CN101040032A - 重质烃油加氢处理的方法 - Google Patents
重质烃油加氢处理的方法 Download PDFInfo
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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Abstract
按照现有技术，通过将自硫和金属含量大于普通原油且API度数为30或更小的重质原油所得的重质烃油组成的原料油进行加氢精制来生产硫含量低至1％(质量)或更低的重质燃料的方法要求较高反应温度且伴随有催化剂失活速率显著增加致使催化剂寿命缩短的现象，因而不能达到加氢精制的目的。按照本发明，通过将100体积份上述API度数为30或更小的重质原油得到的重质烃油与30到1000体积份API度数为35或更大的轻质原油得到的重质烃油混合并将所得的混合油加氢精制的方法可在不降低脱金属率同时减慢催化剂失活速率的条件下有效生产硫含量低至1％(质量)或更少的重质燃料。
Description
技术领域
本发明涉及一种重质烃油的加氢处理方法。更具体地说，本发明涉及一种能够在较低的成本下，由API度数为30或更小的重质原油所衍生的重质烃油组成的原料来生产硫含量为1％(质量)或更少的低硫重质燃料油同时不降低脱金属程度的加氢处理方法。
背景技术
生产低硫重质燃料油的方法是已知的，其中将含较多硫和金属组分的重质烃油组成的原料通过一个装填两种催化剂即脱金属催化剂和脱硫催化剂的固定床反应器来降低原料中的硫含量。
当重质烃油(原料)与加氢处理催化剂接触时，发生脱硫反应，从而除去原料中的硫组分，即从有机硫化合物例如苯并噻吩、二苯并噻吩、硫醇、硫醚和二硫醚中除去硫组分。除了脱硫反应之外，同时还发生除去金属组分例如镍、钒、铁和钠的脱金属反应、裂化反应、脱氮反应。但是，当进行这些反应时，它们会二次形成焦炭和金属，沉积于加氢处理催化剂的孔隙中或表面上。这些沉积物使加氢处理催化剂的活性位点中毒并导致催化剂活性例如脱硫活性的降低。并且，这些沉积物会逐渐累积并堵塞催化剂的孔隙而导致催化剂活性的降低。通常，原料的API度数越低，原料所衍生的重烃油中含有的硫化合物和金属例如镍和钒就越多，则使得催化剂失活速率加快。因此，当处理低API度数原料衍生的重质烃时，必定会大幅度地降低生产能力。重烃油中含金属的分子尺寸大且活性差，因而脱金属程度较低并对后续设备有不利的影响。
低硫重质燃料油用于发电厂、锅炉、船舶和工业炉。当试图通过常规方法从硫和金属组分含量大于普通原油并具有30或更小API度数的重质原油衍生的重质烃油原料中收集低硫重质燃料油时，要求较高的反应温度且伴随有催化剂失活速率显著加快的现象，致使催化剂寿命显著缩短。因此，我们认为通过常规方法实际上不可能生产硫含量为1％(质量)或更少的低硫重质燃料。因此，所带来的问题是低API度数的重质原油不能有效得以利用。
发明内容
作为大量调查和研究的结果，在发现生产硫含量为1％(质量)或更少的低硫燃料油方法的基础上得以有效完成本发明，所述方法通过将按指定数量混合的API度数为30或更小的重质原油衍生的重质烃油与API度数为35或更大的轻质原油衍生的重质烃油的混合油进行加氢处理而使曾认为不可能处理的API度数为30或更小的重质原油衍生的重质烃油进行处理成为可能，不会降低脱金属程度同时减慢了催化剂失活速率。
即，本发明涉及一种重质烃油加氢处理方法，包括将100体积份API度数为30或更小的重质原油衍生的重质烃油与30到1000体积份API度数为35或更大的轻质原油衍生的重质烃油的混合油加氢处理以便生产硫含量为1％(质量)或更少的低硫重质燃料油。
本发明还涉及前述方法，其中混合油是在氢分压为7到25MPa、LHSV为0.01到10h-1、反应温度为250到450℃和氢/油比为500到8000SCF/BBL的条件下进行加氢处理的。
进而，本发明还涉及前述方法，其中使用表面积为1.0×107到1.0×109m2/m3和孔体积为0.20到0.60m3/m3的催化剂，通过组构(building up)一或多种每种包括0.03到10％(摩尔)选自周期表VIII族金属的至少一种金属和0.1到10％(摩尔)选自周期表VIB族金属的至少一种金属负载于主要由氧化铝组成的催化剂载体的催化剂来形成催化剂。
下面将更详细地描述本发明。
本文所用的API度数为30或更小的重质原油表示API度数按以下公式计算为30或更小的原油：API度数＝141.5/(比重60/60)-131.5。
上式中的比重表示按JIS K2249“原油和石油产品-基于标准温度(15℃)的密度和石油测量表的测定方法”所测定的比重。
用于本发明的重质原油的API度数为30或更小、优选29或更小且更优选28或更小。API度数大于30的重质原油可不用本发明方法处理，因为由该原油衍生的重质烃有足够高的反应性。
用于本发明的API度数为30或更小的重质原油的具体例子包括Khafji原油、阿拉伯重质原油和Al Rayyan原油。
API度数为30或更小的重质原油衍生的重质烃油表示通过常压或减压蒸馏API度数为30或更小的重质原油生产的含70％(质量)或更多、优选80％(质量)或更多、更优选90％(质量)或更多且更优选95％(质量)或更多蒸馏温度为300℃或更高馏分的渣油。
对于API度数为30或更小重质原油衍生的重质烃油的特性没有特别的限制。典型的特性如下：
比重(15/4℃)：0.9700到1.100
硫含量：4.0到8.0％(质量)
金属含量(Ni+V)：70到200ppm质量
残碳含量：10到20％(质量)
本文所用的蒸馏温度表示按照JIS K 2254“石油产品-蒸馏特性的测定方法”中描述的“6.减压蒸馏试验方法”所测定的温度。
本文所用的API度数为35或更大的轻质原油表示API度数按上述公式计算为35或更大的原油。
本发明中使用的轻质原油的API度数为35或更大、优选为35.5或更大和更优选为36或更大。API度数低于35的轻质原油不是优选的，因为这样的轻质原油衍生的重质烃油活性低而不能达到减慢催化剂失活的效果。
用于本发明的API度数为35或更大的轻质原油的具体例子包括阿拉伯超轻质原油、低-Zakum原油和Murban原油。
API度数为35或更大的轻质原油衍生的重质烃油表示通过常压或减压蒸馏API度数为35或更大的轻质原油生产的含70％(质量)或更多、优选80％(质量)或更多、更优选90％(质量)或更多的馏分和更优选95％(质量)或更多蒸馏温度为300℃或更高馏分的渣油。
对于API度数为35或更大的轻质原油衍生的重质烃油的特性没有特别的限制。典型的特性如下：
比重(15/4℃)：0.9100到0.9500
硫含量：1.1到3.0％(质量)
金属含量(Ni+V)：3到30ppm质量
残碳含量：2到8％(质量)
在本发明中，将100体积份由API度数为30或更小的重质原油衍生的重质烃油与30到1000体积份、优选40到900体积份和更优选100到700体积份API度数为35或更大的轻质原油衍生的重质烃油混合。如果将超过1000体积份API度数为35或更大的轻质原油衍生的重质烃油与100体积份API度数为30或更小的重质原油衍生的重质烃油混合，由于重质原油衍生的重烃比例降低，不能获得本发明的效果。如果API度数为35或更大的轻质原油衍生的重质烃油少于30体积份或更少，则不能获得减慢催化剂失活速率的效果。
只要对本发明的效果没有不利影响，混合油可以与API度数大于30且小于35的中质原油衍生的重质烃油调合。对这类重质烃油的含量比没有特别的限制。但为使本发明效果能够充分体现，最好100体积份总混合物包含30体积份这类重质烃油。
对于中质原油的特性没有特别的限制。典型的特性如下：
比重(15/4℃)：0.9500到0.9700
硫含量：3.0到4.0％(质量)
金属含量(Ni+V)：30到70ppm质量
残碳含量：8到10％(质量)
接下来，将混合油加氢处理。
对本发明的加氢处理条件没有特别的限制。氢分压优选为7到25MPa、更优选为9到22MPa和更优选为10到21MPa。如果入口的氢分压低于7MPa，由于催化剂上生成过量焦炭，催化剂的寿命将被缩短。如果氢分压大于25MPa，由于必须大幅增加建造反应塔和外围设备的成本，该方法在经济上将是不切实际的。
LHSV优选为0.01到10h-1、更优选为0.02到8h-1和更优选为0.04到6h-1。如果LHSV低于0.01h-1，由于必须大幅增加建造反应塔的成本，该方法在经济上将是不切实际的。如果LHSV高于10h-1，则不能充分发挥催化剂的活性。
对反应模式没有特别的限制，可以选自各种方法例如固定床和移动床反应模式。优选使用固定床反应模式。
对于本发明使用的催化剂没有特别的限制。优选使用表面积为1.0×107到1.0×109m2/m3和孔体积为0.20到0.60m3/m3的催化剂，通过组构一或多种每种包括0.03到10％(摩尔)选自周期表VIII族金属的至少一种金属和0.1到10％(摩尔)选自周期表VIB族金属的至少一种金属负载于主要由氧化铝组成的催化剂载体的催化剂来形成催化剂。
载体的例子包括氧化铝、氧化铝-氧化硅、氧化铝-氧化硼、氧化铝-氧化钛、氧化铝-氧化锆、氧化铝-氧化镁、氧化铝-氧化硅-氧化锆、氧化铝-氧化硅-氧化钛、各种沸石和通过将多孔性无机化合物例如各种粘土矿物像沸石和蒙脱石加到氧化铝上所生产的载体。
周期表中VIB族金属的例子包括铬、钼和钨。周期表中VIII族金属的例子包括铁、钴和镍。
这些金属通常组合使用。组合的具体的例子包括镍-钼、钴-钼、镍-钨、镍-钴-钼和钨-钴-镍。这些金属以金属氧化物或金属硫化物的形式负载。
在本发明中，可以通过任何已知的方法生产催化剂。方法的例子包括浸入、浸渍和共沉淀方法。
通过本发明方法生产的重质燃料油的硫含量为1％(质量)或更少、优选0.8％(质量)或更少和更优选0.6％(质量)或更少。
当所生产的重质燃料油硫含量超过1％(质量)时，即使处理API度数更小的重质原油衍生的重质烃油，催化剂的失活速率是低的。因而不必将重质烃油与API度数大的轻质原油衍生的重质烃油混合，因此不必使用本发明。
对于通过本发明生产的低硫重质燃料油的硫含量下限没有特别的限制。但是，为使本发明优异效果得到应用，下限优选为0.05％(质量)或更高和更优选0.1％(质量)或更高。如果脱硫反应进行到硫含量低于0.05％(质量)，则不管原料的特性如何，催化剂的失活速率迅速增加。
本文所用的硫组分(硫含量)表示按JIS K2541“原油和石油产品-硫含量测定方法”中描述的“6.辐射激发法”所测定的硫含量。
工业应用
本发明使得从曾认为是不能处理的API度数为30或更小的重质原油中收集硫含量为1％(质量)或更少同时不降低脱金属率的低硫重质燃料油成为可能。由此增加了价廉重质原油的生产能力，从而使炼厂的经济效益增加。
实施本发明的最佳方式
参考以下实施例但非限定性地来详细描述本发明。
(实施例1)
使用表2所列催化剂体系，在氢分压为17MPa、氢/油比为5000SCF/BBL、LHSV为0.24h-1和所得油的硫含量为0.3％(质量)的反应条件下，对表1所列的100体积份重质原料1(API度数为30或更小的重质原油衍生的重质烃油)与400体积份轻质原料1(API度数为35或更大的轻质原油衍生的重质烃油)的混合物进行加氢处理。结果在表3中列出。
(实施例2)
除了使用按100体积份：233体积份比例混合重质原料1和轻质原料1所生产的原料外，使用与实施例1相同的催化剂和反应条件进行加氢处理。结果在表3中列出。
(实施例3)
除了使用按100体积份：100体积份比例混合重质原料1和轻质原料1所生产的原料外，使用与实施例1相同的催化剂和反应条件进行加氢处理。结果在表3中列出。
(实施例4)
除了使用100体积份重质原料2(API度数为30或更小的重质原油衍生的重质烃油)与100体积份轻质原料2(由API度数为35或更大的轻质原油衍生的重质烃油)混合所生产的原料外，使用与实施例1相同的催化剂和反应条件进行加氢处理，结果在表3中列出。
(比较实施例1)
除了以表1所列的重质原料1用做原料外，使用与实施例1相同的催化剂和反应条件进行加氢处理，结果在表3中列出。
(比较实施例2)
除了以表1中列出的重质原料1用做原料和LHSV变为0.12h-1外，使用与实施例1相同的催化剂和反应条件进行加氢处理，结果在表3中列出。
(比较实施例3)
除了以表1中列出的重质原料2用做原料和LHSV变为0.12h-1外，使用与实施例1相同的催化剂和反应条件进行加氢处理，结果在表3中列出。
表1
| 原料 | 重质原料1 | 重质原料2 | 轻质原料1 | 轻质原料2 |
| 原料的API度数 | 24.9 | 27.7 | 39.6 | 39 |
| 300℃+馏分 体积％ | 99.9 | 99.9 | 99.9 | 99.9 |
| 比重 (15/4℃) | 1.007 | 0.9854 | 0.9209 | 0.9388 |
| 硫含量 质量％ | 5.4 | 4.4 | 2.4 | 2.6 |
| Ni+V含量 质量ppm | 131 | 116 | 25 | 9 |
| 残碳含量 质量％ | 15 | 13.8 | 3.8 | 2.6 |
表2
| 催化剂层 | 催化剂 | 表面积m2/m3 | 孔体积m3/m3 | 载体 | 负载的金属 | 催化剂层中催化剂的比例体积％ | |
| Mo摩尔％ | Ni摩尔％ | ||||||
| 第一催化剂层 | A | 7.9×107 | 0.34 | 氧化铝 | 6.1 | 3.2 | 33.3 |
| 第二催化剂层 | B | 1.1×108 | 0.39 | 氧化铝 | 8.3 | 4.5 | 33.4 |
| 第三催化剂层 | C | 1.4×108 | 0.37 | 氧化铝 | 8.3 | 4.5 | 33.3 |
表3
| 实施例 | 比较实施例 | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| 混合比 体积％重质原料1重质原料2轻质原料1轻质原料2 | 10004000 | 10002330 | 10001000 | 01000100 | 100000 | 100000 | 010000 |
| 氢分压 MPa | 17 | 17 | 17 | 17 | 17 | 17 | 17 |
| LHSV h-1 | 0.24 | 0.24 | 0.24 | 0.24 | 0.24 | 0.12 | 0.12 |
| 氢/油比 SCF/BBL | 5000 | 5000 | 5000 | 5000 | 5000 | 5000 | 5000 |
| 生产的油的硫含量 质量％ | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 加氢处理的初始反应温度℃ | 363 | 368 | 372 | 370 | 390 | 375 | 373 |
| 催化剂失活速率 ℃/天 | 0.11 | 0.16 | 0.19 | 0.18 | 0.9 | 0.42 | 0.38 |
| 平均脱金属率 质量％ | 83 | 87 | 85 | 84 | 70 | 75 | 74 |
从表3中列出的结果明显看出，通过本发明方法，即通过将API度数为30或更小的重质原油衍生的重质烃油与API度数为35或更大的轻质原油衍生的重质烃油按预定量混合所生产的原料进行加氢处理的方法能使催化剂失活速率大大减缓。为使操作周期可以达到一年，要求催化剂的失活速率为0.20℃/天或更短。关于平均脱金属率，本发明方法可维持在通常要求的80％或更高。
相反，在使用API度数为24.9的重质原油衍生的重质烃油的比较实施例1中，失活速率达到极高的0.9℃/天，脱金属率降低至70％。
在比较实施例2中，API度数为24.9的重质原油衍生的重质烃油的生产能力减半，失活速率高达0.42℃/天，脱金属率降低至75％。
在比较实施例3中，重质烃油衍生自API度数为27.7的重质原油，失活速率高达0.38℃/天，脱金属率降低至74％。
Claims (3)
1、重质烃油的加氢处理方法，包括将100体积份API度数为30或更小的重质原油衍生的重质烃油与30到1000体积份API度数为35或更大的轻质原油衍生的重质烃油的混合油加氢处理以便生产硫含量为1％(质量)或更少的低硫重质燃料油。
2、根据权利要求1的方法，其中混合油是在氢分压为7到25MPa、LHSV为0.01到10h-1、反应温度为250到450℃和氢/油比为500到8000SCF/BBL的条件下进行加氢处理的。
3、根据权利要求1或2的方法，其中使用表面积为1.0×107到1.0×109m2/m3和孔体积为0.20到0.60m3/m3的催化剂，通过组构使用一或多种每个包括0.03到10％(摩尔)选自周期表VIII族金属的至少一种金属和0.1到10％(摩尔)选自周期表VIB族金属的至少一种金属负载于主要由氧化铝组成的催化剂载体的催化剂来形成催化剂。
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| CA2067878A1 (en) * | 1991-05-02 | 1992-11-03 | Jeffrey B. Harrison | Hydroconversion process |
| JPH04356590A (ja) * | 1991-08-02 | 1992-12-10 | Res Assoc Petroleum Alternat Dev<Rapad> | 粗オイルシェール油の精製法 |
| US5395511A (en) * | 1992-06-30 | 1995-03-07 | Nippon Oil Co., Ltd. | Process for converting heavy hydrocarbon oil into light hydrocarbon fuel |
| CA2117571A1 (en) * | 1993-08-30 | 1995-03-01 | Junichi Kubo | Process for hydrotreating heavy hydrocarbon oil |
| JPH07316566A (ja) * | 1994-05-27 | 1995-12-05 | Nippon Oil Co Ltd | 重質油の水素化処理方法 |
| WO1996007477A1 (en) * | 1994-09-02 | 1996-03-14 | Akzo Nobel N.V. | Catalyst comprising at least a hydrogenation metal component and a synthetic clay |
| JP4050364B2 (ja) | 1997-09-11 | 2008-02-20 | 日揮株式会社 | 石油の処理方法および石油の処理装置 |
| JP4798685B2 (ja) * | 2002-09-24 | 2011-10-19 | Ｊｘ日鉱日石エネルギー株式会社 | 石油系重質油の脱金属方法 |
| US7618822B2 (en) * | 2002-12-19 | 2009-11-17 | Bp Corporation North America Inc. | Predictive crude oil compatibility model |
| WO2005005581A1 (es) * | 2003-07-09 | 2005-01-20 | Instituto Mexicano Del Petróleo | Proceso para el hidrotratamiento catalítico de hidrocarburos pesados del petróleo. |
-
2004
- 2004-08-27 JP JP2004248123A patent/JP4578182B2/ja not_active Expired - Lifetime
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2005
- 2005-08-24 CN CN2005800345294A patent/CN101040032B/zh not_active Expired - Fee Related
- 2005-08-24 KR KR1020077006604A patent/KR101230809B1/ko active IP Right Grant
- 2005-08-24 EP EP05781559A patent/EP1795577A4/en not_active Withdrawn
- 2005-08-24 WO PCT/JP2005/015829 patent/WO2006022419A1/ja active Application Filing
- 2005-08-26 TW TW094129273A patent/TW200615371A/zh not_active IP Right Cessation
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2007
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1795577A4 (en) | 2010-04-14 |
| EP1795577A1 (en) | 2007-06-13 |
| WO2006022419A1 (ja) | 2006-03-02 |
| US7651605B2 (en) | 2010-01-26 |
| JP2006063203A (ja) | 2006-03-09 |
| TWI373518B (zh) | 2012-10-01 |
| KR101230809B1 (ko) | 2013-02-06 |
| TW200615371A (en) | 2006-05-16 |
| CN101040032B (zh) | 2010-05-05 |
| US20070138063A1 (en) | 2007-06-21 |
| KR20070056112A (ko) | 2007-05-31 |
| JP4578182B2 (ja) | 2010-11-10 |
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