CN101273113A - 加氢处理工艺中合成气的氢净化 - Google Patents
加氢处理工艺中合成气的氢净化 Download PDFInfo
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Abstract
作为加氢处理反应器进料一部分的含氢循环气体流与低纯度补充氢气和酸性闪蒸气体在循环气压缩机的上游混合,并被循环气压缩机压缩。被压缩气体流过甲烷和更高级(C1+)烃吸收器,以生成具有96-98mol%氢的脱硫氢循环气流,该循环气流被送到加氢处理反应器中。该方法可以用来优化现有方法的设备,以增加加氢处理器的进料流中的氢分压,其中在所述加氢处理器中存在的循环气压缩机并没有被设计用来压缩高纯度氢。
Description
技术领域
本发明涉及提高加氢处理单元中循环气的氢分压的方法,尤其涉及作为加氢处理单元补充氢气的低纯度氢气流的处理。
背景技术
加氢处理方法是精制操作中常用的附加工艺。这些方法提高了低价值重质残余燃料油(即真空瓦斯油或VGO)的价值,或者对含有污染物的精炼厂产物(例如煤油、柴油和汽油)进行处理。在加氢处理方法中,重质或被污染的烃类产品和氢一起通过氢化裂解操作进行共处理,以生成高价值产物(例如来自残余燃料油的汽油),或通过各种加氢处理方法(例如脱氮或脱硫)改良精炼厂产品例如柴油或汽油,以符合这些产品的高质量低污染规格。
氢分压是任何加氢处理单元的最重要工艺参数之一。该参数被定义为氢的纯度与加氢处理反应器操作压力的乘积。氢分压的提高使得催化剂性能提高,因此使得催化剂生命周期更长,从而提高了生产能力,改进了更大规模进料的处理能力和产品质量。
现有技术包括用来显著提高加氢处理方法中氢气分压的处理技术。这种技术的一种代表性应用公开在USP6740226中,其中来自高压分离器的闪蒸气通常含有大约78-83mol%的H2,该气体进入到吸收塔的底部,在那里进入的气体底部与贫溶剂逆流接触。贫溶剂从含氢气体中吸收含有的甲烷、H2S、乙烷、丙烷和戊烷。富溶剂中的吸收组分通过降压分离,并且不需加热的闪蒸再生的贫溶剂返回到甲烷吸收塔顶部。在该方法中,离开吸收塔的塔顶馏出气体的氢气纯度升高到96-98mol%。该净化的循环氢气流与补充H2一起混合以生成总纯度在96-99mol%H2之间的合成气流。氢气分压的提高显著提高了总产量和加氢处理单元的效率,并且可以被有效地用来提高加氢处理、氢化脱硫、氢化脱氮、和加氢脱烷基化反应工艺的性能。
USP6740226的工艺局限性涉及现有循环气压缩机在高氢纯度循环气时可能发生的潜在激变情况,其中高氢纯度将循环气的分子量降低到压缩机设定的值之外。在较低的分子量(2-3)时,对应于高纯度氢气流,现有的压缩机不能生成必需得到加氢处理反应要求的排出压力的压差。因此,压缩机被磨损并被停车。
在USP6740226中,由于提高了氢纯度,用来冷气反应器中的反应流的循环气质量与分子量(MVV)降低成比例降低,即MVV从>5降低到2-3,质量流量减少了五分之二或五分之三的比例。这种减少需要增加通过反应器的循环氢气流的总量,这样反而增加了反应器内的空间利用率并最终降低了生产能力。
另外,在没有首先将气流进行分离净化步骤以增加氢气的摩尔百分比的情况下,在精炼厂通常使用的低氢纯度气流不能用作合成氢气。
对于现有的加氢处理设备,如果循环气体压缩机没有被设计用来处理具有2-3分子量的高纯度气体,则在USP6740226中公开的方法没有提供解决处理这种低分子量的高纯度氢循环气流问题的方法。因为多数现有技术的加氢处理单元通常处理具有高于5的平均分子量的78-85mol%含氢气体,所以进料气流的分子量的降低使得现有压缩机不能产生足够的压头以传送加氢处理反应器需要的操作压力。为了克服该局限,压缩机必需增加负荷或被替代,以上任何一种处理将会引起更大的费用和大量的停工期。由于没有改变压缩装置,设备将不会完全受益于通过结合USP6740226的吸收系统可以得到氢纯度的增加。因此,这限制了将USP6740226的方法应用到新的加氢处理单元中或应用到那些具有内在机动性的装置中,以提供较低分子量高纯度氢循环气。
因此本发明的一个目的是提供一种可以在现有加氢设备中应用的方法和装置结构,其中所述现有加氢设备具有不能由低分子量进气流生成高压进料流的循环气压缩机。
本发明的另一目的是提供一种适合在现有技术的加氢处理系统中使用,而不需要替换或增加现有压缩机负荷的方法。
本发明另一目的是提供一种允许使用在精炼厂中应用的低纯度氢气流作为精炼厂加氢处理反应器的补充氢气的方法。
本发明的另一目的是提供将冷却气流质量流量的改变最小化的装置,用来控制加氢处理反应器内的催化剂床的入口温度。
发明内容
上述目的和其它优点通过将基于吸收的氢净化单元设置在循环气压缩机的下游得到。
因此在加氢处理方法中,现有的补充气流氢净化处理技术的局限和缺点通过本发明被克服,在本发明中通过循环气压缩机下游的共处理,将循环气与低纯度氢气结合的气流的氢纯度增加到96-98mol%,增加了氢气分压。
通过在吸收系统内处理气体之前,将具有MW>5的压缩循环气作为反应部分的冷却气体,,本发明的方法获得了要求的冷却气质量流量。
本发明的方法和装置尤其适用于具有循环气压缩机的现有系统中,其中循环气压缩机并没有设计用于通过本发明的使用能够得到的更高氢纯度。另外,该方法允许使用在精炼厂应用的较低纯度氢气流,所述较低纯度氢气流来自例如连续的催化剂再生(CCR)和固定床(FB)铂重整装置的单元,并且允许使用来自加氢处理单元的低压闪蒸气体来用作补充氢气。事实上,本发明的方法改进允许一些含氢废气可以被共处理,用于回收在补充氢气进料流中使用的氢气。因为进料到吸收系统的>5MW的气体进料可以在循环气压缩机中应用降压,所以本发明的方法通过将>5MW气体作为冷却气体,克服了现有方法的冷却气系统的质量流限制。
附图说明
通过结合附图的以下详细描述,本发明将容易理解,其中:
图1是现有技术中的氢化裂解方法的氢净化系统示意性流程图。
图2是本发明的氢化裂解方法的第一实施方案的示意性流程图。
图3是本发明的氢化裂解方法的第二实施方案的流程图。
为了帮助理解,合适时使用了相同的参考标记来指定附图中相同或类似的单元。
发明的详细描述
在描述本发明的方法之前,将首先描述现有方法的工艺结构用以比较目的,其中在本发明中,基于吸收的氢净化单元位于回收气压缩机的下游。
在氢化裂解中应用的USP5740226的现有方法的一个实施例示意性图示在图1中。在该典型的氢化裂解方法中,真空柴油(VGO)16与氢气流18一起作为合成气流14进入氢化裂解反应器10中,其中反应器10含有床12。一部分气流18用作冷却气流17,以控制催化剂床的温度。离开HP分离器的酸性闪蒸气24具有78mol%H2纯度,其与贫溶剂流76逆流接触以从含氢气体流中吸收除去甲烷和重质烃。分离的气体通过与温度较低、净化循环的氢气流76交叉交换冷却,随后进入制冷单元61中,在那里被冷却到大约-20°F。为了防止任何存在的水凝固,在这些交换的管程中注入乙二醇(EG),并且在冷却气体和冷凝液体进入甲烷吸收塔70之前,在三相凝集过滤器/分离器中分离EG-H2O流。在该系统中,大部分不含H2O的由甲烷、乙烷、丙烷、丁烷和戊烷组成的气体从含氢气流25中吸收脱除。
如图2和3中所示,本发明的方法采用吸收塔通过吸收从含氢气流中除去压缩循环气流中的甲烷和更高碳组分,从而将气体纯度提高到96-98mol%氢。优选的吸收溶剂由进料流18的重质组分组成,如USP6740226中所述,进料流18在溶剂闪蒸再生器80中分离。
在本发明方法的应用中,甲烷和重质组分在稍高的压力下吸收并从氢气中分离出。其中所述稍高压力与循环气压缩机的排出压力保持一致,而比循环气压缩机的吸入压力高。温度和闪蒸再生压力的所有其它操作参数如在USP6740226中所述,在此通过参考结合该文献的全文。
本方法还提供了额外的机动性,通过在循环气压缩机的下游在高压下共处理气体,使用来自CCR/FB铂重整装置的低纯度氢气流或来自加氢处理单元的闪蒸气体作为加氢处理单元的补充氢气。同样,一些含氢废气可以被共处理以回收氢气并添加到补充氢气流中。
如图3所示,当由氢源(例如蒸汽重整装置或气化装置)得到高纯度氢(95-99.99mol%)时,该气流旁路经过循环气压缩机以与被压缩的脱硫循环气结合,所述被压缩的脱硫循环气可能包括另外来自例如CCR/固定床铂重整装置的低纯度源的补充氢气、来自加氢处理单元的闪蒸气体、或其它在精炼厂应用的尾气。
因此,本发明克服了现有加氢处理单元通常的明显局限性,其中在现有加氢处理单元中,现有循环气压缩机并不是设计用来处理高纯度氢气流。
在新的设备中,循环气压缩机可以安装用来压缩高纯度低分子量(2-3)气体。可以在不进行明显改进的情况下就可以使用现有的设计用来处理非常高氢纯度(88-96mol%)的循环气压缩机,以在本发明的方法中应用。如上指出的,为了完全实现通过USP6740226的方法得到96-98mol%氢的净化能力的优点,现有的循环气体压缩机需要增加负荷或被替换;作为必须限制氢纯度的替代,其提高了压缩机的设计能力,通常为88-96mol%氢。在高于压缩机设计值的氢纯度下操作可能使得循环气体压缩机遭受激变情况。
本发明的方法和装置结构克服了现有循环气体压缩机的激变局限性,因为仅有很小的变化,如果有一些是在压缩之前的循环气体净化中,并且向氢化处理单元提供了最高可能的氢分压,从而明显提高了氢化处理催化剂的总效率和性能。
本发明克服的第二局限涉及不能回收精炼厂尾气或CCR/FB铂重整单元的额外氢气,用来补充使用而不用进一步净化。使用本发明的方法,这种含有50mol%H2的气流可以直接作为与循环气体流一起共处理的补充氢气流直接导入,而不会不利地影响加氢处理催化剂的性能。
通过在现有方法中使用具有>5MW的压缩循环气体代替2-3MW气体,克服了必需的冷却气体质量流量的第三局限性(参见气流17的设置和其相关的氢纯度)。
由于提高了现有加氢处理设备中的氢分压,本发明改进的方法显著扩展了商业应用能力。
尽管已经详细图示和描述了本发明的各种实施方案,但是对于那些本领域技术人员来说其它实施方案将会是明显的,并且本发明的范围将根据以下的权利要求确定。
Claims (34)
1、在加氢处理反应器中氢化进料流的方法中,进料流包括重质烃液态组分和氢气进料组分,该氢气进料组分包括循环氢气流和补充氢气流,反应器生成排出液体流和分离的排出气体流,排出气体流包括未反应的氢和甲烷和重质烃,排出气体流在循环气体压缩机中压缩以生成压缩的循环气体流,改进包括:
a、将压缩的循环气体流冷却到+30°F(-1.1℃)至-40°F(-40℃)之间的温度;
b、将冷却的压缩循环气体流与含有C4-C5烃组分的贫液体溶剂流在吸收区内接触,以从所述压缩的循环气体流中吸收甲烷和重质烃,从而生成含有90-99mol%氢的富氢气体流和富液体溶剂流;
c、从吸收区回收富氢气体流;
d、将富氢气体流作为循环气体流加入到加氢处理反应器进料流中,和
e、在至少一个闪蒸阶段中闪蒸所述富液体溶剂流,以产生含有在压缩循环气体流中存在的C4到C5烃组分的贫液体溶剂,用来在步骤(b)中与冷却压缩循环气体流接触,并且生成甲烷和重质烃气体产物流。
2、如权利要求1的方法,其中加氢处理反应器选自加氢脱硫、氢化裂解、氢化脱氮、加氢脱烷基化、加氢处理反应器。
3、如权利要求2的方法,其中反应器是在500psig(35.1kg/cm2g)-5000psig(351.5kg/cm2g)之间压力操作的氢化裂解反应器。
4、如权利要求3的方法,其中氢化裂解反应器在1000psig(70.3kg/cm2g)-3000psig(210.9kg/cm2g)的压力下操作。
5、如权利要求2的方法,其中反应器选自加氢脱烷基化和加氢处理反应器,并且该反应器在200psig(14.1kg/cm2g)-3000psig(210.9kg/cm2g)的压力下操作。
6、如权利要求2的方法,其中来自反应器的流出液体产物和气体流流过高压分离器,所述高压分离器在200psig(14.1kg/cm2g)-5000psig(351.5kg/cm2g)的压力下操作。
7、如权利要求2的方法,其中压缩循环气体流和贫液体溶剂流在压力为200psig(14.1kg/cm2g)-5000psig(351.5kg/cm2g)的吸收区接触。
8、如权利要求7的方法,其中压缩循环气体流和贫液体溶剂流在压力为200psig(14.1kg/cm2g)-3000psig(210.9kg/cm2g)的吸收区接触。
9、如权利要求1的方法,其中反应器进料流的氢气进料组分含有90-99mol%氢。
10、如权利要求1的方法,其中氢气进料组分含有压缩循环气体流和高纯度补充气体流。
11、如权利要求10的方法,其中高纯度补充气体流含有95-99.99mol%氢。
12、如权利要求1的方法,其中排出气体流与低钝度补充气体流混合并在循环气压缩机中压缩形成压缩循环气体流。
13、如权利要求1的方法,其中压缩循环气体流包含压缩排出气体流和压缩的低纯度补充气体流。
14、如权利要求1的方法,其中部分从循环气压缩机中排出的气体流直接作为冷却气体流进料到反应器中,以将反应器中的催化剂温度维持在预定的范围内。
15、如权利要求12的方法,其中低纯度补充气体流含有50-99.99mol%氢。
16、如权利要求12的方法,其中低纯度补充气体流含有50-99.99mol%氢。
17、如权利要求15的方法,其中低纯度补充气体流含有50-90mol%氢。
18、如权利要求2的方法,其中重质烃液体组分进料含有硫,步骤(c)中得到的甲烷和高碳烃气体产物流含有硫化氢,该方法包括步骤(e)后的其它步骤:
f、将甲烷和高碳烃气体产物与贫胺浴液在处理区接触,以除去硫化氢,从而提供脱硫的甲烷和高碳烃产物;
g、从处理区回收富含硫化氢的胺溶液;和
h、富含硫化氢的胺溶液流过再生塔以生成用于在步骤(f)中接触的贫胺溶液。
19、如权利要求1的方法,其中压缩循环气体流被冷却到0°F(-17.9℃)至-20°F(-28.9℃)之间。
20、如权利要求19的方法,其中压缩循环气体流被冷却到-10°F(-23.3℃)至-15°F(-26.1℃)之间。
21、如权利要求1的方法,其中压缩循环气体流含有水并且压缩循环气体流与乙二醇一起共冷却,乙二醇/水混合物在进入吸收器之前从冷却的烃气体和烃液体流中分离出。
22、如权利要求1的方法,其中重质烃组分选自石脑油、煤油、柴油、轻质真空瓦斯油、重质真空瓦斯油、脱金属油、焦化汽油、残油、燃料油和芳烃。
23、如权利要求1的方法,其中从吸收区回收的富氢气体流进一步与压缩循环气体流进行交叉热交换。
24、如权利要求1的方法,其中冷却压缩循环气体流在步骤(b)中与贫液体溶剂逆流接触。
25、如权利要求1的方法,其中贫液体溶剂在温度为+30°F(-1.1℃)至-40°F(-40℃)之间流进入吸收区内。
26、如权利要求25的方法,其中贫液体溶剂在为0°F(-17.8℃)至-20°F(-28.9℃)之间流进入吸收区内。
27、如权利要求26的方法,其中贫液体溶剂在温度为-10°F(-23.3℃)至-15°F(-26.1℃)之间流进入吸收区内。
28、如权利要求1的方法,其中富液体深剂流流过至少两个连续的闪蒸分离器。
29、如权利要求28的方法,其中来自所述至少两个连续闪蒸分离器的第一分离器的被分离气体被压缩并返回到步骤(b)的吸收区内。
30、如权利要求28的方法,其中所述至少两个连续闪蒸分离器为至少两相气液分离塔。
31、如权利要求28的方法,其中所述至少两个连续闪蒸分离器在比吸收区允许压力低的的连续压力下运行。
32、如权利要求6的方法,其中来自高压分离器的分离液体产物被降压以生成低压液体和气体流。
33、如权利要求32的方法,其中所述低压液体和气体流在低压分离器中分离,产生低压富氢气体流。
34、如权利要求33的方法,其中压缩所述低压富氢气体流并与步骤(a)的压缩循环气体共处理。
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CN105517980A (zh) * | 2013-08-19 | 2016-04-20 | 环球油品公司 | 增强的氢气回收 |
CN105517980B (zh) * | 2013-08-19 | 2019-06-07 | 环球油品公司 | 增强的氢气回收 |
CN110845293A (zh) * | 2019-11-13 | 2020-02-28 | 宁波同润和海科技有限公司 | 一种采用深冷吸收原理分离混合气体中甲烷组分的方法 |
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EP1917328A2 (en) | 2008-05-07 |
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