CN102388116B - 抑制烃加工中污垢的方法 - Google Patents

抑制烃加工中污垢的方法 Download PDF

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CN102388116B
CN102388116B CN201080016649.2A CN201080016649A CN102388116B CN 102388116 B CN102388116 B CN 102388116B CN 201080016649 A CN201080016649 A CN 201080016649A CN 102388116 B CN102388116 B CN 102388116B
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naphthalenesulfonate
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CN102388116A (zh
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J·林克
Z·常
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BL Technology Co., Ltd.
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1044Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1048Middle distillates
    • C10G2300/1059Gasoil having a boiling range of about 330 - 427 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4075Limiting deterioration of equipment

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明涉及一种抑制污垢材料形成的方法,该方法包括,在用碱性洗液处理烃介质时,将包含羰基化合物的烃介质与羟胺和萘磺酸盐接触。

Description

抑制烃加工中污垢的方法
发明领域
本发明涉及减少烃加工中污垢(fouling)的方法,且更具体地,涉及减少烃加工中的醛醇聚合物污垢。 
发明背景 
烯烃化合物(诸如乙烯、丙烯、丁烯和戊烯)可由轻质石油化学产品的热裂解产生。在裂解过程中,也可能发生次级反应产生羰基化合物,诸如醛类和酮类。因此,热解烃产物流也可包含显著量的醛类和酮类。 
冷却裂解烃产物流以去除大部分较重烃类,压缩并随后用碱性洗液(pH>7)处理以去除污染性酸性化合物,诸如硫化氢和二氧化碳。当烃流通过碱性洗液时,羰基化合物,特别是醛类,在碱存在下将经历聚合而产生称为醛醇聚合物或红油的缩合聚合物。醛醇聚合物基本不溶于碱性洗液和烃介质,且沉积于加工设备的内表面。这些沉积物会限制通过设备的流动,这使得跨处理容器的压降增加,导致生产力损失且增加运行成本。如果放着不处理,来自污垢组分的沉积可导致裂解操作的过早关机。 
虽然羰基清除剂和分散剂能够用于去除或抑制醛醇产生,期望有改进且更经济的方法,用以抑制污垢材料产生,并最小化污垢化合物在烃加工期间的沉积。 
发明概述 
在一个实施方案中,抑制污垢材料产生的方法包括,在用碱性洗液处理烃介质时,将包含羰基化合物的烃介质与羟胺和萘磺酸盐接触。 
多种实施方案提供用于在石油化学加工中减少醛醇产生并抑制污垢的改进且经济的方法。 
发明详述 
除非上下文另有明确规定,否则单数形式″一″、″一个″和″该″包括复数的指示物。描述相同特性的所有范围的端点是独立地可组合的,且包括所述的端点。所有参考文献通过引用结合到本文中。 
结合数量使用的修饰词″约″包括所述值,且具有由上下文规定的含义(例如,包括与特定数量的测量有关的容许范围)。 
″任选的″或″任选地″是指随后描述的事件或情况可能会发生或可能不会发生,或随后确定的材料可能存在或可能不存在,且该描述包括事件或情况发生或材料存在的情形,以及事件或情况不发生或材料不存在的情形。 
在一个实施方案中,抑制污垢材料产生的方法包括,在用碱性洗液处理烃介质时,将包含羰基化合物的烃介质与羟胺和萘磺酸盐接触。 
在一个实施方案中,羟胺可能以其水合物或盐类的形式存在。盐类可来源于无机酸,诸如硫酸、盐酸或硝酸,或来源于有机酸,诸如乙酸或丙酸。在另一实施方案中,羟胺可为羟胺硫酸盐、羟胺亚硫酸盐、羟胺乙酸盐、羟胺硝酸盐或羟胺盐酸盐。 
萘磺酸盐可作为来自于Hampshire Chemical Company的DAXAD14C从市场上得到。在一个实施方案中,萘磺酸盐可能为其缩合物或盐类的形式。 
在一个实施方案中,羟胺与萘磺酸盐的重量比可为从约0.1∶1到约20∶1。在另一实施方案中,羟胺与萘磺酸盐的重量比可为从约0.1∶1到约10∶1。在另一实施方案中,重量比可为从约0.4∶1到约5∶1。在另一实施方案中,重量比可为从约1∶1到约10∶1。在另一实施方案中,羟胺与萘磺酸盐的重量比可为从约1∶1到约8∶1。 
羟胺和萘磺酸盐的量可以任何有效于减少醛醇污垢的量接触烃介质。在一个实施方案中,基于烃介质的重量,羟胺和萘磺酸盐的组合剂量可从约0.1ppm重量到约1000ppm重量。在另一实施方案中,基于烃介质的重量,组合剂量可从约1ppm重量到约100ppm重量。在另一实施方案中,基于烃介质的重量,组合剂量可从约1ppm重量到约50ppm重量。 
在一个实施方案中,羟胺可以溶液加入。在一个实施方案中,羟胺作为水溶液加入,所述水溶液中羟胺以2到50重量百分数存在。在另一实施方案中,羟胺作为水溶液加入,所述水溶液中含有2到25重量百分数的羟胺。 
在一个实施方案中,萘磺酸盐可以溶液加入。在一个实施方案中,萘磺酸盐作为水溶液加入,所述水溶液中萘磺酸盐以2到50重量百分数存在。在另一实施方案中,萘磺酸盐作为水溶液加入,所述水溶液中含有2到25重量百分数的萘磺酸盐。 
在一个实施方案中,羟胺可与碱性洗液同时加入烃介质。在另一实施方案中,羟胺可在与烃介质接触前加入碱性洗液。 
在一个实施方案中,萘磺酸盐可与碱性洗液同时加入烃介质。在另一实施方案中,萘磺酸盐可在与烃介质接触前加入碱性洗液。 
在一个实施方案中,羟胺可成批或连续地加入。在一个实施方案中,萘磺酸盐可成批或连续地加入。 
烃介质可为任何类型的烃介质。在一个实施方案中,烃介质可为来自于烃类热解的裂解烃流,诸如石油化学产品。在一个实施方案中,石油化学产品在至高约1700℉的温度热裂解。在另一实施方案中,石油化学产品在约1550℉到约1670℉的温度范围热裂解。在一个实施方案中,裂解烃流来自于乙烷、丙烷、丁烷、石脑油、气体油或其混合物的热解。在另一实施方案中,烯烃化合物包括,但不限于,乙烯、丙烯、丁烯、戊烯或其混合物。 
羰基化合物可为具有包含碳双键键合氧原子的官能团的任何类型化合物,并可包括醛类和酮类。烃介质可包含任何量的羰基化合物。在一个实施方案中,羰基化合物在烃介质中的浓度应为约0.5ppm到约500ppm范围。在另一实施方案中,羰基化合物以约1ppm到约100ppm的量存在于烃介质中。在另一实施方案中,羰基化合物以约5ppm到约50ppm的量存在于烃介质中。 
用碱性洗液处理烃介质。碱性洗液可为PH大于7.0的任何碱洗液。在一个实施方案中,碱性洗液为苛性碱洗液。在另一实施方案中,碱性洗液包括氢氧化钠、氢氧化钾或链烷醇胺。 
可通过使烃介质与碱性溶液接触的任何合适的方法或手段洗涤烃介质。在一个实施方案中,烃介质在板式塔或填充塔中与碱性洗液接触。 
在一个实施方案中,将苛性碱流引入苛性碱洗涤系统的上部,并将烃介质引入下部。引入苛性碱洗涤系统的苛性碱向下流动通过容器,而烃介质向上流动通过苛性碱洗涤系统,由此使烃介质与苛性碱密切接触。 
为了使本领域的技术人员能够更好地实施本公开,以下实施例通过例证而不是限制的方式给出。 
实施例
实施例1 
用19.75ml的20%NaOH准备采样瓶。对不同采样瓶加入各种处理物(如表1所示)并摇动瓶以充分混合。一个采样瓶用作空白且不加入处理物。加入0.25ml的50%重量/重量的乙醛在去离子水中的溶液,并充分摇动混合物以彻底混合。将采样瓶静置于室温并在不同时间记录观测结果。以溶液中的颜色变化和混浊性评估处理物对污垢的效果。结果如表2所示。 
表1 
1萘磺酸盐作为来自于Hampshire Chemical Corp的DAXAD14C从市场上得到。 
2EAPF是乙氧基化烷基苯酚甲醛树脂。 
3EO/PO是环氧乙烷/环氧丙烷多元醇。 
4AA是氨基-酰胺阳离子分散剂。 
表2 
防污剂样品1-9显示出与对比例CE-1、CE-2、CE-5、CE-6、CE-7 和空白相比改进的结果。实际上,CE-5、CE-6和CE-7没有显示任何防污垢的效力。CE-3在1-3小时显示澄清的结果,但需要大量的萘磺酸盐。羟胺和萘磺酸盐的组合对防止醛醇化合物的污垢有协同效应。 
尽管为了例证的目的阐明了典型的实施方案,但不应认为前面的描述是对本文范围的限制。因此,本领域的技术人员能想到各种的变更、适应和替代,而不偏离本文的精神和范围。 

Claims (16)

1.一种抑制污垢材料产生的方法,所述方法包括,在用碱性洗液处理烃介质时,将包含羰基化合物的烃介质与羟胺和萘磺酸盐接触,其中所述羟胺选自羟胺硫酸盐、羟胺亚硫酸盐、羟胺乙酸盐、羟胺硝酸盐和羟胺盐酸盐。
2.权利要求1所述的方法,其中羟胺与萘磺酸盐的重量比为从0.1:1到20:1。
3.权利要求2所述的方法,其中羟胺与萘磺酸盐的重量比为从0.1:1到10:1。
4.权利要求3所述的方法,其中所述重量比为从0.4:1到5:1。
5.权利要求3所述的方法,其中所述重量比为从1:1到10:1。
6.权利要求5所述的方法,其中所述重量比为从1:1到8:1。
7.权利要求1所述的方法,其中羟胺和萘磺酸盐的组合剂量为从0.1ppm重量到1000ppm重量,基于烃介质的重量。
8.权利要求7所述的方法,其中羟胺和萘磺酸盐的组合剂量为从1ppm重量到100ppm重量,基于烃介质的重量。
9.权利要求8所述的方法,其中羟胺和萘磺酸盐的组合剂量为从1ppm重量到50ppm重量,基于烃介质的重量。
10.权利要求1所述的方法,其中所述羟胺与所述碱性洗液同时加入所述烃介质中。
11.权利要求1所述的方法,其中所述萘磺酸盐与所述碱性洗液同时加入所述烃介质中。
12.权利要求1所述的方法,其中所述羟胺在与所述烃介质接触前加入所述碱性洗液中。
13.权利要求1所述的方法,其中所述萘磺酸盐在与所述烃介质接触前加入所述碱性洗液中。
14.权利要求1所述的方法,其中所述烃介质是来自于烃类热解的裂解烃流。
15.权利要求14所述的方法,其中所述裂解烃流来自于乙烷、丙烷、丁烷、石脑油、气体油或其混合物的热解。
16.权利要求1所述的方法,其中所述碱性洗液选自氢氧化钠、氢氧化钾或链烷醇胺。
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