CN1259390C - 防止氯化铵和硫酸铵引起的污垢和腐蚀的方法 - Google Patents
防止氯化铵和硫酸铵引起的污垢和腐蚀的方法 Download PDFInfo
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- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 21
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- 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
- C23F11/10—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
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
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Abstract
一种防止氯化铵和硫酸铵引起的污垢和腐蚀的方法，其特征在于该方法包括注入胆碱或其衍生物作为添加剂。
Description
本发明涉及防止尤其是在原油精炼过程中形成的或存在的氯化铵和硫酸铵引起的污垢和腐蚀的方法。
从文献和本领域的经验可以知道，氯化铵和硫酸铵的气体形式、固体形式或者是溶液形式都具有腐蚀性。氯化铵呈酸性，可与金属离子络合并且含有腐蚀性的氯离子。硫酸铵呈酸性，并且可与金属离子络合。因此，在通过工艺本身产生或者从其它装置随着原料输入氯化铵和硫酸铵的炼油操作中，防腐是主要关心的问题之一。可以观察到数种腐蚀形式。
腐蚀的程度主要取决于例如NH4Cl的浓度、pH和温度。从铁、铝、铅、不锈钢或不含铁的金属制成的设备特别容易出现应力腐蚀裂痕。
固态氯化铵的比重d4 20为1.530，其在298至372°K之间的平均比热Cp为1.63kJ/kg。
氯化铵有两种变体。在457.6°K(184.5℃)下两者之间的转化是可逆的：
α-NH4Cl(立方晶系，CsCl型)β-NH4Cl(立方晶系，NaCl型)ΔH＝+4.3kJ/mol。
α变体是室温下稳定的变体。β-NH4Cl在793.2°K及3.45MPa下熔化；它在常压下升华。实际上，NH4Cl在较低的温度下是相当易挥发的，分离成NH3和HCl：
| T，°K | 523.2 | 543.2 | 563.2 | 583.2 | 603.2 | 611.2 |
| p，kPa | 6.6 | 13.0 | 24.7 | 45.5 | 81.4 | 101.3 |
NH4Cl在水中的溶解度随着温度而增加：
| T，°K | 273.2 | 293.2 | 313.2 | 333.2 | 353.2 | 373.2 | 389.2 |
| c，wt％ | 22.9 | 27.2 | 31.5 | 35.6 | 39.7 | 43.6 | 46.6 |
饱和NH4Cl溶液的分压表明NH4Cl具有弱吸湿性：
| T，°K | 283.2 | 293.2 | 303.2 | 313.2 | 323.2 | 389.2 |
| p，kPa | 1.0 | 1.9 | 3.3 | 5.4 | 8.8 | 101.3 |
鲜为人知的是，硫酸铵和尤其是硫酸氢铵在如上所述的炼油过程中也会以污垢物或腐蚀剂的形式沉淀析出。
硫酸铵在常压下在不经分解而释放出氨气并留下硫酸氢铵的情况下不会熔化。然而，纯的、无水硫酸铵的氨蒸气压在高达80℃下基本是零。在300℃以上，除了氨气之外，分解还产生N2、SO2、SO3和H2O。
所述盐类不会形成水合物。硫酸铵的溶解度因加入氨而大大减小：在10℃，从100g水中溶有73g(NH4)2SO4几乎线性地变成100g 24.5％氨水溶液中溶有18g盐。
在原油精炼过程中，例如加氢处理、加氢裂化、催化重整、催化裂化(但不限于这些过程)中的污垢和腐蚀现象是操作者非常关心的问题。典型的转化炼油厂在维修、设备更新方面花费了大量资金，同时装置的停工时间给生产和利润造成巨大损失。
与氯化铵污垢接触的设备必须用碱性溶液彻底地洗涤，以避免应力腐蚀裂痕。与氯化铵相比，硫酸氢铵在较高的温度下沉积，因此，更难于通过用水洗涤而将其除去。
污垢和腐蚀的典型区域是例如但不限于来自于反应器和蒸馏塔的原料-流出物交换器、将含有氯化铵的氢气传送至反应器原料的旋环气体压缩机、稳定器、再沸器和顶部部分。
US5,256,276涉及通过向原油蒸馏装置中加入磷脂，优选卵磷脂，来抑制和除去在该装置中形成的氯化铵(其升华并产生沉积物)的方法。这样的磷脂组分对于下游的加氢处理和重整催化剂的效率可能具有不利的影响，并且由于其乳化作用，还可能对在分离鼓中进行的石脑油-水混合物的分离有不利的影响。
US5,965,785公开了一种通过引入定制的多胺混合物来抑制氯化铵引起的污垢和腐蚀的方法。但是，众所周知，由于形成粘性沉积物时所含的水的酸度，和/或由于胺与盐酸和/或硫酸和/或氯化铵和或硫酸铵的反应产物溶解在顶部系统的低温区的冷凝水中时作为盐的这些反应产物的离解，所述产物会引起二次腐蚀。
还众所周知，胺的盐酸盐通过热分解而离解成胺和盐酸，或通过加热以胺-HCl盐的形式蒸发(升华)并然后沉积在较低温度的顶部系统中，引起上述的腐蚀问题。
为了克服上述缺点，例如胺需要在塔顶馏出物之前或之后的多点注入，这是相当复杂的处理，不同于本发明。
US4,600,518公开了一种通过加入胆碱来中和在炼油厂产品如燃料和润滑油中含有的环烷酸的方法。该方法利用了胆碱的强碱性来中和酸性的环烷酸组分。中和反应的反应产物将留在所述液体产品中。
本发明的目的是提供防止氯化铵和硫酸铵引起的污垢和腐蚀的方法。
根据本发明，该目的通过注入作为添加剂的胆碱或其衍生物，更具体地说是具有下列通式之一的衍生物来实现：
(CH3)3N+-CH2CH2-O-，
(CH3)3N+-CH2CH2-OH-O-H，和
(CH3)3N+-CH2CH2-OH-O-R，其中R＝C1-C20的烷基。
胆碱(也被称为胆碱碱)是液态强有机碱：通式为[(CH3)3N+-CH2CH2-OH]-OH-的氢氧化三甲基(2-羟基乙基)铵。它通常不以游离碱的形式存在，而是以盐或衍生物，例如可商购获得的脱羟基胆碱(choline hydroxyde)、胆碱盐酸盐、胆碱酒石酸氢盐、柠檬酸三胆碱的形式存在，并且可用于医学应用以及作为营养物。
通过将添加剂注入到工艺流程中，可以将氯化铵和硫酸铵转化成无腐蚀性的、非沉积的成分，这些成分出乎意料地是液态并且呈中性，使各种工艺过程不出现氯化铵和硫酸铵引起污垢和腐蚀。
为了抑制腐蚀，加入胺是已知的，但是这些胺形成保持粘性的盐(形成糊状物)或者固体，并且当溶于水时表现出酸性的pH值(＜7.0)。
同样出乎意料的是，所述添加剂形成的氯化物盐是挥发性的氯化物，其可通过汽提或气体循环从工艺物流中除去。
该方法在原油精炼工艺中特别有用。
在被称作催化重整装置的具体装置中，形成的挥发性成分可通过氢气循环气流循环到反应器中，由此减少用于活化重整催化剂的有机氯化物的量。在一个中试装置中，已证明可以节约最多达40％的有机氯化物。
所注入的添加剂的量优选为1ppm至5000ppm，取决于存在的氯化物或硫酸盐的量。
所述添加剂优选以溶液的形式注入，该溶液在溶剂例如醇，优选最多含有8个碳原子的脂肪醇、醚、芳香族化合物或水中含有1重量％至65重量％的添加剂。溶液中胆碱衍生物的胆碱的浓度可以为例如1重量％至65重量％。可以加入诸如未取代的羟基胺盐之类的稳定剂。
通常将添加剂在氯化铵和硫酸氨形成或沉积的上游进料，从而防止氯化铵和硫酸铵的形成或者将氯化铵和硫酸铵转化成其它成分。
还可以将添加剂在氯化铵和硫酸铵形成或沉积的下游进料，以将氯化铵和硫酸铵转化成其它成分，但不是将其进料点限制在工艺过程中的具体位置。
下面的实施例解释本发明。
将附图所示的具有连续再生催化剂的中试催化重整装置用于测试所述添加剂在氨和氯化物的各种水平下的性能。如图所示，该重整装置主要包括串联安装的反应器1、空气翅片冷却器2、分离器3和稳定器4。
将原料通过原料-流出物交换器5和催化重整炉6进料至反应器1。
原料由含有变化量的氨气、终沸点为192℃的典型重质全程石脑油构成。氢与烃的摩尔比是4.0，在出口温度为510℃的条件下操作，反应器1内的压力为9.8bar。
所用的催化剂是得自UOP的R22，并且如参考数字7所示连续循环。将有机氯化物催化剂活化剂以2ppm的比率进料。调节反应器1内的条件，以将重整产品的RON(研究法辛烷值)维持在98。
将来自分离器3的气体在压缩机8内压缩并重新引入到原料中。将来自分离器4的液体进料至重整产品稳定器4。将气体在空气翅片冷却器9内冷却，接着通过水冷却器10冷却，然后将其收集在顶部储油器11中。将剩余气体通过废气管线12排空，同时将液体以回流物的形式返回到稳定器4的上部。将重整产品从稳定器4的底部排出，并且将其中的一部分通过稳定器再沸炉13进行循环。
空白试验：
| 产物分析 | 原料ppm | 反应器出口的重整产品ppm | 稳定器的进料ppm | 循环气体ppm | 稳定器的废气ppm | 稳定化的重整产品ppm |
| NH3 | 1.5 | - | - | - | - | - |
| HCl | 0.5 | - | - | - | - | - |
| NH4Cl | - | 2.5 | 1.3 | 0.3 | ＜0.1 | ＜0.1 |
| RCl | 2* | - | - | - | - | - |
*进料至反应器的有机氯化物
| 分析/观察 | 氢气循环的空气翅片冷却器 | 稳定器顶部的空气翅片冷却器 | 稳定器顶部的水冷却器 | 稳定器顶部的储油器 |
| 腐蚀速率 | 0.559mmpy(22mpy) | 1.143mmpy(45mpy) | 1.727mmpy(68mpy) | 0.940mmpy(37mpy) |
| 盐的沉积 | 有 | 有 | 有 | 无 |
| pH饱和水 | 2.7 | 23 | 1.7 | 35 |
试验数据：
将其中加有作为稳定剂的1％羟基胺乙酸盐的44wt％氢氧化三甲基(2-羟基乙基)铵或胆碱的甲醇溶液，以4.5ppm/ppm氯化物(基于质量流速)的给料速率在原料-流出物交换器5之前进料到离开反应器1的重整产品中，如图中的箭头14所示。
中试数据显示，因氯化铵产生的腐蚀可减小到低于0.1270mmpy(毫米/年)，相当于5mpy(mill/年)，并且可以完全消除因氯化铵产生的污垢。
另外，进料至反应器的RCl(有机氯化物)的量可减小40％，如通过循环气流中CH3Cl的分析结果所示的那样。
| 产物分析 | 原料ppm | 反应器出口的重整产品ppm | 稳定器的进料ppm | 循环气体ppm | 稳定器的废气ppm | 稳定化的重整产品ppm |
| NH3 | 1.5 | - | - | - | - | - |
| HCl | 0.5 | - | - | - | - | - |
| NH4Cl | - | 2.5 | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| CH3Cl | - | - | ＜0.1 | 1.1 | ＜0.1 | ＜0.1 |
| RCl | 2* | - | - | - | - | - |
*进料至反应器的有机氯化物
| 分析/观察 | 氢气循环的空气翅片冷却器 | 稳定器顶部的空气翅片冷却器 | 稳定器顶部的水冷却器 | 稳定器顶部的储油器 |
| 腐蚀速率 | 0.076mmpy(3mpy) | 0.051mmpy(2mpy) | 0.102mmpy(4mpy) | 0.038mmpy(1.5mpy) |
| 盐的沉积 | 无 | 无 | 无 | 无 |
| PH饱和水 | 6.3 | 7.6 | 7.0 | 7.1 |
添加剂可以在宽范围的温度和压力下，通常是在20kPa(0.02bara)至20MPa(200bara)和-10℃至+250℃下应用。
在其它实施方案中，添加剂是具有以下通式的胆碱衍生物：
(CH3)3N+-CH2CH2-O-，
(CH3)3N+-CH2CH2-OH-O-H，或
(CH3)3N+-CH2CH2-OH-O-R，其中R＝C1-C20的烷基，例如胆碱酒石酸氢盐、柠檬酸二氢胆碱、柠檬酸三胆碱或葡萄糖酸胆碱。
一般通过分析或计算出的氨和盐酸的浓度，或者通过氯化铵或硫酸铵升华的露点计算值来确定用量。用量可以低至1mg/l至最高5000mg/l。
Claims (10)
1、一种防止氯化铵和硫酸铵引起的污垢和腐蚀的方法，其中该方法包括注入作为添加剂的胆碱或其衍生物，其特征在于加入具有下列通式之一的胆碱衍生物：
(CH3)3N+-CH2CH2-O-，
(CH3)3N+-CH2CH2-OH-O-H，和
(CH3)3N+-CH2CH2-OH-O-R，其中R＝C1-C20的烷基。
2、权利要求1所述的方法，其特征在于将由添加剂形成的挥发性的成分通过汽提或气体循环除去。
3、权利要求2所述的方法，其特征在于由添加剂形成的挥发性的成分通过氢气循环气流循环。
4、权利要求1-3中任意一项所述的方法，其特征在于所述添加剂在2kPa至20MPa的工艺压力和-10℃至+250℃的温度下注入。
5、权利要求1-3中任意一项所述的方法，其特征在于所注入的添加剂的量为1ppm至5000ppm，根据存在的氯化物或硫酸盐的量决定。
6、权利要求1-3中任意一项所述的方法，其特征在于所述添加剂以在溶剂中含有1重量％至65重量％添加剂的溶液形式注入。
7、权利要求6所述的方法，其特征在于胆碱或胆碱衍生物在醇、醚、芳香族化合物或水中的溶液。
8、胆碱衍生物作为添加剂在原油精炼工艺中防止氯化铵和硫酸铵引起的污垢和腐蚀的应用，其特征在于该胆碱衍生物包含具有下列通式之一的物质：
(CH3)3N+-CH2CH2-O-，
(CH3)3N+-CH2CH2-OH-O-H，和
(CH3)3N+-CH2CH2-OH-O-R，其中R＝C1-C20的烷基。
9、权利要求8所述的胆碱衍生物的应用，其特征在于，其用于催化重整装置，并且由添加剂形成的挥发性的成分通过氢气气流循环除去，和由添加剂形成的挥发性的成分通过汽提或气体循环除去。
10、权利要求8或9所述的胆碱衍生物的应用，其特征在于，所述添加剂在2kPa至20MPa的工艺压力和-10℃至+250℃的温度下注入油流中。
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| EP01203659.6 | 2001-09-27 | ||
| EP01203659A EP1298185B1 (en) | 2001-09-27 | 2001-09-27 | Method for preventing fouling and corrosion caused by ammonium chloride and ammonium sulphates |
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| JP3962919B2 (ja) * | 2002-11-12 | 2007-08-22 | 栗田工業株式会社 | 金属防食剤、金属防食方法、原油常圧蒸留装置における塩化水素発生防止剤および塩化水素発生防止方法 |
| US7585404B2 (en) * | 2006-12-06 | 2009-09-08 | Chevron U.S.A. Inc. | Decomposition of waste products formed in slurry catalyst synthesis |
| US9150793B2 (en) | 2008-11-03 | 2015-10-06 | Nalco Company | Method of reducing corrosion and corrosion byproduct deposition in a crude unit |
| US9458388B2 (en) | 2008-11-03 | 2016-10-04 | Nalco Company | Development and implementation of analyzer based on control system and algorithm |
| US20100242490A1 (en) * | 2009-03-31 | 2010-09-30 | General Electric Company | Additive delivery systems and methods |
| US9982200B2 (en) | 2012-07-24 | 2018-05-29 | Reliance Industries Limited | Method for removing chlorides from hydrocarbon stream by steam stripping |
| TWI580771B (zh) | 2012-07-25 | 2017-05-01 | 奈寇公司 | 以控制系統及演算法爲基礎之分析器之設計開發與實施 |
| US9297081B2 (en) | 2014-02-21 | 2016-03-29 | Ecolab Usa Inc. | Use of neutralizing agent in olefin or styrene production |
| TWI591054B (zh) | 2015-07-29 | 2017-07-11 | 藝康美國公司 | 用於烯烴或苯乙烯生產之重胺中和劑 |
| US10767116B2 (en) | 2015-09-29 | 2020-09-08 | Dow Global Technologies Llc | Method and composition for neutralizing acidic components in petroleum refining units |
| CN106281411B (zh) * | 2016-08-11 | 2018-12-28 | 华东理工大学 | 一种催化重整装置组合脱盐防腐的方法 |
| WO2018066717A1 (ja) | 2016-10-07 | 2018-04-12 | エム・テクニック株式会社 | 有機顔料組成物の製造方法、塗膜の製造方法及び塗膜の輝度の評価方法 |
| KR102505843B1 (ko) | 2018-04-26 | 2023-03-03 | 쿠리타 고교 가부시키가이샤 | 4차 트리알킬알칸올아민 하이드록사이드를 포함하는 조성물의 안정화 |
| JP6933238B2 (ja) * | 2018-12-27 | 2021-09-08 | 栗田工業株式会社 | 蒸留塔の差圧解消方法 |
| JP6648814B1 (ja) * | 2018-12-27 | 2020-02-14 | 栗田工業株式会社 | 蒸留塔の差圧解消方法 |
| WO2021066798A1 (en) | 2019-09-30 | 2021-04-08 | Halliburton Energy Services, Inc. | Means and methods for managing ammonia, amine and normal salt fouling in oil production and refining |
| EP4097274A4 (en) * | 2020-01-30 | 2024-01-03 | Kurita Water Ind Ltd | METHOD FOR REDUCING OR PREVENTING CORROSION OR POLLUTION CAUSED BY ACID COMPOUNDS |
| CN113278977A (zh) * | 2021-03-24 | 2021-08-20 | 江阴市亦乐科技发展有限公司 | 一种催化脱戊烷塔专用缓蚀分散剂 |
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| US2990431A (en) * | 1958-09-17 | 1961-06-27 | Phillips Petroleum Co | Corrosion control in condensing systems |
| US4600518A (en) * | 1985-07-15 | 1986-07-15 | Nalco Chemical Company | Choline for neutralizing naphthenic acid in fuel and lubricating oils |
| US4594147A (en) * | 1985-12-16 | 1986-06-10 | Nalco Chemical Company | Choline as a fuel sweetener and sulfur antagonist |
| US4867865A (en) * | 1988-07-11 | 1989-09-19 | Pony Industries, Inc. | Controlling H2 S in fuel oils |
| JPH04147651A (ja) * | 1990-04-02 | 1992-05-21 | Toshiba Corp | 半導体装置およびその製造方法 |
| JP3174614B2 (ja) * | 1992-04-08 | 2001-06-11 | 富士通株式会社 | 半導体装置 |
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| US5965785A (en) * | 1993-09-28 | 1999-10-12 | Nalco/Exxon Energy Chemicals, L.P. | Amine blend neutralizers for refinery process corrosion |
| DE69432621T2 (de) * | 1993-09-28 | 2004-02-26 | Ondeo Nalco Energy Services, L.P., Sugarland | Verfahren zur Verhinderung von chlorider Corrosion in nassem Kohlenwasserstoff-Kondensationsystemen unter Verwendung von Amin-Mischungen |
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| CN1558940A (zh) | 2004-12-29 |
| MXPA04002739A (es) | 2005-07-25 |
| CA2461215A1 (en) | 2003-04-03 |
| KR20040039402A (ko) | 2004-05-10 |
| ATE293155T1 (de) | 2005-04-15 |
| DE60110072D1 (de) | 2005-05-19 |
| ES2239647T3 (es) | 2005-10-01 |
| EP1298185B1 (en) | 2005-04-13 |
| WO2003027209A1 (en) | 2003-04-03 |
| RU2279464C2 (ru) | 2006-07-10 |
| PT1298185E (pt) | 2005-08-31 |
| DE60110072T2 (de) | 2006-01-26 |
| US7279089B2 (en) | 2007-10-09 |
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