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TW200536931A - Processing natural gas to form longer-chain hydrocarbons - Google Patents

Processing natural gas to form longer-chain hydrocarbons Download PDF

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Publication number
TW200536931A
TW200536931A TW094107636A TW94107636A TW200536931A TW 200536931 A TW200536931 A TW 200536931A TW 094107636 A TW094107636 A TW 094107636A TW 94107636 A TW94107636 A TW 94107636A TW 200536931 A TW200536931 A TW 200536931A
Authority
TW
Taiwan
Prior art keywords
gas
fischer
patent application
tropsch synthesis
steam
Prior art date
Application number
TW094107636A
Other languages
English (en)
Inventor
Michael Joseph Bowe
Original Assignee
Gtl Microsystems Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gtl Microsystems Ag filed Critical Gtl Microsystems Ag
Publication of TW200536931A publication Critical patent/TW200536931A/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • 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
    • 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
    • C01B3/34—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 by reaction of hydrocarbons with gasifying agents
    • C01B3/38—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 by reaction of hydrocarbons with gasifying agents 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
    • C01B3/34—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 by reaction of hydrocarbons with gasifying agents
    • C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—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 by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2453—Plates arranged in parallel
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2456—Geometry of the plates
    • B01J2219/2458—Flat plates, i.e. plates which are not corrugated or otherwise structured, e.g. plates with cylindrical shape
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
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    • B01J2219/2461—Heat exchange aspects
    • B01J2219/2465—Two reactions in indirect heat exchange with each other
    • 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
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    • B01J2219/2401—Reactors comprising multiple separate flow channels
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    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2479—Catalysts coated on the surface of plates or inserts
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2482—Catalytically active foils; Plates having catalytically activity on their own
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2483—Construction materials of the plates
    • B01J2219/2485—Metals or alloys
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/1047—Group VIII metal 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
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1025—Natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • 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
    • Y02P20/10—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

200536931 九、發明說明： 【發明所屬之技術領域】
V 本發明關係一種轉化天然氣成爲較長鏈烴之化學方法 ，和適合用於進行此方法之設備，包括催化反應器。 【先前技術】 一種方法記載於 WO 01/51194 和 WO 03/048034 (Accentusplc)，在其中甲烷與水蒸汽反應，在第1個催化 反應器內產生一^氧化碳和氨；然後所生成之氣體混合物在 φ 第二催化反應器內進行Fischer-Tropsch合成。整個結果是 將甲烷轉化爲分子量較高之烴，其在週遭條件下通常是液 體。此方法之兩階段，水蒸汽/甲烷重組及F i s c h e r _ T r 〇 p s c h 合成，於每階段需不同催化劑及催化反應器。各催化反應 器分別能夠把熱傳輸至反應氣體或從中傳出，依各反應分 別爲吸熱和放熱而定；水蒸汽/甲烷重組所需之熱可由燃燒 供給。兩個階段之運轉以在不同壓力爲最有效，但是在兩 個階段之間提高壓力爲花費多而耗用能量。 φ 【發明內容】 根據本發明，提供一種處理天然氣以產較長鏈烴之製 程，此製程包含使天然氣與水蒸汽在〇·4至〇.6MPa(百萬帕 斯卡）（4至6個大氣壓）下產生一氧化碳與氫之混合物’冷 卻該混合物，利用兩個連續的壓縮階段壓縮此混合物，在 兩階段之間冷卻至於1.8至2.2 MPa(l 8至22個大氣壓）； 然後使此混合物接受Fischer-Tropsch合成法而產生較長鏈 烴。 通常在重組之前，天然氣與水蒸汽混合須先調整天然 200536931 氣之壓力至一適當壓力（亦即在0.4和〇 者Fischer-Tropsch合成進行於19-21大 。（在各種情形中壓力之値爲絕對壓力） 製程也產生一種尾氣，含有氫和一 者爲部份尾氣被用於產生電力，例如作 之渦輪機燃料。如此所提供之電力不但 例如各壓縮機之運轉，且亦提供多餘之 〇 尾氣也可以用於轉化天然氣內之二 化碳，其係在Fischer-Tropsch合成法之 氣轉換反應。 較佳者，水蒸汽/甲烷之重組反應^ 合成兩者用緊密的催化反應器進行。如 好包含成爲一疊之多個金屬片，其形狀 第二流體之流動通路，各通路被交替排 其中各流體之間有良好的熱接觸。適當 置，隨反應之需要而定。爲了確具所需 爲水蒸汽/甲烷重組反應器，第一和第二 2毫米和1 0毫米間之深度，較佳者其與 深度小於6毫米，更佳者深爲在5毫米 若爲Fischer-Tropsch反應器，用於反應 於1 0毫米。波形或波紋之金屬箔、金屬 之金屬毯板可在各流動通路中用作催化 提高熱的傳輸和催化劑表面積。此等催 .6 Μ P a之間）。較佳 氣壓範圍內之壓力 〇 部份氣態烴。較佳 爲用於驅動發電機 用於製程之運轉， 電力供作其他用途 氧化碳使成爲一氧 上游進行可逆之水 0 Fischer-Tropsch 此之催化反應器最 和排列界定第一和 列於疊中，確保在 催化劑應依需要設 之良好熱接觸，若 流動通路兩者可在 各片成正交方向者 至3毫米範圍內； 之各通路較佳深小 網、或波形或摺皺 劑結構之基底，以 化劑結構最好可從 200536931， 管內之溝槽取出，使其在催化劑耗盡時可被替換。 此型反應器具備短的擴散途徑長度，使熱和質量傳輸 速率可以升高，且使化學反應之速率也高。如此之反應器 因而能夠提供高的釋能密度。 【實施方式】 本發明關係一種用於轉化天然氣（主要爲甲烷）成爲長 鏈烴之化學製程。第一階段涉及水蒸汽重組，其可謂天然 氣與水蒸汽混合而後進行反應如 H20+CH4 — CO+3H2 此反應爲吸熱的，且可在第一氣流通道用铑或鉑/鍺催化劑 催化。促成此反應所需之熱可由諸如甲烷和氫等可燃氣體 之燃燒提供，爲放熱的，並可在相鄰之第二氣流通道內用 鈀催化劑催化。在兩種情形中，催化劑較宜置於經過安定 化之礬土支承物上，通常是形成厚度小於1 0 0微米厚之塗 層於金屬基板上。燃燒反應可以發生於大氣壓力，但重組 反應器發生於4與5個大氣壓之間。燃燒所生之熱將通過 分隔相鄰通道之金屬片被傳導。 然後水蒸汽/甲烷重組所生氣體混合物被用於進行 Fischer-Tropsch合成而產生長鏈烴，亦即： nCO + 2nH2 — (CH2)n + nH20 此爲放熱反應，於提升溫度下發生，通常在190 °C與 2 8 0 °C之間，例如21(TC ;和升高之壓力，通常在1.8MPa 和2 · 1 Μ P a (絕對値）之間，例如2.0 Μ P a，在有催化劑如鐵、 鈷或熔化之磁鐵石等催化劑與鉀促進劑之存在中。用於 200536931.
Fischei-Tropsch合成之較佳催化劑含有比表面積爲140-2 3 0米2 /克之珈瑪氧化鋁與約} 〇 _ 4 〇 %之鈷（與氧化鋁之重量 比），並有促進劑如鈸、鉑或釓，其爲少於鈷重量之1 〇%。 在金屬箔表面帶鈷之珈瑪氧化鋁層通常爲120-180微米厚 〇 兹參考第1圖，整體化學法以流程圖表示，在其中顯 示設備各組分。天然氣給料5主要由甲烷組成，在此實施 例中’並有一百分比較高級C2至C i !之烴。通常此等高級 烴隨天然氣來源而呈達10%v/v(容積比）。氣體給料5可爲 例如在l.OMPa之壓力（1〇大氣壓）。 用閥8調節氣體壓力至〇.6MPa，然後氣體5於熱交換 器1 〇內，利用由催化燃燒之熱廢氣預熱至約4 0 0 °C，然後 給至固體床除硫系統1 2 ’減低氣體內之硫含量至〇 . 1 p p m (百萬之1)或更少。已除硫之天然氣然後與水蒸汽混合，例 如在一流體旋渦混合器1 4內。氣體/水蒸汽混合物在熱交 換器1 6內利用催化燃燒之熱廢氣加熱，使氣體混合物於 5 0 0 °C之溫度。此混合物進入一絕熱固定床預重組器1 8， 在其中接觸鎳或鉑/铑基之甲烷化催化劑。較高級之烴與水 蒸汽反應而形成甲烷和C 0。 氣體混合物，主要包含甲烷和水蒸汽與小比例之一氧 化碳，於通常爲4 5 0°C之較低溫度從預重組器1 8流出。然 後用閥19降低壓力至〇.45MPa(絕對壓力）於進入重組器2〇 之前。重組器20是一個密接的催化反應器如上述型式，由 一疊界定流動途徑之板所組成，用於使吸熱和發熱反應於 200536931. 良好熱接觸之中，其中適當含有催化劑，例如，在波形金 屬箔基板上。在重組器20中之重組器通道含有鉛/铑催化 劑，且水蒸汽與甲烷反應形成一氧化碳和氫。重組器中之 溫度從入口之4 5 0 °C升高在出口處約8 0 0 - 8 5 (TC。水蒸汽和 氣體被供至混合器1 4之流速爲使給入至重組器20時水蒸 汽與碳之莫耳比爲在1.2-1.6之間，較佳在1.3與1.5之間 。隨氣體5所含之烴量較高而定，在預重組器18入口之水 蒸汽對碳之比例須較此爲較高。 在重組反應器20內用於吸熱反應之熱是由Fischer-Trop sch合成之尾氣22內之短鏈烴與氫之混合物，合倂鼓 風機24所送空氣，以催化燃燒而提供。燃燒發生於重組器 20內相鄰各流動通道中之鈀/鉑催化劑上。燃燒氣體之途徑 至少大約相對於重組器氣體之途徑而並行。催化劑可含有 珈瑪氧化鋁作爲支承物，塗覆鈀/鉑3 : 1混合物，在寬廣溫 度範圍內爲一種有效之催化劑。可燃之氣體混合物可由沿 反應器2 0之各階段供給，保持全部燃燒通道在長度上發生 燃燒。 一氧化碳和氫之混合物於8 0 0 °C以上從重組器2 0排出 ，並因通過蒸汽汽化之熱交換器2 6而被淬冷至4 0 (TC以下 。水由泵2 8供至此熱交換器2 6，且用於重組程序之蒸汽 因而經過控制閥3 0供至混合器1 4。用冷卻水進一步冷卻 氣體混合物於熱交換器32中至約爲60 °C，於是多餘之水 冷凝，並經過旋渦器3 3和分離容器3 4而被分離。然後氣 體混合物被壓縮機3 6壓縮至約爲2.5倍之壓力，並在通過 200536931. , 第二旋渦器41和分離容器42之前用熱交換器40再加冷卻 而除任何冷凝之水。所分離之水循環回至蒸汽汽化環路。 然後热體於弟一^壓縮機14被壓縮至20大氣壓。 然後高壓之一氧化碳和氫氣流給入至一催化之 Fischer-Tropsch反應器50，此又再爲一密接之催化反應器 ，由一疊板片形成如上述；反應物混合物流經一組通道， 而冷卻劑流經另一組。 從Fischer-Tropsch合成之反應生成物，主要爲水和烴 • 類如烷烴，經過熱交換器5 4和旋渦分離器5 6冷卻而凝結 爲液體，繼在分離室5 8，在其中分離三相之水、烴類和尾 氣，烴生成物被安定於大氣壓力。存在氣相之烴和多餘之 氫氣（Fischer-Tropsch尾氣22)被收集並分開。一部份通過 減壓閥60以供在重組器20中催化燃燒程序作爲燃料（如上 述）。剩餘之尾氣62給至氣渦輪機63，其以電能產生器64 驅動。 氣渦輪機64產生設備所需之全部動力，並有能力輸出 φ 餘量。主要設備需要電力者爲壓縮機36和44，與泵24和 2 8 ;電力也可以用於運作真空蒸餾單元以提供製程中之水 ，供產生蒸汽，並提供飲水。 應了解由上述各式所論，蒸汽重組階段形成比Fischer-Tropsch 合成所 需者更 多的氣 。因 此尾氣 22 含有足 重的氫 ，和低級烷（如C!至C5)。然而，尾氣22也含有足量的一 氧化碳。所以他們可藉通過第二個如此之反應器（未示）而 接受第二次的Fischer-Tropsch合成’使整體的一氧化碳轉 化作用增加，獲得較多的需求產品。 -10- 200536931 • 壓縮機3 6和44的實際壓縮比約爲2.5 : 1。運作各壓縮 機於較局壓力比將升筒氣體溫度至於甚高程度，轉軸動力 需求將變爲過量。如果 Fischer-Tropsch合成進行於約 2.0MPa，兩個壓縮機36和44只要運轉於〇.4MPa以上之壓 力即足供重組器2 0所需。在此種升高之壓力，水蒸汽/甲 烷重組反應器2 0之運轉有降低甲烷轉化率之缺點，通常約 少5 - 1 0%，但是這比在投資和運轉成本之折減者爲多。反 之，爲了用單一壓縮機操作，將須使重組進行於約〇 . 8 Μ P a • 之壓力，如此將降低甲烷轉化率約1 5 %，且在另一方面， 若重組反應器進行於〇· IMP a(l大氣壓），則將需四個連續 的壓縮階段，而且動力需求大約將爲加倍。 提高壓力而行重組之其他優點是對管路所需求的規模 。氣體的速度通常不高於1 8米秒-1，所以對於特別的質量 流速，在氣體壓力和密度降低時，所需管徑明顯增大。例 如，一個每日產量1〇〇〇桶產能之工廠，在壓力爲〇.5MPa 時，氫/一氧化碳混合物（合成氣）之容積流速約爲48，0 00米3 ® 小時_ 1，則需約爲1 . 〇米直徑之管路。反之，如果壓力爲大 氣壓，氣體容積將加大5倍而管路將須爲約2.2米直徑。 在若干情形中，天然氣亦含有二氧化碳。在上述製程 之一項變更中，若干尾氣22(富含氫）被回饋至在混合器Μ 之天然氣/水蒸汽混合物內，使其流經預重組器1 8。因而進 入重組器2 0之氣體混合物含有甲烷、水蒸汽、氫和二氧化 碳。根據可逆的水氣移動反應，氫能夠與二氧化碳形成： C〇2 + H2 -> co + h2o -11- 200536931. 此反應將發生於重組器2 0內，並使二氧化碳濃度降低 至在重組器20內壓力和溫度條件之平衡程度。（即使如果 天然氣5不含二氧化碳、水蒸汽/甲烷爲1 . 5比率’其間仍 有小量約5 %之二氧化碳產生於重組器2 0中）°因此在給入 氣體中任何額外之二氧化碳，其間若有足夠的自由氫存在 ，則可被轉化成爲一氧化碳。在尾氣22中出現之水氣，以 及由此可逆水氣轉移反應所產生之水，在選擇混合器1 4之 初始水蒸汽/甲烷比率時必須列入計算。 【圖式簡單說明】 本發明茲進一步特別說明，其僅爲實施例，並參考所 附各圖，其中： 第1圖表示本發明一化學方法之流程。 【主要元件符號說明】 5 天然氣給料 8 閥 10 熱交換器 12 除硫系統 14 流體旋渦混合器 16 熱交換器 18 預重組器 19 閥 20 重組器 22 尾氣 24 鼓風機 -12- 200536931
26 熱交換器 2 8 泵 3 0 控制閥 3 2 熱交換器 3 3 旋渦器 34 分離器 36 壓縮機 40 熱交換器 4 1 旋渦器 42 分離容器 44 壓縮機 50 Fischer-Tropsch 反應器 52 熱交換器 54 熱交換器 56 旋渦分離器 58 分離室 60 閥 62 剩餘尾氣 63 氣渦輪機 64 電能產生器 -13-

Claims (1)

  1. 200536931. 十、申請專利範圍： 1 . 一種處理天然氣使產生長鏈烴之方法，該方法包含使天 然氣與水蒸汽重組於在0.4至0.6MPa範圍內之壓力而產 生一氧化碳與氫之混合物；冷卻該混合物；用兩個連續 的壓縮階段，並於兩階段之間予以冷卻，至達1 .8至 2.2MPa範圍內之壓力；然後使混合物接受 Fischer-Tropsch合成作用而產生長鏈烴。 2·如申請專利範圍第1項之方法，其中Fischer-Tropsch合 B 成作用是進行於壓力在1.9-2.IMPa之範圍內。 3·如申請專利範圍第1項之方法，其中Fischer-Tropsch合 成作用之輸出物以冷凝分離成爲液相和尾氣，且該尾氣 至少有一部份被用於產生電力。 4 ·如申請專利範圍第3項之方法，其中產自尾氣之電力提 供進行兩個壓縮階段之動力。 5 .如申請專利範圍第丨至4項中任一項之方法，其中供水 蒸汽重組反應之水至少部份獲自真空蒸餾單元。 6 ·如申請專利範圍第3項之方法，其中供水蒸汽重組反應 之水至少部份獲自從尾氣所產生電力爲動力之真空蒸餾 單兀。 7 ·如申請專利範圍第1至4項中任一項之方法，其中水蒸 汽/甲烷重組反應和F i s c h e r - T r 〇 p s c h合成反應兩者是使 用個別而緊密的催化反應器，各含由多數金屬片所形成 之一疊，並界定第一與第二流體流動通道，各通道交替 安排於疊內使確有良好的熱接觸。 -14- 200536931. 8 ·如申請專利範圍第1至4項中任一項之方法，其中天然 氣含有若干二氧化碳，且該方法亦包括分離從Fischer-Tropsch合成作用之輸出成爲液相與尾氣，並至少利用部 份尾氣進行Fischer-Tropsch合成作用之逆向水氣轉變反 應之上游。 9 . 一種用於進行如申請專利範圍第7項方法之工廠設備， 設備包含用於水蒸汽/甲烷重組之第一反應器，和用於 Fischer-Tropsch合成之第二反應器，在第一和第二反應 器之間的兩個連續之壓縮機，在兩具壓縮機之間冷卻已 壓縮氣體之機構，且其中各反應器含有成疊之金屬片， 界定第一和第二流動通道，各通道被交替排列於疊內以 保其間之流體之間有良好的熱接觸。 ^如申請專利範圍第9項之工廠設備，其中發生反應於其 中之各個流動通道含有一種催化劑結構於金屬支承物上 ，該催化劑結構爲可移動。
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Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2904832B1 (fr) * 2006-08-08 2012-10-19 Inst Francais Du Petrole Procede de production de gaz de synthese avec conversion de co2 a l'hydrogene
RU2461603C2 (ru) 2007-01-19 2012-09-20 Вилосис Инк. Способ, установка и композиция для превращения природного газа в высокомолекулярные углеводороды посредством микроканальной технологии
US20080260631A1 (en) 2007-04-18 2008-10-23 H2Gen Innovations, Inc. Hydrogen production process
US8100996B2 (en) 2008-04-09 2012-01-24 Velocys, Inc. Process for upgrading a carbonaceous material using microchannel process technology
CN104355957A (zh) 2008-04-09 2015-02-18 万罗赛斯公司 使用微通道工艺技术将碳质材料转化为甲烷、甲醇和/或二甲醚的方法
BRPI0919785A2 (pt) 2008-10-10 2019-05-21 Velocys Inc processo e equipamento empregando tecnologia de processo de microcanal
US20110083997A1 (en) * 2009-10-09 2011-04-14 Silva Laura J Process for treating heavy oil
JP5695837B2 (ja) * 2010-04-01 2015-04-08 株式会社東芝 改質ガスあるいは水素の製造システム
RU2422491C1 (ru) * 2010-05-04 2011-06-27 Открытое акционерное общество "Газпром" Способ получения жидких углеводородов из синтез-газа
US8168686B2 (en) 2010-12-22 2012-05-01 Rentech, Inc. Integrated biorefinery for production of liquid fuels
JP5767497B2 (ja) * 2011-03-31 2015-08-19 独立行政法人石油天然ガス・金属鉱物資源機構 重質炭化水素の除去方法
GB201120327D0 (en) * 2011-11-24 2012-01-04 Compactgtl Plc Oil well product treatment
JP6057643B2 (ja) 2012-09-21 2017-01-11 三菱重工業株式会社 液体燃料を製造するとともに発電する方法およびシステム
US9676623B2 (en) 2013-03-14 2017-06-13 Velocys, Inc. Process and apparatus for conducting simultaneous endothermic and exothermic reactions
WO2014181256A1 (en) * 2013-05-06 2014-11-13 Saudi Basic Industries Corporation Recycling gas to heat the hydrodesulphurization section
US9701910B2 (en) 2013-07-31 2017-07-11 Saudi Basic Industries Corporation Process for the production of olefins through FT based synthesis
EP3027553A2 (en) * 2013-07-31 2016-06-08 Saudi Basic Industries Corporation A process for the production of olefins through fischer-tropsch based synthesis
RU2555043C1 (ru) * 2013-09-11 2015-07-10 Общество с ограниченной ответственностью "Газохим Техно" Способ очистки воды, образующейся на стадии синтеза углеводородов в процессе gtl, и способ ее использования
EA033831B1 (ru) 2013-12-02 2019-11-29 Haldor Topsoe As Способ конверсии природного газа в углеводородные продукты и установка для осуществления способа
US20230330620A1 (en) * 2020-08-21 2023-10-19 Topsoe A/S Off-gas utilization in electrically heated reforming plant
JP7577556B2 (ja) * 2021-02-10 2024-11-05 株式会社神鋼環境ソリューション 水素ガス製造装置および水素ガス製造方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568953A (en) * 1947-10-31 1951-09-25 Kellogg M W Co Process for the synthesis of organic compounds
US3986349A (en) * 1975-09-15 1976-10-19 Chevron Research Company Method of power generation via coal gasification and liquid hydrocarbon synthesis
US4098339A (en) * 1976-06-21 1978-07-04 Mobil Oil Corporation Utilization of low BTU natural gas
US5733941A (en) * 1996-02-13 1998-03-31 Marathon Oil Company Hydrocarbon gas conversion system and process for producing a synthetic hydrocarbon liquid
US6306917B1 (en) * 1998-12-16 2001-10-23 Rentech, Inc. Processes for the production of hydrocarbons, power and carbon dioxide from carbon-containing materials
NO311081B1 (no) * 1999-12-09 2001-10-08 Norske Stats Oljeselskap Optimalisert FT-syntese ved reformering og resirkulering av tail-gass fra FT-syntesen
MXPA02006855A (es) 2000-01-11 2003-05-23 Accenstus Plc Reactor catalitico.
GB0116894D0 (en) 2001-07-11 2001-09-05 Accentus Plc Catalytic reactor
EP1434652B1 (en) * 2001-10-12 2005-02-16 GTL Microsystems AG Catalytic reactor
GB0125035D0 (en) 2001-10-18 2001-12-12 Accentus Plc Catalytic reactor
BR0206966A (pt) 2001-12-05 2004-03-09 Accentus Plc Processo para realizar reforma de vapor/metano para gerar monóxido de carbono e hidrogênio, e, planta para processar metano

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RU2361900C2 (ru) 2009-07-20
MXPA06010430A (es) 2007-02-16
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CA2559793A1 (en) 2005-09-29
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JP2007529594A (ja) 2007-10-25
MY139077A (en) 2009-08-28
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AU2005223463A1 (en) 2005-09-29
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US20050209347A1 (en) 2005-09-22
AP2006003736A0 (en) 2006-10-31
RU2006136143A (ru) 2008-04-27
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US7067560B2 (en) 2006-06-27

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