CN1618728A - 制备氢气和合成气体的方法 - Google Patents
制备氢气和合成气体的方法 Download PDFInfo
- Publication number
- CN1618728A CN1618728A CNA2004101005691A CN200410100569A CN1618728A CN 1618728 A CN1618728 A CN 1618728A CN A2004101005691 A CNA2004101005691 A CN A2004101005691A CN 200410100569 A CN200410100569 A CN 200410100569A CN 1618728 A CN1618728 A CN 1618728A
- Authority
- CN
- China
- Prior art keywords
- methanol
- liquid phase
- catalyst
- water
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007789 gas Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 163
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012071 phase Substances 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 238000002407 reforming Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- UTARHJMVJBSOKZ-UHFFFAOYSA-N [O-2].[Al+3].[Zn+2].[Cu+2] Chemical compound [O-2].[Al+3].[Zn+2].[Cu+2] UTARHJMVJBSOKZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- -1 copper-zinc-aluminum Chemical compound 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- 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
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
通过甲醇转化生成包含一氧化碳、二氧化碳和氢气的合成气体的制备方法，包括下列步骤：(a)将液相甲醇引入含有悬浮于液相的甲醇和水中的固体甲醇转化催化剂的反应器；(b)使液相的甲醇和水在一定温度和压力下在有悬浮催化剂条件下反应，其中保持甲醇处于液相；和(c)从反应器回收在液体甲醇和水相反应期间生成的气相合成气体。
Description
技术领域
本发明涉及甲醇和如甲醛和/或甲基甲酸盐的甲醇衍生物转变成合成气体和特别是氢气的方法。特别地，本发明是一种在浆液床式反应器中进行的氢气制备工艺，其中将液体甲醇分解成氢气和其他合成气体组分。为了使甲醇分解反应中的催化剂有活性利用甲醇原料作为悬浮液介质。悬浮液介质和甲醇原料也可以包含水。
由该工艺制备的合成气体是包含氢气和二氧化碳和/或一氧化碳的任何气体组合物。
背景技术
多相甲醇转化的工业方法是在有铜基催化剂存在下使甲醇根据下列反应式进行反应：
甲醇转化催化剂也催化水气转化(WGS)反应，
和反向水气转化(RWGS)反应，
在大规模的氢气设备中，富含氢气气体制备的主要方法是烃的气流转化。典型地，烃原料经提纯步骤去除微量硫、氯化物等。加热经提纯步骤的原料并在燃烧管式反应器中进行气流转化。气流转化的通常温度范围是700-1100℃。用燃烧加热器加热反应器。可选择地，可以使用自热转化。
我们还知道将甲醇气流转化成合成气体包括上述的反应(1)和(4)。两个反应为适度吸热的并且以低压促进甲醇转化。该转化受热力学平衡常数的限制。典型地在适度压力下使用温度为250-300℃。通常以气体形式进行反应，其中将气相的甲醇和气流与甲醇转化催化剂接触。
人们已知几种催化剂在气相下的甲醇气流转化成氢气中是有效的。那些催化剂组合物包括铜、锌、钯和/或铂(美国专利6,583,084)、铝、铜和至少一种选自铁、钌和锇(美国专利6,589,909)和锰、铜和铬(美国专利4,407,238)的金属原子。工业中使用的最典型的催化剂是铜、锌和铝和/或铬催化剂。
美国专利6,699,457公开了一种用于在含有金属的催化剂的存在条件下在气相中或浓缩液相中由氧化的烃制备氢气的工艺。该催化剂包含VIII族过渡金属或这些金属的合金。该工艺优选的催化剂是镍、钯、铂、钌和铑、铱。工艺中使用的氧化的烃具有2到12个碳原子。当在液相中进行转化反应时，优选用于反应的原料是葡萄糖、山梨糖醇和蔗糖。
现在已经发现通过与悬浮于包含甲醇和水的悬浮液体中的铜-锌-铝氧化物和/或铬氧化物催化剂接触甲醇可在液相中转化，其中在催化剂的表面上形成氢气或合成气体并以气相离开反应器。
发明内容
因此，本发明提供了一种用于通过甲醇转化制备氢气或包含一氧化碳、二氧化碳和氢气的合成气体的工艺，包括如下步骤：
(a)提供液相的甲醇和水中包含铜、锌、铝和/或铬的氧化物的催化剂悬浮液；
(b)将包含液相甲醇的原料引入含有悬浮于液相的甲醇和水中的固体甲醇转化催化剂的反应器；
(b)使原料在一定操作压力和温度下在有悬浮的催化剂存在的液相中反应，其中使甲醇保持液相；和
(c)从液相中回收气相氢气或合成气体。
根据本发明的工艺利用甲醇原料的浓缩条件。由气相平衡常数计算出的甲醇分压比给定温度下甲醇的沸腾压力更大并因此形成包含甲醇和水的液相。因为氢气或合成气体为气相，当连续地从液体反应介质中回收气相时，上述反应不受平衡限制。该平衡和饱和组成受温度影响。为了升高温度，需要增大压力来获得液相反应条件。
本发明的液相甲醇转化工艺提供了一种通过在反应器中安装热交换面来解决熟知的甲醇转化工艺中加热问题的方法。通过液相反应，以简单方式控制温度并且不形成温度梯度。最终更有效利用催化剂。
具体实施方式
通过本发明在悬浮于甲醇和水中的催化剂表面上进行液相中甲醇转化制造合成气体。在不发生催化剂严重失活条件下允许水的百分数在催化剂悬浮液中高达50体积％。
在该工艺中如利用泵将液体甲醇原料输送给反应器。液体甲醇可以包含水。在反应器中使甲醇转化反应中的活性催化剂悬浮于甲醇和水的混合物中。反应器中的甲醇转化如下：
和反向水气转化(RWGS)反应，
产物是包含氢气、一氧化碳和二氧化碳的合成气体。
该工艺有利地是非循环过程。
用反应器包含液相的方式控制引入反应器中的原料。催化剂悬浮液中的压力和温度一定要调节至临界值，使原料和催化剂床的悬浮液介质保持液相。在液相中运行该工艺依赖的运行温度压力典型地将为0.1到24Mpa、反应温度为50到240℃。产物以气相离开反应器。为了使存在于反应器中气相的水和甲醇量最小，可选择在反应器出口管线装有热交换器。该热交换器降低产物气相的温度和部分或完全地浓缩在反应条件下存在于气相中的微量甲醇和水。
优选活化之后用于工艺中的催化剂为包含55wt％氧化铜的铜-锌-铝催化剂，其来自丹麦Haldor Topse A/S，商品名称为MDK-20。除了甲醇，其它类似种类的如甲酸甲酯、甲醛、二甲醚或蚁酸也可作为原料和溶剂。
实施例
实施例1
13.75g MDK-20，一种丹麦Haldor Topse A/S提供的用于液相甲醇转化的催化剂，通过在300cc反应器内部的舱中与氢气和氮气的气体混合物接触而活化。在活化后，将催化剂悬浮于包含有10wt％水的140cc甲醇中。加入氮是为了使压力达到2MPa。将设备加热到200℃。测量总压力并且观察到压力升高达到的甲醇、水和添加氮气的分压之上。因此该组试验表明形成了其它额外的气体。
实施例2
如实施例1所述，激活和悬浮13.75g的MDK-20催化剂。将反应器与冷凝器相连并且利用反压阀使运行压力保持在8MPa。启动泵将水含量为10wt％的甲醇/水混合物以1ml/min送入反应器。分析从反应器中收回的干燥产物气体成份，其包含74.9％H2，11.5％N2，0.8％CO和12.7％CO2。干燥气体产率是每小时4.8NL。
在1.5小时之后气体产率仍然为每小时4.8NL。氮气浓度降低了。干燥气体的成份是79.0％H2，10.8％N2，0.8％CO和9.4％CO2。
Claims (7)
1.通过甲醇转化制备氢气或包含一氧化碳、二氧化碳和氢气的合成气体的方法，包括下列步骤：
(a)提供在液相的甲醇和水中包含铜和锌、铝和/或铬的氧化物的活化催化剂的悬浮液；
(b)将包含液相甲醇的原料引入含有悬浮于液相的甲醇和水中的固体甲醇转化催化剂的反应器；
(b)使原料在操作压力和温度下在有悬浮催化剂存在的液相中反应，其中使甲醇保持液相；和
(c)从液相中回收气相氢气或合成气体。
2.如权利要求1的工艺，其中液相中存在的水量是0-50wt％。
3.如权利要求1的工艺，其中操作压力是0.1-24MPa。
4.如权利要求1的工艺，其中操作温度是50-240℃。
5.如权利要求1的工艺，其中原料还包含液相水。
6.如权利要求1的工艺，其中催化剂在活化之前包含至少30wt％氧化铜。
7.如权利要求1的工艺，其中催化剂在活化之前包含至少50wt％氧化铜。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA200301727 | 2003-11-22 | ||
| DKPA200301727 | 2003-11-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1618728A true CN1618728A (zh) | 2005-05-25 |
| CN1618728B CN1618728B (zh) | 2011-03-09 |
Family
ID=34429213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004101005691A Expired - Fee Related CN1618728B (zh) | 2003-11-22 | 2004-11-22 | 制备氢气和合成气体的方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7329291B2 (zh) |
| EP (1) | EP1533271B1 (zh) |
| JP (1) | JP2005154267A (zh) |
| KR (1) | KR20050050028A (zh) |
| CN (1) | CN1618728B (zh) |
| CA (1) | CA2487791A1 (zh) |
| ES (1) | ES2399221T3 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102548893A (zh) * | 2009-09-25 | 2012-07-04 | 环球油品公司 | 在二氧化碳生产中保持低一氧化碳浓度 |
| CN107429175A (zh) * | 2014-10-31 | 2017-12-01 | 德国汉莎航空公司 | 用于制备合成气体的方法和设施 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101036158B1 (ko) * | 2003-07-29 | 2011-05-23 | 매그나칩 반도체 유한회사 | Ｓｒａｍ 및 로직 복합 소자의 제조 방법 |
| US7998455B2 (en) * | 2006-11-16 | 2011-08-16 | Archer Daniels Midland Company | Process for hydrogen gas production from carbohydrate feedstocks |
| US8741258B2 (en) | 2008-09-18 | 2014-06-03 | University Of Massachusetts | Production of hydrogen, liquid fuels, and chemicals from catalytic processing of bio-oils |
| RU2455068C2 (ru) * | 2010-08-30 | 2012-07-10 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Катализатор, способ его приготовления и способ получения синтез-газа из синтетических углеводородных топлив |
| KR102173150B1 (ko) * | 2013-06-18 | 2020-11-02 | 서강대학교 산학협력단 | 광촉매를 이용한 메탄올로부터의 수소 제조방법 |
| KR102232201B1 (ko) * | 2020-10-27 | 2021-03-26 | 서강대학교산학협력단 | 광촉매를 이용한 메탄올로부터의 포름알데히드 또는 포름산의 제조방법 |
| EP4163255A1 (de) | 2021-10-06 | 2023-04-12 | Covestro Deutschland AG | Verfahren zur herstellung von phosgen |
| CN116395732A (zh) * | 2023-04-11 | 2023-07-07 | 北京化工大学 | 一种利用含碳混合气与水合氯化钙自催化耦合脱水制备无水氯化钙方法及装置 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1017647A (en) | 1963-05-22 | 1966-01-19 | British Petroleum Co | Mixtures of carbon dioxide and hydrogen |
| US4407238A (en) * | 1981-10-26 | 1983-10-04 | Conoco Inc. | Methanol dissociation using a copper-chromium-manganese catalyst |
| FR2608144B1 (fr) * | 1986-12-16 | 1989-03-24 | Inst Francais Du Petrole | Procede de production d'hydrogene par reformage catalytique du methanol a la vapeur d'eau |
| FR2611194B1 (fr) * | 1987-02-19 | 1989-05-19 | Inst Francais Du Petrole | Procede de fabrication de gaz de synthese ou d'hydrogene, par conversion catalytique du methanol en phase liquide |
| JP2807053B2 (ja) * | 1989-07-21 | 1998-09-30 | 三井化学株式会社 | メタノールの分解方法 |
| CN1040198C (zh) * | 1995-03-07 | 1998-10-14 | 中国科学院山西煤炭化学研究所 | 甲醇催化重整制氢的工业生产方法 |
| DE19739773A1 (de) * | 1997-09-10 | 1999-03-11 | Basf Ag | Verfahren und Katalysator zur Dampfreformierung von Methanol |
| JP4048332B2 (ja) * | 1997-12-03 | 2008-02-20 | 三菱瓦斯化学株式会社 | 水素の製造方法 |
| JP2000117107A (ja) * | 1998-10-20 | 2000-04-25 | Osaka Gas Co Ltd | メタノール改質触媒の製造方法 |
| JP4446029B2 (ja) * | 2000-03-31 | 2010-04-07 | 独立行政法人物質・材料研究機構 | メタノール水蒸気改質用触媒の製造方法 |
| US6583084B2 (en) * | 2000-07-18 | 2003-06-24 | Mitsui Chemicals, Inc. | Catalyst for steam reforming of methanol and method for producing hydrogen therewith |
| JP2002079101A (ja) * | 2000-09-08 | 2002-03-19 | Hiroshima Industrial Technology Organization | メタノール水蒸気改質用触媒前駆体並びにメタノール水蒸気改質用触媒及びその製造方法 |
| US6699457B2 (en) * | 2001-11-29 | 2004-03-02 | Wisconsin Alumni Research Foundation | Low-temperature hydrogen production from oxygenated hydrocarbons |
-
2004
- 2004-11-08 EP EP04026433A patent/EP1533271B1/en not_active Not-in-force
- 2004-11-08 ES ES04026433T patent/ES2399221T3/es active Active
- 2004-11-16 CA CA002487791A patent/CA2487791A1/en not_active Abandoned
- 2004-11-17 KR KR1020040093970A patent/KR20050050028A/ko not_active Application Discontinuation
- 2004-11-17 US US10/989,306 patent/US7329291B2/en active Active
- 2004-11-19 JP JP2004335203A patent/JP2005154267A/ja active Pending
- 2004-11-22 CN CN2004101005691A patent/CN1618728B/zh not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102548893A (zh) * | 2009-09-25 | 2012-07-04 | 环球油品公司 | 在二氧化碳生产中保持低一氧化碳浓度 |
| CN102548893B (zh) * | 2009-09-25 | 2014-08-13 | 环球油品公司 | 在二氧化碳生产中保持低一氧化碳浓度 |
| CN107429175A (zh) * | 2014-10-31 | 2017-12-01 | 德国汉莎航空公司 | 用于制备合成气体的方法和设施 |
| CN107429175B (zh) * | 2014-10-31 | 2020-12-01 | 卡菲尼亚有限责任公司 | 用于制备合成气体的方法和设施 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2399221T3 (es) | 2013-03-26 |
| EP1533271A1 (en) | 2005-05-25 |
| JP2005154267A (ja) | 2005-06-16 |
| CN1618728B (zh) | 2011-03-09 |
| CA2487791A1 (en) | 2005-05-22 |
| US7329291B2 (en) | 2008-02-12 |
| KR20050050028A (ko) | 2005-05-27 |
| EP1533271B1 (en) | 2013-01-09 |
| US20050108941A1 (en) | 2005-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5149796B2 (ja) | プロセス | |
| JPS5953245B2 (ja) | メタンフユウガスノ セイゾウホウホウ | |
| KR20060071338A (ko) | 개선된 일산화탄소 제조 방법 | |
| US20110300596A1 (en) | Preparation method for alcohol from carboxylic acid by one-step process | |
| CN1618728A (zh) | 制备氢气和合成气体的方法 | |
| AU2004201447A1 (en) | Process for preparation of methanol | |
| WO2006061554A1 (en) | Process for the production of methanol | |
| US8507566B2 (en) | Process for the preparation of synthesis gas | |
| JP2008290927A (ja) | 有機ハイドライドを用いる水素精製法およびその装置 | |
| Itkulova et al. | CO2 reforming of methane over Co-Pd/Al2O3 catalysts | |
| WO2016083313A1 (en) | Process for deoxygenation of alcohols by co with formation of alkanes and/or long chain alcohols | |
| CN1259300C (zh) | 固体多相催化合成乙酸的方法 | |
| KR20060002904A (ko) | 수소-부화 스트림의 제조방법 | |
| JPH03258737A (ja) | メタノールの製造方法 | |
| US9346725B2 (en) | Process for the preparation of higher alcohols | |
| JP2764114B2 (ja) | メタノールの製造方法 | |
| WO2008010743A1 (fr) | Procédé de fabrication de méthanol | |
| CA1218080A (fr) | Procede de preparation de trifluoroethanol | |
| CA2488189A1 (en) | Method for producing hydrogenous gases | |
| JP2024004110A (ja) | 高極性反応生成物の製造方法 | |
| CN1172764A (zh) | 一种由甲烷直接催化氧化制合成气的方法 | |
| Turaka et al. | NICKEL CATALYTIC ACTIVITIES ON THE SUPPORTS OF SILICA AND ACTIVATED CARBON EXTRACTION FROM LOCAL RICE HUSK FOR NITROBENZENE HYDROGENATION: A COMPARATIVE STUDY | |
| JPH11157803A (ja) | 水素の製造方法 | |
| EP1897851A1 (en) | Process for the preparation of synthesis gas | |
| JPH02121946A (ja) | コハク酸の連続製造法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110309 Termination date: 20211122 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |