CN101405371B - 降低液体烃质原料总酸值(tan)的方法 - Google Patents
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Abstract
一种降低液体烃质原料的总酸值(TAN)的方法，其中在含氢气体的存在下、在200-400℃的温度下和在高压下使原料与包含元素周期表的3或4栏金属或者镧系元素的氧化物的催化剂接触以获到具有降低的总酸值的液体烃质产物，所述催化剂基本不含5-10栏金属或其化合物。
Description
技术领域
本发明提供一种降低液体烃质原料、特别是原油的总酸值(TAN)的方法。
背景技术
具有高含量酸的原油和其它液体烃质物流难于精炼。尤其是在原油炼厂的蒸馏设备中，高含量的酸导致腐蚀问题。已知通过加氢处理除去酸，即其中从液体烃质原料中除去其它杂原子比如硫和氮的相同方法。然而，加氢处理是一种在炼油厂中的蒸馏设备的下游进行的方法。
为了避免由原油的酸含量引起的腐蚀问题，通常将不同的原油物流共混以得到具有可接受的酸含量的原油原料。
原油或其它烃质液体的酸含量通常被表示为这类液体的总酸值(TAN)。TAN表示根据描述于ASTM D664中的程序中和酸所需的毫克KOH/克液体。
在现有技术中需要这样一种方法，其能够降低在炼油厂用作原料的液体烃质物流例如原油的TAN，同时最小化含硫和含氮化合物以及不饱和烃的转化。通过这种方法，将获得具有最少氢消耗的可接受的炼油厂原料。
发明内容
已经发现，基本不含通常用于加氢转化反应例如加氢脱硫、加氢脱氮和加氢裂化的加氢组分、即元素周期表5-10栏的任一金属的化合物的催化剂，可用于液体烃质物流、特别是原油中酸的选择性加氢。
因此，本发明提供一种降低液体烃质原料的总酸值(TAN)的方法，其中在含氢气体的存在下、在200-400℃的温度下和在高压下使原料与包含元素周期表的3或4栏的金属或者镧系元素的氧化物的催化剂接触，以获得具有降低的总酸值的液体烃质产物，所述催化剂基本不含5-10栏金属或其化合物。
根据本发明的方法的优点在于原料的总酸值通过加氢降低，同时其它加氢反应例如加氢脱硫、加氢脱氮和不饱和烃的饱和被最小化。
具体实施方式
在根据本发明的方法中，在含氢气体的存在下、在200-400℃的温度下和在高压下使液体烃质原料与包含3或4栏金属或者镧系元素的氧化物的催化剂接触，所述催化剂基本不含5-10栏金属或其化合物。
原料可以是包含羧酸即有机酸的任意液体烃质物流。本方法特别适合于包含环烷酸的原料。优选地，原料是原油、馏分油物流例如石脑油或瓦斯油、常压原油蒸馏的残余馏分或不符合TAN产物规格的烃质馏分油产物例如取暖用油。根据本发明的方法特别适合于降低原油的总酸值。
含氢气体优选为氢气或合成气。在其中不能获得氢气例如在偏远位置如近海石油平台的情况下，使用合成气作为含氢气体特别有利。
原料与催化剂接触的温度和压力使得羧酸发生加氢，即至少200℃。该温度低于羧酸发生热分解的温度，即低于400℃。优选地，温度为250-390℃，更优选300-380℃。
本方法在高压即高于大气压下进行。优选地，压力为2-200barg，更优选10-150barg，甚至更优选25-120barg。
催化剂包含元素周期表(最新的IUPAC命名法)的3或4栏金属或者镧系元素的氧化物。该氧化物也可以是两种或更多种这些金属的混合氧化物。催化剂还可以包含两种或更多种这些氧化物的混合物。催化剂基本不含元素周期表(最新的IUPAC命名法)的5-10栏金属或其化合物。这里提及的基本不含某些化合物的催化剂，是指催化剂不含这些化合物，除去通常为ppm范围或更低的最小量之外，此时它们可能作为无意的杂质或者作为源自用于获得3或4栏金属或镧系元素的氧化物的矿石精炼方法的残余物存在。
优选地，催化剂包含4栏金属或镧系元素的氧化物。优选的4族金属氧化物是氧化钛和氧化锆，优选的镧系元素氧化物是二氧化铈。更优选地，催化剂由氧化钛和/或氧化锆组成，甚至更优选由氧化锆组成。
催化剂可以通过本领域已知的任意制备方法制备。优选地，制得的催化剂的比表面积为至少10m2/g，更优选至少30m2/g。
用于根据本发明的方法的原料优选具有至少0.2mg KOH/g原料、优选至少0.5mg KOH/g原料、更优选至少1.0mg KOH/g原料的总酸值。这里提及的总酸值是指通过ASTM D664测量的每克原料的KOH用量(以mg计)。
液体烃质产物优选具有至多0.2mg KOH/g原料、更优选至多0.1mgKOH/g原料、甚至更优选至多0.05mg KOH/g原料的TAN。
优选TAN降低的程度使具有降低的总酸值的液体烃质产物具有原料TAN的至多50％，更优选至多30％。
实施例
加氢方法
在微流反应器中，在含氢气体或氮气的存在下使原油与固体惰性材料(0.1mm碳化硅颗粒)或者与下述的其中一种催化剂(用碳化硅颗粒稀释的催化剂颗粒：1/1v/v)接触至少100小时。使用两种不同的原油。对于实验1-8和13-16，使用西非原油(原油1)；对于实验9-12，使用源自中东的原油(原油2)。两种原油的规格示于表1中。表2中给出用于各实验的确切条件。
各实验的液体流出物的总酸值(TAN)根据ASTM D664测量。气相流出物中的硫化氢浓度通过气相色谱测量。液体流出物的TAN和气相流出物中的硫化氢浓度也示于表2中。
实验3、4、6、7、9、10、12和14-16是根据本发明的实验。实验1、2、5、8、11和13是对比实验。
表1原油规格
| 性能 | 原油1 | 原油2 |
| 硫含量(％wt) | 0.41 | 4.1 |
| Ni含量(mg/kg) | 32 | 36 |
| V含量(mg/kg) | 4 | 138 |
| TAN(mg KOH/g油) | 2.7 | 1.3 |
| 密度(g/ml) | 0.93 | 0.91 |
| 沉淀物(mg/kg) | 10 | 1250 |
| 水含量(％wt) | 0.08 | 0.27 |
| C5+沥青质(mg/kg) | 0.26 | 9.7 |
催化剂
在加氢实验中使用以下催化剂。
氧化钛催化剂1
还称为氧化钛1的氧化钛催化剂如下制备。在混合-研磨机揉制机(Simpson)中将数量为3192g的氧化钛粉末(P25，购自Degussa；烧失量：在540℃下为4.4wt％)与100g草酸二水合物混合。在4分钟混合-研磨之后，加入981g去离子水和100g聚乙二醇和继续混合-研磨12分钟。然后加入100g甲基纤维素和继续混合-研磨20分钟。借助于挤出通过1.7mm直径三叶形模板使由此形成的混合物成形。将三叶体在120℃下干燥2小时和在500℃下煅烧2小时。
得到的氧化钛三叶体具有通过氮吸附(BET方法)测得的52m2/g的表面积和通过压汞法测得的0.31ml/g的孔体积。
氧化钛催化剂2
将可作为X096商购获得的氧化钛颗粒(购自CRI CatalystCompany)用作氧化钛催化剂(还称为氧化钛2)。这些氧化钛颗粒具有通过氮吸附(BET方法)测得的120m2/g的表面积和通过压汞法测得的0.32ml/g的孔体积。
氧化锆催化剂
氧化锆催化剂如下制备。在揉制机(Werner&Pfeider Sigma揉制机类型LUK0.75)中将数量为264g氧化锆粉末(RC100，购自Daiichi；烧失量：在540℃下为5.3wt％)与90g去离子水中的5wt％的聚乙烯醇溶液混合。在7分钟揉制之后，加入2.5g阳离子聚丙烯酰胺(Superfloc，购自Cytec)和在20分钟揉制之后加入8g去离子水。再将混合物揉制22分钟。由此形成的混合物通过挤出成形为1.7mm直径三叶体。将挤出物在120℃下干燥2小时和在550℃下煅烧2小时。
得到的氧化锆三叶体具有通过氮吸附(BET方法)测得的54m2/g的表面积和通过压汞法测得的0.35ml/g的孔体积。
氧化铝上的NiMo
使用可作为CRITERION RM-5030商购获得的(购自CriterionCatalyst Company)包含于氧化铝上的Ni和Mo的常规加氢脱硫催化剂。
Claims (12)
1.一种降低液体烃质原料的总酸值的方法，其中在含氢气体的存在下、在200-400℃的温度下和在2-200barg的压力下使原料与包含元素周期表的3或4栏金属或者镧系元素的氧化物的催化剂接触，以获得具有降低的总酸值的液体烃质产物，所述催化剂基本不含5-10栏金属或其化合物。
2.权利要求1的方法，其中氧化物是4栏金属或镧系元素的氧化物。
3.权利要求2的方法，其中催化剂基本由氧化钛和/或氧化锆组成。
4.权利要求1-3任一项的方法，其中压力为10-150barg。
5.权利要求4的方法，其中压力为25-120barg。
6.权利要求1-3任一项的方法，其中温度为250-390℃。
7.权利要求6的方法，其中温度为300-380℃。
8.权利要求1-3任一项的方法，其中含氢气体是合成气或氢气。
9.权利要求1-3任一项的方法，其中原料具有至少0.2mg KOH/g原料的总酸值。
10.权利要求1-3任一项的方法，其中液体烃质产物具有至多0.2mg KOH/g原料的总酸值。
11.权利要求1-3任一项的方法，其中具有降低的总酸值的液体烃质产物的总酸值为原油产物的总酸值的至多50％。
12.权利要求1-3任一项的方法，其中液体烃质原料是原油。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2006/061302 WO2007112782A1 (en) | 2006-04-04 | 2006-04-04 | A process for reducing the total acid number (tan) of a liquid hydrocarbonaceous feedstock |
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| CN101405371A CN101405371A (zh) | 2009-04-08 |
| CN101405371B true CN101405371B (zh) | 2012-07-18 |
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| Country | Link |
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| EP (1) | EP2001976A1 (zh) |
| JP (1) | JP5399234B2 (zh) |
| CN (1) | CN101405371B (zh) |
| AU (1) | AU2006341463A1 (zh) |
| CA (1) | CA2647760C (zh) |
| MX (1) | MX2008012567A (zh) |
| WO (1) | WO2007112782A1 (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB496779A (en) * | 1937-01-04 | 1938-12-06 | Bataafsche Petroleum | A process for removing naphthenic acids from mineral lubricating oils or lubricating oil fractions |
| US3846288A (en) * | 1973-07-05 | 1974-11-05 | Gulf Research Development Co | Acid number reduction of hydrocarbon fractions using a solid catalyst and methanol |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6547957B1 (en) * | 2000-10-17 | 2003-04-15 | Texaco, Inc. | Process for upgrading a hydrocarbon oil |
| US20020148754A1 (en) * | 2001-02-08 | 2002-10-17 | Gong William H. | Integrated preparation of blending components for refinery transportation fuels |
| NL1027755C2 (nl) * | 2003-12-19 | 2006-07-13 | Shell Int Research | Systemen, methoden en katalysatoren voor het produceren van een ruwe-oliehoudend product. |
| EP1781760A1 (en) * | 2004-07-07 | 2007-05-09 | California Institute Of Technology | Process to upgrade oil using metal oxides |
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2006
- 2006-04-04 JP JP2009503427A patent/JP5399234B2/ja not_active Expired - Fee Related
- 2006-04-04 CN CN200680053992.8A patent/CN101405371B/zh not_active Expired - Fee Related
- 2006-04-04 MX MX2008012567A patent/MX2008012567A/es unknown
- 2006-04-04 EP EP06725538A patent/EP2001976A1/en not_active Withdrawn
- 2006-04-04 AU AU2006341463A patent/AU2006341463A1/en not_active Abandoned
- 2006-04-04 CA CA2647760A patent/CA2647760C/en not_active Expired - Fee Related
- 2006-04-04 WO PCT/EP2006/061302 patent/WO2007112782A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB496779A (en) * | 1937-01-04 | 1938-12-06 | Bataafsche Petroleum | A process for removing naphthenic acids from mineral lubricating oils or lubricating oil fractions |
| US3846288A (en) * | 1973-07-05 | 1974-11-05 | Gulf Research Development Co | Acid number reduction of hydrocarbon fractions using a solid catalyst and methanol |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007112782A1 (en) | 2007-10-11 |
| EP2001976A1 (en) | 2008-12-17 |
| CN101405371A (zh) | 2009-04-08 |
| JP2009532536A (ja) | 2009-09-10 |
| MX2008012567A (es) | 2008-10-10 |
| CA2647760C (en) | 2013-12-10 |
| AU2006341463A1 (en) | 2007-10-11 |
| CA2647760A1 (en) | 2007-10-11 |
| JP5399234B2 (ja) | 2014-01-29 |
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