CN103097023A - 在合成气调节的同时低温耐硫脱除焦油和硫 - Google Patents
在合成气调节的同时低温耐硫脱除焦油和硫 Download PDFInfo
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Abstract
一种包含NiO、Al2O3和ZnO的催化剂。所述催化剂能在300-600°C的温度下从合成气中脱除超过5%的硫。
Description
相关申请的交叉引用
本申请为PCT国际申请,其要求于2010年9月13日提交的标题为“LowTemperature Sulfur Tolerant Tar and Sulfur Removal with ConcomitantSynthesis Gas Conditioning”的美国临时专利申请61/382,211的权益和优先权,在此通过引用并入本文。
关于联邦政府资助的研究或开发的声明
无。
技术领域
用于清洁并调节合成气以脱除焦油和硫的催化剂。
背景技术
合成气含有各种杂质,如焦油、H2S、NH3和颗粒物。焦油(通常定义为在含碳材料如木材、煤炭或泥炭热解过程中形成的多核芳族化合物)导致操作问题,如堵塞工艺管道和使换热表面结垢,这导致加工效率降低和装臵停车。焦油具有起导致气化炉下游的催化剂失活的焦炭前体作用的倾向。此外,焦油的一些组分为已知的致癌物。因此,重要的是从合成气流中脱除焦油以将合成气经济地转化为具有附加值的产物。
焦油浓度可随原料、气化炉类型和操作条件而变化。大多数下游转化工艺和设备对焦油具有零或非常低的耐受性(ppb范围内)。尽管催化脱除焦油是最简单且最经济的方法,然而即使在25年的持续研究和开发工作后,也不存在商业化的低温(<500°C)焦油脱除催化剂。本领域中目前所用的催化剂要求温度至少为600°C,优选800°C,这需要加热和昂贵的设备。由于将合成气从发生器中取出,无需采用任何额外的加热附加成本和机器。
需要寻找显示出如下性能且同时脱除焦油和硫的催化剂:1)对焦油脱除的耐硫性;2)耐焦化;3)耐受高温和还原环境的能力;4)在NH3、HCl和一些重金属存在下工作的能力;和5)耐磨损性。
公开内容简述
一种催化剂,其包含或基本上包含NiO、Al2O3和ZnO。所述催化剂能在300-600°C的温度下从合成气中脱除超过5%的硫。
在另一实施方案中,所述催化剂包含或基本上包含以1-10重量%的量存在的NiO、Al2O3和ZnO。在该实施方案中,所述催化剂能在350-550°C的温度和14.7-1,200psig的压力下从合成气中脱除超过20%的硫,同时从所述合成气中脱除焦油。
在另一实施方案中,所述方法起始于合成气的制备。然后使所述合成气与催化剂接触以制备经处理的合成气。在该实施方案中,所述催化剂包含或基本上包含NiO、Al2O3和ZnO。所述催化剂能在300-600°C的温度下从合成气中脱除超过5%的硫。然后将所述经处理的合成气引入催化化学反应中。在该实施方案中,在与所述催化剂接触之前,不对所述合成气进行加热,且在进行催化化学反应之前,不对所述经处理的合成气进行冷却。
在又一实施方案中,所述方法起始于合成气的制备。然后使所述合成气与催化剂接触以制备经处理的合成气。在该实施方案中,所述催化剂包含或基本上包含以1-10重量%的量存在的NiO、Al2O3和ZnO。所述催化剂能在350-550°C的温度和14.7-1,200psig的压力下从合成气中脱除超过20%的硫,同时从所述合成气中脱除焦油。然后将所述经处理的合成气引入催化化学反应中。在该实施方案中,在与所述催化剂接触之前,不对所述合成气进行加热,且在发生催化化学反应之前,不对所述经处理的合成气进行冷却。
附图简介
通过参照与附图一起的下文描述,可更全面理解地本发明及其益处,在所述附图中:
图1描述了具有再生炉的循环流化床设计的装臵。
图2描述了在350°C下于500psig和11h-1下的萘转化。
发明详述
现在开始详细描述本发明的优选方案,应当理解的是本发明的特征和概念可体现于其他方案中,且本发明的范围不受限于所描述或示意的实施方案。本发明的范围旨在仅由下文权利要求的范围所限定。
在一个实施方案中,所述催化剂包含NiO、Al2O3和ZnO。在该实施方案中,所述催化剂能在300-600°C的温度下从合成气中脱除超过5%的硫。
在一个实施方案中,NiO以0.5-15重量%,1-10重量%,或者甚至以7.5-12.5重量%的量存在。
在另一实施方案中,ZnO以0.5-15重量%,1-10重量%,或者甚至以7.5-12.5重量%的量存在。
可将所述催化剂臵于固定床设计或任选臵于循环流化床设计之上。用于该循环流化床设计且具有再生炉的反应器装臵示于图1中。在该图中,流化床反应器10含有催化剂12。使具有焦油和H2S的合成气14流入流化床反应器10中并与催化剂12反应。该反应步骤的温度可低于425°C,325-425°C,或者甚至为350-400°C。所述反应可在14.7-1,200psig的压力下运行,然后使废催化剂16和清洁的合成气18流入在其中将其分离的分离器20,如旋风分离器中。然后使废催化剂16流入再生炉22中,其中使用空气24使所述催化剂再生为再生的催化剂26。然后使所述再生的催化剂流入所述循环流化床设计中以再次用作催化剂。
与催化剂反应的合成气可为含有不同量的一氧化碳和氢气的任何气体混合物。在一个实施方案中,合成气进料可含有呈萘形式的焦油和呈H2S形式的硫。所述合成气进料中的焦油和硫含量可为数ppm至15,000ppmv,这取决于原料、气化炉类型和操作条件。
在一个实施方案中,在与所述催化剂接触之前,不对所述合成气进行加热。本领域中目前所用的催化剂需要至少800°C的温度,这需要加热和昂贵的设备。由于将合成气从发生器中取出,不需要使用任何额外加热附加成本和机器。此外,通过使所述合成气与所述催化剂在300-600°C的温度下接触,在用于催化化学反应之前,不需对所述经处理的合成气进行冷却。
所述催化化学反应可包括诸如将合成气转化成二甲醚、汽油的费-托反应或甲烷化反应。费-托反应可用于生产液体燃料。其他催化反应可用于生产合成天然气、汽油、醇、氨或其他化工产品。
在一个实施方案中,金属氧化物位点可还原,从而导致还原的金属位点与金属氧化物位点的组合。所述还原反应可通过如下方法实现:在中等温度下使用氢气以与所述金属氧化物反应,从而形成水和还原的金属。
在一个实施方案中,所述合成气含有超过1,000ppmv的硫,甚至超过10,000ppmv或者甚至15,000ppmv的硫。在一个实施方案中,所述合成气的硫含量可为10,000-20,000ppmv。此外,在一个实施方案中,所述催化剂能将H2S脱除至低于1ppmv,这通常为费-托反应所需的水平。
在另一实施方案中,所述催化剂包含1-10重量%的NiO、Al2O3和ZnO。所述催化剂能在350-550°C的温度和14.7-1,200psig或者甚至250-1,000psig的压力下从合成气中脱除超过20%的硫,同时从所述合成气中脱除焦油。
在又一实施方案中,所述方法公开了制备合成气,随后通过使所述合成气与催化剂接触从而制备经处理的合成气。在该实施方案中,所述催化剂可包含NiO、Al2O3和ZnO。然后将所述经处理的合成气引入催化化学反应中。在该实施方案中,在与所述催化剂接触之前,不对所述合成气进行加热,且在进行所述催化化学反应之前,不对所述经处理的合成气进行冷却。
由于在与所述催化剂接触之前不对所述合成气进行加热,因此不需要额外的热源。此外,在所述经处理的合成气进行催化化学反应之前,不需对所述经处理的合成气进行额外的冷却。
在另一实施方案中,所述方法公开了制备合成气,随后通过使所述合成气与催化剂接触而制备经处理的合成气。在该实施方案中,所述催化剂可包含1-10重量%的NiO、Al2O3和ZnO。所述催化剂能在350-550°C的温度和250-1,000psig的压力下从合成气中脱除超过20%的硫,同时从所述合成气中脱除焦油。然后将经处理的合成气引入催化化学反应中。在该实施方案中,在与所述催化剂接触之前不对所述合成气进行加热,且在进行所述催化化学反应之前,不对所述经处理的合成气进行冷却。
给出了本发明特定实施方案的如下实施例。各实施例以阐述本发明、本发明的许多实施方案之一的方式提供,且下文实施例不应视为限制或限定本发明的范围。
实施例1
对包含17重量%的Ni和ZnO且位于氧化铝-珍珠岩载体上的催化剂进行评估。对所述催化剂在500psig和350-400°C的温度下脱除萘焦油进行评估。合成气流由28.5%H2、42%CO、12%CO2、16%H2O、1.5%H2S(相当于15,000ppmv H2S)和约200ppmv萘构成。在所述反应开始之前,将所述催化剂在H2存在下于450°C和大气压下还原1.5小时。反应条件为350°C、500psig和11h-1。
如图2所示,在所述反应条件下,50%萘转化率在2天内保持恒定。没有迹象显示所述催化剂失活。甲烷和焦炭为该反应的主要产物,且在废催化剂上存在约9重量%的碳。废催化剂的分析还表明其含有21重量%的硫,因此,所述催化剂同时脱除焦油和H2S。此外,所述催化剂在NH3和HCl存在下显示出脱硫活性,且无任何降低效果。
实施例3
对不同的催化剂进行试验以评估其在低温下的焦油裂化、甲烷化、水煤气变换和脱硫能力。在下表中,WHSV意指重时空速。
测试了六种不同的催化剂。
催化剂 | 位点类型 | 金属位点的形式 |
二氧化硅-氧化铝 | 酸性位点 | - |
钨酸化的氧化锆 | 酸性位点,一些金属 | 还原的金属/氧化物 |
超稳Y沸石 | 酸性位点 | - |
NiW/沸石载体 | 金属和酸性位点 | 硫化物 |
NiMo/沸石载体 | 金属和酸性位点 | 硫化物 |
Ni、Al2O3和ZnO | 金属位点 | 还原的金属/氧化物 |
所述催化剂实施焦油裂化的能力如下所示。
催化剂 | 温度 | 压力 | WHSV | 萘转化率 |
°C | psig | h-1 | % | |
二氧化硅-氧化铝 | 400-600 | 500 | 11 | <20% |
钨酸化的氧化锆 | 400-600 | 500 | 11 | 10-60% |
超稳Y沸石 | 400-600 | 500 | 11 | 40-60% |
NiW/沸石载体 | 400-600 | 500 | 11 | 60-75% |
NiMo/沸石载体 | 350-550 | 500 | 2.2-11 | >90% |
Ni、Al2O3和ZnO | 350-550 | 500 | 11 | 20-60% |
所述催化剂实施甲烷化的能力如下所示。
催化剂 | 温度 | 压力 | WHSV | CH4的形成速率 |
°C | psig | h-1 | μmol/g催化剂/s | |
二氧化硅-氧化铝 | 400-600 | 500 | 11 | <20 |
钨酸化的氧化锆 | 400-600 | 500 | 11 | 100-400 |
超稳Y沸石 | 400-600 | 500 | 11 | <10 |
NiW/沸石载体 | 400-600 | 500 | 11 | 300-700 |
NiMo/沸石载体 | 350-550 | 500 | 2.2-11 | 150-800 |
Ni、Al2O3和ZnO | 350-550 | 500 | 11 | <20 |
所述催化剂实施水煤气变换反应的能力如下所示。
催化剂 | 温度 | 压力 | WHSV | CO转化率 |
°C | psig | h-1 | % | |
二氧化硅-氧化铝 | 400-600 | 500 | 11 | <5% |
钨酸化的氧化锆 | 400-600 | 500 | 11 | 20% |
超稳Y沸石 | 400-600 | 500 | 11 | <5% |
NiW/沸石载体 | 400-600 | 500 | 11 | 30% |
NiMo/沸石载体 | 350-550 | 500 | 2.2-11 | 30-50% |
Ni、Al2O3和ZnO | 350-550 | 500 | 11 | 10-20% |
所述催化剂实施脱硫的能力如下所示。
催化剂 | 温度压力 | WHSV | 硫吸收率 |
°C psig | h-1 | ||
二氧化硅-氧化铝 | 400-600500 | 11 | 0 |
钨酸化的氧化锆 | 400-600500 | 11 | 3% |
超稳Y沸石 | 400-600500 | 11 | 0 |
NiW/沸石载体 | 400-600500 | 11 | <0.1% |
NiMo/沸石载体 | 350-550500 | 2.2-11 | <0.1% |
Ni、Al2O3和ZnO | 350-550500 | 11 | 20% |
最后,应注意的是对任何引用文献的论述并非认可其是本发明的现有技术,尤其是公开日可在本申请的优先权日之后的任何引用文献。同时,下文的各权利要求在此作为本发明的附加实施方案并入该发明详述或说明书中。
尽管已对本文所述的***和方法进行了详细描述,然而应理解的是可在不偏离由下文权利要求书所限定的本发明精神和范围下进行各种变化、代替和变更。本领域技术人员可研究优选实施方案并确定不精确按照本文所述的实施本发明的其他方式。发明人的意图在于,本发明的变更和等同方案处于权利要求书的范围之内,而不将说明书、摘要和附图用于限制本发明的范围。本发明尤其意欲如下文权利要求及其等同方案一样宽。
Claims (20)
1.一种催化剂,其包含:
(a)NiO;
(b)Al2O3;和
(c)ZnO,
其中所述催化剂能在300-600°C的温度下从合成气中脱除超过5%的硫。
2.根据权利要求1的催化剂,其中温度为350-550°C。
3.根据权利要求1的催化剂,其中脱硫压力为14.7-1,200psig。
4.根据权利要求1的催化剂,其中脱硫压力为250-1,000psig。
5.根据权利要求1的催化剂,其中所述催化剂在脱硫过程中同时从所述合成气中脱除焦油。
6.根据权利要求1的催化剂,其中在与所述催化剂接触之前,不对所述合成气进行热处理。
7.根据权利要求1的催化剂,其中350°C下的焦油脱除转化率大于55%。
8.根据权利要求1的催化剂,其中NiO以1-10重量%的量存在。
9.根据权利要求1的催化剂,其中从所述合成气中脱除超过10%的硫。
10.根据权利要求1的催化剂,其中所述合成气中的硫含量大于1000ppmv。
11.一种催化剂,其包含:
(a)以1-10重量%的量存在的NiO;
(b)Al2O3;和
(c)ZnO,
其中所述催化剂能在350-550°C的温度和14.7-1,200psig的压力下从合成气中脱除超过20%的硫,同时从所述合成气中脱除焦油。
12.一种方法,其包括:
制备合成气;
通过使所述合成气与包含如下物质的催化剂接触而制备经处理的合成气;
(a)NiO;
(b)Al2O3;和
(c)ZnO;
将所述经处理的合成气引入催化化学反应中;
其中在与所述催化剂接触之前,不对所述合成气进行加热,且在进行所述催化化学反应之前,不对所述经处理的合成气进行冷却。
13.根据权利要求12的方法,其中所述合成气与所述催化剂接触的温度为350-550°C。
14.根据权利要求12的方法,其中NiO以1-10重量%的量存在。
15.根据权利要求12的方法,其中所述催化剂能在300-600°C的温度下从合成气中脱除超过5%的硫。
16.根据权利要求12的方法,其中所述催化剂能在350°C下以大于55%转化率的量从所述合成气中脱除焦油。
17.根据权利要求15的方法,其中脱硫压力为14.7-1,200psig。
18.根据权利要求15的方法,其中脱硫压力为250-1,000psig。
19.根据权利要求15的方法,其中所述催化剂在脱硫过程中同时从所述合成气中脱除焦油。
20.一种方法,其包括:
制备合成气;
通过将所述合成气与包含如下物质的催化剂接触而制备经处理的合成气;
(a)以1-10重量%的量存在的NiO;
(b)Al2O3;和
(c)ZnO,和
将所述经处理的合成气引入催化化学反应中;
其中所述催化剂能在350-550°C的温度和14.7-1,200psig的压力下从所述合成气中脱除超过20%的硫,同时从所述合成气中脱除焦油;和
其中在与所述催化剂接触之前,不对所述合成气进行加热,且在进行所述催化化学反应之前,不对所述经处理的合成气进行冷却。
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JP2013537848A (ja) | 2013-10-07 |
WO2012037113A1 (en) | 2012-03-22 |
AU2011302289A1 (en) | 2013-05-02 |
CA2810530C (en) | 2020-02-18 |
US20120065059A1 (en) | 2012-03-15 |
US8945424B2 (en) | 2015-02-03 |
KR20180059563A (ko) | 2018-06-04 |
CA2810530A1 (en) | 2012-03-22 |
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