CN105209373B - 联产氨、尿素和甲醇的方法 - Google Patents

联产氨、尿素和甲醇的方法 Download PDF

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CN105209373B
CN105209373B CN201480027679.1A CN201480027679A CN105209373B CN 105209373 B CN105209373 B CN 105209373B CN 201480027679 A CN201480027679 A CN 201480027679A CN 105209373 B CN105209373 B CN 105209373B
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P·J·达尔
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Abstract

本发明提供一种由天然气联产氨、尿素和甲醇的方法，该方法包括以下步骤：(a)通过将天然气同时进料到自热重整器(ATR)和蒸汽甲烷重整器(SMR)中来制造合成气，所述两个重整器平行运行；(b)将空气进料到空气分离单元(ASU)中，在该单元中空气被分离为进料到所述ATR中的氧气，和氮气；(c)对来自SMR的合成气施以水煤气变换；(d)从来自步骤(c)的合成气中除去二氧化碳，并将其引导至尿素合成单元中的尿素合成；(e)将来自步骤(d)的富氢气体与来自步骤(b)的氮气结合，从该气体混合物中除去催化剂毒物，并将该气体混合物引导至氨合成单元中的氨合成；(f)任选从来自步骤(a)的ATR的合成气中除去一部分二氧化碳，并将其引导至尿素合成单元中的尿素合成；和(g)将来自步骤(f)的合成气引导至甲醇合成单元，其中来自步骤(a)的合成气可以由ATR出口引导至在该变换阶段上游的SMR出口或该通道也可能反转。

Description

联产氨、尿素和甲醇的方法
发明领域
本发明涉及同时生产(联产)氨、尿素和甲醇的方法，所述方法由合成气的生产开始。更具体地，构成本发明的主题思想的基础包括使用ATR(自热重整器)和SMR(蒸汽甲烷重整器)前端的组合以制造用于氨、尿素和甲醇产物的一系列组合的所需合成气。
发明背景
自热重整是通常用于生产合成气的技术，其中烃原料(在这种情况下为天然气)的转化在单一反应器中通过部分燃烧和绝热蒸汽重整的组合来进行。烃进料的燃烧用低于化学计量量的空气、富氧空气或氧气通过火焰反应在燃烧器燃烧区域中进行。部分燃烧的氢原料的蒸汽重整随后在蒸汽重整催化剂的固定床中进行。
在蒸汽重整过程中，通过以下反应由烃原料制造合成气：
CnHm+H2O→nCO+(n+m/2)H2 (1)
CO+H2O→CO2+H2 (2)
CH4+H2O→CO+3H2 (3)
该反应在外部加热的反应器——蒸汽甲烷重整器(SMR)，其为初级重整器——中进行。进入该初级重整器的进料可以是与水蒸气或来自之前的预重整步骤的部分转化气体产物混合的脱硫烃进料。该初级重整器通常是由放置在通过一个或多个燃烧器加热的炉中的填充有催化剂的管组成的直燃式管式重整器。其在其中来自填充有催化剂的管的出口温度相对较高(通常为650至950℃)的条件下运行。
在自热重整中，上述蒸汽重整反应(1)-(3)补充以部分燃烧，其可以由以下反应表示：
CH4+1/2O2→CO+2H2 (4)
申请人的公开申请WO 2013/013895 A1描述了用于由烃原料生产合成气体(合成气)的灵活方法。所述方法特别适于大型甲醇、氨和液态烃工厂。该合成气体在两个单线蒸汽重整步骤中制造。该公开申请的方法可用于合成氨、甲醇、二甲醚(DME)、液体烃及其组合。
用于联产氨和尿素以及甲醇和氨的各种方法是已知的。由此，经由氨基甲酸盐合成来组合生产氨和尿素的方法由US 2001/0002245 A1已知，并且生产氨的工厂与生产尿素的工厂的同时现代化的方法(同样经由氨基甲酸盐合成)由EP 1 041 038 B1已知。用于联产氨和尿素的气化法由US 6,448,441 B1已知，其中使用两个平行的气化器以优化合并的合成气产品中H2/CO2的比，由此尽量提高氨和尿素的生产。
US 2008/0207948 A1公开了由天然气制造尿素的方法，其中天然气在第一步骤中用含有氧的气体经历部分氧化或自热重整，并且所得粗合成气(基本由CO、CO2、CH4和H2组成)可以通过CO和H2O的催化转化来转化以形成CO2和H2，由此CO和CH4在多步骤烟气净化工艺中去除，在添加氮气时将氢转化为氨。该氨随后与之前分离的CO2在第二步骤中重新合并，由此将氨完全转化为尿素。
制造氨和尿素的方法描述在WO 2012/126673 A1中，其中在氨段制得的液氨在氨合成压力下直接进料至尿素段，并且其中液氨在高压下通过以下方法纯化：冷却，在高压下从冷却的液氨中分离包含氢气和氮气的气态馏分，和在分离气态馏分后重新加热该液氨，由此获得具有一定温度的重新加热的纯化氨，其适于进料至尿素合成工序。
US 2012/0148472 A1描述了联产甲醇和氨的方法，其中基本由一氧化碳、二氧化碳和氢气组成的合成气混合物首先在甲醇直流式反应器中部分反应，未反应的合成气分为第一和第二料流，第一料流被提纯并进料至氨合成段，第二料流进料至甲醇合成与纯化段。该方法能够在集成的单一工序中从天然气和空气开始制造甲醇和氨，以及平衡生产氨和二氧化碳以进一步允许集成尿素的联产。
最后，US 2007/0299144描述了在多段工艺中由天然气联产甲醇和氨的方法，由此天然气、水蒸气和氧气在第一反应器中混合，其中天然气被部分氧化并附加地催化重整。来自第一反应器的气体混合物分为用于甲醇合成的料流和用于制氢的另一料流。存在于用于制氢的料流中的CO在具有中间冷却的另一反应器中催化转化为CO2，并洗脱剩余杂质如甲烷、痕量的CO和氩气。该CO2被分化用于尿素合成。该甲醇合成气催化转化为甲醇，通过蒸馏使其达到所需纯度，并将氨合成气压缩并催化转化为氨，通过部分冷凝将其从回收的合成气中分离。
发明概述
属于本申请人的上述公开申请WO 2013/013895 A1描述了用于制备合成气的组合平行SMR与ATR重整方案，所述合成气可以按需进一步转化和/或提纯用于制造氢气、一氧化碳、氢气与一氧化碳的混合物，以及用于制造甲醇、氨、二甲醚(DME)和液体烃类。本发明进一步开发了该公开申请中描述的工艺方案。本发明涉及集成来自空气分离单元(ASU)的氮气和CO2优化以便联产氨、尿素和甲醇。
更具体而言，本发明涉及由天然气联产氨、尿素和甲醇的方法，包括以下步骤：
(a)通过将天然气同时进料到自热重整器(ATR)和蒸汽甲烷重整器(SMR)中来制造合成气，所述两个重整器平行运行；
(b)将空气进料到空气分离单元(ASU)中，在该单元中空气被分离为进料到所述ATR中的氧气，和氮气；
(c)对来自所述SMR的合成气施以水煤气变换(water gas shift)；
(d)从来自步骤(c)的合成气中除去二氧化碳，并将其引导至尿素合成单元中的尿素合成；
(e)将来自步骤(d)的富氢气体与来自步骤(b)的氮气结合，从该气体混合物中除去催化剂毒物和一部分惰性物质，并将所述气体混合物引导至氨合成单元中的氨合成；
(f)从来自步骤(a)的所述ATR的合成气中除去一部分二氧化碳，并将其引导至尿素合成单元中的尿素合成；和
(g)将来自步骤(f)的合成气引导至甲醇合成单元，
其中来自步骤(a)的合成气可以由ATR出口引导至在该变换阶段上游的SMR出口或该通道也可能反转。
结合使用平行运行的SMR与ATR能够在同一工厂中以CO2的最佳利用来制造氨(其可以进一步转化为尿素)和甲醇。由于氨、尿素和甲醇均为期望的产品，空气分离单元(ASU)被充分利用，因为氧气去往工厂的甲醇部分，而氮气去往工厂的氨部分。使用ATR与SMR的这种组合能够制造所需合成气用于产品氨、尿素和甲醇的一系列不同组合。通过使用ATR，可以降低整体成本，并且与仅具有SMR前端相比，进一步有可能建造具有更大生产能力的联产单元。
当使用SMR前端由天然气制造尿素时，这通常会导致需要过度重整的CO2不足。在本发明的方法中，来自SMR的贫CO2气体与来自ATR的富CO2气体混合，这提供了优化CO2平衡的手段。
如附图中所示进行本发明的方法。天然气(NG)进料至两个重整器的每一个中，即自热重整器(ATR)和蒸汽甲烷重整器(SMR)。同时，空气进料至空气分离单元(ASU)，在该单元中，空气被分离为经由管线1导入ATR的O2，和经由管线3被导向NH3合成以作为氮气源的N2。在去除CO2后残留的氢气在其与来自ASU的氮气混合前穿过甲烷化器，或穿过氮气洗涤。在两种情况下，将所得N2和H2的混合物经由管线4送至NH3合成。
在ATR中制得的合成气的一部分经由管线5进料至CO2去除单元，并由此进料至甲醇合成。所述合成气的剩余部分可以如该图中所示经由管线2送至该变换阶段的入口，但是该通道也可能反转，即从SMR至甲醇合成。
从来自步骤(c)的合成气中除去二氧化碳可以通过任何常规手段在本领域中已知的物理或化学洗气器中进行。优选通过本身已知的能够容易地回收用于尿素合成的所吸收的二氧化碳的任何方法来去除二氧化碳。
从上述合成气中分离的二氧化碳与变换阶段后去除的二氧化碳混合，所得气体经由管线6送入尿素合成。
进行来自步骤(d)的富氢气体与来自步骤(b)的氮气的混合作为H2/N2净化，其中一氧化碳在至少一个甲烷化反应器、优选为含有甲烷化催化剂的固定床的绝热反应器中转化为甲烷。
含有恰当比例的氢气与氮气(H2:N2摩尔比为3:1)的来自甲烷化阶段的氨合成气任选穿过压缩机(未显示)以获得所需氨合成压力，如120至200巴，优选大约130巴。随后以常规方式通过包含至少一个含有至少一个氨催化剂固定床的氨转化塔的氨合成回路(具有床间冷却)来制造氨。氨可以通过冷凝和随后的分离从含氨流出物中以液氨形式回收。优选地，从氨合成阶段抽取含有氢气、氮气和甲烷的废气流，因为也是富氢料流(>90体积％的H2)。这些料流可以例如来自吹扫气体回收单元。
所需蒸汽/碳比(S/C比)——定义为在蒸汽重整步骤中添加到该过程中的水蒸气总量和烃进料中所含碳之间的摩尔比——取决于特定的蒸汽重整技术。用于合成气制备的典型S/C值分别对ATR为>0.4和对SMR为>1.4。通过在本发明的组合工厂中使用ATR，有可能以总体较低的S/C比运行，这是优点，因为能够在建设方面节约10至15％。如上所述使用来自ASU的N2作为用于NH3合成的N2源将在气体制备和冷却段的建设方面提供进一步的节约，因为N2并不通过这些单元。
在本发明的方法中，来自ATR的合成气具有0.4至1.8的S/C比，其优选为大约0.6。来自SMR的合成气具有1.4至3.3的S/C比，优选大约2.5。
本发明允许优化CO2管理以便制造甲醇和尿素的全系列产品组合。
-如果需要更多甲醇，将SMR合成气引导至甲醇合成。
-如果需要更多尿素，将ATR合成气引导至ATR下游的变换反应，并任选从送往甲醇合成并用于制造尿素的合成气进料中去除CO2。
本发明还可用于制造液氨(与甲醇和尿素联产)。在这种情况下，本发明将有助于减少或在某些情况下甚至避免过量的工艺CO2。
通过参考附图在以下实施例中更详细地描述本发明，其描述本发明的概念。
实施例
用于ATR重整段和SMR重整段的条件列举在表1中。纯甲烷在该实施例中用作进料，但是其可以是任何典型的烃进料。对于含有更高烃类和/或CO2的天然气的结果将导致与该实施例中相比相对更大的SMR段(与ATR段相比)。
下表1列出了合成气的干燥气体组成，氧气消耗和可用的氮气。
该干燥气体组成显示了在氢与碳组成方面的差异，这使得能够优化CO2管理，以使得在没有过量CO2的情况下进行整个过程。
表1
重整步骤 ATR SMR
流量,Nm3/h 160000 21000
蒸汽/碳,S/C 0.6 2.5
CH4,摩尔％ 100 100
合成气,Nm3/h 470000 80850
H2,摩尔％ 66 74
CO,摩尔％ 27.5 16.5
CO2,摩尔％ 5 6
CH4,摩尔％ 1.5 3.5
氧气,Nm3/h 78000
氮气,Nm3/h 300000
显然，即使所有合成气用于制造尿素，也将会存在过量的氮气。
在下表2中，计算了各种产品方案的结果。所有情况的共同特征是所有工艺CO2用于制造尿素和/或甲醇。
该表显示，该概念允许在没有过量的来自该工艺的CO2的情况下在尿素与甲醇之间的任何产品拆分。
表2
*)MTPD＝公吨/天

Claims (7)

1.由天然气联产氨、尿素和甲醇的方法，包括以下步骤：
(a)通过将天然气同时进料到自热重整器(ATR)和蒸汽甲烷重整器(SMR)中来制造合成气，所述两个重整器平行运行；
(b)将空气进料到空气分离单元(ASU)中，在该单元中空气被分离为进料到所述ATR中的氧气，和氮气；
(c)对来自所述SMR的合成气施以水煤气变换；
(d)从来自步骤(c)的合成气中除去二氧化碳并将其引导至尿素合成装置中的尿素合成；
(e)将来自步骤(d)的富氢气体与来自步骤(b)的氮气结合，从该气体混合物中除去催化剂毒物和一部分惰性物质，并将所述气体混合物引导至氨合成单元中的氨合成；
(f)从来自步骤(a)中的所述ATR的合成气中除去一部分二氧化碳，并将其引导至尿素合成单元中的尿素合成；和
(g)将来自步骤(f)的合成气引导至甲醇合成单元，
其中来自步骤(a)的合成气由ATR出口引导至在该水煤气变换阶段上游的SMR出口；或来自所述SMR的合成气从SMR至甲醇合成。
2.如权利要求1所述的方法，其中来自所述ATR的合成气具有0.4至1.8的蒸汽/碳比(S/C比)。
3.如权利要求1所述的方法，其中来自所述SMR的合成气具有1.4至3.3的S/C比。
4.如权利要求1所述的方法，其中将来自所述SMR的合成气送至甲醇合成单元以提高甲醇生产率。
5.如权利要求1所述的方法，其中将来自所述ATR的合成气送至在ATR下游的变换反应，并任选从送往甲醇合成的所述合成气进料中去除CO2以提高尿素生产率。
6.如权利要求1所述的方法，其中在需要更高比例的甲醇的情况中，将SMR合成气引导至甲醇合成。
7.如权利要求1所述的方法，其中在需要更高比例的尿素的情况中，将ATR合成气引导至ATR下游的变换反应，并任选从送往甲醇合成并用于尿素合成的所述合成气进料中去除CO2。
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