的有机环保型融雪剂。
本发明的有益效果在于：首次提出利用卤水净化过程中产生的两碱法盐泥和有机酸反应制备出有机环保型融雪剂，充分利用了盐泥中的钙、镁离子，而且由于微量离子的存在对融雪化冰能力有明显的协同提升作用；实现了盐泥固废的循环利用，变废为宝大幅降低有机环保类融雪剂的生产成本，而且省去了盐泥的处理费用，降低了环境污染。
所制备的CMA类型融雪剂是市场上公认的一种环保型化学品，与氯化钠类融雪剂相比较，CMA具有熔点低、可生物降解、对公路基础设施中的混凝土与金属的腐蚀性小、基本上对土壤和水源不造成污染等优点。非常符合国家节能减排、绿色环保的方针政策。
具体实施方式
实施例1
本实施例中所使用的两碱法盐泥的组成按重量份数计算为CaCO3 94.5份、NaCl 1.2份、Mg(OH)2 9.5份、CaSO4 2.5份、Fe(OH)3 0.7份、Al(OH)3 0.9份、SiO2 2.0份，
(1)将含有500gCaCO3的上述两碱法盐泥在500mL水中常温(25℃)搅拌分散为浆料，再于搅拌状态下向该浆料中滴加纯乙酸直至反应体系没有气泡出现；
(2)对步骤(1)得到的反应体系过滤，将所得滤液于0.06Mpa、75℃下减压浓缩，并离心喷雾干燥得到固体粉末；
(3)将步骤(2)中得到的固体粉末对辊造粒得到颗粒大小为4～6mm、形状为椭球型的有机环保型融雪剂。
实施例2
本实施例中所使用的两碱法盐泥的组成按重量份数计算为CaCO3 93份、NaCl 0.8份、Mg(OH)2 10份、CaSO4 3.2份、Fe(OH)3 0.85份、Al(OH)3 0.8份、SiO2 0.5份，
(1)将含有500gCaCO3的上述两碱法盐泥在500mL水中常温(25℃)搅拌分散为浆料，再于搅拌状态下向该浆料中滴加纯甲酸直至反应体系没有气泡出现；
(2)对步骤(1)得到的反应体系过滤，将所得滤液于0.07Mpa、80℃下减压浓缩，并离心喷雾干燥得到固体粉末；
(3)将步骤(2)中得到的固体粉末对辊造粒得到颗粒大小为4～6mm、形状为椭球型的有机环保型融雪剂。
对比实施例1
按照实施例1的两碱法盐泥中CaCO3、NaCl、Mg(OH)2、CaSO4、SiO2的量以纯净物的形式加入：
(1)将含有500gCaCO3且组分按重量份数计算为CaCO3 94.5份、NaCl 1.2份、Mg(OH)2 9.5份、CaSO4 2.5份、SiO2 2.0份的混合物一并加入500mL水中，并常温(25℃)搅拌分散为浆料，再于搅拌状态下向该浆料中滴加纯乙酸直至反应体系没有气泡出现；
(2)对步骤(1)得到的反应体系过滤，将所得滤液于0.06Mpa、75℃下减压浓缩，并离心喷雾干燥得到固体粉末；
(3)将步骤(2)中得到的固体粉末对辊造粒得到颗粒大小为4～6mm、形状为椭球型的有机环保型融雪剂。
对比实施例2
按照实施例2的两碱法盐泥中CaCO3、NaCl、Mg(OH)2、CaSO4、Fe(OH)3、SiO2的量以纯净物的形式加入：
(1)将含有500gCaCO3且组分按重量份数计算为CaCO3 93份、NaCl 0.8份、Mg(OH)2 10份、CaSO4 3.2份、Fe(OH)3 0.85份、SiO2 0.5份的混合物一并加入500mL水中并常温(25℃)搅拌分散为浆料，再于搅拌状态下向该浆料中滴加纯甲酸直至反应体系没有气泡出现；
(2)对步骤(1)得到的反应体系过滤，将所得滤液于0.07Mpa、80℃下减压浓缩，并离心喷雾干燥得到固体粉末；
(3)将步骤(2)中得到的固体粉末对辊造粒得到颗粒大小为4～6mm、形状为椭球型的有机环保型融雪剂。
对比实施例3
在实施例1的基础上，增加Fe(OH)3、Al(OH)3的含量：
本实施例中所使用的两碱法盐泥的组成按重量份数计算为CaCO3 94.5份、NaCl 1.2份、Mg(OH)2 9.5份、CaSO4 2.5份、Fe(OH)3 5份、Al(OH)3 4份、SiO2 2.0份，
(1)将含有500gCaCO3的上述两碱法盐泥在500mL水中常温(25℃)搅拌分散为浆料，再于搅拌状态下向该浆料中滴加纯乙酸直至反应体系没有气泡出现；
(2)对步骤(1)得到的反应体系过滤，将所得滤液于0.06Mpa、75℃下减压浓缩，并离心喷雾干燥得到固体粉末；
(3)将步骤(2)中得到的固体粉末对辊造粒得到颗粒大小为4～6mm、形状为椭球型的有机环保型融雪剂。
对比实施例4
按照实施例2的两碱法盐泥中CaCO3、NaCl、Mg(OH)2、CaSO4、Al(OH)3、SiO2的量以纯净物的形式加入：
(1)将含有500gCaCO3且组分按重量份数计算为CaCO3 93份、NaCl 0.8份、Mg(OH)2 10份、CaSO4 3.2份、Al(OH)3 0.8份、SiO2 0.5份的混合物一并加入500mL水中并常温(25℃)搅拌分散为浆料，再于搅拌状态下向该浆料中滴加纯甲酸直至反应体系没有气泡出现；
(2)对步骤(1)得到的反应体系过滤，将所得滤液于0.07Mpa、80℃下减压浓缩，并离心喷雾干燥得到固体粉末；
(3)将步骤(2)中得到的固体粉末对辊造粒得到颗粒大小为4～6mm、形状为椭球型的有机环保型融雪剂。
检测实验1
有机环保型融雪剂对金属碳钢腐蚀：
首先配制腐蚀溶液，在7个2000mL的烧杯中分别加入氯化钠(纯度≥99.9％)和实施例1、实施例2、对比实施例1、对比实施例2、对比实施例3、对比实施例4中的有机环保型融雪剂产品，加水均按照溶质质量分数为18.0％配制为试液；
试样为长方形20号碳钢片(GB/T 699)，尺寸为5mm×2.5mm×0.2mm，试样在实验前用滤纸擦去表面油脂，经丙酮和无水乙醇浸泡后烘干，最后将试样逐个用滤纸包裹，置于干燥器中备用。实验开始后用分析天平准确称重各试样后浸泡于上述相应编号的腐蚀溶液中，实验温度为40℃，试片线速度为0.35m/s，浸泡过程中不通入空气，不间断浸泡48小时后擦拭掉表面铁锈再经酸洗、碱洗、水洗后用无水乙醇除去多余水分，烘干后再次称重，
根据腐蚀减量测定缓蚀速率，腐蚀速率计算公式如下：
Figure PCTCN2017093783-appb-000001
上式中，m为经过上述配制的腐蚀液所浸泡的试片质量的最终损失，单位g；m1为试片仅经过上述酸洗、碱洗、水洗、无水乙醇洗后的质量损失平均值，单位g；
s为试片的表面积，单位cm2；ρ为试片的密度，单位g/cm3；t为试验时间，单位h；8760为与1年相当的小时数，单位h/a；10为与1cm相当的毫米数；
通过上式测得的腐蚀速率计算各样品的缓蚀率X2(具体检测、计算结果请见表1)：
Figure PCTCN2017093783-appb-000002
式中：X0为上述配制的氯化钠腐蚀试液对试片的腐蚀速率，单位mm/a；
X1为上述各实施例、对比实施例的成品所配制的腐蚀试液对试片的腐蚀速率，单位mm/a。
表1
  氯化钠 实施例1 实施例2 对比例1 对比例2 对比例3 对比例4
腐蚀速率 0.5058 0.0756 0.0701 0.1385 0.1276 0.1162 0.1289
缓蚀率 / 85.05％ 86.14％ 72.62％ 74.77％ 77.03％ 74.52％
从表1的碳钢腐蚀结果可以看出，本发明的有机环保型融雪剂能明显降低对标准碳钢片的腐蚀，氯化钠对碳钢的腐蚀速率相当于本发明有机类融雪剂的数倍；而对比实施例产品的缓蚀效果低于本发明。
检测实验2
有机环保型融雪剂的融冰速度：
参照融雪盐国家标准中融雪化冰能力的测试方法，称取实施例1、实施例2、对比实施例1、对比实施例2、对比实施例3、对比实施例4中的有机环保型融雪剂产品各200g，分别置于6个400mL烧杯中，加水溶解后分别转移至6个1000mL的容量瓶中，摇匀、定容备用；将各容量瓶中实施例1、实施例2、对比实施例1、对比实施例2、对比实施例3、对比实施例4的融雪剂产品的试液依次标计为：试液1、试液2、试液3、试液4、试液5、试液6；
取6个150mL相同直径和高度的样品瓶，分别加入100mL水并置于-10℃的低温恒温箱中至充分结冰；分别移取25mL上述试液1、试液2、试液3、试液4、试液5、试液6，并分别移入6个50mL的烧杯中，置于-8℃的低温恒温箱中12h后备用；
从低温恒温箱中取出充分结冰的各样品瓶，擦干外壁的水和冰，迅速称量(精确至0.1g)，将备用的试液1、试液2、试液3、试液4、试液5、试液6一一对应迅速倒入盛有冰块的样品瓶中，然后放回-10℃的低温恒温箱中，分别在20分钟、40分钟、60分钟取出该样品瓶，立即倾倒其液体，并迅速称量烧杯和剩余冰块的质量，所得各温度融雪化冰能力数据如表2所示：
表2
Figure PCTCN2017093783-appb-000003
可见，微量铁、铝的共同存在，才能够协同融雪剂的主成份促使融雪化冰作用大幅提高； 就对比例3来看，当Fe、Al元素含量过高时，融雪效果反而不佳。
检测实验3
有机环保型融雪剂的冰点测试：
在7个烧杯中分别加入氯化钠(纯度≥99.9％)和实施例1、实施例2、对比实施例1、对比实施例2、对比实施例3、对比实施例4中的有机环保型融雪剂产品，加水均按照溶质质量分数为18.0％配制为试液，对各试液分别移取70.0mL，按照SH/T 0090的要求进行测定，使用BSY-188Z发动机冷却液冰点测定仪进行测试，结果如表3所示：
表3
  氯化钠 实施例1 实施例2 对比例1 对比例2 对比例3 对比例4
冰点/℃ -14.3 -19.2 -19.7 -8.3 -8.8 -9.1 -8.6
从各对比例的检测数据来看，常规的羧酸钙镁盐融雪剂的冰点在氯化钠融雪剂之上，这是该类型融雪剂在性能上不如常规氯化钠的一个方面；但是本申请中通过相关微量成份掺杂后的羧酸钙镁盐融雪剂的冰点有了明显的降低。

Claims (8)

  1. 一种利用两碱法盐泥制备有机环保融雪剂的方法，其特征在于：所述方法为，将两碱法盐泥和有机酸反应，过滤后滤液经过浓缩、离心喷雾干燥、造粒后得到有机环保融雪剂。
  2. 如权利要求1所述的制备有机环保融雪剂的方法，其特征在于：所述方法的具体步骤为，
    (1)将有机酸与两碱法盐泥在常温下搅拌反应；
    (2)对步骤(1)得到的反应体系过滤，将所得滤液减压浓缩并离心喷雾干燥得到固体粉末；
    (3)将步骤(2)中得到的固体粉末造粒，得到有机环保型融雪剂。
  3. 如权利要求2所述的制备有机环保融雪剂的方法，其特征在于：步骤(1)中，控制两碱法盐泥的组成按重量份数计算为，CaCO385～95份、NaCl 0.5～1.5份、Mg(OH)28.5～13.2份、CaSO41.5～4.0份、Fe(OH)30.5～1.5份、Al(OH)30.5～1.0份、SiO20.1～2.0份。
  4. 如权利要求2所述的制备有机环保融雪剂的方法，其特征在于：步骤(1)中所述的有机酸为甲酸、乙酸、丙酸或木醋酸。
  5. 如权利要求2所述的制备有机环保融雪剂的方法，其特征在于：步骤(1)中的具体操作为，将两碱法盐泥在水中分散为浆料，再于搅拌状态下向该浆料中滴加有机酸直至反应体系没有气泡出现。
  6. 如权利要求2所述的制备有机环保融雪剂的方法，其特征在于：步骤(1)中所述的两碱法盐泥的颗粒粒径为30～85μm。
  7. 如权利要求2所述的制备有机环保融雪剂的方法，其特征在于：步骤(2)中，减压浓缩时的真空度为0.06～0.09Mpa，温度为70～80℃。
  8. 如权利要求2所述的制备有机环保融雪剂的方法，其特征在于：步骤(3)中，对固体粉末对辊造粒得到颗粒大小为4～7mm、形状为椭球型的有机环保型融雪剂。
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