CN101052698A - 高温腐蚀抑制剂 - Google Patents

高温腐蚀抑制剂 Download PDF

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CN101052698A
CN101052698A CNA2005800376682A CN200580037668A CN101052698A CN 101052698 A CN101052698 A CN 101052698A CN A2005800376682 A CNA2005800376682 A CN A2005800376682A CN 200580037668 A CN200580037668 A CN 200580037668A CN 101052698 A CN101052698 A CN 101052698A
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S·E·勒雷尔
S·B·普吕特
L·V·米内夫斯基
J·G·埃蒙森
A·E·戈利亚什夫斯基
F·邵
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Abstract

在高温加工原油或其高温馏分的过程中抑制由环烷酸引起的腐蚀的方法，该处理方法包括使用(I)四官能取代芳香化合物和(II)偏苯三酸的酯或酸酐进行处理。

Description

高温腐蚀抑制剂
                        技术领域
本发明通常涉及抑制炼制操作中产生腐蚀的方法。特别是抑制原油中的环烷酸引起的腐蚀。
                        背景技术
石油炼制操作中的腐蚀问题和原油中的环烷酸成分相关，很多年前人们就意识到这一点。这种腐蚀在约350～790温度范围内的常压或减压蒸馏装置特别严重。其它影响含环烷酸原油腐蚀性的因素包括：环烷酸的含量，含硫化合物的浓度，装置中流体的流速和湍流度，以及在装置中的位置(例如，液/气界面)
在蒸馏炼制原油时，原油连续流经炉子和一个或多个分馏塔，例如常压塔和减压塔。在大多数操作中，操作温度低于约350时，环烷酸腐蚀不是问题。传统的基于氮的成膜腐蚀抑制剂在温度高于约350时会失效，其它防止环烷酸腐蚀的方法例如中和法存在操作问题或者无效。
应该注意到，术语“环烷酸”包括一元羧酸和二元羧酸，通常占整个原油中酸性组分的约50％重量。许多环烷酸可以用以下分子式表示：
Figure A20058003766800041
其中R是烷基或环烷基，n为2～10之间的整数。
此结构或此分子量进行诸多变化都是可能的。一些实例(practitioner)包括环烷酸的范畴内的烷基有机酸。
环烷酸在约350(180℃)～约790(420℃)的温度范围具有腐蚀性。在更高温度下，环烷酸就进入气相，且分解的速度增加。在更低温度下，腐蚀速率并不严重。原油和馏分的腐蚀性也受硫化物存在的影响，例如硫化氢，硫醇，元素硫，硫化物，二硫化物，多硫化物和苯硫酚。温度低至450时，含硫化合物导致的腐蚀变得显著。硫醇热分解催化产生硫化氢已被确定为硫腐蚀的一个原因。
降低或防止环烷酸腐蚀的尝试包括下述方法：
a)将环烷酸浓度高的油品与环烷酸浓度低的油品混合；
b)中和及脱除油品中的环烷酸；和
c)使用腐蚀抑制剂。
因为这些方法并不能完全令人满意，在工业上可以接受的方法就是使用例如高质量的不锈钢或铬钼含量高的合金类的抗蚀金属构造蒸馏单元或暴露于环烷酸腐蚀的部分。但是，在没有进行如此构造的单元中，需要提供针对此种腐蚀的防腐处理。现有技术的环烷酸环境下的腐蚀抑制剂包括基于氮的成膜腐蚀抑制剂。但是，这些腐蚀抑制剂在含环烷酸油的高温条件下的效果相对较差。
常压和减压蒸馏系统在加工特定原油时遭受环烷酸的腐蚀。目前使用的处理是在工作温度下热反应。当使用磷基抑制剂时，人们认为会生产金属磷酸盐表面膜，该膜比基底钢材更能抵抗环烷酸的腐蚀。这些抑制剂相对易挥发，馏程相当窄。根据使用的温度范围，抑制剂被加入到塔中腐蚀点上部或下部。多硫化物抑制剂分解为含硫更多和更少的多硫化物以及可能的元素硫和硫醇的复杂混合物。这样，抑制剂的挥发性和赋予的保护性就不可预测。
                            发明详述
本发明提供抑制设备内金属表面腐蚀的方法，该设备用来加工原油或衍生自原油的高温石油馏分。该方法包括向原油或馏分中添加有效量的，足够抑制腐蚀的，四官能团取代的芳香化合物(I)和/或偏苯三酸酯或偏苯三酸酐(II)。
上述四官能团取代的芳香化合物(I)可以用如下通式表示：
Figure A20058003766800051
其中W，X，Y和Z全部存在，并可以是相同或不同的，它们独立地选自OH，COOH和COOR1，前提条件是W，X，Y，Z的相邻基团对可以是
Figure A20058003766800061
也就是酸酐功能；式中R1是碳原子数为约1～约16的烷基，Ar是芳香部分。
偏苯三酸酯或偏苯三酸酐(II)用下式(II)表示，
其中R2和R3是 或
Figure A20058003766800064
前提条件是：当R2或R3之一为
Figure A20058003766800065
或
Figure A20058003766800066
时，那么另一基团是足以形成酐基团也就是 的
Figure A20058003766800068
或
Figure A20058003766800069
该酐基团连接芳香部分的1位和2位；R2和R3也可是COOR5，其中每个R5独立地选自碳原子数为约1～约16的烷基，R4是COOR6，其中R6是C1-C16烷基基团。
符合上述式(I)的代表性化合物包括没食子酸丙酯，没食子酸，1，2，4，5-苯四酸(也就是1，2，4，5-苯四甲酸)；1，2，4，5-苯四甲酸二酸酐，没食子酸辛酯，和1，2，4，5-苯四酸四辛酯。优选1，2，4，5-苯四酸。
当提到上述上述式(II)包括的化合物时，可以提到1，2，4-苯三甲酸酐和偏苯三酸三辛酯。
根据本发明的一个方面，所述处理，也就是说上述化合物I和/或化合物II可以直接加入原油原料中，例如，在原油塔和减压塔的下部提供保护。相反的是，抑制处理剂可以在工艺料流的任何地方加入，其中抑制处理剂会和加工介质例如原油或原油馏分接触。
腐蚀抑制剂的最有效使用量根据本发明可以变化，取决于局部操作条件和加工的特定烃。这样，酸腐蚀系统的温度和其它特性就会影响所用抑制剂或抑制剂混合物的使用量。一般说来，操作温度和/或酸浓度越高，需要使用的腐蚀抑制剂的量就相应越大。人们已经发现，腐蚀抑制剂在原油的浓度为约1ppm～5000ppm体积。人们还发现优选开始加入2000～3000ppm的相对高剂量率的抑制剂，在相对较短的时间内保持这种高剂量，直至抑制剂的存在在金属表面导致形成防腐涂层。腐蚀抑制剂可以直接加入或稀释加入。一旦保护表面形成了，需要维持这种保护的剂量率就会降低至约100～1500ppm的正常操作范围，而基本不会牺牲保护性能。
实施例
现在通过下述实施例来进一步描述本发明，这些实施例目的是用来阐述本发明，而不是限制本发明。
高压釜试块(coupon)重量损失试验被用来评价用于环烷酸腐蚀的化合物。试验样品是经清洁，预先称重的低碳钢或5Cr防腐试块，该试验试块放置在玻璃载片上。链烷烃油里加入环烷酸使其总酸值为6.0，并加入试验高压反应釜中。在室温下呈固态的备选处理剂被加入到高压反应釜中并经过混合。油样用氩气脱气。在一些实验中，硫化物对腐蚀性和抑制性的影响是通过加入含硫化合物来确定的，在实施例2中这种含硫化合物为正十二烷基甲基硫醚，在实施例5中这种含硫化合物为二丁基硫醚，在这些实验中这些硫化物的加入量为0.5％。高压反应釜被加热到600或500的理想测试温度下。经过20小时暴露，将试块取出，清洁，再称重。试验结果如下所示。在加入正十二烷基甲基硫醚的试验中，仅用低碳钢试块来确定腐蚀抑制效果，因为使用5Cr试块的腐蚀速率非常低，小于10mpy。
实施例1
316C，不加硫化物
未经处理的腐蚀速率：低碳钢＝108.2MPY，5Cr钢＝153.9MPY
抑制剂                    剂量            防腐％
                                          MS        5Cr
没食子酸                  100             -32       40
没食子酸                  1000            92        93
1，2，4，5-苯四甲酸       100             95        99
1，2，4，5-苯四甲酸       1000            98        99
没食子酸丙酯              100             30        97
没食子酸丙酯              1000            96        99
实施例2
316C，加0.5％的正甲基十二烷基硫醚
未经处理的腐蚀速率：低碳钢＝39.9MPY
抑制剂                     剂量        防腐％
                                       MS
没食子酸                   100         25
没食子酸                   1000        78
1，2，4，5-苯四甲酸        100         78
实施例3
216C，不加硫化物
未经处理的腐蚀速率：低碳钢＝45.5MPY，5Cr钢＝36.3MPY
抑制剂                     剂量        防腐％
                                       MS        5Cr
没食子酸                   100         32        91
没食子酸                   1000        98        84
实施例4
316C，不加硫化物
未经处理的腐蚀速率：1010低碳钢＝143MPY
试验化合物                   剂量，ppm         防腐，％
1，2，4，5-苯四甲酸          25                84
1，2，4，5-苯四甲酸          100               82
1，2，4，5-苯四甲酸          250               93
1，2，4，5-苯四甲酸二酸酐    25                31
1，2，4，5-苯四甲酸二酸酐    100               84
1，2，4，5-苯四甲酸二酸酐    250               93
没食子酸辛酯                 25                -21
没食子酸辛酯                 100               -12
没食子酸辛酯                 250               -15
没食子酸丙酯                   25             27
没食子酸丙酯                   100            9
没食子酸丙酯                   250            41
1，2，4，5-苯四酸四辛酯        25             -30
1，2，4，5-苯四酸四辛酯        100            50
1，2，4，5-苯四酸四辛酯        250            60
偏苯三甲酸三辛酯               25             -9
偏苯三甲酸三辛酯               100            34
偏苯三甲酸三辛酯               250            23
1，2，4-苯三甲酸酐             100            35
1，2，4-苯三甲酸酐             250            58
实施例5
316C，加0.5％的硫化物二丁基硫醚
未经处理的腐蚀速率：1010MS＝76MPY
  试验化合物  剂量，ppm   防腐％
  1，2，4，5-苯四甲酸   100   35
  1，2，4，5-苯四甲酸   250   43
  1，2，4，5-苯四甲酸   1000   52
  1，2，4，5-苯四甲酸酐   100   22
  1，2，4，5-苯四甲酸酐   250   34
  1，2，4，5-苯四甲酸酐   1000   57
  没食子酸   250   40
  没食子酸   1000   82
  没食子酸辛酯   250   57
  没食子酸辛酯   1000   72
  没食子酸丙酯   250   38
  没食子酸丙酯   1000   54
  1，2，4，5-苯四酸四辛酯   250   45
  1，2，4，5-苯四酸四辛酯   1000   21
  偏苯三甲酸三辛酯   250   0
  偏苯三甲酸三辛酯   1000   0
  1，2，4-苯三甲酸酐   250   14
  1，2，4-苯三甲酸酐   1000   58
实施例6
一种高温高压反应釜被用来评价在由Venezuelan原油获得的脱气HVG0中多个对比腐蚀抑制剂和本发明腐蚀抑制剂。一块碳钢试块被静悬在气相中。两块碳钢试块以约2fps的速率在液相中旋转。液相温度控制在600约20小时。经处理和未经处理的试块的总体腐蚀速率用重量损失、表面积和浸泡时间来评估，单位为mpy。结果如下。
  试验化合物  剂量，ppm  腐蚀，mpy
  空白   14.2
  亚磷酸苯基二癸基酯C-1   50   13.4
  亚磷酸苯基二癸基酯C-1   100   7.2
  二壬基苯铵盐
  磺酸C-2   100   11.8
  没食子酸   100   9.8
  没食子酸   200   10.7
  连苯三酚C-3   100   11.9
  邻苯二酚C-4   100   11.5
  水杨酸C-5   100   12.2
  苯甲酸C-6   100   15.2
  邻苯二甲酸C-7   100   11.2
上述用C字母做前缀标识的试验化合物代表对比例。如上述实施例所示，芳香四酸化合物(I)和偏苯三酸酯和偏苯三酸酐II有效减少与高温原油接触的金属表面的腐蚀，特别是含有环烷酸的原油。本发明的处理剂不包括含磷或硫化物部分，这些物质被分别证明在可能使催化剂中毒或热稳定性差方面存在问题。
同样有必要指出，本发明的处理方法在针对同时含有环烷酸和含硫化合物的原油和石油馏分时，也是有效的腐蚀抑制剂。正如本领域技术人员熟知，在有含硫化合物，特别是硫化氢的存在下，环烷酸的腐蚀表现得特别明显。

Claims (10)

1、一种抑制设备内金属表面腐蚀的方法，该设备用于加工被加热到约350～约790的温度范围内的原油或者高温馏分，该方法包括向原油或高温石油馏分中加入腐蚀抑制量的腐蚀抑制剂，该腐蚀抑制剂选自组(I)和组(II)以及它们的混合物，其中所述的腐蚀抑制剂(I)分子式如下：
Figure A2005800376680002C1
其中W，X，Y和Z全部存在并且为相同或不同的，独立地选自OH，COOH和COOR1，前提条件是：W，X，Y和Z的相邻基团对可以选自
Figure A2005800376680002C2
R1是碳原子数为约1～16的烷基部分；Ar是芳族化合物，
所述腐蚀抑制剂(II)分子式如下：
Figure A2005800376680002C3
其中R2和R3是COOR5，
Figure A2005800376680002C4
前提条件是当R2或R3之一为
Figure A2005800376680002C5
Figure A2005800376680002C6
时，那么另一基团为足以形成连接R2和R3官能团的酐基团的
Figure A2005800376680002C7
每个R5独立地选自碳原子数为约1～约16的烷基基团，R4是COOR6，其中R6是碳原子数为约1～约16的烷基基团。
2、权利要求1所述的方法，其中Ar为取代苯。
3、权利要求2所述的方法，其中所述的腐蚀抑制剂(I)选自没食子酸，1，2，4，5-苯四酸，没食子酸丙酯，没食子酸辛酯，四辛基均苯四酸酯，和1，2，4，5-苯四甲酸二酸酐。
4、权利要求3所述的方法，其中腐蚀抑制剂(I)是1，2，4，5-苯四酸。
5、权利要求2所述的方法，其中腐蚀抑制剂(II)选自1，2，4-苯三甲酸酸酐，三辛基偏苯三酸酯。
6、权利要求3所述的方法，其中所述原油或石油馏分含有环烷酸，且所述的腐蚀抑制剂是环烷酸引起的腐蚀。
7、权利要求6所述的方法，其中所述原油或石油馏分进一步含有含硫化合物。
8、权利要求1所述的方法，其中向原油或馏分中加入腐蚀抑制剂(I)和/或(II)的量足以产生约1～5000ppm的体积浓度。
9、权利要求8所述的方法，其中浓度为约100～约1500ppm。
10、权利要求3所述的方法，其中所述腐蚀抑制剂是1，2，4，5-苯四甲酸二酸酐。
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