CN101878326A - 缓蚀剂 - Google Patents

缓蚀剂 Download PDF

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CN101878326A
CN101878326A CN200880112431XA CN200880112431A CN101878326A CN 101878326 A CN101878326 A CN 101878326A CN 200880112431X A CN200880112431X A CN 200880112431XA CN 200880112431 A CN200880112431 A CN 200880112431A CN 101878326 A CN101878326 A CN 101878326A
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acid
alcohol
glycerol
inhibiter
formic acid
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B·O·米沃尔德
K·桑德森格里特兰德
T·斯达洛
R·布瓦普
B·赛尔杰巴肯克劳森
G·E·弗雷德海姆
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Borregaard Industries Ltd
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    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid 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
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    • 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
    • C23F11/10—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 organic inhibitors
    • 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
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

出人意料地，已发现简单二元醇和三元醇能用作浓有机和无机酸的缓蚀剂，例如用作工厂和车间的金属设备中的添加剂。这些缓蚀剂便宜且易于大量获得。所述二元醇和三元醇还能减少酸的蒸发，从而改善工作环境。

Description

缓蚀剂
本发明涉及以下发现，即对于生产工厂或生产车间的金属或金属设备而言，当向其中使用的用以降低或抑制微生物生长的酸或含酸组合物中加入二元醇或三元醇或其混合物时，所述二元醇或三元醇或其混合物能够提供降低或抑制腐蚀的效果。所述工厂或车间可为用于青贮饲草、青贮鱼和/或鱼制品、继续处理/青贮屠场废料和食品废料的工厂或车间，或农场动物例如家禽或猪的饮水设施。使用大量酸的工厂或车间的其它实例还有制革厂、冶金工业和纸浆厂。
对于防治微生物生长而言，有机酸具有很多有益的效果。因此，其常用于有机物质的保存。丙酸被用作谷物保存剂、用于青贮饲草和作为饲料添加剂。甲酸用于青贮鱼、屠场废料、食品废料和饲草，并用于猪和鸡饲料中。乙酸用于鱼的保藏。苯甲酸用于鱼的青贮。其它酸或酸的混合物也可使用。有机酸还用于特别是猪和家禽的饮用水中。将有机酸添加至猪、绵羊、山羊、家禽、牛、马、狗、猫和毛皮动物的配合饲料中可有效地影响它们的生长和健康。此外，将酸添加至配合饲料中还能降低每千克生长量消耗的配合饲料的量，而不会产生影响肉质量的增加的生长量。这可通过缩短饲养期并促进更好的住舍利用来降低饲养成本。
强酸如硫酸、亚硫酸和盐酸可在多种方法中使用。制革、冶金和制浆仅是一些实例。
然而，酸的使用，特别是强酸例如甲酸或矿物酸的使用还存在一些问题，包括设备腐蚀。酸具有腐蚀性，每年因使用这些酸而造成的腐蚀就耗费数百万美元。特别是，在颗粒饲料的生产线中，对储罐、管道、阀门和混合设备造成的腐蚀相当严重。这抬高了生产成本，并造成增加的维护和***监测的额外负担。
使用挥发物来处理产品也存在一些问题。甲酸具有特别强的皮肤腐蚀性，可因侵蚀而造成损伤，这是为什么需要全身防护的原因。一个实例是，在造粒过程中，温度升至80-95℃，部分酸会蒸发。这引起部分酸的汽化，其蒸汽吸入时可能是危险的。蒸发造成的酸的损失不仅带来环境问题，而且还影响经济成本。
之前，一些不良影响已通过添加一种聚合的强酸、例如木质素磺酸或其盐而缓解(专利WO 00/27220、PCT/NO99/00309)。
在本发明中，以上提及的与使用酸相关的问题已通过添加一种二元醇或三元醇、特别是丙三醇而减轻。出人意料地，已显示出，降低的腐蚀率远超过由于酸的稀释而产生的预期速率。
二元醇是指具有两个羟基的任意有机化合物，例如乙二醇或丙二醇。三元醇是指具有三个羟基的任意有机化合物，例如丙三醇。二元醇和三元醇均可通过发酵、水解或酯交换而制备。在生物柴油生产过程中，在脂肪皂化和脂肪酯交换制备脂肪酸甲酯的过程产生大量的丙三醇。
二元醇或三元醇的加入量为含有酸的最终混合物的10至90％，优选40至60％。
糖和糖醇之前已作为缓蚀剂被描述(FR 2 391 261A)。简单的二元醇和三元醇有一些优点。它们廉价。它们在室温下呈液态，因而易于以任意剂型使用。通过使用二元醇(如乙二醇)或作为三元醇的丙三醇，我们不必使用稀少食物资源作为化学原料。
丙三醇已表现出能够降低经氨水部分中和的甲酸对皮肤的腐蚀(NO 307 591 B)。在此，我们表明二元醇或三元醇也可作为金属缓蚀剂，而完全无需对酸进行中和。
下列实施例意欲说明本发明，而不以任意方式限制其范围。
实施例
腐蚀试验
碳钢样片C1018用于该腐蚀试验中。将样片在丙酮中声处理10分钟，然后在加热箱中干燥，在干燥器中冷却并称重。将它们挂在装有酸和添加的缓蚀剂的试验瓶内的聚丙烯条上。用塑料膜将瓶密封以防止酸蒸发。将试验瓶置于磁力搅拌器上以防止溶液内的扩散梯度。3天后，将钢样片从瓶中取出并用温水和丙酮冲洗，然后将其在加热箱中干燥，在干燥器中冷却并称重。所有试验均重复两次，给出平均腐蚀率。
使用以下方程式由钢样片的重量损失确定腐蚀率CR(mm/年)：
ρ钢＝7.718g/cm3
表面积＝27.2cm2
不同试验的结果示于下表。
表1.丙三醇浓度对强有机酸的效果
  组合物   腐蚀率/mm/年   改善/％
  10％水-90％甲酸   6.7   ---
  10％丙三醇-90％甲酸   4.1   38.8
  25％水-75％甲酸   5.0   ---
  25％丙三醇-75％甲酸   3.2   36.0
  50％水-50％甲酸   7.5   ---
  50％木质素磺酸盐溶液-50％甲酸   2.8   62.7
  50％丙三醇-50％甲酸   1.3   82.7
我们看到所有浓度的丙三醇至少与工业上使用的木质素磺酸盐同样有效。
表2.丙三醇浓度对弱有机酸的效果
  组合物   腐蚀率/mm/年   改善/％
  10％水-90％丙酸   4.52   ---
  10％丙三醇-90％丙酸   0.70   84.5
  25％水-75％丙酸   5.57   ---
  25％木质素磺酸盐溶液-75％丙酸   0.55   90.1
  25％丙三醇-75％丙酸   0.06   99.0
  50％水-50％丙酸   2.80   ---
  50％木质素磺酸盐溶液-50％丙酸   1.15   58.9
  50％丙三醇-50％丙酸   0.031   98.9
我们看到所有浓度的丙三醇至少与工业上使用的木质素磺酸盐同样有效。
表3.50∶50重量％混合比时对于多种酸的效果
  组合物   腐蚀率/mm/年   改善/％
  50％水-50％浓盐酸   114.8   ---
  50％丙三醇-50％浓盐酸   83.8   27.0
  50％水-50％硫酸(30％)   181   ---
  50％丙三醇-50％硫酸(30％)   25.9   85.7
  50％水-50％丙酸   2.8   ---
  50％丙三醇-50％丙酸   1.2   58.9
  50％水-50％甲酸   7.5   ---
  50％丙三醇-50％甲酸   1.3   82.7
我们看到丙三醇对多种矿物酸和有机酸有效。
表4.各种醇的效果
  组合物   腐蚀率/mm/年   改善/％
  50％水-50％甲酸   7.5   ---
  50％丙三醇-50％甲酸   1.3   82.7
  50％乙二醇-50％甲酸   2.9   61.7
  50％乙醇-50％甲酸   9.8   -31.1
我们看到二元醇和三元醇表现出良好的缓蚀性，而简单的醇不具备。
蒸发试验
制备500ml的50∶50重量％的丙三醇∶甲酸、木质素磺酸盐∶甲酸、水∶甲酸溶液。也包括纯甲酸作为参照。将各自精确的100g溶液置于2个不同烧杯中。
在搅拌和不搅拌下将试样保持在室温。在4小时、26小时、58小时和89小时记录重量。结果示于图1和2中。我们看到所有添加剂均降低了室温时的重量损失，但三元醇比其它添加剂有效得多。

Claims (4)

1.二元醇或三元醇或者二元醇和/或三元醇的混合物作为有机或无机酸或酸的混合物的缓蚀剂的用途。
2.权利要求1的用途，其中所述二元醇或三元醇或其混合物构成总混合物的10-90％。
3.权利要求1和2的用途，其中所述三元醇为丙三醇且所述二元醇为乙二醇。
4.权利要求1至3的用途，其中所述混合物包含其它缓蚀剂。
CN200880112431XA 2007-09-13 2008-09-15 缓蚀剂 Pending CN101878326A (zh)

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