CN86101791A - 对低压合成甲醇中吹扫气体的再加工方法 - Google Patents
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Abstract
关于对低压合成甲醇中吹扫气体的再加工方法,目的在于提高由含碳固体气化而得到的合成气中的氢含量。该吹扫气体已经过催化重整,这一措施旨在提供一种节能方法,最大限度地减少合成气的损失而使大部分甲烷用来生产合成气。
这一方法是通过将催化重整后的气体经过一氧化碳转化完成的,排除的气体在压力振荡吸附装置中被分离成氢气和惰性气体成分。
Description
本发明涉及对低压合成甲醇中吹扫气体的再加工方法,其目的是提高由含碳固体的气化而得到的合成气体的氢含量,该吹扫气体已经催化重整阶段。
参阅DE-PS2445884,已知吹扫气体在10至30巴,700至850℃下,通过催化蒸气重整阶段,生成氢气和一氧化碳,在升高至合成压力之前,将生成的气体冷卸并加入纯化过的甲醇合成气中,部分吹扫气体用作燃料,产生重整过程中需要的热。
这一已知的加工过程一个明显的不足之处在于,不可转化的惰性气体氮气和氩气,只有一部分随着吹扫气体流排出,用于燃烧,以至惰性在合成气体中的体积含量必定会在合成甲醇吹扫气体中增加。
这一已知加工过程的另一明显的不足之处是,必须限制重整阶段的压力,以保证较低的残存甲烷的含量。吹扫气体膨胀到重整压力,再增加生成气体的压力至合成压力,意味着能量的损失。
本发明的目的是提供一个方法,这个方法从能量需求的角度看效率更高,也能最大限度地减少夹带在吹扫气体中的合成气体的损失,从而大部分甲烷能被用于合成气体的生产。
关于上面简述的方法中存在的问题,可通过本发明解决,采用催化重整步骤生产的气体经过一氧化碳转化,被转化的气体再分离为氢气和惰性气体,该过程具体可在压力振荡吸附装置(简称PSA)中进行。
本发明所提供的方法保证吹扫气体转化成氢气的高转化率,而不能被利用的气体成份,诸如氮气、氩气、二氧化碳同时被回收,该合成气体基本不含惰性气体,因为这些惰性气体不象原来的加工程序那样进行循环。
回收氢气,甲烷和惰性气体的加工过程从DO-PS84629可得知,这些气体成份被用来进一步加工。
本发明较好的实施方案是将氢气分离,例如用压力振荡吸附装置分离并使氢气又回到合成甲醇的工序中。这种方法的优点是,更少的含在由煤气化而得的原料气中的CO被转化而结果是减小后面二氧化碳装置的负荷。本发明另一个优点在于:原料气中由于甲烷和氢气的含量高而完全可以省去转化步骤,例如那些在高压下从气化木头,泥碳等得到的气体。
本发明另一个较好实施方案提供了用气化阶段的氧气,其纯度低于或等于百分之九十九,特别是在百分之九十至九十五之间,本发明第一次使用这些氧气成为可能,这意味着这一工序在经济效益方面的显著提高。
为了进一步改进整个过程,本发明将氮气在加工过程中用于密封各种闸门,这也意味着增加了加工过程的经济效率,而过去的加工过程忽视了这一问题。
本发明可在一些实施例和参考图的基础上得以解释,这些参考图说明了加工过程流程图。
煤(K),蒸气(D)和氧气(S)如图标有字母的箭头所示进入煤气化装置1中。气化过程产生的原料气进入转化的装置2中,然后进入二氧化碳和硫化氢(H2S)洗气装置中,最后通过压缩机12进入甲醇合成装置4。
甲醇从箭头5指示的方向离开加工程序。吹扫气体加工的路径由箭头6表示。吹扫气体首先被送入重整装置7,然后进入转化装置8,最后进入压力振荡吸附装置(PSA)9。
路径10为加工过程中的惰性气体提供了出口,而氢气如图所示通过路径11回到合成甲醇的装置4之前的主气流中。
该加工过程可举例说明如下:
含水重量为12%(DBC12)的干燥褐煤。用蒸汽和氧气在流化床中20巴压力下气化。冷却时利用部分显热进行水蒸汽饱和,冷却后可得到的原料气体量为1.405Nm3/t DBC(干量),其组成如下:
(体积%)
二氧化碳 16.8
一氧化碳 45.1
氢气 33.5
甲烷 3.9
N2+Ar 0.5
H2S+COS 0.2
近百分之七十五的原料气进行一氧化碳转化,而后与残余气体结合。从16巴再加压至37巴以后,气体经提纯完全除去硫化氢并使二氧化碳的含量减少至约百分之五(体积)。这时,1223Nm3/t DBC12气体量有下列成分:
体积%
二氧化碳 5.6
一氧化碳 27.8
氢气 61.9
甲烷 4.2
氮气和氢气 0.5
根据本发明,128Nm3的纯氢气从吹扫气体再加工装置加入到原料气中可得到1351Nm3含下列成份的甲醇合成气:
体积%
二氧化碳 5.0
一氧化碳 25.2
氢气 65.5
甲烷 3.8
氮气和氩气 0.5
该气体在低压合成甲醇装置中从35巴加压到101巴,转化为550公斤的甲醇。102Nm3含有下列成分的纯气体从循环气体中收回。
体积%
二氧化碳 6.3
一氧化碳 3.4
氢气 42.3
甲烷 42.6
氮气和氩气 5.4
在40巴,950℃下,32Nm3和141Nm3蒸气被渗入该纯气体中,该气体经催化自动热重整后再经高温转化。201Nm3的气体离开转化阶段,冷却后进入PSA装置。
体积%
二氧化碳 21.3
一氧化碳 4.3
氢气 71.0
甲烷 0.7
氮气和氩气 2.7
在压力振荡吸附装置中,在37巴压力下,将氢气(128Nm3)分离,效率为百分之九十八,而废气(74Nm3)在接近大气压的状态下离开压力振荡吸附装置,并且该废气可用作气体燃料。它的成分如下:
体积%
二氧化碳 58.0
一氧化碳 11.6
氢气 21.2
甲烷 1.9
氮气和氩气 7.3
根据上述实例,吹扫气体再加工与没有吹扫气体再加工相比,在同样的甲醇生产率下,装置能力降低如下:
气化(1) 约12%
一氧化碳转化(原料气)(2) 约33%
再加压(3) 约16%
二氧化碳清洗(4) 约20%
氧气需水 约5%
当然上面概述的实例可在不偏离本发明基本构思的情况下进行多种改进。
Claims (5)
1、对低压合成甲醇中吹扫气体的再加工方法,目的是提高由含碳固体气化得到的合成气中的氢含量,这一吹扫气体已经过催化重整,其特征为:
来自催化重整的排出气体进行一氧化碳转化步骤,该排出气体在一个压力振荡吸附装置中被分离为氢气和惰性气体。
2、根据权利要求1的方法,其特征在于催化重整是用氧气进行的。
3、根据权利要求1的方法,其特征为:从吸附设备出来的氢气,在合成甲醇之前回到加工程序中。
4、根据权利要求1或权利要求2的方法,该方法在于加压下含碳固体的气化,其特征为:用于气化的氧气,其纯度低于或等于百分之九十九,最好为百分之九十至九十五。
5、根据权利要求3的方法,其特征为:获得的氮气在全部系统中用于对各种阀门密封。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3510096.6 | 1985-03-20 | ||
DE19853510096 DE3510096A1 (de) | 1985-03-20 | 1985-03-20 | Verfahren zur aufbereitung eines restgases aus einer niederdruckmethanolsynthese |
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Publication Number | Publication Date |
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CN86101791A true CN86101791A (zh) | 1986-09-17 |
CN1011697B CN1011697B (zh) | 1991-02-20 |
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ID=6265820
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Application Number | Title | Priority Date | Filing Date |
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CN86101791A Expired CN1011697B (zh) | 1985-03-20 | 1986-03-19 | 对低压合成甲醇中排出气体的再加工方法 |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0195200A3 (zh) |
CN (1) | CN1011697B (zh) |
AU (1) | AU584677B2 (zh) |
DE (1) | DE3510096A1 (zh) |
NZ (1) | NZ215244A (zh) |
ZA (1) | ZA862023B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103264989A (zh) * | 2013-05-20 | 2013-08-28 | 西南化工研究设计院有限公司 | 一种合成气合成甲醇装置弛放气回收的工艺方法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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ZA876418B (en) * | 1986-10-01 | 1988-03-17 | The Boc Group, Inc. | Process for the co-production of gaseous carbon dioxide and hydrogen |
AU602438B2 (en) * | 1988-01-14 | 1990-10-11 | Air Products And Chemicals Inc. | One-step process for dimethyl ether synthesis utilizing a liquid phase reactor system |
DD279939B5 (de) * | 1989-02-03 | 1993-09-16 | Leuna Werke Ag | Verfahren zur entfernung und teilweisen gewinnung von methanol aus syntheserestgas |
EP0839890A3 (de) * | 1996-10-29 | 1999-02-03 | Thermoselect Aktiengesellschaft | Verfahren zur vollständigen, stofflichen, emissionslosen Nutzung des beim Hochtemperaturrecycling von Abfällen aller Art gewonnenen Synthesereingases |
NO314989B1 (no) * | 1999-12-28 | 2003-06-23 | Statoil Asa | Fremgangsmåte for ökning av produksjonen i et eksisterende prosessanlegg for konvertering av naturgass til et produkt, samt prosessanlegg |
DE102009016402A1 (de) * | 2009-04-07 | 2010-10-14 | Uhde Gmbh | Verfahren und Anlage zur Behandlung von Synthesegas aus der Vergasung Kohlenstoff-haltiger Feststoffe |
GB201019940D0 (en) | 2010-11-24 | 2011-01-05 | Davy Process Techn Ltd | Process |
CN109266413B (zh) * | 2018-10-30 | 2021-09-07 | 青岛联信催化材料有限公司 | 一种利用氢回收非渗透气生产合成天然气的方法 |
DE102019124078A1 (de) * | 2019-09-09 | 2021-03-11 | Thyssenkrupp Ag | Verfahren zur Synthese eines Stoffs |
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DD84629A (zh) * | 1900-01-01 | |||
GB1190071A (en) * | 1967-01-20 | 1970-04-29 | Ici Ltd | Methanol Production |
DE2445884C2 (de) * | 1974-09-26 | 1983-12-15 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Herstellung von Methanol |
DE2603204C2 (de) * | 1976-01-29 | 1982-12-02 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Herstellung von Methanol |
US4181675A (en) * | 1978-09-19 | 1980-01-01 | Monsanto Company | Process for methanol production |
US4348487A (en) * | 1981-11-02 | 1982-09-07 | Exxon Research And Engineering Co. | Production of methanol via catalytic coal gasification |
US4398926A (en) * | 1982-04-23 | 1983-08-16 | Union Carbide Corporation | Enhanced hydrogen recovery from low purity gas streams |
FR2529544B1 (fr) * | 1982-07-05 | 1987-11-13 | Inst Francais Du Petrole | Produit d'alcools a partir de gaz de synthese |
US4443560A (en) * | 1982-07-28 | 1984-04-17 | The M. W. Kellogg Company | Adiabatically reforming a reformed gas for producing methanol |
US4546111A (en) * | 1983-04-22 | 1985-10-08 | Foster Wheeler Energy Corporation | Process for the production of oxygenated organic compounds such as methanol |
CA1263671A (en) * | 1986-02-10 | 1989-12-05 | David Leon Banquy | Process for the production of synthesis gas |
-
1985
- 1985-03-20 DE DE19853510096 patent/DE3510096A1/de active Granted
-
1986
- 1986-01-25 EP EP86101012A patent/EP0195200A3/de not_active Withdrawn
- 1986-02-20 AU AU53803/86A patent/AU584677B2/en not_active Ceased
- 1986-02-21 NZ NZ215244A patent/NZ215244A/xx unknown
- 1986-03-19 ZA ZA862023A patent/ZA862023B/xx unknown
- 1986-03-19 CN CN86101791A patent/CN1011697B/zh not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103264989A (zh) * | 2013-05-20 | 2013-08-28 | 西南化工研究设计院有限公司 | 一种合成气合成甲醇装置弛放气回收的工艺方法 |
CN103264989B (zh) * | 2013-05-20 | 2015-08-05 | 西南化工研究设计院有限公司 | 一种合成气合成甲醇装置弛放气回收的工艺方法 |
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Publication number | Publication date |
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ZA862023B (en) | 1986-11-26 |
NZ215244A (en) | 1988-10-28 |
AU584677B2 (en) | 1989-06-01 |
CN1011697B (zh) | 1991-02-20 |
AU5380386A (en) | 1986-09-25 |
EP0195200A2 (de) | 1986-09-24 |
DE3510096C2 (zh) | 1989-10-12 |
DE3510096A1 (de) | 1986-09-25 |
EP0195200A3 (de) | 1989-09-06 |
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