CN106675623B - 烃物流的重级分的光化学加氢 - Google Patents
烃物流的重级分的光化学加氢 Download PDFInfo
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- CN106675623B CN106675623B CN201611040674.XA CN201611040674A CN106675623B CN 106675623 B CN106675623 B CN 106675623B CN 201611040674 A CN201611040674 A CN 201611040674A CN 106675623 B CN106675623 B CN 106675623B
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- hydrocarbon stream
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- hydrogenation process
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- 241000735215 Lepidocybium flavobrunneum Species 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
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Abstract
本发明描述了用于烃物流的重级分的光化学加氢方法，其中存在于所述级分中的芳族和多(聚)芳族化合物在醇盐的存在下，在经受电磁辐照时选择性反应。
Description
技术领域
本发明提供用于烃物流的重级分的光化学加氢方法，所述重级分转化成较轻级分，以改进这样的流的物理化学特性，尤其是粘度和密度。
发明背景
油是世界上第二最大的能源来源，随着全球发现重油(12至22.3°API，由ANP[
Nacional do Petróleo,Gás Natural e Biocombustíveis(BrazilianNational Agency of Petroleum,Natural Gas and Biofuels)]定义)和超重油(≤12°API，由ANP定义)的增多，这些油的生产、运输和精炼成为研究和探讨的主题。
油的价值和生产和精炼的成本与它的物理化学特性相关。它的粘度和密度越小，原油的附加值越大和生产链成本越低。
存在于原油中的一些芳族化合物会导致密度和粘度的增加，尤其是较重级分例如树脂和沥青质。沥青质构成较重且极性的原油化合物的级分，通常具有多稠合(缩聚)芳族结构，和包含不同的官能团、分子结构和相对大的分子质量分布。
除了提供增加的油密度和粘度以外，在获得原油时沥青质沉淀的倾向会导致严重的后果，例如油流动降低或甚至在油的生产、运输和精炼期间堵塞加工生产线，和可以使催化剂在精炼过程中中毒。
最小化沥青质的有害作用的一个选项是它的加氢，因为加氢降低沥青质分子的芳族烃的“核”之间的吸引力，以及降低悬浮液中分子的沉淀或团簇的发生，这最终导致它的粘度的降低。
因此，已经对该主题进行了许多研究。文献US2013/0277273例如描述了在催化剂和氢气的存在下存在于原油中的芳族化合物的加氢。所使用的催化剂为包含来自元素周期表的IB族、IVB族、VB族、VIB族、VIIB族或VIII族的金属的负载催化剂，所述金属包括但是不限于：铬，铁，锰，钼，钨，钒，银，金，镍，钯，铂，铑，钌或其混合物。
同时，文献US5,824,214描述了直接在石油生产井的底部在金属加氢催化剂的存在下通过声能以400Hz-10kHz的低频率处理包含至少1重量％的水的重原油。在该方法中，如由以下反应所定义的，由水形成氢气:
2H2O>>>2H2+O2
在本发明的另一个实施方案中，如果重原油不具有充足的水含量，可以通过使重原油在井底部与包含氨、肼和甲酸的化学化合物接触而原位形成氢气，这在金属加氢催化剂和声能的存在下，通过引起加氢反应导致氢气的形成和由此导致粘度降低。
然而，没有用于加氢存在于烃物流中的芳族化合物，特别是沥青质以降低这样的流的粘度和密度而不需要使用催化剂的方法的文献、描述或建议，和在下文中进行描述和要求保护该方法。
发明内容
以广泛的方式，本发明是关于通过光化学方法加氢来自烃物流的包括沥青质的含有一个或多个芳环的芳族重级分的方法，其中重级分的这些芳族化合物在醇盐存在下在经受电磁辐照时加氢。
附图描述
图1示出了作为温度的函数的在异丙醇钠和80质量％的油的存在下进行的实验中的粘度(以厘泊计)降低。
图2示出了在2-丙醇中在碱性介质(200mM NaOH)中的萘样品的同步荧光光谱，和曲线A对应于未受辐照时的样品和曲线B对应于在UV-VIS辐照之后的样品。
图3示出了对在2-丙醇中在碱性介质(200mM NaOH)中未受辐照的萘样品的GCMS分析结果.
图4示出了对在2-丙醇中在碱性介质(200mM NaOH)中辐照达8小时的萘样品的GCMS分析结果。
图5示出了在2-丙醇中在碱性介质(200mM NaOH)中的菲样品的同步荧光光谱，和曲线A对应于未受辐照时的样品和曲线B对应于在UV-VIS辐照之后的样品。
图6示出了在2-丙醇中在碱性介质(200mM NaOH)中未受辐照的的菲样品的GCMS分析结果。
图7示出了在2-丙醇中在碱性介质(200mM NaOH)中辐照达8小时的菲样品的GCMS分析结果。
图8示出了在2-丙醇中在碱性介质(200mM NaOH)中的石油样品的同步荧光光谱，和曲线A对应于未受辐照时的样品和曲线B对应于在UV-VIS辐照之后的样品。
具体实施方式
一般而言，本发明是基于存在于烃物流的重级分中的芳族化合物与醇盐在经受电磁辐照时的反应性。
在沥青质的情况下，由于它们具有表现出特征吸收光谱的芳族多稠合结构，它们能够吸收宽范围的波长的电磁辐射。取决于芳环稠合程度，分子吸收UV(紫外)波长范围直至近红外(NIR)波长范围的辐射，经过整个可见光谱(VIS)。
该方法包括使用电磁辐射，电磁辐射可以在紫外光谱(UV-100-400nm的波长)或可见光谱(400-780nm的波长)，优选在450和700nm之间。在该激发态的芳族分子中，可以从烷氧自由基提取电子，之后提取氢自由基，所述烷氧自由基可以由碱与羟基有机化合物的反应获得。
因此，在羟基有机化合物和碱的存在下，芳族分子在芳环中存在的不饱和度方面选择性降低。通常，反应是部分的，但这作为施加辐射的函数而变得更加具有选择性。因此，该方法对于重油级分和尤其是对于芳族化合物如沥青质具有选择性，而不干扰轻级分，如在图2-8中示出的对于萘样品、菲样品和油样品所获得的通过GCMS的结果分析和同步荧光光谱中可以观察到的。
因此，本发明是关于使烃物流与醇盐在UV-VIS范围的辐射作用下反应来加氢重级分而获得具有低的密度和粘度的烃物流的方法，所述方法包括以下步骤:
a)提供该方法的载料，所述载料由烃物流组成，所述烃物流包含烃的含有具有一个或多个稠环的芳族化合物(浓度高于0.1质量％)的重级分；
b)在搅拌下，在20-60℃的温度和在大气压力下，相对于待还原的烃以1：1摩尔的比例，将至少一种醇盐加入所述载料，以获得载料/醇盐的均匀混合物；
c)使所获得的混合物经受UV-VIS范围波长的电磁辐射达5分钟至48小时的时间，以获得密度和粘度小于初始载料的经处理的物流。
优选地，该方法的载料为包含不可忽略水平的沥青质的烃物流，和这些化合物在载料的粘度方面很显著。这样的物流可具有浓度大于0.1质量％的它们的重级分，优选包含1-80质量％的沥青质级分的链。
重级分基本上包含芳族化合物，特别是具有自动关联能力和显著影响载料的密度和粘度的高分子量的多(聚)芳族化合物。
更具体地，本发明的烃物流的重级分的光化学加氢方法涉及使醇盐与处于激发态的芳族化合物选择性反应。该机理涉及四个步骤:
-由于使用UV-VIS范围波长的电磁辐射的样品辐照，形成激发态的芳族化合物；
-该激发态氧化和从醇盐提取电子；
-芳族化合物的阴离子型自由基从烷氧自由基提取氢自由基，生产酮；和
-芳族阴离子提取中间质子。
反应产物为由醇羰基化的化合物和来自芳族化合物的环状不饱和化合物。
待加氢的芳族化合物的选择通过一定波长的可施加的电磁辐射(光)进行。波长越长，发生反应的在烃物流中存在的芳族化合物所包含的环的稠合程度越高。
在直接使用醇盐的情况下，原则上，这为包含1-6个碳原子的链和具有一个或多个羟基的任何有机化合物的任何共轭碱，例如，例如：乙醇盐，异丙醇盐，甲醇盐，甘油化盐(glyceroxide)等。醇盐应该以化学计算量存在以还原物流中希望的类型。
此外，醇盐可以为醇和碱之间的反应结果。待使用的醇原则上可以包含1-6个碳原子，为单羟基或多羟基，例如乙醇，异丙醇，和优选甘油(或丙三醇)，或其混合物。
在该方法中，碱仅用于增加反应介质中的醇盐阴离子的浓度，但也可以为能够从所用的羟基化合物或其混合物除去质子的任何碱。这些包括：氢氧化钠，氢氧化钾，金属钠，甲酸钠，甲酸钙，氧化钙，或其混合物。
当使用时，该方法中需要的碱和醇的量为对于以摩尔比例1:1:1转化各种油和/或其级分中的待加氢的芳族化合物成分而言化学计量的。
以下实施例对应于实验室规模实验，而没有限制该方法的范围，在此进行详细描述。
实施例
实施例1
下文所述的测试在光化学反应器中进行，其中芳族化合物以10-1000mg/L范围的不同浓度溶解于二氯甲烷。为了辐照样品，使用中压汞灯和450W。该灯主要发射250和450nm之间的UV。在存在和不存在反应介质中的氧气的情况下，每种样品在恒定搅拌下受辐照达12小时。
以下用作芳族化合物：由不同的巴西油获得的萘、菲、芘、苯并芘、六苯并苯、卟啉和沥青质样品。
为了与芳族化合物反应，使用通过使碱与醇反应获得的醇盐。
相对于醇测试芘：甲醇、乙醇、异丙醇和甘油。仅相对于乙醇测试其它芳族化合物。醇以10mg/L-10％的浓度使用。
对于碱，相对于碱测试芘：氢氧化钠、氢氧化钙和甲酸钙。仅相对于氢氧化钠测试其它芳族化合物。还相当于乙醇钠测试了芘，没有添加更多的醇。
该方法伴随有反应混合物的UV-VIS和荧光光谱。UV-VIS光谱记录在200和500nm之间。荧光光谱通过同步方法记录，已经观察到在激发和发射之间发射250-500nm和20nm的距离，UV-VIS光谱迁移至更短的波长和荧光光谱的强度降低，表明存在于介质中的芳环稠合降低。
实施例2
本发明是基于在通过使碱和醇反应获得的醇盐存在下在经受由来自使用汞蒸气450瓦灯的反应器的紫外或可见光的辐照时芳族化合物的反应性。该灯主要发射250和450nm之间的UV。在存在和不存在反应介质中的氧气的情况下，样品在恒定搅拌下受辐照达12小时。在UV-VIS辐照时在NaOH溶液存在下在2-丙醇中以化学计量比例部分加氢菲和萘。
所研究的芳族化合物为来自具有8-30°API的不同API程度的油的芘、苯并芘、六苯并苯、卟啉和沥青质样品。在该方法中所使用的一系列醇由甲醇、乙醇、2-丙醇、丁醇、戊醇、己醇和甘油组成。所使用的碱为氢氧化钠、氢氧化钾、甲酸钙。该方法方案在下表中给出:
在所用的所有系列醇中，以及使用测试的三种类型碱，发现芳族样品的加氢。2-丙醇与氢氧化钠一起产生最满意的结果，也就是相比于研究的其它物质，得到更高水平的加氢。
Claims (7)
1.用于烃物流的重级分的光化学加氢方法，其特征在于它包括使存在于烃物流的重级分中的芳族化合物与醇盐在UV-VIS范围的电磁辐照的存在下和在20-60℃的温度和大气压力下反应，所述醇盐通过使共轭碱与包含1至6个碳原子的醇反应而形成。
2.根据权利要求1所述的用于烃物流的重级分的光化学加氢方法，其特征在于它包括以下步骤：
a)提供该方法的载料，所述载料由烃物流组成，所述烃物流包含浓度高于0.1质量％的烃的重级分，所述重级分含有具有一个或多个稠环的芳族化合物；
b)在搅拌下，在20-60℃的温度和在大气压力下，相对于待还原的烃以1：1摩尔的比例，将至少一种醇盐加入所述载料，以获得载料/醇盐的均匀混合物；
c)使所获得的混合物经受UV-VIS范围波长的电磁辐射达5分钟至48小时的时间，以获得密度和粘度小于初始载料的经处理的物流。
3.根据权利要求1或2所述的用于烃物流的重级分的光化学加氢方法，其特征在于所述芳族化合物选自：菲、萘、芘、苯并芘、六苯并苯、沥青质、卟啉和它们的衍生物，或其混合物。
4.根据权利要求1所述的用于烃物流的重级分的光化学加氢方法，其特征在于所述醇为一元醇。
5.根据权利要求1所述的用于烃物流的重级分的光化学加氢方法，其特征在于所述醇为多元醇。
6.根据权利要求1的用于重油级分的光化学加氢方法，其特征在于所述醇选自：乙醇、2-丙醇、甘油或其混合物。
7.根据权利要求1所述的用于烃物流的重级分的光化学加氢方法，其特征在于共轭碱选自：氢氧化钠、氢氧化钾、金属钠、甲酸钠、甲酸钙、氧化钙或其混合物。
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| CN104386849A (zh) * | 2014-10-13 | 2015-03-04 | 同济大学 | 一种选择性降解水中微量多环芳烃的方法 |
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| Publication number | Publication date |
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| BR102015028294B1 (pt) | 2020-05-12 |
| AU2016256749B2 (en) | 2022-04-28 |
| CA2948166C (en) | 2023-04-11 |
| BR102015028294A2 (pt) | 2017-05-23 |
| MX2016014669A (es) | 2018-05-08 |
| CN106675623A (zh) | 2017-05-17 |
| AU2016256749A1 (en) | 2017-05-25 |
| CA2948166A1 (en) | 2017-05-10 |
| US20170128907A1 (en) | 2017-05-11 |
| US10258958B2 (en) | 2019-04-16 |
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