CN112261993A - 使用低铁催化剂生产甲醇的方法 - Google Patents
使用低铁催化剂生产甲醇的方法 Download PDFInfo
- Publication number
- CN112261993A CN112261993A CN201980038505.8A CN201980038505A CN112261993A CN 112261993 A CN112261993 A CN 112261993A CN 201980038505 A CN201980038505 A CN 201980038505A CN 112261993 A CN112261993 A CN 112261993A
- Authority
- CN
- China
- Prior art keywords
- methanol
- catalyst
- synthesis
- gas
- iron
- 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.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 52
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 231100000572 poisoning Toxicity 0.000 abstract description 13
- 230000000607 poisoning effect Effects 0.000 abstract description 13
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 37
- 239000010949 copper Substances 0.000 description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 230000009849 deactivation Effects 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 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
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1837—Loop-type reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
通过在合成过程中使用最多包含100ppmw Fe的催化剂，可以抵消由于催化剂的铁中毒引起的甲醇合成催化剂的劣化。该方法在甲醇合成设备中特别有用，该设备包括补充气体压缩机和甲醇回路中的合成反应器，并且在补充气体压缩机和甲醇回路之间安装有直流预转化器。
Description
技术领域
本发明涉及用于抵消由催化剂的铁中毒引起的甲醇合成催化剂的劣化的措施。更具体地说，本发明涉及避免甲醇合成催化剂中毒的最佳操作条件。
发明背景
甲醇由合成气体(合成气)合成，合成气由H2、CO和CO2组成。合成气的转化是在催化剂上进行的，该催化剂通常是铜-氧化锌-氧化铝(Cu/ZnO/Al2O3)催化剂。由合成气转化而来的甲醇合成可以表示成二氧化碳的氢化反应，并伴有变换反应，并且可以概括为以下包括以下反应(1)-(3)的顺序反应：
CO+2H2<->CH3OH (1)
CO2+3H2<->CH3OH+H2O (2)
CO+H2O<->CO2+H2 (3)
其中反应(3)是水煤气变换(WGS)反应。
在Cu/ZnO/Al2O3催化剂的铜金属表面上发生的合成反应主要是反应(2)，即由二氧化碳形成甲醇。在过去的几十年中，尽管已经对甲醇合成催化的反应动力学和反应机理以及催化活性部位的性质等方面进行了研究，但与之相比，有关甲醇合成催化剂失活的文献却相对较少。一个例外情况是1992年H.H.Kung对甲醇催化剂失活的综述(Catalysis Today92(1992)，443)，其重点关注的是硫中毒问题，而铁的失活仅是指铁在催化剂表面的沉积可能会阻塞活性位点并提供不希望的催化活性，例如通过Fischer-Tropsch反应形成烃，然后变成竞争反应。
Cu/ZnO/Al2O3甲醇催化剂的活性与材料的铜表面积直接相关。因此，催化剂的制造需要制备将提供高且稳定的铜表面积的相。在实际的甲醇设备运行期间，甲醇合成催化剂可能发生三个主要的失活过程：热烧结、催化剂中毒和反应物引起的失活。热烧结是温度引起的铜表面积随时间的损失，催化剂中毒是催化剂毒物与工艺气体一起输送到甲醇转化器中，而反应物引起的失活是由反应物气体组成引起的失活。这些失活过程将全部导致催化剂活性的永久性损失，最后，催化剂中毒将导致催化剂选择性的永久性损失。
发明内容
本发明特别处理由铁引起的甲醇催化剂中毒，该中毒是由与工艺气体一起运输到甲醇转化器中的设备的金属部分引起的。铁作为挥发性铁物种Fe(CO)5(五羰基铁或仅羰基铁)运输到转化器中，这是由富含CO的气体与设备其他部分的金属表面的低温反应生成的。然而，在更高的温度下，例如在合成转化器中发现的那些温度下，羰基铁在与高表面积铜催化剂接触时将易于分解。与硫中毒不同(在催化剂的配制方式允许氧化锌组分作为硫中毒的吸收剂的情况下，可以减少对活性的影响)，在Cu/ZnO/Al2O3催化剂中铁没有天然的吸收作用(Ind.Eng.Chem.Res.32,1993,pg.1610-1621)。
关于热烧结，温度是控制金属和氧化物的烧结速率的主要因素。与其他常用的金属催化剂(例如铁(1535℃)和镍(1455℃))相比，铜的熔点较低(1083℃)。
在Cu/ZnO/Al2O3催化剂上，存在大量的材料，这些材料原则上可以作为毒物，但是在对排放的催化剂样品进行分析后，通常只能发现其中的几种。例如，二氧化硅(会降低合成活性并促进副产物形成)和氯化物(会导致很高的铜微晶烧结率)都是铜催化剂的毒药，但是在运作良好的甲醇设备中，它们很少以任何显著的量运输到合成催化剂上。但是，在排放的甲醇合成催化剂上，除了镍和硫之外，特别是还经常发现大量铁(如上所述，已作为羰基铁被带入转化器)。除了使催化剂中毒外，甲醇设备中铁的存在还具有形成甲烷、石蜡和有害的长链蜡的作用。
申请人现已发现，为了避免Cu/ZnO/Al2O3甲醇催化剂失活，最佳条件是使用最大Fe含量为100ppmw的催化剂。使用含铁量超过100ppmw的催化剂将导致催化剂快速失活。这可用于在甲醇反应器周围的任何设备设计或布局中使用催化剂，例如带有或不带有预转化器的甲醇回路，而不论布局是新颖的设计还是改造设计。
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。
因此，本发明涉及一种根据上述合成反应(1)至(3)通过在升高的温度和升高的压力下进行平衡反应而从合成气生产甲醇的方法，所述方法通过使用最多含100ppmw的Fe的催化剂进行。
在现有技术中，已显示出烃原料中的铁污染物会毒化催化剂并降低其活性。因此，EP 3 052 232 B1涉及一种用于使铁污染的FCC(流体催化裂化)催化剂再活化的方法。当铁堵塞催化剂表面时会发生中毒，这(除中毒以外)会导致催化剂的表观堆积密度显著降低。根据EP文件，包含氧化镁-氧化铝水滑石材料的铁转移剂用于使FCC催化剂再活化。
在US 9.314.774 B1中，尝试通过使用具有非常特殊组成的催化剂来推迟Cu/ZnO/Al2O3催化剂的失活，即Zn/Cu摩尔比为0.5至0.7，Si/Cu摩尔比为0.015至0.05，来自锌的峰与来自铜的峰的最大强度比不大于0.25，并且来自铜的峰的半峰宽(2θ)为0.75至2.5。此外，所述催化剂可具有至多0.01mol％的锆含量。
US 2012/0322651 A1描述了一种用于制备甲醇的多阶段方法，其包括多个串联合成阶段，其中基于反应温度和/或合成气中一氧化碳的浓度的反应条件的严格性沿着流动方向从第一反应阶段到最后反应阶段降低。第一反应阶段具有低活性但长期稳定性高的第一催化剂，而最后反应阶段具有高活性但长期稳定性低的第二催化剂。每次通过每个反应阶段，只能将合成气部分转化为甲醇，因此必须将未转化的合成气再循环到反应阶段。
在US 2014/0031438 A1中公开了一种由富含惰性气体的合成气生产甲醇的方法。催化预反应器安装在合成回路的上游，合成气的第一部分在催化预反应器中转化为甲醇。此外，惰性气体分离阶段，如PSA系统或膜系统连接在合成回路的下游，从而可以将富氢的合成气流返回到合成回路。在富含甲烷的合成气的处理中，惰性气体分离阶段还可以包括自热重整器，其中甲烷被转化为碳氧化物和氢，它们也被返回到合成回路中。
在申请人的WO 2017/025272 A1中，描述了由劣质合成气生产甲醇的方法，其中相对较小的绝热反应器可以更有效地运行，从而避免了用于甲醇生产的绝热反应器的一些缺点。这可以通过快速调节再循环气来控制预转化器中的出口温度，即通过控制预转化器中的气体时空速度来完成。
WO 2016/179476 A1中公开了组合的厌氧消化器和气液系统。厌氧消化器需要热量并产生甲烷，而气液系统会将甲烷转化为更高价值的产物，包括甲醇和甲醛。
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，每次通过甲醇催化剂时合成气转化为甲醇的转化率也相对较低。
由于在直流(once-through)转化过程中甲醇的产率低，因此本领域的常规做法是将与反应流出物分离的未转化的合成气进行再循环，并用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在新鲜的合成气上操作，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的气体稀释，或者在含有甲醇和未转化的合成气的反应器流出物上操作。在通常实践中，再循环比(再循环气与新鲜合成原料气的比率)为2:1至7:1。如果在补充气体压缩机和甲醇回路之间安装了预转化器，则预转化器将捕获来自前端的铁。尽管已知铁的存在以及CO的分压和温度会影响长链蜡的形成，但其机理和极限尚不完全清楚。
关于催化剂本身，已经计算出，Fe含量为100ppmw的Cu/ZnO/Al2O3催化剂的预期寿命为4年。实际的使用寿命也证明是4年。
对于具有更大的Fe含量，更具体地为1500ppmw的Fe含量的Cu/ZnO/Al2O3催化剂，已经计算出预期寿命为3年。然而，在这种情况下，实际寿命仅为1.5年，这证明了高铁含量使催化剂的寿命缩短得比预期中的更长。
Claims (3)
1.一种用于通过平衡反应由合成气生产甲醇的方法，该平衡反应在升高的温度和升高的压力下根据如下反应进行：
CO+2H2<->CH3OH (1)
CO2+3H2<->CH3OH+H2O (2)
CO+H2O<->CO2+H2 (3)
所述方法通过使用最多含有100ppmw Fe的催化剂进行。
2.根据权利要求1所述的方法，其中所述催化剂是Cu/ZnO/Al2O3甲醇催化剂。
3.一种设备，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，并且在所述补充气体压缩机和所述甲醇回路之间安装有直流预转化器，其中所使用的催化剂含铁量最高为100ppmw。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201800268 | 2018-06-12 | ||
| DKPA201800268 | 2018-06-12 | ||
| PCT/EP2019/065132 WO2019238634A1 (en) | 2018-06-12 | 2019-06-11 | A process for methanol production using a low-iron catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112261993A true CN112261993A (zh) | 2021-01-22 |
Family
ID=66867121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980038505.8A Pending CN112261993A (zh) | 2018-06-12 | 2019-06-11 | 使用低铁催化剂生产甲醇的方法 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20210221758A1 (zh) |
| EP (1) | EP3806991A1 (zh) |
| KR (1) | KR20210018932A (zh) |
| CN (1) | CN112261993A (zh) |
| AU (1) | AU2019286313A1 (zh) |
| BR (1) | BR112020025334A2 (zh) |
| CA (1) | CA3101861A1 (zh) |
| EA (1) | EA202190012A1 (zh) |
| MX (1) | MX2020013396A (zh) |
| WO (1) | WO2019238634A1 (zh) |
| ZA (1) | ZA202006734B (zh) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279781A (en) * | 1979-10-09 | 1981-07-21 | United Catalysts Inc. | Catalyst for the synthesis of methanol |
| US4623668A (en) * | 1983-05-25 | 1986-11-18 | Basf Aktiengesellschaft | Preparation of methanol |
| US5179129A (en) * | 1991-03-01 | 1993-01-12 | Air Products And Chemicals, Inc. | Staged liquid phase methanol process |
| CN1422692A (zh) * | 2001-11-29 | 2003-06-11 | 中国石化集团齐鲁石油化工公司 | 一种甲醇合成催化剂的保护剂及其制备方法 |
| US20050020700A1 (en) * | 2001-11-16 | 2005-01-27 | Hans-Joachim Bahnisch | Method for catalytic production of methanol and a device for implementing said method |
| CN101224871A (zh) * | 2008-02-03 | 2008-07-23 | 湖北省化学研究院 | 合成气的深度净化方法 |
| WO2017134162A1 (en) * | 2016-02-02 | 2017-08-10 | Haldor Topsøe A/S | Atr based ammonia process and plant |
| CN107235826A (zh) * | 2017-06-16 | 2017-10-10 | 中国石油大学(华东) | 基于级间吸收分离的合成气流化床制甲醇工艺 |
| CN107922297A (zh) * | 2015-08-12 | 2018-04-17 | 托普索公司 | 用于从低质量合成气生产甲醇的新方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69123432D1 (de) | 1990-09-18 | 1997-01-16 | Csir | Katalysator für die Methanolsynthese |
| DE102010008857A1 (de) | 2010-02-22 | 2011-08-25 | Lurgi GmbH, 60439 | Verfahren zur Herstellung von Methanol |
| DE102011017300A1 (de) | 2011-04-15 | 2012-10-18 | Lurgi Gmbh | Verfahren und Anlage zur Herstellung vom Methanol aus inertenreichem Synthesegas |
| SG11201408066UA (en) | 2012-06-04 | 2015-03-30 | Mitsui Chemicals Inc | Catalyst for methanol production, method of producing the same and process of methanol production |
| EP3052232B1 (en) | 2013-10-04 | 2018-01-10 | Johnson Matthey Process Technologies, Inc. | Process for reactivating an iron-contaminated fcc catalyst |
| WO2016179476A1 (en) | 2015-05-06 | 2016-11-10 | Maverick Biofuels, Inc. | Combined anaerobic digester and gtl system and method of use thereof |
-
2019
- 2019-06-11 EP EP19730735.8A patent/EP3806991A1/en active Pending
- 2019-06-11 AU AU2019286313A patent/AU2019286313A1/en active Pending
- 2019-06-11 EA EA202190012A patent/EA202190012A1/ru unknown
- 2019-06-11 MX MX2020013396A patent/MX2020013396A/es unknown
- 2019-06-11 US US17/055,399 patent/US20210221758A1/en active Pending
- 2019-06-11 BR BR112020025334-0A patent/BR112020025334A2/pt unknown
- 2019-06-11 WO PCT/EP2019/065132 patent/WO2019238634A1/en active Application Filing
- 2019-06-11 CN CN201980038505.8A patent/CN112261993A/zh active Pending
- 2019-06-11 KR KR1020217000621A patent/KR20210018932A/ko not_active Application Discontinuation
- 2019-06-11 CA CA3101861A patent/CA3101861A1/en active Pending
-
2020
- 2020-10-28 ZA ZA2020/06734A patent/ZA202006734B/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279781A (en) * | 1979-10-09 | 1981-07-21 | United Catalysts Inc. | Catalyst for the synthesis of methanol |
| US4623668A (en) * | 1983-05-25 | 1986-11-18 | Basf Aktiengesellschaft | Preparation of methanol |
| US5179129A (en) * | 1991-03-01 | 1993-01-12 | Air Products And Chemicals, Inc. | Staged liquid phase methanol process |
| US20050020700A1 (en) * | 2001-11-16 | 2005-01-27 | Hans-Joachim Bahnisch | Method for catalytic production of methanol and a device for implementing said method |
| CN1422692A (zh) * | 2001-11-29 | 2003-06-11 | 中国石化集团齐鲁石油化工公司 | 一种甲醇合成催化剂的保护剂及其制备方法 |
| CN101224871A (zh) * | 2008-02-03 | 2008-07-23 | 湖北省化学研究院 | 合成气的深度净化方法 |
| CN107922297A (zh) * | 2015-08-12 | 2018-04-17 | 托普索公司 | 用于从低质量合成气生产甲醇的新方法 |
| WO2017134162A1 (en) * | 2016-02-02 | 2017-08-10 | Haldor Topsøe A/S | Atr based ammonia process and plant |
| CN107235826A (zh) * | 2017-06-16 | 2017-10-10 | 中国石油大学(华东) | 基于级间吸收分离的合成气流化床制甲醇工艺 |
Non-Patent Citations (1)
| Title |
|---|
| HOWARD F.RASE: "《HANDBOOK OF COMMERCIAL CATALYSTS》", 31 December 2000, CPC PRESS * |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA202006734B (en) | 2024-02-28 |
| BR112020025334A2 (pt) | 2021-03-09 |
| AU2019286313A2 (en) | 2021-01-14 |
| CA3101861A1 (en) | 2019-12-19 |
| EP3806991A1 (en) | 2021-04-21 |
| US20210221758A1 (en) | 2021-07-22 |
| MX2020013396A (es) | 2021-02-26 |
| AU2019286313A1 (en) | 2021-01-07 |
| EA202190012A1 (ru) | 2021-03-16 |
| KR20210018932A (ko) | 2021-02-18 |
| WO2019238634A1 (en) | 2019-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8961829B2 (en) | Catalytic hyrogenation of carbon dioxide into syngas mixture | |
| AU2009326172B2 (en) | Integrated gas refinery | |
| US8962702B2 (en) | Mixed oxide based catalyst for the conversion of carbon dioxide to syngas and method of preparation and use | |
| US9249079B2 (en) | Process for increasing the carbon monoxide content of a syngas mixture | |
| US20090111900A1 (en) | Simple low-pressure fischer-tropsch process | |
| EP2911975A1 (en) | Process for the preparation of hydrocarbons | |
| CA2633937C (en) | Process for producing condensed-phase product from one or more gas-phase reactants | |
| Trimm et al. | Steam reforming and methanol synthesis | |
| WO2020154075A1 (en) | Methanol production process with higher carbon utilization by co2 recycle | |
| CN112261993A (zh) | 使用低铁催化剂生产甲醇的方法 | |
| US11834394B2 (en) | Methanol production process with increased energy efficiency | |
| CN101193845A (zh) | 将合成气体转化为含氧化合物的方法 | |
| US20170157595A1 (en) | Novel catalyst for the water gas shift reaction | |
| EA044713B1 (ru) | Способ получения метанола с увеличенной энергетической эффективностью |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |