CN101595079B - 制备费-托烯烃石脑油和加氢馏出物的改良工艺 - Google Patents
制备费-托烯烃石脑油和加氢馏出物的改良工艺 Download PDFInfo
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Abstract
一种从费-托工艺生产烯烃石脑油和加氢馏出物燃料的工艺，烯烃石脑油适用于乙烯裂化器，其中，烯烃增强了乙烯的生成；加氢馏出物燃料可以用作喷气燃料或柴油燃料。任选地，所述烯烃石脑油含低含量的酸。通过调整费-托单元中H2/CO比值为1.8-2.05或者使用金属氧化物处理费-托单元中流出物以除去其中的酸，使酸含量低。
Description
背景技术
典型工艺条件下，费-托产品经过加氢精制和加氢裂化后，基本上不含有烯烃、醇类、酸类和其他含氧化合物。他们本身具有高度的稳定性，采用适当的预防措施可使石油衍生的馏出物燃料制备出优质馏出物燃料的调合组分。当含氧化合物残留在柴油中时，他们将有助于过氧化物的形成。该问题可通过使用美国专利申请20040152930和20040148850中描述的抗氧剂得以解决。
经由费-托产品获得的石脑油产品由烷烃、烯烃和含氧化合物(醇、酸、和痕量其他化合物)组成。所有的化合物主要是直链(正构烷烃、直链烯烃、直链醇等)。直链烷烃，尤其是直链烯烃适用于在石油裂化器中制备烯烃。醇类，尤其是酸类是不可取的，因为后者会导致腐蚀。
从费-托缩合物中去除醇和酸来制备生产乙烯的烯烃石脑油的技术已被开发，并在美国专利申请No.10/355,279和10/354,956中被描述。
然而，在某些情况下，客户会优选不含烯烃的馏出物燃料，因此，制备烯烃石脑油的同时制备加氢馏出物燃料是有希望的。本发明满足这种综合需要。
定义
加氢馏出物燃料是指馏出物燃料的所有组分都在这一或那一时间被加氢，加氢压力高于大气压，优选为250到3000psig。反应器流线性空间流速(LHSV)为0.5-5，反应温度为450至800°F。将这些参数组合用于一种催化剂上，该催化剂包括第VIII族金属，和任选VI族金属，优选的催化剂为硫化的镍钼/氧化硅-氧化铝、硫化的镍钨/氧化硅-氧化铝、和铂/氧化铝，加氢馏出物燃料不需要去除所有的烯烃和含氧化合物，但需要在60℃存储4周后形成过氧化物的浓度低于5ppm，美国专利Nos.10/464,546和10/464,635中对此已有描述。优选加氢馏出物燃料中检不出美国专利No.20040152930所述燃料A中的含氧化物。
费-托衍生的是指在其加工中在某一点衍生自费-托工艺的产物。费-托工艺的原料是合成气(包括一氧化碳、氢气和任选的其它气体的混合物，上述其他气体如二氧化碳、水、和痕迹其它气体等)。所述合成气体可通过各种含烃原料形成：如，甲烷(或天然气)、煤、石油、石油副产品如渣油和焦炭、焦油砂、城市垃圾、农业废料等。原料可通过地面设施转化为合成气，也可通过地下转换，特别是可地下气化的石油、焦油砂、煤炭。优选费-托工艺为低温费托(LTFT)工艺，该工艺温度一般低于250℃，该工艺在美国专利6,846,402中已描述并纳入此处作为参考。最优选的费-托工艺是淤浆床模式的低温费-托工艺。最最优选的工艺还包括使用钴催化剂，钴催化剂比铁催化剂生成更少量的氧化物产品，因为这个原因优选钴催化剂。
石油衍生的是指经由石油衍生的产品，但还没有转化为合成气和在费托工艺中进行处理。
发明概述
本发明描述了一种同时制备烯烃石脑油和加氢馏出物的方法。
附图说明
图1显示了获得烯烃石脑油和加氢馏出物的LTFT工艺图。
图2为本发明的一个可供选择的实施方案。
图3为本发明的另一个可供选择的实施方案。
发明详述
本工艺会产生两种产物流，塔顶蒸气物流和蜡状液体物流。在一优选实施方案中，塔顶蒸气物流至少通过两个冷凝器冷却。第一冷凝器产生第一冷凝物，其所含物料的沸点在馏出物范围(300°F和更高温度)。在第一冷凝器中沸点大于300°F以上的物料的含量大于或等于50wt％，优选大于或等于75wt％，更优选大于或等于90wt％。所述冷凝物被加氢处理形成一种加氢馏出物燃料。任选地，蜡也被加氢处理，优选与第一冷凝物混合。经由第一冷凝器冷却的未冷凝产品在第二冷凝器中被冷却并分离产生第二冷凝物。所述第二冷凝物包含较少的300°F馏出物范围的物料。第二冷凝物中沸点高于300°F以上的物料的含量小于或等于90wt％，优选小于或等于75wt％，更优选小于或等于50wt％，最优选小于或等于25wt％。
因为石脑油裂化器的物料操作温度可以在300°F-和300°F+以上，所以石脑油中沸点300°F+的物料含量并不是决定性的。任选地，可通过引入一些分馏设备，如塔盘、填料、塔顶冷凝回流和其他本领域熟知的设备，来提高冷凝器的分离效率。第二冷凝物包括烯烃，并用来制备烯烃石脑油。第二冷凝物可与其他材料例如加氢处理第一冷凝物和/或蜡所得的石脑油混合。第二冷凝物也可以与气田操作回收所得的冷凝物混合。第二冷凝物中烯烃的含量应大于10wt％，优选是10-80wt％，最优选的情况是，第二冷凝物的烯烃含量为10-80wt％；非烯烃重量为20-90wt％。其中，非烯烃包括含量大于50wt％的石蜡；硫的重量含量低于10ppm；氮的重量含量低于10ppm；芳烃的含量低于10wt％；总酸值低于1.5，C5的沸点范围达到400°F，该性质在美国专利No.2004/0149626已描述，此处引入供参考。
费-托产品可以包含酸类。在某些情况下，这些是有益的，例如可以减少在运输过程中的腐蚀或改进其润滑性，但是过量的酸却是不可取的。按照美国专利No.2004/0149626中所描述的ASTM D 664方法来测量，烯烃石脑油的酸值应小于1.5mg KOH/g。优选酸值应该小于0.5mg KOH/g，最优选酸值小于0.1mgKOH/g。烯烃石脑油中的酸含量，和高温下的金属氧化物有关。另外，降低烯烃石脑油的酸含量可通过调整费-托单元的条件-通过使用钴催化剂、而不是铁催化剂，或控制反应器入口中的H2/CO摩尔比为1.65-2.0，优选1.75-1.95，最优选1.80-1.90。
优选实施方案描述
图1显示了一种同时生产烯烃石脑油和加氢馏出物的实施方案。该操作中甲烷作为工艺原料，但也可以使用其他原料如煤炭、有机物等，这并不背离本发明的实质。甲烷(10)在合成气形成反应器(20)中转化为合成气(30)。合成气(30)在费-托单元(40)中反应形成蒸气产品(60)和蜡质液体产品(50)。蜡质液体产品在加氢裂化装置(110)中经加氢处理形成加氢馏分(220)。费-托反应器形成的气体产品经热交换器(未显示)后进入第一冷凝器(70)，形成第一冷凝物(90)和第一未冷凝气体(80)。第一冷凝物与蜡质液体混合后进入加氢裂化装置(110)。第一未冷凝气体通过热交换器(未显示)进一步冷却，并进入第二冷凝器(72)形成第二冷凝物(92)，其中至少有一部分为烯烃石脑油产品(210)。第二未冷凝气体(200)产生。这种未冷凝气体(20)可用作燃料，循环至费托反应器，循环到合成气形成反应器，或这些用途的组合。任选地，加氢裂化装置将石脑油产品(115)与第二冷凝物(92)混合后形成烯烃石脑油产品(210)。任选地，通过使用钴催化剂和比例为1.75-1.95的合成气的条件运行费-托单元，以使烯烃石脑油的酸值小于0.5mg KOH/g。
图2显示了另一种生产烯烃石脑油和加氢馏出物的实施方案，该实施方案包括一个对第二冷凝物的处理步骤以从石脑油中去除含氧化合物。图1的附图标记继续适用于图2的实施方案。在本实施方案中，第二冷凝物下行通过净化装置(100)，操作温度为680°F、操作压力为50psig和反应流线性空间流速为5LHSV并且不添加气态成分。净化装置包含氧化铝。净化装置去除80％以上的含氧化合物，增加了烯烃含量，并降低了烯烃石脑油(105)的酸度。至少有部分经此精制的烯烃石脑油在市售烯烃石脑油(210)中使用。任选地，加氢裂化装置中的石脑油产品被包含在市售的烯烃石脑油中。
图3显示了一种生产烯烃石脑油和加氢馏出物的另一实施方案，该实施方案包括对费-托蒸气产品的处理步骤以从石脑油中除去含氧化合物。图1和图2的附图标记继续适用于图3的实施方案。本实施方案中，费托反应器的蒸气产品(60)下行通过净化装置(100)，操作温度为680°F、操作压力为50psig和反应流线性空间流速为1LHSV，并且不添加气体组分。该LHSV根据费托蒸气产品中的C4+产品定义的。本实施方案的优点是在冷凝器前消除了酸，因而减少了这些单元的潜在腐蚀问题。处理后的蒸气产品(62)被冷却并通往送入第一分离器(70)，得到第一冷凝物(90)和第一未冷凝气体(80)。
费-托反应器形成的水(和在图3净化装置中形成的水)在第一冷凝器、第二冷凝器或两个两冷凝器中作为第三相被分离。为了简洁，没有显示分离后的水流。
任选地，第一和/或第二冷凝器包含提高分离效率的设备，如塔盘、填料、塔顶冷凝回流和其他本领域熟知的设备。最优选第一冷凝器包含这些设备。
Claims (12)
1.一种生产烯烃石脑油和加氢馏出物的工艺，该工艺包括：
a.将至少部分烃转化成合成气；
b.在费-托工艺装置中，将至少部分合成气转化成蒸气产品和蜡质液体产品；
c.在第一冷凝器中，冷却蒸气产品并分离出第一冷凝物和第一未冷凝气体；
d.在第二冷凝器中，冷却第一未冷凝气体并分离出第二冷凝物和第二未冷凝气体；
e.通过升高的温度下与金属氧化物接触对第二冷凝物进行处理；
f.从至少部分第二冷凝物制备烯烃石脑油；
g.从选自第一冷凝物、蜡质液体产品及其组合的原料，制备加氢馏出物。
2.如权利要求1所述的工艺，其中，费-托工艺使用钴催化剂。
3.如权利要求1所述的工艺，其中，进料到费-托反应器中的合成气的H2/CO摩尔比大于或等于1.65，并小于或等于2.0。
4.如权利要求3所述的工艺，其中所述摩尔比大于或等于1.75，并小于或等于1.95。
5.如权利要求4所述的工艺，其中所述摩尔比大于或等于1.80，并小于或等于1.90。
6.如权利要求1所述的工艺，其中所述金属氧化物选自氧化铝，氧化硅，氧化硅-氧化铝，沸石，粘土和它们的混合物。
7.如权利要求6所述的工艺，其进一步包括将处理步骤中形成的水和二氧化碳与净化的烯烃石脑油分开的步骤。
8.如权利要求7所述的工艺，其中所述处理步骤降低了烯烃石脑油中固体、酸和醇的含量。
9.如权利要求1所述的工艺，其中离析的烯烃石脑油的总酸值小于1.5mgKOH/g。
10.如权利要求9所述的工艺，其中所述总酸值小于0.5mg KOH/g。
11.如权利要求10所述的工艺，其中所述总酸值小于0.01mg KOH/g。
12.如权利要求1所述的工艺，其中所述加氢馏出物经60℃储存4周后，形成少于5ppm的过氧化物。
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| US87007406P | 2006-12-14 | 2006-12-14 | |
| US60/870,074 | 2006-12-14 | ||
| PCT/US2007/087535 WO2008076865A1 (en) | 2006-12-14 | 2007-12-14 | Improved process for making fischer-tropsch olefinic naphtha and hydrogenated distillates |
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| CN101595079A CN101595079A (zh) | 2009-12-02 |
| CN101595079B true CN101595079B (zh) | 2013-10-23 |
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| US (1) | US7884138B2 (zh) |
| JP (1) | JP5721327B2 (zh) |
| CN (1) | CN101595079B (zh) |
| AU (1) | AU2007333907B2 (zh) |
| GB (1) | GB2458070B (zh) |
| WO (1) | WO2008076865A1 (zh) |
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| FR2940919B1 (fr) * | 2009-01-12 | 2011-12-09 | Inst Francais Du Petrole | Utilisation d'une composition a base de tio2 pour la captation de composes halogenes contenus dans un melange gazeux |
| EP2474592B1 (en) | 2009-08-31 | 2016-10-12 | Japan Oil, Gas and Metals National Corporation | Method for recovery of liquid hydrocarbon |
| US20150073188A1 (en) * | 2012-03-01 | 2015-03-12 | The Trustees Of Princeton University | Processes for producing synthetic hydrocarbons from coal, biomass, and natural gas |
| WO2014039095A1 (en) * | 2012-09-07 | 2014-03-13 | Afognak Native Corporation | Systems and processes for producing liquid transportation fuels |
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| US3862899A (en) * | 1972-11-07 | 1975-01-28 | Pullman Inc | Process for the production of synthesis gas and clean fuels |
| US7608181B2 (en) * | 2001-10-19 | 2009-10-27 | Chevron U.S.A. Inc. | Distillate fuel blends from Fischer Tropsch products with improved seal swell properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6515034B2 (en) * | 2001-05-11 | 2003-02-04 | Chevron U.S.A. Inc. | Co-hydroprocessing of Fischer-Tropsch products and crude oil fractions |
| US20070187292A1 (en) * | 2001-10-19 | 2007-08-16 | Miller Stephen J | Stable, moderately unsaturated distillate fuel blend stocks prepared by low pressure hydroprocessing of Fischer-Tropsch products |
| US20070187291A1 (en) * | 2001-10-19 | 2007-08-16 | Miller Stephen J | Highly paraffinic, moderately aromatic distillate fuel blend stocks prepared by low pressure hydroprocessing of fischer-tropsch products |
| US6846402B2 (en) * | 2001-10-19 | 2005-01-25 | Chevron U.S.A. Inc. | Thermally stable jet prepared from highly paraffinic distillate fuel component and conventional distillate fuel component |
| GB2401112C (en) * | 2002-02-13 | 2007-01-16 | Sasol Technology | Process for starting up a fischer-tropsch reactor |
| AU2004200270B2 (en) * | 2003-01-31 | 2009-11-12 | Chevron U.S.A. Inc. | High purity olefinic naphthas for the production of ethylene and propylene |
| US7179311B2 (en) * | 2003-01-31 | 2007-02-20 | Chevron U.S.A. Inc. | Stable olefinic, low sulfur diesel fuels |
| US7479168B2 (en) * | 2003-01-31 | 2009-01-20 | Chevron U.S.A. Inc. | Stable low-sulfur diesel blend of an olefinic blend component, a low-sulfur blend component, and a sulfur-free antioxidant |
| US7431821B2 (en) * | 2003-01-31 | 2008-10-07 | Chevron U.S.A. Inc. | High purity olefinic naphthas for the production of ethylene and propylene |
| US7179364B2 (en) * | 2003-01-31 | 2007-02-20 | Chevron U.S.A. Inc. | Production of stable olefinic Fischer-Tropsch fuels with minimum hydrogen consumption |
| US20060016722A1 (en) * | 2004-07-08 | 2006-01-26 | Conocophillips Company | Synthetic hydrocarbon products |
| US20080000806A1 (en) * | 2004-12-23 | 2008-01-03 | Dirkx Jacobus Mathias H | Process to Prepare a Lubricating Base Oil |
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2007
- 2007-12-14 JP JP2009541609A patent/JP5721327B2/ja active Active
- 2007-12-14 US US11/956,455 patent/US7884138B2/en not_active Expired - Fee Related
- 2007-12-14 WO PCT/US2007/087535 patent/WO2008076865A1/en active Application Filing
- 2007-12-14 GB GB0912045A patent/GB2458070B/en not_active Expired - Fee Related
- 2007-12-14 CN CN200780045926.0A patent/CN101595079B/zh not_active Expired - Fee Related
- 2007-12-14 AU AU2007333907A patent/AU2007333907B2/en not_active Ceased
- 2007-12-14 ZA ZA200904069A patent/ZA200904069B/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862899A (en) * | 1972-11-07 | 1975-01-28 | Pullman Inc | Process for the production of synthesis gas and clean fuels |
| US7608181B2 (en) * | 2001-10-19 | 2009-10-27 | Chevron U.S.A. Inc. | Distillate fuel blends from Fischer Tropsch products with improved seal swell properties |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101595079A (zh) | 2009-12-02 |
| JP5721327B2 (ja) | 2015-05-20 |
| AU2007333907B2 (en) | 2013-01-17 |
| US20080319094A1 (en) | 2008-12-25 |
| ZA200904069B (en) | 2010-08-25 |
| JP2010513606A (ja) | 2010-04-30 |
| GB2458070A (en) | 2009-09-09 |
| AU2007333907A1 (en) | 2008-06-26 |
| GB0912045D0 (en) | 2009-08-19 |
| US7884138B2 (en) | 2011-02-08 |
| GB2458070B (en) | 2011-08-03 |
| WO2008076865A1 (en) | 2008-06-26 |
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