CN116730801A - 生产甲醇的方法和设备 - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 238000000034 method Methods 0.000 title claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 51
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000000446 fuel Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 76
- 239000000203 mixture Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 101150026303 HEX1 gene Proteins 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000005514 two-phase flow Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Abstract
本发明涉及一种通过平衡反应从合成气生产甲醇的方法,该平衡反应是在甲醇预转化器中在特定操作窗口内进行的,所述操作窗口由一氧化碳分压相对于水温为210至270℃的沸水温度的近似线性曲线下方的区域所限定。通过在操作窗口的特定区域中操作,可以获得不同产品等级的甲醇。
Description
本申请是申请日为2019年6月11日,申请号为:2019800385096,名称为“生产甲醇的方法和设置”的发明专利申请的分案申请。
技术领域
本发明涉及用于生产甲醇的方法和设备。本发明尤其关注于甲醇反应器的操作。更具体地,主要关注于甲醇反应器中的操作窗口。
发明背景
通过催化转化含有氢和碳氧化物的合成气来生产甲醇的方法是本领域技术人员长久以来所熟知的。因此,甲醇主要是在高压和高温下由一氧化碳、二氧化碳和氢的混合物,即甲醇合成气催化生产的,最常用的是铜-氧化锌-氧化铝(Cu/ZnO/Al2O3)催化剂。
甲醇通过以下平衡反应从合成气(合成气)生产,该反应在升高的温度和升高的压力下进行。合成反应为:
CO + 2H2<->CH3OH + 热量 (1)
CO2 + 3H2<-> CH3OH + H2O + 热量 (2)
CO + H2O <-> CO2 + H2 + 热量 (3)
由于反应(1)至(3)是放热的,因此化学平衡常数随温度升高而降低。因此,低的反应器温度应改善转化率,前提是反应温度不低至特定反应速率过低。对于给定的反应器尺寸和特定的所需转化率,随着反应器温度降低,再循环流量增加,这意味着更高的压缩机工作量。
发明内容
事实证明,在由描述CO的分压和反应器温度之间的关系的曲线所限定的操作窗口中进行甲醇合成反应是有利的。更具体地,在CO分压和温度的某些组合内操作将导致催化剂的快速失活。这适用于甲醇反应器周围的任何布局,例如带有或不带有预转化器的甲醇回路,而不论布局是新颖设计还是改造设计。
根据CO分压和沸水温度的特定组合,可以在操作窗口内获得不同的甲醇等级,例如AA级甲醇或燃料级甲醇。
典型的使用天然气进料运行的甲醇设备分为三个主要部分。在设备的第一部分中,天然气被转化为合成气。合成气在第二部分反应生成甲醇,然后在设备的尾端将甲醇纯化至所需纯度。在标准的合成回路中,使用甲醇反应器,最常见的是沸水反应器(BWR),将来自重整器/气化器单元的合成气和再循环气(即未转化的合成气)的混合物转化为甲醇。
已经发现,可以建立CO分压和反应器温度(实际上是沸水温度)的特定组合的区域,在该区域内,在获得有利结果的意义上而言操作被认为是“安全的”。更具体地,对于210℃至270℃之间的沸水温度,可以绘制出近似线性的曲线。在此特定温度范围内,与给定温度相对应的CO分压从210℃下的20kg/cm2到270℃下的32.5kg/cm2呈近似线性增加。该曲线下方的区域定义了操作的“安全”区域。
因此,本发明涉及一种通过平衡反应从合成气生产甲醇的方法,该平衡反应根据上述合成反应(1)至(3)在升高的温度和升高的压力下进行,所述方法在甲醇预转化器中在操作窗口内进行,所述操作窗口为
-由一氧化碳分压相对于水温为210至270℃的沸水温度的近似线性曲线下方的区域所限定,其中一氧化碳的分压从210℃下的20kg/cm2增加到270℃下的32.5kg/cm2,并且
-由一氧化碳分压相对于沸水温度的估计的副产物曲线划分为两个区域,这些区域导致生产出不同产品质量的甲醇。
该方法优选在估计的副产物曲线的左侧和下方的操作窗口内的区域中进行,该区域指示获得AA级甲醇或类似质量的甲醇的上限。估计的副产物曲线在图1中示出,其确定了在根据本发明的方法中使用的操作窗口。
在本领域中众所周知,衍生自天然气或重质烃和煤的合成气对于直接甲醇合成具有高的反应性,并且对催化剂有害。此外,使用这种高反应性的合成气导致形成大量的副产物。
碳氧化物和氢转化为甲醇的反应受到平衡的限制,即使使用高反应性的合成气,合成气每次通过甲醇催化剂到甲醇的转化率也相对较低。
由于在直流转化过程中甲醇的产率低,因此本领域的常规做法是使从反应流出物中分离出的未转化的合成气再循环,并用该再循环气稀释新鲜的合成气。
这通常导致具有一个或多个串联连接的反应器的所谓的甲醇合成回路以新鲜的合成气操作,该新鲜的合成气用从反应器流出物中分离的再循环的未转化气体稀释;或者以含有甲醇和未转化的合成气的反应器流出物操作。在常规实践中,再循环比(循环气与新鲜合成进料气)为2:1至7:1。
当现有甲醇设备中的甲醇反应器成为产能改造项目的瓶颈时,标准解决方案是串联或并联安装一个额外的反应器,或对现有反应器进行改造。通常,这都是在回路内完成的。然而,事实证明,在补充气体压缩机和甲醇回路之间安装一个直流预转化器是一个优势。此概念保持现有回路不变。
因此,根据本发明的优选实施方案,在补充气体压缩机和甲醇回路之间安装了直流预转化器,所述预转化器在本发明的操作窗口内操作,该操作窗口由描述CO分压与反应器温度之间的关系的曲线限定。
关于现有技术,申请人的WO 2015/193440 A1描述了一种在串联连接的反应器中生产甲醇的方法,其中一个方面是将流程应用为改造的一部分,从而提供了一种提高现有甲醇设备产能的方法。
在申请人的WO 2014/012601 A1中,描述了一种用于制备甲醇的反应系统,其包括两个反应单元,其中第一单元以新鲜合成气和未转化的合成气的混合物操作,而第二单元仅以未转化的合成气操作。
US 5.631.302A描述了在200至350℃的温度下在20至120巴的压力下由合成气在含铜催化剂上生产甲醇。合成气绝热地通过第一合成反应器,该反应器包含含铜催化剂固定床,而没有任何合成气的再循环。未在第一合成反应器中反应的气体混合物与再循环气体一起通过第二合成反应器,该第二合成反应器包含置于管中并通过沸水间接冷却的含铜催化剂。
在也属于本申请人的WO 2014/095978 A2中,描述了一种生产高级(C4+)醇的方法,其中醇合成气任选地首先在多相醇预转化器中反应,从而生产甲醇,然后将来自预转化器的流出物(或,没有预转化步骤的情况下,合成气)在反应器中进行反应,以合成高级醇。
在WO 2017/121981 A1中,描述了一种甲醇合成方法,其包括以下步骤:(i)使包含补充气体的第一合成气混合物通过第一合成反应器以形成第一产物气流,(ii)从第一产物气流中回收甲醇,从而形成第一甲醇贫化的气体混合物,(iii)将第一甲醇贫化的气体混合物与回路再循环流合并,以形成第二合成气混合物,(iv)使第二合成气体混合物通过第二合成反应器,以形成第二产物气流,(v)从第二产物气流中回收甲醇,从而形成第二甲醇贫化的气体混合物,以及(vi)使用第二甲醇贫化的气体混合物的至少一部分作为回路再循环气流。在该方法中,第一合成反应器每立方米催化剂的热传递比第二合成反应器高,并且没有将回路再循环气流供入第一合成气混合物中,并且回路再循环气流形成第二合成气混合物的再循环比的范围为1.1∶1至6∶1。据指出,通过对不同类型的反应器使用不同的再循环比,可以提高多级甲醇合成的效率。
根据本发明使用的预转化器的最佳选择是沸水反应器,因为它具有反应性非常高的合成气。为了限制副产物的形成,通常将需要预转化器中的沸水温度比现有反应器中更低,这反过来又需要单独的蒸汽鼓。
根据本发明的预转化器概念提供了处理来自上游单元的额外补充气体所需的额外催化剂。预转化器本身使用新鲜的补充气体运行。它优选是沸水反应器(BWR)类型的,并且将需要附加的冷却系统,并且可能还需要单独的冷却和将冷凝的甲醇与预转化器分离。新鲜的补充气体对副产物的形成反应性非常高。因此,与现有的反应器相比,可以预见更低的催化剂温度,因此需要额外的冷却系统。
附图简要说明
参考附图更详细地描述本发明,其中,
图1示出了在根据本发明的方法中使用的操作窗口,
图2示出了根据本发明的预转化器概念的实施方案,以及
图3示出了根据本发明的预转化器概念的替代实施方案。
发明详述
在图1中,根据本发明的方法中使用的操作窗口由一氧化碳的分压相对于水的沸水温度的近似线性的虚线曲线(失活曲线)以下的区域限定,其中水温为210至270℃,其中一氧化碳的分压从210℃下的20kg/cm2增加到270℃下的32.5kg/cm2。
如已经提到的,取决于CO的分压和沸水温度的组合,可以在操作窗口内获得不同的甲醇等级。在图1中,实线(副产物曲线)表示获得AA级甲醇或类似高质量的甲醇的上限。在该曲线上方运行将使甲醇产物变为含更多副产物的甲醇产物,但是该产物的纯度仍然足以用作燃料级或甲醇制烯烃(MTO)级甲醇。
此外,虚线表示的失活曲线描述了催化剂失活的极限。在该曲线上方操作将导致催化剂快速失活。在图2中,压缩的补充合成气1(未示出压缩机)在进入预转化器(A)之前在进料/流出物热交换器(hex1)中被加热。经过预转化器后,气体2在进料/流出物热交换器(hex1)中被冷却,并被送入冷凝器c1,任选地以物流9送入另一个冷凝器c2。在第一分离器(s1)中分离两相流之前,将尽可能多的甲醇在冷凝器c1中冷凝。然后将来自分离器(s1)的气体3与来自第二分离器(s2)的气体4混合,或者任选地将其作为物流5直接送至再循环器(R)的下游。
混合之后,气体在所述再循环器(R)中被压缩。在进入反应器(B)之前,所得在流入反应器(B)的进料气6在进料/流出物热交换器(hex2)中被预热。
流出的气体7在进料/流出物热交换器(hex2)中冷却,然后在冷凝器c2中进行尽可能多的冷却,以使尽可能多的甲醇冷凝。然后在第二分离器(s2)中分离两相流。
来自分离器(s2)的少量气体8被送入吹扫以避免惰性成分的累积。来自分离器(s2)的其余气流与来自分离器(s1)的气体混合。最后,将来自两个分离器(s1)和(s2)的液体混合,然后将混合物送入低压分离器,然后再送出甲醇段。
图3示出了与图2所示的实施方案不同的另一实施方案。在此,补充合成气(1')被压缩(压缩机未示出),并且压缩后的气体与来自再循环器R'的部分再循环气体混合,在进料/流出物热交换器(hex1')中被加热,然后进入预转化器(A')。通过预转化器后,气体2'在进料/流出物热交换器(hex1')中冷却。然后将来自预转化器(A')的冷却气体与来自反应器(B')的冷却气体混合。混合后,两相流在冷凝器c1'中进一步冷却,以冷凝出尽可能多的甲醇。
当气体尽可能地冷却后,两相流在分离器(s1')中分离。从分离器出来的一些流出气体被送往吹扫,以避免惰性成分的累积。其余的气体被送至再循环器R',并用作反应器(B')的进料气。在进入反应器之前,流向反应器(B’)的进料气在进料/流出物热交换器(hex2’)中被加热。在反应器(B')之后,气体在进料/流出物热交换器(hex2')中冷却,并与来自预转化器(A')的冷却气体混合。
任选地,将来自预转化器(A’)的冷却后的气体送入另一个冷凝器c2’,以尽可能多地冷凝甲醇。气体冷却后,两相流在另一个分离器(s2')中分离,气相从那里被输送到再循环器R'的入口,同时液相与来自分离器s1'的液相混合。
新鲜的补充气体对副产物的形成反应性非常高。因此,可以预见比现有反应器更低的催化剂温度;以及因此可以预见额外的冷却系统。
Claims (5)
1.一种用于通过平衡反应从合成气生产甲醇的方法,该平衡反应在催化剂的存在下根据以下合成反应在升高的温度和升高的压力下进行,
CO + 2H2<-> CH3OH + 热量 (1)
CO2 + 3H2<-> CH3OH + H2O + 热量 (2)
CO + H2O <-> CO2 + H2 + 热量 (3)
所述方法在操作窗口内在甲醇预转化器中进行,所述操作窗口为-由一氧化碳分压相对于水温为210至270℃的沸水温度的近似线性曲线下方的区域限定,其中一氧化碳的分压从210℃下的20kg/cm2增加至270℃下的32.5kg/cm2,和
-由一氧化碳分压相对于沸水温度的估计的副产物曲线划分的两个区域,所述区域导致生产出不同产品质量的甲醇。
2.根据权利要求1所述的方法,所述方法在所述操作窗口内在副产物曲线的左侧和下方区域中进行,所述区域指示获得AA级甲醇或类似质量的甲醇的上限。
3.根据权利要求1所述的方法,所述方法在所述操作窗口内在副产物曲线的右侧和上方区域中进行,其中甲醇产物是含有更多副产物的甲醇产物,但是其纯度仍然足以满足燃料级甲醇或甲醇制烯烃(MTO)级甲醇的要求。
4.根据权利要求1所述的方法,其中所述催化剂是基于Cu/ZnO的催化剂。
5.一种设备,其用于通过权利要求1或2所述的方法生产甲醇,所述设备包括补充气体压缩机和在甲醇回路中的合成反应器,其中在补充气体压缩机和甲醇回路之间安装有直流预转化器,所述预转化器在由一氧化碳分压相对于水温为210至270℃的沸水温度的近似线性虚线曲线下方的区域所限定的操作窗口内运行,其中一氧化碳的分压从210℃下的20kg/cm2增加到270℃下的32.5kg/cm2。
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