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CN1143602A - 富氢气体的制备方法 - Google Patents

富氢气体的制备方法 Download PDF

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Publication number
CN1143602A
CN1143602A CN96108879A CN96108879A CN1143602A CN 1143602 A CN1143602 A CN 1143602A CN 96108879 A CN96108879 A CN 96108879A CN 96108879 A CN96108879 A CN 96108879A CN 1143602 A CN1143602 A CN 1143602A
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dme
catalyst
rich gas
reaction
hydrogen
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CN1077084C (zh
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P·E·H·尼尔森
P·李尔曼
N·J·布罗姆
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Topsoe AS
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Haldor Topsoe AS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及从由二甲醚和水蒸汽组成的原料中制备富氢气体的方法，其中二甲醚在以物理混合物形式置于固定床反应器中的选自固体酸类的醚水合催化剂和甲醇分解催化剂存在下与水蒸汽反应。

Description

富氢气体的制备方法
本发明涉及富氢气体的制备方法。更具体地讲，本发明是由含有二甲醚(DME)的原料中制备富氢气体的方法。
DME通过两步反应分解成氢气。在第一步反应中，该醚通过下面的反应水合成甲醇：
                (1)
           △H298.1＝5.28千卡/摩尔和在DME的水合过程中生成的甲醇在第二步中分解成二氧化碳和氢气：
                (2)
                    (3)
这两步反应可在气相和液相中进行。
反应(1)在弱酸存在下以非常低的反应速率进行，并且该反应在热力学方面对甲醇不利。通过上面的反应(2)和(3)的甲醇的分解已知能被固体催化剂、通常是基于铜、锌和氧化铝的固体催化剂催化。在热力学上，高温、低压和高水蒸汽浓度是有利的。
现已发现，DME通过反应(1)水合成甲醇的反应在固体酸存在下进行时，该水合过程中的反应速率被大大提高。
此外还观察到，当通过将按照上述的反应(2)和(3)通过甲醇成为氢气和二氧化碳的反应生成的甲醇去除以克服DME水合反应的平衡限度时，DME通过下面的反应
     
     △H298.1＝29.28千卡/摩尔DME       (4)成为富氢气体的整个反应能以适当的反应速率、高的产品收率和生成氢气和二氧化碳的高选择性进行。
依据上述发现和观察，本发明是一种从由二甲醚和水蒸汽组成的原料中制备富氢气体的方法，其中二甲醚在以物理混合物形式置于固定床反应器中的选自固体酸类的醚水合催化剂和甲醇分解催化剂存在下与水蒸汽反应。
适宜于二甲醚水合的催化剂是任何一种所述固体酸。该水合催化剂最好包括酸性沸石，H-式的ZSM-5更好。
将DME水合催化剂与最好是Cu-Zn-氧化铝(由Haldor TopsφeA/S提供)的甲醇分解催化剂以在1∶5-5∶1之间的重量比相混合
在与原料气接触之前，使该催化剂成为其活化形式，对于水合催化剂来说，这是通过将该催化剂与给质子溶液进行离子交换获得的氢形式。甲醇分解催化剂按常规通过将该催化剂与还原气接触来活化。
有用的催化剂形式是挤出物、丸、颗粒等在固体催化剂颗粒的固定床中常规使用的形式。
在实施上述方法时，将DME原料与水蒸汽按1∶1-1∶10、最好是1∶2-1∶5的摩尔比一起加入。然后使该混合的DME/水蒸汽工作气体在1-100巴之间的压力下以1000-5000小时-1空间速度通过该催化剂床。
在反应温度高于200℃、最好是250℃以上时，DME向氢气和二氧化碳的转化率在上述反应条件下基本上是完全的。
本发明的上述方面和特征将在下列举例说明本发明的具体实施方案的实施例中进一步描述。实施例1
将3.00g由常规甲醇分解用Cu-Zn-Al催化剂(可得自HaldorTopsφeA/S，丹麦，商品名为MDK-20)和来自Condea的二氧化硅-氧化铝(Siral-5)以1∶1的重量比组成的催化剂混合物按固定床的方式置于管状反应器中。
该催化剂混合物为0.5-1.0mm颗粒的形式。
将工作气体DME和H2O(1/4摩尔/摩尔)以1.6g DME/小时的流速在1.2巴的压力下引入反应器中。
该操作在如下表1中给定的不同的温度下等温进行。结果见表1。
                          表1
T℃ H2 CO     mole％CO2 CH4 CH3OH H2O DME
    250     2.5     0.0     0.8     0.00     2.3     77.1   17.3
    300     44.0     0.4     14.5     0.03     0.2     34.5   6.4
    325     65.2     3.2     19.5     0.03     0.0     12.1   0.1
    350     64.0     4.3     18.9     0.03     0.0     12.8   0.0
    375     63.3     5.2     18.0     0.03     0.0     13.6   0.0
    400     62.8     6.1     16.7     0.03     0.0     14.6   0.0
实施例2
以与实施例1中所述类似的方法，将DME在下表2中所给的温度下转化成富氢气体。在本实施例中，反应器中装有由3.0g MDK-20甲醇分解催化剂和ZSM-5组成的活化的催化剂混合物(以1∶1的重量比混合；粒径为0.5-1.0mm的颗粒)。
由本实施例的方法获得的结果见表2。
                           表2
T℃ H2 CO  mole％CO2 CH4 CH3OH H2O DME
    225     57.1     0.3  18.8     0.00     1.2     19.7     2.9
    250     67.0     1.0  21.3     0.00     0.1     10.5     0.1
    300     65.3     2.4  20.8     0.00     0.0     10.4     0.0

Claims (6)

1.从由二甲醚和水蒸汽组成的原料中制备富氢气体的方法，其中二甲醚在以物理混合物形式置于固定床反应器中的选自固体酸类的醚水合催化剂和甲醇分解催化剂存在下与水蒸汽反应。
2.按照权利要求1的方法，其中的二甲醚水合催化剂选自沸石材料、硅酸铝、二氧化硅-氧化铝、氧化铝和它们的混合物。
3.按照权利要求1的方法，其中的二甲醚水合催化剂包括氢形式的ZSM-5和/或Siral-5。
4.按照权利要求1的方法，其中甲醇分解催化剂与DME水合催化剂之重量比在1∶5-5∶1之间。
5.按照权利要求1的方法，其中所述反应在150-450℃之间的温度和1-100巴的压力下进行。
6.按照权利要求5的方法，其中所述反应在200-400℃之间的温度和2-50巴的压力下进行。
CN96108879A 1995-07-21 1996-07-19 富氢气体的制备方法 Expired - Fee Related CN1077084C (zh)

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DK199500852A DK173416B1 (da) 1995-07-21 1995-07-21 Fremgangsmåde til fremstilling af hydrogenrig gas

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CN1123530C (zh) * 1998-01-21 2003-10-08 赫多特普索化工设备公司 制备富含氢气气体的方法
CN1331731C (zh) * 2003-04-01 2007-08-15 赫多特普索化工设备公司 制备富氢物流的方法
CN101177240B (zh) * 2007-11-09 2010-04-07 清华大学 一种集成式二甲醚水蒸气重整制氢装置及方法
CN103223343A (zh) * 2013-04-15 2013-07-31 天津大学 二甲醚水蒸气重整制氢碱金属改性铜基催化剂及制备方法

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CN102794166B (zh) * 2011-05-25 2014-02-26 中国科学院大连化学物理研究所 二甲醚水蒸气重整制氢的催化剂及制备和应用
CN102795598B (zh) * 2011-05-25 2014-02-12 中国科学院大连化学物理研究所 一种二甲醚水蒸气重整制氢的方法
KR101401418B1 (ko) * 2012-10-29 2014-06-02 한국과학기술연구원 고체산 혼합물을 이용한 수소 제조 방법
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CN1123530C (zh) * 1998-01-21 2003-10-08 赫多特普索化工设备公司 制备富含氢气气体的方法
CN1331731C (zh) * 2003-04-01 2007-08-15 赫多特普索化工设备公司 制备富氢物流的方法
CN101177240B (zh) * 2007-11-09 2010-04-07 清华大学 一种集成式二甲醚水蒸气重整制氢装置及方法
CN103223343A (zh) * 2013-04-15 2013-07-31 天津大学 二甲醚水蒸气重整制氢碱金属改性铜基催化剂及制备方法

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DK85295A (da) 1997-01-22
DK173416B1 (da) 2000-10-02
US5837217A (en) 1998-11-17
RU2203215C2 (ru) 2003-04-27
ES2139990T3 (es) 2000-02-16
KR100192527B1 (ko) 1999-06-15
EP0754649A1 (en) 1997-01-22
AU6058396A (en) 1997-01-30
CN1077084C (zh) 2002-01-02
KR970006161A (ko) 1997-02-19
NO962964D0 (no) 1996-07-15
AU712528B2 (en) 1999-11-11
DE69604736D1 (de) 1999-11-25
JPH09118501A (ja) 1997-05-06
ATE185775T1 (de) 1999-11-15
NZ299022A (en) 1997-12-19
DE69604736T2 (de) 2000-04-06
NO962964L (no) 1997-01-22
JP4018175B2 (ja) 2007-12-05
NO318181B1 (no) 2005-02-14
EP0754649B1 (en) 1999-10-20

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