CN108884008A - 用于大生产容量的甲醇合成工艺布局 - Google Patents
用于大生产容量的甲醇合成工艺布局 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title description 18
- 230000002194 synthesizing effect Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 239000013589 supplement Substances 0.000 claims abstract description 6
- 238000005201 scrubbing Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 86
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940112112 capex Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- FEBLZLNTKCEFIT-VSXGLTOVSA-N fluocinolone acetonide Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O FEBLZLNTKCEFIT-VSXGLTOVSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
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Abstract
用于大规模甲醇合成的工艺布局包括串联的一个或多个沸水反应器和一个或多个径向流反应器,沸水反应器用近似新鲜的补充合成气进料。甲醇合成回路包括补充气压缩机K1、再循环气体压缩机K2、两个或更多个用于甲醇合成的沸水转换器(A1、A2、...)、用于甲醇合成的径向流转换器(B)、蒸汽滚筒(V1)、高压分离器(V2)、低压分离器(V3)、进料流出物换热器(E1和E2)、洗涤塔(C)、空气冷却器(E3)和水冷却器(E4)。
Description
本发明涉及用于甲醇合成回路的新工艺布局,其适用于大规模甲醇生产装置,即生产容量高于1000MTPD,优选高于5000MTPD的甲醇。
为了减少投资,利用规模经济,甲醇装置的产能不断增加。因此,世界级甲醇装置的产能从几十年前的2500MTPD增加到今天的约5000MTPD。考虑了甚至更大的装置,以进一步提高经济性并提供甲醇到烯烃(MTO)工艺的原料。
甲醇装置可以被分为三个主要工段:在装置的第一工段中,诸如天然气的进料气体被转化为合成气。合成气在第二工段中反应以生成甲醇,然后在装置尾端的第三工段中将甲醇纯化至所需纯度。
大规模甲醇装置的投资成本很高。合成气生产,包括需要时的压缩和氧气生产,可以占投资的60%或更多。在今天的许多装置中,管式蒸汽重整或两步重整被用于合成气的生产。然而,通过最大化单线产能和最小化投资,低蒸汽/碳(S/C)比下的独立自热重整是大规模装置的优选技术;例如,参见申请人的WO 2015/128456 A1,其描述了用于生产合成气(例如用于甲醇生产)的独立自热重整器。
独立自热重整(ATR)是一种用于生产合成气的技术,其中烃原料或来自预重整步骤的部分转化的气体向合成气的转化通过部分燃烧和绝热蒸汽重整的组合在单个反应器中完成。烃类进料的燃烧使用亚化学计量量的空气、富集的空气或氧气在燃烧器的燃烧区域中通过火焰反应进行。随后在固定床蒸汽重整催化剂中进行部分燃烧的烃原料的蒸汽重整。
独立ATR在一个紧凑型耐火衬里反应器中结合了亚化学计量的燃烧和催化蒸汽重整,以生产用于大规模甲醇生产的合成气。独立ATR在低S/C比下操作,从而减少了通过装置的流量并使投资最小化。独立ATR生产的合成气非常适合生产燃料级且高纯度的甲醇;例如参见申请人的WO 2013/013895 A1。
甲醇合成工段的设计至关重要。最佳设计和操作参数的选择取决于所需的产品规格。在许多装置中,使用沸水反应器(BWR)。然而,使用或并入绝热反应器可能是有利的。
甲醇由合成气(synthesis gas或syngas)合成,合成气由H2、CO和CO2组成。合成气的转化在催化剂上进行,催化剂通常是铜-氧化锌-氧化铝催化剂。通过合成气转化的甲醇合成可以用公式表示为伴随变换反应的二氧化碳的氢化,并且可以通过包括以下反应的以下反应顺序来概括:
CO2+3H2<->CH3OH+H2O
CO+H2O<->CO2+H2
如上所述,转化是在铜-氧化锌-氧化铝催化剂上进行的。该催化剂的实例包括申请人的催化剂MK-121和MK-151FENCETM。
由于甲醇的广泛使用,特别是作为制造其他化学品的原料,全世界的甲醇生产量巨大,因此用于大规模生产的方法和装置需求量很大。然而,大型甲醇装置受到反应器和工艺设备的尺寸限制所施加的限制。为了扩大规模,在相对小型的工艺设备中处理大量合成气的能力变得越来越重要。因此,在Surface Science and Catalysis 147,7-12(2004)的研究中,证明了这一目标可以通过将甲醇合成技术与合成气技术结合来实现,甲醇合成技术由结合的甲醇合成和缩合(CMSC)组成,且合成气技术包括以非常低的S/C比操作的ATR。
富含用于合成气制备的煤和天然气资源的国家已经投入大量精力开发大型甲醇生产装置。这些主要基于CN 1847208 A中描述的具有均匀温度的低压甲醇合成反应器。
在Johnson Matthey PLC的US 2009/0018220 A1中,公开了一种从缺乏氢的合成气合成甲醇的方法。Lurgi GmbH的US 2011/0065966 A1公开了一种用于生产甲醇的方法和装置,其中使合成气通过第一(优选水冷却)反应器,在其中将一部分碳氧化物转化为甲醇。然后将所得混合物进料到第二(优选气体冷却)反应器中,在其中将另一部分碳氧化物转化为甲醇。为了即使使用老化的催化剂也实现最大的甲醇产率,使合成气的部分料流绕过第一反应器并直接引入到第二反应器中。
在US 8.629.191 B2中,Lurgi GmbH描述了用于生产甲醇的方法和装置。使合成气通过第一水冷却反应器,在其中将一部分碳氧化物催化转化成甲醇。将得到的含有合成气和甲醇蒸气的混合物进料到第二气体冷却反应器,在其中将另一部分碳氧化物转化为甲醇。随后,将甲醇与合成气分离,然后将其再循环到第一反应器中。冷却气体与从第一反应器中排出的混合物并流流过第二反应器。
Johnson Matthey PLC的US 2010/0160694 A1公开了一种用于甲醇生产的方法,包括(a)使由回路气体和补充气体组成的合成气混合物通过含有甲醇合成催化剂的第一合成反应器,所述反应器在压力下被沸水冷却,形成含有甲醇的混合气体,(b)冷却含有甲醇的混合气体,(c)使所述冷却的混合气体通过含有甲醇合成催化剂的第二合成反应器,在其中合成另外的甲醇以形成产物气体流,(d)冷却所述产物气体以冷凝甲醇和(e)回收甲醇并将未反应的气体作为回路气体返回第一合成反应器,其中来自第一合成反应器的含有甲醇的混合气体通过与所述回路气体或所述补充气体进行热交换而被冷却。
在CN 103232321 A中公开了一种大规模的甲醇合成方法。在该方法中,原料气体首先进入缓冲罐,从而除去部分液体。然后,气体进入合成气压缩机进行加压,并在精脱硫保护床中进行脱硫。从精脱硫保护床排出的合成气体被分为两个流:第一合成气流与第二循环气流混合,进行热交换,混合物进入第一合成反应器。在反应后,高温气体进入第一气体/气体换热器,以与进料气体进行热交换。然后,气体进入粗甲醇加热器以加热粗甲醇,冷却循环气体并分离粗甲醇,从而形成第一循环气流。将第一循环气流与第二合成气流混合,将混合物加压并加热,并进入第二合成反应器。从第二合成反应器排出的高温气体被冷却并输送到第二分离器中;分离粗甲醇,并形成第二循环气流。据报道,该装置的规模可以被扩大到每年2.000.000至2.400.000吨甲醇产品,并且单程转化率可以达到7-13%。
CN 105399604 A描述了一种用于生产甲醇的方法,其中使合成气的流通过压缩机和两个换热器,然后分成两个流,每个流进入水冷却甲醇反应器。这两个甲醇反应器并联设置。
申请人的US 2015/0175509 A1公开了用于制备甲醇的方法和反应***,其包含两个反应单元,其中第一单元对新鲜合成气和未转化的合成气的混合物进行操作,而第二单元仅用未转化的合成气进行操作。该方法使用从第一和第二反应单元收集的未转化的合成气。因此,至第一和第二单元的再循环气体可以通过共用循环器加压和循环,这使得再循环流中的压力损失显著低于包含两个反应单元的其他***中的压力损失,因为两个反应单元在同样的压力下操作。
基本上,本发明涉及用于甲醇合成回路的新工艺布局,提供了优于现有技术的许多优点。更具体地,本发明涉及用于甲醇合成的工艺布局,其包括串联的一个或多个沸水反应器和一个或多个径向流反应器,其中沸水反应器用近似新鲜的补充合成气进料。
根据本发明的这种用于甲醇合成回路的新工艺布局包括补充气(MUG)压缩机K1、再循环气体压缩机K2、两个或更多个用于甲醇合成的沸水转换器(BWC)(A1、A2、...)、用于甲醇合成的径向流转换器(B)、蒸汽滚筒(V1)、高压分离器(V2)、低压分离器(V3)、进料流出物换热器(E1和E2)、洗涤塔(C)、空气冷却器(E3)和水冷却器(E4)。
优选地,吹扫气体作为湿气(包括甲醇)从流出物产物气体中分离出来并用水洗涤以在大约合成回路压力下回收甲醇。优选通过调节吹扫气体并因此调节反应器入口中的惰性气体的水平来控制径向流反应器温度。
在优选的实施方案中,径向流反应器具有不需要冷却装置的结构。此外,优选仅使用一列冷却设备。
在下文中,将参考附图描述根据本发明的工艺布局。图中的合成回路布局包括补充气(MUG)(1),其在K1中加压,如果需要的话(例如在运行开始期间,当BWR中的催化剂极其活跃时)与一部分再循环气体(2)混合,并在E1中预热。将预热的流(3)引入到两个(或更多个)BWC A1、A2...中,从其中抽出产物气体(4)并将其在E1中进行进料-流出物(F/E)热交换。来自换热器的部分冷却的流(5)与来自径向流转换器B的流出物(6)混合,并在空气冷却器E3中进一步冷却。来自E3的出口气体(7)在E4中被水冷却,并且将所得的两相流(8)分成两个流,液体流(9)和气体流(10),后者在K2中压缩成流(11)。
将加压的流(11)分成两个流(12和2)。流2是流11的较小部分,并且如果需要控制催化剂峰值温度并因此控制在BWR中形成合成副产物,则可以使用。流12在进料-流出物(F/E)换热器E2中进行热交换(预热)。将预热的气体引入到径向流转换器B中,得到流出物产物气体13,将其部分地在E2中冷却并且(作为流6)添加到E3的入口气体中。将E2出口的一部分作为吹扫气体17抽出。在洗涤塔C中用水21洗涤吹扫气体以从流中主要除去甲醇。不含甲醇的气体18被清除并可用作燃料。
将洗涤过的产物16与来自高压分离器V2的粗甲醇流9一起引入到低压分离器V3中。由于分离器V3在低压下操作,所以溶解在粗甲醇中的气体作为流14释放。将粗甲醇产物送至蒸馏单元进行进一步纯化。
径向流转换器B是向外径向流转换器,其具有位于转换器壳体和用于在催化剂床上分配气体的中心管之间的甲醇合成催化剂。在该径向流转换器中,不使用冷却装置。来自合成反应热的催化剂温度仅通过调节吹扫气体流即流18来控制。通过减少吹扫气体流量,在转换器B入口中增加惰性气体的浓度。由于转换器B中的压降不显著,可以以相对高的再循环流量运行合成回路。
径向流转换器(RFC)和沸水转换器(BWC)是化学工业中众所周知的设备。所公开的合成回路配置以创新的方式使用这些众所周知的单元操作,从而为从合成气合成甲醇提供了更有效的方法。
通过使用根据本发明的用于甲醇合成回路的新工艺布局,获得了许多优于先前已知的优点。主要优点是:
-对于典型的5000MTPD甲醇合成回路,只需要两个BWC,而不是三个甚至四个BWC;
-与仅具有一个BWC的标准合成回路相比,获得了潜在的低CAPEX(资本支出,即开发产品或***或为其提供非消耗部件的成本);
-在根据本发明的合成回路中观察到高碳效率;
-跨过转换器观察到较低的压降,
-布局简单实用,适用于工业实施,且
-两组转换器只需要一列冷却和冷凝。
通过以下实施例进一步说明本发明。
实施例
使用根据本发明的基于天然气(NG)的甲醇合成回路,其容量为5000 MTPD甲醇。前端独立ATR提供510.000Nm3/h的富含氢气(来自氢气回收单元的吹扫气体)的补充气(MUG)流,其具有以下组成:69%H2、21%CO、8.5%CO2、1%CH4和0.5%N2。
甲醇催化剂的总体积为174m3,更具体地分成在两个BWC中108m3,在RFC中66m3。两个BWC共包括11000个管,每个管的内径为40.3mm,外径为44.5mm,长度为7.7m。在RFC中,中心管的内径为1.0米,壳体直径为3.6米,床高为7米。
从运行开始(SOR)到运行结束(EOR),80kg/cm2的合成回路操作压力保持恒定。从SOR到EOR,BWT(沸水温度)在225℃至260℃之间变化。
在4年的操作时间内,假设RFC的催化剂活性损失为60%,BWC的催化剂活性损失为65%。
在运行结束(EOR)时,即在4年的操作时间之后,计算下表1中所示的流组成结果(以摩尔%计)(流编号(S.no)参考附图):
表1
操作4年后的流组成
流编号 | H2 | CO | CO2 | N2 | CH4 | MeOH | H2O |
1 | 69.0 | 21 | 8.5 | 0.5 | 1 | 0 | 0 |
3 | 66.9 | 11.3 | 5.8 | 5.5 | 10.2 | 0.25 | 0.02 |
4 | 61.4 | 6.9 | 5.6 | 6.3 | 11.6 | 7.2 | 1 |
10 | 65.7 | 5.6 | 4.1 | 8.6 | 15.6 | 0.4 | 0.03 |
13 | 63.5 | 4.8 | 3.4 | 8.9 | 16.1 | 2.3 | 0.9 |
18 | 65.1 | 4.9 | 3.5 | 9.2 | 16.6 | 0 | 0.7 |
来自低压分离器V3的产物流15由85.7重量%的粗甲醇(相当于5009 MTPD纯甲醇)组成。流15含有1120ppmw乙醇和9ppm甲基乙基酮。
各个流(S)的流量(f)如表2所示。
表2
各个流的流量*
1 | 2 | 3 | 4 | 6 | 10 | 12 | 13 | 14 | 18 |
510 | 867 | 1377 | 1210 | 3315 | 4335 | 3468 | 3342 | 3 | 26 |
*)上一行:流编号,下一行:流量(x 1000Nm3/h)
在该生产单元中使用的各个压缩机和换热器的的功率和负荷如下:
压缩机
K1:39.7MWe K2:12.5MWe(效率均为65%)
换热器
E1:75MW E2:256MW E3:143MW E4:50MW
合成回路碳效率从SOR的98.6%略微下降至EOR的97%(操作4年后)。RFC和BWC中催化剂床的压降分别从0.1和0.9巴增加到0.3和1.8巴。
Claims (6)
1.用于甲醇合成的工艺布局,其包括串联的一个或多个沸水反应器和一个或多个径向流反应器,其中沸水反应器用近似新鲜的补充合成气的进料。
2.用于甲醇合成回路的工艺布局,其包括补充气(MUG)压缩机K1、再循环气体压缩机K2、两个或更多个用于甲醇合成的沸水转换器(BWC)(A1、A2、...)、用于甲醇合成的径向流转换器(B)、蒸汽滚筒(V1)、高压分离器(V2)、低压分离器(V3)、进料流出物换热器(E1和E2)、洗涤塔(C)、空气冷却器(E3)和水冷却器(E4)。
3.根据权利要求2所述的用于甲醇合成回路的工艺布局,其中吹扫气体作为湿气(包括甲醇)从流出物产物气体中分离出来,并用水洗涤以在大约合成回路压力下回收甲醇。
4.根据权利要求2或3所述的用于甲醇合成回路的工艺布局,其中通过调节吹扫气体并因此调节反应器入口中的惰性气体的水平来控制径向流反应器温度。
5.根据权利要求2-4中任一项所述的用于甲醇合成回路的工艺布局,其中径向流反应器具有不需要冷却装置的结构。
6.根据权利要求2-5中任一项所述的用于甲醇合成回路的工艺布局,其中仅使用一列冷却设备。
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CN114901619A (zh) * | 2020-01-02 | 2022-08-12 | 沙特基础全球技术有限公司 | 由富惰性物的合成气生产甲醇的方法 |
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