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TW200911687A - Integrated processes for generating carbon monoxide for carbon nanomaterial production - Google Patents

Integrated processes for generating carbon monoxide for carbon nanomaterial production Download PDF

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Publication number
TW200911687A
TW200911687A TW097121343A TW97121343A TW200911687A TW 200911687 A TW200911687 A TW 200911687A TW 097121343 A TW097121343 A TW 097121343A TW 97121343 A TW97121343 A TW 97121343A TW 200911687 A TW200911687 A TW 200911687A
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TW
Taiwan
Prior art keywords
gas stream
carbon dioxide
hydrocarbon
carbon
unit
Prior art date
Application number
TW097121343A
Other languages
Chinese (zh)
Inventor
Kevin Mckeigue
wei-bin Jiang
Ramachandran Krishnamurthy
Original Assignee
Linde Inc
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
Priority claimed from US11/974,953 external-priority patent/US20080305029A1/en
Priority claimed from US11/974,954 external-priority patent/US20080305030A1/en
Priority claimed from US11/974,952 external-priority patent/US20080305028A1/en
Application filed by Linde Inc filed Critical Linde Inc
Publication of TW200911687A publication Critical patent/TW200911687A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • 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
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    • 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
    • C01B3/382—Multi-step processes
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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Abstract

The integrated processes of the dry reforming or partial oxidation upstream of the carbon nanotube-producing reactor are described allowing the carbon monoxide to be produced on an as-needed basis, negating the need to transport carbon monoxide to the production site or store large quantities of carbon monoxide on-site. The apparatuses allowing to carry out such integrated processes are also provided. Carbon dioxide emissions may be eliminated from the carbon nanotube production process. This may be achieved by recycling the carbon dioxide byproduct and mixing it with the feed to the partial oxidation process.

Description

200911687 九、發明說明： 【發明所屬之技術領域】 本揭示案大體而言係關於用於製造奈米碳材料之方法， 且更特定而言，係關於基於共同原料之部分氧化產生一氧 化碳且使用由此產生之一氧化碳製造奈米碳材料之整合性 方法。200911687 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present disclosure relates generally to a method for producing a nanocarbon material, and more particularly to the production of carbon monoxide based on partial oxidation of a common raw material and using This produces an integrated approach to the production of nanocarbon materials from carbon oxide.

Ο 本申請案根據35 U.S.C.§119(e)主張2〇〇7年6月6日申請之 美國專利申請案第60/933,599號及2007年6月6日申請之美 國專利申請案第60/933,600號及2007年6月6曰申請之美國 專利申請案第60/933,598號之優先權，該等申請案以引用 之方式全部併入本文中。 【先前技術】 包括單壁碳奈米管、多壁碳奈米管及碳奈米纖維之各種 奈米碳材料可使用適合商業方法經由布料反應（B〇u細 react—由一氧化碳製造。該方法可包括供應一氧化碳及 觸媒前驅體氣體給混合區，該觸媒前驅體氣體保持在觸媒 _分解溫度以下。另一可用方法包括藉由在足以催化 製造碳奈米管之溫度下，在反應器單元中使金屬催化粒子 與有效量之含碳氣體接觸來製造碳奈米f =Γ鳩米管，且可使用之金屬催化粒子包： 、Μ或第赐族金屬。利用布達特反應之其他方 法亦可用以製造奈米碳材料。 上述方法之特徵為某 及可燃性一氧化碳進料 些缺點及缺陷。舉例而言，高毒性 氣體之儲存及處理引起許多安全問 132047.doc 200911687 題。另外，該等方法通常引起大量溫室氣體之排放，諸如 每噸所製造之奈米碳材料排放約4噸二氧化碳。 為避免或減少上文提及之缺陷引起之效應以及出於改良 總方法效率之目的，需要使用更好方法製造奈米碳材料。 【發明内容】 . 在若干實施例中，提供獲得奈米碳材料之方法。一種方 法包含將烴氣流、二氧化碳氣流及氧氣流組合以形成組合 • 氣流，且在轉化反應器中，使組合氣流中之烴經歷轉化過 ㈣形成包含氫、-氧化碳、二氧化碳、氧之未反應部分 及烴之未反應部分的轉化氣流，接著藉由使轉化氣流經歷 ' 脫氧而自轉化氣流中移除氧之未反應部分，以產生包含 氫、一氧化碳、二氧化碳及烴之未反應部分之脫氧氣流。 移除氧之未反應部分之步驟可在脫氧設備中進行。 可隨後（例如）使用一階段或多階段膜分離器或者使用變 壓吸附方法以形成主流及副產物流而自脫氧氣流中分離 氫，其中主流包含一氧化碳、二氧化碳及烴之未反應部 ί】 分’且副產物流包含氫。 - 了隨後將主、"IL引導至奈米碳材料製造單元以製造奈米碳 • 材料及二氧化碳，且一氧化碳可再循環且引導至轉化反應 器中。或者，可使主流經歷進一步分離以移除大部分二氧 化碳及烴之未反應部分，以形成大體上純的一氧化碳氣 流，隨後可將其引導至奈米碳材料製造單元。該主流之純 化將合意地製造某些類型之奈米碳材料，尤其單壁碳奈米 管。 132047.doc 200911687 分離脫氧氣流之其他方法亦可用，包括（但不限於）低溫 分離方法。在一實施例中，分離該氣流之方法將主要視製 造規模及奈米碳材料製造方法所需之一氧化碳純度而定。 在一實施例中，本發明提供一種用於製造奈米碳材料之 設備，其包含將烴、二氧化碳及氧之混合物轉化成包含 氫、一氧化礙、二氧化碳、氧之未反應部分及烴之未反應 部分之轉化氣流的轉化反應器，及與轉化反應器流體流通 ' 之脫氧單元。脫氧單元可用於自轉化氣流中移除氧之未反 fs 應部分且產生包含氫、一氧化碳、二氧化碳及烴之未反應 部分之脫氧氣流。 . 設備可另外包括與脫氧單元流體流通之一階段或多階段 膜分離器，以用於自脫氧氣流中分離氫且形成包含一氧化 碳、二氧化碳及烴之未反應部分之主流。 在一實施例中，設備可另外包括與脫氧單元流體流通之 變壓吸附單元或低溫分離單元來替代膜分離器，以用於自 脫氧氣流中分離氫且形成包含一氧化碳、二氧化碳及烴之 1 / 未反應部分之主流。 _ 設備可另外包括與膜分離器流體流通之奈米碳材料製造 單元，其中奈米碳材料製造單元製造奈米碳材料及二氧化 碳氣流；及與奈米碳材料製造單元流體流通之用於再循環 一氧化碳之構件，其用於將二氧化碳氣流引導至轉化反應 器。 【實施方式】 除非另外描述，否則下文使用以下定義及縮寫： 132047.doc 200911687 術語”單壁碳奈米管" 具有在約0 · 4與約4奈米 形的管。 定義為由大體上化學純之碳製得且 之間之直徑的中空、大體上呈圓柱 術語”多壁碳奈米管，， 具有在約3與約1 〇〇奈米 形之管的同軸配置。 定義為由大體上化學純之碳製得且 之間的外徑之密排的大體上呈圓柱 術語’’碳奈米管I，係指 干土咴不水官及多壁碳争米營 術語”碳奈米纖維丨，定義為罝右户认 厌不木s Μ由大約1與_奈米之間的直 直A Μ… 4侍的大體上呈圓柱形之結構， 其為始排截錐之堆疊配置。 1。=米碳材料"定義為在至少-個方向上具有小於 妒材V:括尺寸之由大體上化學純之碳製得的結構。奈米 ;材=:1單壁碳奈米管、多壁碳奈米管、碳奈米 角、呶奈米纖維及單層及多層石墨板。 術語"烴"定義為有機化 观其刀子僅由碳及氫組成。 ::’觸媒”定義為在方法中改變化學反應之速度或產率 自身大體上不消耗或另外化學上不改變之物質。 術語”貴金屬"係指盥大吝勃 〃大多數鹼金屬相對之高度抗腐蝕或 :乳化且不易溶解之金屬。實例包括(但不限於)翻、纪、 金、銀、鈕或其類似物。 術語”驗金屬”係指能夠容易地氧化之任何非貴金屬。實 例包括(但不限於)錦、錮、鶴、姑或其類似物。 術語”布達特反應"係指以下化學反應⑴： 2 CO -> c + c〇2 ⑴。 132047.doc •10· 200911687 術語，，重整”係指藉由通常在觸媒存在下使用熱、壓力使 刀子化干重組（重整）以形成不同產物之化學方法。 術語”乾重整”係指使用i氧化碳重整例如烴之化合物（諸 如曱烷）產生合成氣之方法。 術語”蒸汽重整”係指使用水重整例如自之化合物（諸如甲 烧）產生合成氣之方法。 術語"合成氣（syngas)"為術語，，合成氣體（別加如邮），, 之縮寫，且係指含有不同量之-氧化碳及氫之氣體混合 物。 術浯部分氧化"為一種類型之乾重整，且係指藉由將預 熱之烴及氧注人燃燒室中來將含烴氣體轉化成氫、一氧化 石厌及諸如—氧化碳、水及其他烴之額外痕量組分之混合物 的方法，*中烴之氧化係以小於完全燃燒所需之氧之化學 計量量發生。 術π催化„卩分氧化”係指在觸媒存在下在適當支撐結構 上進行之部分氧化，該觸媒諸如貴金屬，諸如鉑、鈀或 铑；或鹼性過渡金屬，諸如鎳。 術浯冷相”係指含有諸如換熱器及蒸餾塔之低溫處理儀 器，裝置’其可用於將至少一氧化碳及氫之混合物分離成 氧化奴及氫之個別氣流。若低分子量烴存在於混合物 中’則其亦可使用該裝置分離。 術膜係私薄障壁，其允許存在於流體混合物中之一 些物質以比其他物質大之速率通過。 術扣良壓吸附"係指使用吸附劑以在高壓下優先吸附流 132047.doc 200911687 體混合物中之至少一種物質且在較低壓力下釋放至少一部 分所吸附物質之分離方法。 實施方式 在製造奈米碳材料之反應器上游併入重整或部分氧化製 程允許根據需要產生一氧化碳，而無需將一氧化碳運送至 製造場所或就地儲存大量一氧化碳。在整合性方法中，幾 乎所有二氧化碳排放皆可由碳奈米管製造過程消除。此可 藉由使二氧化碳副產物再循環且使其與部分氧化方法之進 料混合來達到。整合性方法更適於各種規模或分布的製造 廠，包括相對少量之氫副產物將另使純化及壓縮不經濟之 彼等工廠。 合成氣可藉由諸如甲烷之烴之乾重整方法獲得。可使用 各種烴，且使用該等烴之乾重整方法在此項技術中為已 知。乾重整之一種可能路徑，亦即部分氧化，可藉由反應 (II)示意地說明： 2 CH4 + C02 + 〇2 -> 3 CO + 3 H2 + H2〇 ⑴）。 更具體而言，反應（II)所示之部分氧化方法通常係在高 溫（例如約70(TC與約i，400。(；之間的溫度）及高壓（例如高達 約150個大氣壓之壓力）下進行。該方法可在觸媒存在下進 <亍適^觸媒可選自此項技術中已知之各種可用選擇。舉 例而言，可使用之觸媒可包含貴金屬，例如鉑、鈀或铑； 或者過渡鹼金屬，諸如鎳。金屬可嵌埋於諸如氧化鋁或沸 石之多孔載體中。 各種條件可用於進行反應（11)所說明之部分敦化方法。 132047.doc 12 200911687 可選擇用於部分氧化之最適當條件，亦即溫度、壓力、觸 媒及烴/氧比率。舉例而言，可使用高於約之溫度 (諸如約1，300。〇，及高達150個大氣壓之壓力。 如反應流程（II)所示產生之合成氣可包括氫、一氧化 碳、剩餘未反應之二氧化碳及剩餘未反應之氧。可另外藉 由移除所有其他組分（亦即氫、未反應之二氧化碳及未反 應之氧）來處理該混合物以獲得經純化的一氧化碳。純化 方法可如下所述。Ο U.S. Patent Application Serial No. 60/933,599, filed on Jun. 6, 2008, and U.S. Patent Application Serial No. 60/933,600, filed on Jun. 6, 2011-0. The priority of U.S. Patent Application Serial No. 60/933,598, the entire disclosure of which is incorporated herein by reference. [Prior Art] Various nanocarbon materials including single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanofibers can be produced by a commercially suitable method via a cloth reaction (B〇u fine react-made from carbon monoxide). The method may include supplying carbon monoxide and a catalyst precursor gas to the mixing zone, the catalyst precursor gas remaining below the catalyst decomposition temperature. Another useful method includes reacting at a temperature sufficient to catalyze the production of the carbon nanotubes The metal catalyst particles are contacted with an effective amount of carbon-containing gas to produce a carbon nano-f = glutinous rice tube, and the metal catalyzed particles can be used: ruthenium or samarium metal. Other methods can also be used to make nanocarbon materials. The above method is characterized by some disadvantages and defects in the combustion of a certain flammable carbon monoxide. For example, the storage and handling of highly toxic gases causes many safety issues. 132047.doc 200911687 These methods usually cause a large amount of greenhouse gas emissions, such as about 4 tons of carbon dioxide per ton of manufactured nanocarbon material. To avoid or reduce the above And the effect of the defect and the need to improve the efficiency of the overall process, the need to use a better method to manufacture the nanocarbon material. [Invention] In several embodiments, a method of obtaining a nanocarbon material is provided. The hydrocarbon gas stream, the carbon dioxide gas stream, and the oxygen stream are combined to form a combined gas stream, and in the conversion reactor, the hydrocarbons in the combined gas stream are subjected to conversion (iv) to form unreacted portions and hydrocarbons including hydrogen, carbon oxide, carbon dioxide, oxygen. The unreacted portion of the reformed gas stream is then subjected to 'deoxidation' to remove unreacted portions of oxygen from the reformed gas stream to produce a deoxygenated stream comprising hydrogen, carbon monoxide, carbon dioxide, and unreacted portions of the hydrocarbon. The step of unreacted portion of oxygen can be carried out in a deoxygenation unit. Hydrogen can be separated from the deoxygenation stream, for example, using a one-stage or multi-stage membrane separator or using a pressure swing adsorption process to form a mainstream and by-product stream, wherein The mainstream contains carbon monoxide, carbon dioxide, and unreacted parts of hydrocarbons, and the by-product stream contains hydrogen. - The main, "IL is then directed to the nanocarbon material manufacturing unit to produce the nanocarbon material and carbon dioxide, and the carbon monoxide can be recycled and directed to the conversion reactor. Alternatively, the main stream can be further separated for migration. Except for most of the carbon dioxide and unreacted portions of the hydrocarbon to form a substantially pure carbon monoxide gas stream which can then be directed to a nanocarbon material manufacturing unit. This mainstream purification will desirably produce certain types of nanocarbon materials, In particular, single-walled carbon nanotubes. 132047.doc 200911687 Other methods of separating the deoxygenation stream may also be used, including but not limited to cryogenic separation methods. In one embodiment, the method of separating the gas stream will primarily depend on the scale of manufacture and the nanometer. In one embodiment, the present invention provides an apparatus for producing a nanocarbon material comprising converting a mixture of hydrocarbons, carbon dioxide, and oxygen into a hydrogen-containing, oxidizing barrier. a conversion reactor for the conversion gas stream of carbon dioxide, unreacted portion of oxygen and unreacted portion of hydrocarbon, and Fluid flow 'of the deoxo unit. The deoxygenation unit can be used to remove oxygen from the reformed gas stream and to produce a deoxygenation stream comprising hydrogen, carbon monoxide, carbon dioxide, and unreacted portions of the hydrocarbon. The apparatus may additionally comprise a one-stage or multi-stage membrane separator in fluid communication with the deoxygenation unit for separating hydrogen from the deoxygenation stream and forming a mainstream comprising unreacted moieties of carbon monoxide, carbon dioxide and hydrocarbons. In an embodiment, the apparatus may additionally comprise a pressure swing adsorption unit or a cryogenic separation unit in fluid communication with the deoxygenation unit in place of the membrane separator for separating hydrogen from the deoxygenation stream and forming a carbon monoxide, carbon dioxide and hydrocarbons. The mainstream of the unreacted part. The apparatus may additionally comprise a nanocarbon material manufacturing unit fluidly circulated with the membrane separator, wherein the nanocarbon material manufacturing unit manufactures a nanocarbon material and a carbon dioxide gas stream; and is circulated with the nanocarbon material manufacturing unit for recycling A component of carbon monoxide that is used to direct a flow of carbon dioxide to a conversion reactor. [Embodiment] Unless otherwise stated, the following definitions and abbreviations are used below: 132047.doc 200911687 The term "single-walled carbon nanotube" has a tube of about 0.4 and about 4 nanometers. A hollow, generally cylindrical term "multi-walled carbon nanotube" made of chemically pure carbon and having a diameter between them, having a coaxial configuration of tubes of about 3 and about 1 inch. Defined as a substantially cylindrical term 'carbon nanotube tube' made of substantially chemically pure carbon and having an outer diameter between them, refers to the term “dry soil” and “multi-wall carbon”. "Carbonone fiber 丨, defined as 罝 right household 认 不 不 s Μ Μ Μ 大约 大约 大约 大约 大约 大约 大约 大约 大约 大约 大约 大约 大约 大约 Μ 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Stacking configuration: 1. = m carbon material " defined as a structure made of substantially chemically pure carbon having a size smaller than the coffin V in at least one direction. Nano; material =: 1 single wall Carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, nanofibers and single-layer and multi-layer graphite sheets. The term "hydrocarbon" is defined as an organic matter whose knives consist only of carbon and hydrogen. : 'Catalyst' is defined as a substance that changes the rate or rate of chemical reaction in the process itself by substantially no consumption or otherwise chemically unchanged. The term "precious metal" refers to a metal that is highly resistant to corrosion or emulsified and insoluble in most alkali metals. Examples include, but are not limited to, turn, gold, silver, buttons or the like. The term "metallizing" refers to any non-noble metal that can be easily oxidized. Examples include, but are not limited to, brocade, scorpion, crane, aortic or the like. The term "Buddatt reaction" refers to the following chemical reactions (1) : 2 CO -> c + c〇2 (1). 132047.doc •10· 200911687 The term "reform" refers to a chemical method in which the knife is reorganized (reformed) by heat and pressure in the presence of a catalyst to form different products. The term "dry reforming" Means a process for producing a synthesis gas using a carbon monoxide for reforming a compound such as a hydrocarbon such as decane. The term "steam reforming" refers to a process for producing a synthesis gas from a compound such as tomazan using water reforming. The term "syngas" is a term, syngas (abbreviated as postal), an abbreviation, and refers to a gas mixture containing varying amounts of carbon monoxide and hydrogen. Partial oxidation " One type of dry reforming, which refers to the conversion of hydrocarbon-containing gas to hydrogen, monoxide, and additional traces such as carbon monoxide, water, and other hydrocarbons by injecting preheated hydrocarbons and oxygen into the combustion chamber. The method of mixing a mixture of components, * the oxidation of hydrocarbons occurs in a stoichiometric amount less than the oxygen required for complete combustion. The π catalysis of "deuterium oxidation" refers to the presence of a suitable support structure in the presence of a catalyst. Partial oxidation, Catalysts such as noble metals such as platinum, palladium or rhodium; or basic transition metals such as nickel. "Cryogenic phase" refers to cryogenic processing equipment containing, for example, heat exchangers and distillation columns, which can be used to at least carbon monoxide and The mixture of hydrogen is separated into individual streams of oxidized slaves and hydrogen. If a low molecular weight hydrocarbon is present in the mixture, then it can also be separated using the apparatus. The membrane is a thin barrier that allows some of the material present in the fluid mixture to pass at a greater rate than other materials. "Good pressure adsorption" refers to a separation method that uses an adsorbent to preferentially adsorb at least one substance in a bulk mixture at a high pressure and releases at least a portion of the adsorbed species at a lower pressure. Embodiments Incorporating a reforming or partial oxidation process upstream of a reactor for producing nanocarbon materials allows carbon monoxide to be produced as needed without transporting carbon monoxide to a manufacturing site or storing large amounts of carbon monoxide in situ. In the integrated approach, almost all CO2 emissions are eliminated by the carbon nanotube manufacturing process. This can be achieved by recycling the carbon dioxide by-product and mixing it with the feed to the partial oxidation process. The integrated approach is more suitable for plants of all sizes or distributions, including relatively small amounts of hydrogen by-products that would otherwise make purification and compression uneconomical. Syngas can be obtained by a dry reforming process of a hydrocarbon such as methane. Various hydrocarbons can be used, and dry reforming processes using such hydrocarbons are known in the art. One possible path for dry reforming, i.e., partial oxidation, can be illustrated schematically by reaction (II): 2 CH4 + C02 + 〇 2 -> 3 CO + 3 H2 + H2 〇 (1)). More specifically, the partial oxidation process shown by reaction (II) is usually carried out at a high temperature (for example, about 70 (TC and about i, 400. (temperature between) and high pressure (for example, pressure of up to about 150 atmospheres). The method can be carried out in the presence of a catalyst. The catalyst can be selected from various available options known in the art. For example, the catalyst that can be used can comprise a noble metal such as platinum, palladium or Or a transitional alkali metal such as nickel. The metal may be embedded in a porous support such as alumina or zeolite. Various conditions may be used to carry out the partial Dunning process described in reaction (11). 132047.doc 12 200911687 The most suitable conditions for partial oxidation, i.e., temperature, pressure, catalyst, and hydrocarbon/oxygen ratio. For example, temperatures above about (e.g., about 1,300 Å, and pressures up to 150 atmospheres can be used. The syngas produced in Reaction Scheme (II) may include hydrogen, carbon monoxide, remaining unreacted carbon dioxide, and remaining unreacted oxygen. Alternatively, all other components (ie, hydrogen, unreacted carbon dioxide, and The mixture is treated with unreacted oxygen to obtain purified carbon monoxide. The purification method can be as follows.

可藉由使用部分氧化方法將合成氣流脫氧而自合成氣流 中移除氧之未反應部分。進行脫氧方法所需之適當方法及 儀器可選自許多已知選擇。因此，可形成包含氫、一氧化 碳及二氧化碳之脫氧氣流。 可將氫自脫氧氣流中分離以形成^含一氧化碳、二氧化 碳及烴之未反應部分之主流，及包含氫之副產物流。該氮 自脫氧合成氣之分離可藉由使用膜之分離來完成。 可選擇適當的膜。可使用録膜，包括聚合、金屬多孔 支撐物等等，且膜在此項技術中為已知。膜可包含沈積於 多孔氧化鋁支撐物上之薄二氧化矽層。孔可具有在約5與 約10奈米之間的直徑。可藉由在約的吖與“吖之間的溫 度下氬氛圍中化學氣相沈積原石夕酸四乙醋直至氫渗透性已 達到所要程度而於氧化减板上形成二氧切層。由此與 一氧化碳氣流分離之氫無需進—步純化。取而代之的是氣 可視需要回收且輸出以用作燃料’如下文所討論。 在已如上文所討論分離氫後，可將包含—氧化碳、二氧 132047.doc •13- 200911687 化石反及經之未反應部分之主流引導至奈米碳材料製造單元 則吏用上文所τ之布達特反應⑴來製&奈米碳材料及二氧 化碳aw危。包括由布達特反應所形成之氣流之二氧化碳氣 二可再循核且用於部分氧化中。進行布達特反應以製造奈 米碳材料所需之條件在此項技術中為已知且熟習此項技術 . 者可選擇最佳條件。 . 要奈来碳材料之特定類型、尺寸及純度而定，可理 “地自主抓移除二氧化碳及烴之未反應部分且將大體上純 D 7一氧化碳進料至奈米碳材料製造單元中。此可藉由若干 可用方法中之任-種完成’包括：膜方法'變壓吸附方 • t、吸附方法等等。在各狀況下，可將經純化-氧化碳氣 、流引導至奈米碳材料製造單元且可將二氧化碳及烴氣流再 循環至重整單元。 現參看圖1，將煙1引導至預處理反應器A。烴預處理反The unreacted portion of oxygen can be removed from the syngas stream by deoxygenation of the syngas stream using a partial oxidation process. Suitable methods and apparatus for performing the deoxygenation process can be selected from a number of known options. Therefore, a deoxygenation stream containing hydrogen, carbon monoxide and carbon dioxide can be formed. Hydrogen can be separated from the deoxygenation stream to form a mainstream of unreacted moieties containing carbon monoxide, carbon dioxide and hydrocarbons, and a by-product stream comprising hydrogen. The separation of the nitrogen from the deoxygenated syngas can be accomplished by separation using a membrane. A suitable membrane can be selected. Films can be used, including polymeric, metallic porous supports, and the like, and membranes are known in the art. The membrane may comprise a thin layer of ruthenium dioxide deposited on a porous alumina support. The pores may have a diameter of between about 5 and about 10 nanometers. The dioxic layer can be formed on the oxidation reduction plate by chemical vapor deposition of the original tetrahydroacetic acid in an argon atmosphere at a temperature between about 吖 and 吖 until the hydrogen permeability has reached a desired level. The hydrogen separated from the carbon monoxide gas stream does not require further purification. Instead, the gas can be recovered and exported for use as a fuel as discussed below. After the hydrogen has been separated as discussed above, it can contain carbon monoxide, dioxane. 132047.doc •13- 200911687 The mainstream of the unreacted part of the fossils and the unconverted part of the process led to the nanocarbon material manufacturing unit, using the Budat reaction (1) above to produce & nano carbon materials and carbon dioxide aw risk The carbon dioxide gas comprising the gas stream formed by the Budat reaction can be recycled and used in partial oxidation. The conditions required to carry out the Budat reaction to produce the nanocarbon material are known and familiar in the art. The technology can choose the best conditions. According to the specific type, size and purity of the carbon material, it can be used to remove the unreacted part of carbon dioxide and hydrocarbons and will be substantially pure D 7 The carbon oxide is fed to a nanocarbon material manufacturing unit. This can be accomplished by any of a number of available methods, including: membrane methods, pressure swing adsorption methods, adsorption methods, and the like. In each case, the purified carbon monoxide gas stream can be directed to a nanocarbon material manufacturing unit and the carbon dioxide and hydrocarbon gas streams can be recycled to the reforming unit. Referring now to Figure 1, the smoke 1 is directed to the pretreatment reactor A. Hydrocarbon pretreatment

自動熱催化重整器威非牖# I 只处太主汉應器A後，烴經由管線3 煙轉化反應器B可為進行催化部 化設備。烴轉化反應器B亦可為Automated Thermal Catalytic Reformer Weifei牖# I After only the main reactor A, hydrocarbons can be converted to reactor B via line 3. The hydrocarbon conversion reactor B can also be

迥當觸媒存在下進行。 132047.doc -14· 200911687 隨後反應產物經由管線4離開烴轉化反應器B ^氣流可包 含氫、一氧化碳、二氧化碳、未反應之氧、諸如甲烷之未 反應之烴及水。在各種熱回收過程後，將該氣流4引導至 脫氧單元C以移除痕量未反應之氧。隨後，經由壓縮單元 D將與來自第二階段膜F之再循環氣流11組合之氣流5壓 縮，且經由管線6引導至第一階段膜單元e。滲透廢氣流1〇 可含有大多數氫且可作為燃料輸出。將具有相對較高壓力 之一氧化碳富集氣流7引導至第二階段膜單元ρ以產生較高 純度一氧化碳氣流，其進一步用作奈米碳材料製造單元G 之原料8以製造奈米碳材料。隨後，將來自奈米碳製造單 元G之二氧化碳副產物氣流9再循環回烴轉化單元B。 奈米碳製造單元G可包含若干子單元，包括奈米碳製造 反應器、用於將固體奈米碳產物與排出氣流分離之分離 裔、用於分離及再循環未反應之進料氣體之裝置，及視需 要用於將不需要之副產物與二氧化碳副產物氣流分離之裝 置。 現參看圖2,合成氣可藉由諸如曱烷之烴之乾重整方法 獲侍，但不使用氧。無氧乾重整之一種可能路徑可由反應 (ΠΙ)示意地說明： CH4 + C〇2 -> 2 CO + 2 H2 (III)。 更具體而言，反應（III)所示之乾重整方法通常係在高溫 (例如約70CTC與約i，00(rC之間的溫度)及高壓(例如高達約 15〇個大氣壓之壓力）下進行。該方法可在觸媒存在下進 行。適當觸媒可選自各種已知選擇。舉例而言，可使用之 132047.doc -15· 200911687 :或者過渡鹼金屬，It is carried out in the presence of a catalyst. 132047.doc -14· 200911687 The reaction product then exits the hydrocarbon conversion reactor via line 4. The gas stream may comprise hydrogen, carbon monoxide, carbon dioxide, unreacted oxygen, unreacted hydrocarbons such as methane, and water. After various heat recovery processes, the gas stream 4 is directed to a deoxygenation unit C to remove traces of unreacted oxygen. Subsequently, the gas stream 5 combined with the recycle gas stream 11 from the second stage membrane F is compressed via the compression unit D and directed to the first stage membrane unit e via line 6. The permeate exhaust stream 1〇 can contain most of the hydrogen and can be used as a fuel output. A carbon monoxide rich gas stream 7 having a relatively high pressure is directed to the second stage membrane unit ρ to produce a higher purity carbon monoxide gas stream, which is further used as the raw material 8 of the nanocarbon material manufacturing unit G to produce a nanocarbon material. Subsequently, the carbon dioxide by-product gas stream 9 from the nanocarbon production unit G is recycled back to the hydrocarbon conversion unit B. The nanocarbon manufacturing unit G may comprise several subunits, including a nanocarbon production reactor, a separation source for separating the solid nanocarbon product from the exhaust gas stream, and a device for separating and recycling unreacted feed gas. And, if desired, means for separating unwanted by-products from the carbon dioxide by-product gas stream. Referring now to Figure 2, syngas can be obtained by a dry reforming process of a hydrocarbon such as decane, but without the use of oxygen. One possible path for anaerobic dry reforming can be illustrated by the reaction (ΠΙ): CH4 + C〇2 -> 2 CO + 2 H2 (III). More specifically, the dry reforming process shown by the reaction (III) is usually carried out at a high temperature (for example, about 70 CTC and about i,00 (temperature between rC) and high pressure (for example, pressure of up to about 15 Torr). The process can be carried out in the presence of a catalyst. Suitable catalysts can be selected from a variety of known options. For example, 132047.doc -15· 200911687 can be used: or a transitional alkali metal,

之形成，可視需要使用乾重整與蒸汽重整之組 觸媒可包含貝金屬，例如鉑、鈀或铑；或 諸如錄。金屬可嵌埋於諸如氧化銘或沸石 合。蒸汽重整之一種可能路徑可由反應（IV)示意地說明： CH4 + H20 -> CO + 3 Η2 (IV；)。 若使用，則可選擇欲用於蒸汽重整之最佳條件（亦即温 度、壓力、觸媒）。對奈米碳材料製造而言，理想的為使 重正器中產生之一氧化碳量最大化且使所產生之氫量最小 化。因此，重整器之進料可僅包括與避免焦炭形成所需一 樣多之蒸汽。 在圖2之一態樣中，如反應流程（III)所示產生之合成氣 包括氫、一氧化碳、剩餘未反應之二氧化碳及剩餘未反應 之煙。可另外藉由移除所有其他組分（亦即氫、未反應之 二氧化碳及未反應之烴）達到所要程度來處理該混合物以 獲得經純化一氧化碳。純化方法可如下所述。 可移除氫及未反應之烴’留下包含一氧化碳及二氧化碳 之主流’及包含氫及未反應之烴之副產物氣流。該氫及未 反應之煙自合成氣之分離可藉由使用如上所述之一個或複 數個膜來完成。膜可與圖1所述相同。或者，該分離可使 用諸如變壓吸附方法及/或低溫分離方法之其他適合方法 來完成。 在已使用膜分離出氫及未反應之烴後，可將包含一氧化 碳及二氧化碳之主流引導至奈米碳材料製造單元以使用如 132047.doc -16· 200911687 上文所討論之布達特反應⑴來製造奈米碳材料及二氧化碳 氣流。或者’可自主流移除二氧化碳達到所要程度來產生 大體上純的一氧化碳氣流，可隨後將其引導至奈米碳材料 製造單元中。二氧化碳氣流（包括存在於主流中之二氧化 碳之未反應部分及由布達特反應形成之二氧化碳）可再循 環且用於如上文所討論之乾重整或組合乾重整及蒸汽重整 方法中。 參考圖2對其進行更詳細地描述。如可自圖2所見，可將 烴201引導至預處理反應器2a。烴預處理反應器單元允許 移除硫；使可能存在之各種烯烴飽和；且視需要允許預先 重整烴201。一部分未經處理之烴氣流2〇2可供應燃料給烴 轉化反應器2B。 離開預處理反應器2A後，烴可經由管線203進入烴轉化 反應器2B中。如圖2所示，採用烴轉化反應器2B以進行二 氧化碳乾重整方法及催化蒸汽重整方法。若需要，則可選 擇各種其他烴轉化反應器2B。 煙氣流203、蒸汽215及再循環二氧化碳氣流1〇可進入烴 轉化反應器2B甲’其中轉化過程可在約7〇(Tc與約1 ,〇〇〇。〇 之間的溫度下及高達150個大氣壓之壓力下視需要在適當 觸媒存在下進行。反應產物可作為氣流2〇4離開烴轉化反 應器2B。 在圖2中，氣流204包含氫、一氧化碳、未反應之蒸汽、 未反應之二氧化碳’及未反應之煙，諸如甲烧。可隨後將 氣流204引導至熱回收裝置2C’其包含處理熱鍋爐、各種 132047.doc -17- 200911687 換熱器及將氣流204冷卻至所需下游溫度之冷卻塔（未圖 示）。因此，氣流205可以與氣流204相同之化學組成但比 氣流204低之溫度離開‘回收裝置2C。可在該過程中產生 處理蒸汽215及來自水213之輸出蒸汽214。 隨後氣流205可進入第一階段膜單元2D，其中大多數氫 及二氧化碳與該氣流之其餘部分分離，導致2種分離氣流 之形成。該等2種氣流為包含大多數一氧化碳連同一部分 未反應之二氧化碳及一部分未反應之烴之主流206，及主 要包含氫連同大多數未反應之二氧化碳之滲透廢氣流 216 ° 可隨後將滲透廢氣流216作為燃料引導至烴轉化單元2B 中。燃料燃燒之產物可經由排出氣流2 1 7離開單元2B。隨 後可將具有相對較高壓力之一氧化碳富集主流206引導至 第二階段膜單元2E，其中將一氧化碳及剩餘未反應之二氧 化碳進一步分離以產生較高純度之一氧化碳氣流207及富 集二氧化碳之滲透氣流2 11。 一氧化碳氣流207可進一步用作奈米碳材料製造單元2F 之原料以製造奈米碳材料208及廢二氧化碳氣流209。富集 二氧化碳之滲透氣流211可經由壓縮單元2G壓縮且隨後經 由管線212再循環回第一階段膜單元2D中，且來自奈米碳 材料製造單元2F之廢二氧化碳氣流209可經由壓縮單元2H 壓縮且經由氣流2 1 0再循環至烴轉化單元2B中。 在一些情況下，奈米碳材料製造單元2F可包含若干子單 元（未圖示），包括奈米碳材料製造反應器、用於將固體奈 132047.doc -18· 200911687 米奴材料產物208與排出氣流分離之裝置、用於分離及再 循％未反應之進料氣體之子單元，及可能地用於將不需要 之田彳產物與二氧化碳副產物氣流分離之裝置。 圖所示之α又備及方法之許多變化係可能的。重整器所 需之熱可藉由燃燒來自重整器之氫產物之一部分而產生。 另外，氫產物可出售且可使用天然氣對重整器加燃料。另 外，由奈米碳材料反應器單元2F中之放熱反應釋放之熱可 用以預熱重整斋之進料，由此降低該過程所需之燃料量。 在一實施例中，可自外部來源輸入額外量之二氧化碳且 將其與重整器之進料混合以達到額外優點。當進料至重整 器之烴為甲烷時，多至相等莫耳量之外部二氧化碳亦可： 由氣流218進料至反應器中。在該等條件下，總過程可由 總反應（V)示意地說明： CH4 + C02 ^ 2 C + 2 H2〇 (V)。 該過程提供消耗二氧化碳且因此防止其釋放至大氣中之 方式，在大氣中二氧化碳被視為全球變暖之重要促成因 素。因為總反應（V)為放熱的，且該過程之各個單元操作 具有有效能量整合’所以碳奈米管之組合製造及外部產生 二氧化碳之隔離可以極少或無需額外化石燃料燃燒來完 成。 在參考圖3描述之其他情況下，合成氣亦可藉由反應产 程（III)所示之乾重整方法來獲得。乾重整方半 /ίΓ可大體上類 似於關於圖2所述之彼方法，包括蒸汽重整之 〜J選利用。 如前所述，二氧化碳副產物可再循環且盥會敕 ，、里蹩之進料混 132047.doc 19 200911687 合’其增加重整器所產生之一氧化碳量。 然而，可使用一些額外特徵。該等額外特徵可包括使用 冷箱替代膜分離器用於氫及未反應之烴自合成氣之分離。 該特徵可用於大規模製造廠。又，該方法允許產生氫作為 有價值之副產物。 參考圖3可更詳細地對其進行描述。如自圖3可見，可將 丈二301引導至預處理反應器3a中。正與圖2相同，烴預處理 反應器3A允許移除硫；使可能存在之各種烯烴飽和；且視 需要預先重整烴301。一部分烴氣流3〇2可供應燃料給烴轉 化反應器3B。 在離開預處理反應器3八後，烴可經由管線3〇3進入烴轉 化反應器3B中。採用圖3中之烴轉化反應器3B進行二氧化 石厌乾重整方法及催化蒸汽重整方法。若需要，則可選擇各 種其他烴轉化反應器3B。 烴氣流303、蒸汽3 1 6及再循環二氧化碳氣流3丨3可在烴 轉化反應器3B内在約700。(：與約1，〇〇〇。(：之間的溫度下反 應。反應產物可經由管線304離開烴轉化反應器3B。氣流 304可包含氫、一氧化碳 '二氧化碳，及未反應之烴，諸 如甲烷。可隨後將該氣流3〇4引導至熱回收裝置3C。熱回 收裝置3C亦可含有處理熱鍋爐、各種換熱器及將氣流3〇4 冷卻之冷卻塔（未圖示）。 已冷卻至所需下游溫度之氣流3〇4可隨後作為氣流3〇5進 入一氧化呶移除單元3D。氣流305以與氣流304相同之化學 組成但比氣流304低之溫度離開熱回收構件3c。亦可在熱 132047.doc -20- 200911687 回收構件3 C中產生處理蒸汽3 1 6及輸出蒸汽3 1 5 (來自水 314)。在二氧化碳移除單元3D中，二氧化碳氣流312及耗 盡一氧化碳之氣流3 0 6可自氣流3 0 5獲得。 隨後可將經分離之二氧化碳氣體3 12引導至二氧化碳壓 縮單元3H且隨後作為氣流313再循環至烴轉化單元3B中。 • 耗盡一氧化碳之氣流306可行進至一氧化碳分離單元3e以 產生產物一氧化碳氣流307及原氫氣流309。可使用之典型 一氧化碳分離裝置可包括冷箱、膜系統或變壓吸附單元。 〇 可選擇最適當之一氧化碳分離裝置。離開一氧化碳分離單 元3E之廢氣流318可再循環且用作烴轉化單元3B之燃料。 • 排出氣流3丨9可包含燃燒供應至烴轉化單元3B之燃料之產 物。 可將一氧化碳分離單元3E中產生之一氧化碳307引導至 奈米碳材料製造單元3F。可將來自奈米碳材料製造單元冗 之廢二氧化碳氣流311引導至二氧化碳壓縮單元3H且隨後 可將壓縮氣流引導至烴轉化反應器3B。氣流3〇8含有固體 ί. 奈米碳產物且可（例如）包含沈積於篩網或過濾器上之固體 - 奈米碳材料，或者可包含富集於奈米碳材料產物中之排出 氣流（諸如一氧化碳、二氧化碳等等）。 奈米碳製造單元3F可包含若干子單元（未圖示），諸如奈 米石厌製造反應器、用於將固體奈米碳產物與排出氣流分離 之裝置、用於分離及再循環未反應之進料氣體之裝置，及 可能地用於將不需要之副產物與二氧化碳副產物氣流分離 之裝置。 132047.doc 200911687 原氫氣流309可進入通常包括吸附材料之變壓吸附裝置 3G中。通常，該吸附材料為活性碳或沸石5八吸附材料。 變壓吸附過程之產物可為處於高壓之氫，其將作為氣流 離開單元3G。存在於該氣流中之剩餘氣體將經由管線 31^開單元3G ’且可用作烴轉化單幻时之燃料氣體。 可·•又叶上述方法之許多變化。舉例而言，重整器所需之 熱可藉由燃燒來自重整器之氫產物之一部分而產生。另 外，氫產物可出售且可使用天然氣對重整器加燃料。另 外’由奈米碳材料反應器單元317中之放熱反應釋放之熱可 用以預熱重整器之進料，由此降低該過程所需之燃料量。 在-實施例中’可自外部來源輸入額外量之二氧化碳且 與重整器之進料混合以達到額外優點。當進料至重整器之 烴為曱烷時，多至相等莫耳量之外部二氧化碳亦可經由氣 流320進料至反應器中。在該等條件下’總過程可由總反 應（V)示意地說明。將輸入二氧化碳添加至重整器會降低 該過程產生之氫副產物之量。 該過程提供消耗二氧化碳且因此防止其釋放至大氣中之 弋在大氧中一氧化碳被視為全球變暖之重要促成因 素因為總反應（V)為放熱的，且該過程之各個單元操作 具有有效此里整合，所以碳奈米管之組合製造及外部產生 二氧化碳之隔離可以極少或無需額外化石燃料燃燒來完 成。 上文所討論之所有方法整合流程可幫助消除實際上所有 來自奈米石厌材料製造過程之二氧化碳排放。亦可能輸入二 132047.doc -22- 200911687 氧化碳以用作該方法之進料之一部分。因此整合性方法可 用作以有價值產物（奈米碳材料）之形式隔離二氧化碳之有 效方法。 應瞭解，本文中所述之方法及設備僅僅為示範性的，且 熟習此項技術者可在不脫離本揭示案之主旨及範疇的情況 • 下進行變更及修改。所有該等變更及修改欲包括在如上文 所述之揭示案之範疇内。另外，所揭示之所有代表性實例 未必為備選的，因為各個態樣可組合以提供所要結果。因 此，吾人之揭示案僅受以下申請專利範圍限制。 【圖式簡單說明】 圖1不意地說明根據本發明之一實施例之用於製造奈米 碳材料之設備。 圖2示意地說明根據本發明之另一實施例之用於製造奈 米碳材料之設備。 μ 圖3示意地說明根據本發明之另一實施例之用於製造奈 米碳材料之設備。 〇 【主要元件符號說明】 . 1 烴 2 氧氣流 2Α 預處理反應器 2Β 烴轉化反應器 2C 熱回收裝置，其包含處理熱鍋爐、各種換熱器 及將氣流204冷卻至所需下游溫度之冷卻塔 2D 第一階段膜單元 132047.doc . 200911687 2E 第二階段膜單元 2F 奈米碳材料製造單元，其可包含若干子單元 2G 壓縮單元 2H 壓縮單元 3 管線/烴氣流 3 A 預處理反應器 3B 烴轉化反應器 3C 熱回收裝置，其含有處理熱鍋爐、各種換熱器 及將氣流304冷卻之冷卻塔 3D 二氧化碳移除單元 3E 一氧化碳分離單元 3F 奈米碳材料製造單元，其可包括若干子單元 3G 變壓吸附裝置，其通常包括吸附材料 3 Η 二氧化碳壓縮單元 4 管線/氣流，該氣流包含氫、一氧化碳、二氧 化碳、未反應之氧、未反應之烴（諸如甲烷）及 水 5 氣流 6 管線 7 具有相對較高壓力之一氧化碳富集氣流 8 奈米碳材料製造單元G之原料，其為較高純度 之一氧化碳氣流 9 來自奈米碳製造單元G之二氧化碳副產物氣流 10 滲透廢氣流 132047.doc -24- 200911687 11 再循環氣流 201 烴 202 一部分未經處理之烴氣流 203 管線/烴氣流 204 氣流，其包含氫、一氧化碳、未反應之蒸汽、 未反應之二氧化碳及未反應之烴 205 氣流，其具有與氣流204相同之化學組成但比 * 氣流204低之溫度 ζΛ 206 主流，其包含大多數一氧化石炭連同一部分未反 應之二氧化碳及一部分未反應之烴 . 207 較高純度之一氧化碳氣流 208 固體奈米碳材料產物 209 來自奈米碳材料製造單元2F之廢二氧化碳氣流 210 氣流 211 富集二氧化碳之滲透氣流 212 管線 C； 213 水 ^ 214 來自水213之輸出蒸汽 215 蒸汽 216 滲透廢氣流，其主要包含氫連同大多數未反應 之二氧化破 217 排出氣流 218 氣流 301 烴 I32047.doc -25 - 200911687 302 一部分烴氣流 303 管線/烴氣流 304 管線/氣流’該氣流包含氫、一氧化碳、二氧 化碳，及未反應之烴，諸如甲烧 305 氣流’其具有與氣流304相同之化學組成但比 氣流304低之溫度 306 耗盡二氧化碳之氣流 307 一氧化碳分離單元3E中產生之一氧化碳 308 氣流，其含有固體奈米碳產物且例如可包含沈 積於篩網或過濾器上之固體奈米碳材料或者可 包含富集於奈米碳材料產物中之排出氣流 3 09 原氫氣流 310 氣流 311 來自奈米碳材料製造單元3F之廢二氧化碳氣流 312 二氧化碳氣流 313 再循環二氧化碳氣流 314 水 315 來自水3 14之輸出蒸汽 316 蒸汽 317 管線 318 離開一氧化碳分離單元3E之廢氣流 319 排出氣流 320 氣流 A 預處理反應器 132047.doc ·26. 200911687 B 烴轉化反應器 C 脫氧單元 D 壓縮單元 E 第一階段膜單元 F 第二階段膜單元 G 奈米碳材料製造單元，其包含若干子單元 132047.doc -27-The formation may be carried out by using a combination of dry reforming and steam reforming. The catalyst may comprise a shell metal such as platinum, palladium or rhodium; or such as a recording. Metals can be embedded in, for example, oxidized or zeolite. One possible route for steam reforming can be illustrated schematically by reaction (IV): CH4 + H20 - > CO + 3 Η 2 (IV;). If used, the optimum conditions (ie temperature, pressure, catalyst) to be used for steam reforming can be selected. For the manufacture of nanocarbon materials, it is desirable to maximize the amount of carbon monoxide produced in the reformer and to minimize the amount of hydrogen produced. Thus, the feed to the reformer can include only as much steam as is required to avoid coke formation. In one aspect of Figure 2, the syngas produced as shown in Reaction Scheme (III) includes hydrogen, carbon monoxide, remaining unreacted carbon dioxide, and remaining unreacted fumes. The mixture may be additionally treated to remove purified carbon monoxide by removing all other components (i.e., hydrogen, unreacted carbon dioxide, and unreacted hydrocarbons) to the desired extent. The purification method can be as follows. The removable hydrogen and unreacted hydrocarbons leave a main stream comprising carbon monoxide and carbon dioxide and a by-product gas stream comprising hydrogen and unreacted hydrocarbons. Separation of the hydrogen and unreacted fumes from the syngas can be accomplished by using one or more membranes as described above. The film can be the same as described in Figure 1. Alternatively, the separation can be accomplished by other suitable methods such as pressure swing adsorption methods and/or cryogenic separation methods. After the membrane has been used to separate hydrogen and unreacted hydrocarbons, the mainstream containing carbon monoxide and carbon dioxide can be directed to the nanocarbon material manufacturing unit to use the Budat reaction (1) discussed above, such as 132047.doc -16· 200911687 To make nano carbon materials and carbon dioxide gas flow. Alternatively, the carbon dioxide can be removed by auto-flow to the desired extent to produce a substantially pure carbon monoxide gas stream which can then be directed to a nanocarbon material manufacturing unit. The carbon dioxide gas stream (including the unreacted portion of the carbon dioxide present in the main stream and the carbon dioxide formed by the Budat reaction) can be recycled and used in the dry reforming or combined dry reforming and steam reforming processes as discussed above. This will be described in more detail with reference to FIG. 2. As can be seen from Figure 2, hydrocarbon 201 can be directed to pretreatment reactor 2a. The hydrocarbon pretreatment reactor unit allows for the removal of sulfur; saturates various olefins that may be present; and allows for pre-reforming of hydrocarbon 201 as needed. A portion of the untreated hydrocarbon stream 2〇2 can be supplied to the hydrocarbon conversion reactor 2B. After leaving the pretreatment reactor 2A, hydrocarbons can enter the hydrocarbon conversion reactor 2B via line 203. As shown in Fig. 2, a hydrocarbon conversion reactor 2B is employed to carry out a carbon dioxide dry reforming process and a catalytic steam reforming process. If desired, various other hydrocarbon conversion reactors 2B can be selected. The flue gas stream 203, the steam 215, and the recycled carbon dioxide gas stream can enter the hydrocarbon conversion reactor 2B', wherein the conversion process can be at about 7 Torr (Tc and about 1, 〇〇〇. 〇 at temperatures and up to 150 The pressure at atmospheric pressure is optionally carried out in the presence of a suitable catalyst. The reaction product can exit the hydrocarbon conversion reactor 2B as a gas stream 2〇4. In Figure 2, the gas stream 204 contains hydrogen, carbon monoxide, unreacted steam, unreacted carbon dioxide. 'and unreacted smoke, such as a methane. The gas stream 204 can then be directed to a heat recovery unit 2C' which contains a process heat boiler, various 132047.doc -17-200911687 heat exchangers and cools the gas stream 204 to the desired downstream temperature. A cooling tower (not shown). Thus, stream 205 can exit the 'recovery unit 2C' at the same chemical composition as stream 204 but at a lower temperature than stream 204. Process steam 215 and output steam from water 213 can be produced in the process. 214. The gas stream 205 can then enter the first stage membrane unit 2D, wherein most of the hydrogen and carbon dioxide are separated from the remainder of the gas stream, resulting in the formation of two separate gas streams. A main stream 206 comprising a majority of carbon monoxide along with a portion of unreacted carbon dioxide and a portion of unreacted hydrocarbons, and an infiltrated exhaust stream comprising primarily hydrogen and most unreacted carbon dioxide 216 ° can then direct the permeate off-gas stream 216 as a fuel to the hydrocarbon conversion In unit 2B, the product of fuel combustion may exit unit 2B via exhaust gas stream 2 17. The carbon monoxide enrichment main stream 206 having a relatively high pressure may then be directed to second stage membrane unit 2E, wherein carbon monoxide and remaining unreacted The carbon dioxide is further separated to produce a higher purity one of the oxidized carbon gas stream 207 and the carbon dioxide-enriched permeate stream 2 11. The carbon monoxide gas stream 207 can be further used as a raw material for the nanocarbon material manufacturing unit 2F to produce a nanocarbon material 208 and a waste carbon dioxide gas stream 209. The carbon dioxide-enriched permeate gas stream 211 can be compressed via the compression unit 2G and then recycled back to the first stage membrane unit 2D via line 212, and the spent carbon dioxide gas stream 209 from the nanocarbon material production unit 2F can be compressed via the compression unit 2H. And recycling to hydrocarbon transfer via gas stream 2 10 0 In the case of the unit 2B, in some cases, the nano-carbon material manufacturing unit 2F may comprise several sub-units (not shown), including a nano-carbon material manufacturing reactor, for use in the solid helium 132047.doc -18· 200911687 A means for separating the material product 208 from the effluent gas stream, a subunit for separating and recirculating the % unreacted feed gas, and possibly means for separating the unwanted field product from the carbon dioxide byproduct gas stream. Many variations of the alpha process are possible. The heat required for the reformer can be generated by burning a portion of the hydrogen product from the reformer. Additionally, the hydrogen product can be sold and a natural gas to reformer can be used. Refueling. In addition, the heat released by the exothermic reaction in the nanocarbon material reactor unit 2F can be used to preheat the feed of the reforming, thereby reducing the amount of fuel required for the process. In one embodiment, an additional amount of carbon dioxide can be input from an external source and mixed with the feed to the reformer to achieve additional advantages. When the hydrocarbon fed to the reformer is methane, up to an equivalent amount of external carbon dioxide can also be: fed to the reactor by gas stream 218. Under these conditions, the overall process can be illustrated by the total reaction (V): CH4 + C02 ^ 2 C + 2 H2 〇 (V). This process provides a means of consuming carbon dioxide and thus preventing its release into the atmosphere, where carbon dioxide is considered an important contributor to global warming. Since the total reaction (V) is exothermic and the individual unit operations of the process have effective energy integration, the combination of carbon nanotubes and externally produced carbon dioxide can be accomplished with little or no additional fossil fuel combustion. In other cases described with reference to Figure 3, syngas can also be obtained by a dry reforming process as shown in Reaction Process (III). The dry reforming half can be substantially similar to the method described with respect to Figure 2, including steam reforming. As mentioned earlier, the carbon dioxide by-product can be recycled and the helium will be mixed, and the feed of the lining will be increased by 132047.doc 19 200911687. However, some additional features can be used. Such additional features may include the use of a cold box instead of a membrane separator for the separation of hydrogen and unreacted hydrocarbons from the syngas. This feature can be used in large scale manufacturing plants. Again, this method allows the production of hydrogen as a valuable by-product. This can be described in more detail with reference to FIG. 3. As can be seen from Figure 3, the second 301 can be directed to the pretreatment reactor 3a. As in Fig. 2, the hydrocarbon pretreatment reactor 3A allows the removal of sulfur; saturates various olefins that may be present; and pre-reforms the hydrocarbon 301 as needed. A portion of the hydrocarbon gas stream 3〇2 can supply fuel to the hydrocarbon conversion reactor 3B. After leaving the pretreatment reactor 3, hydrocarbons can enter the hydrocarbon conversion reactor 3B via line 3〇3. The carbon dioxide conversion reforming process and the catalytic steam reforming method are carried out using the hydrocarbon conversion reactor 3B of Fig. 3. Various other hydrocarbon conversion reactors 3B can be selected if desired. The hydrocarbon gas stream 303, the steam 3 16 and the recycled carbon dioxide gas stream 3 丨 3 may be at about 700 in the hydrocarbon conversion reactor 3B. (: reacts with a temperature between about 1, 〇〇〇. (: the reaction product can exit the hydrocarbon conversion reactor 3B via line 304. The gas stream 304 can comprise hydrogen, carbon monoxide 'carbon dioxide, and unreacted hydrocarbons such as methane The gas stream 3〇4 can then be directed to a heat recovery unit 3C. The heat recovery unit 3C can also contain a heat treatment boiler, various heat exchangers, and a cooling tower (not shown) that cools the gas stream 3〇4. The desired downstream temperature stream 3〇4 can then enter the niobium monoxide removal unit 3D as stream 3〇5. Stream 305 exits heat recovery member 3c at the same chemical composition as stream 304 but at a lower temperature than stream 304. Process steam 3 16 and output steam 3 1 5 (from water 314) are produced in heat recovery 132047.doc -20- 200911687. In carbon dioxide removal unit 3D, carbon dioxide gas stream 312 and carbon monoxide depleted gas stream 3 0 6 can be obtained from gas stream 350. The separated carbon dioxide gas 3 12 can then be directed to a carbon dioxide compression unit 3H and subsequently recycled as stream 313 to the hydrocarbon conversion unit 3B. • Depleted carbon monoxide gas stream 306 It may be passed to the carbon monoxide separation unit 3e to produce a product carbon monoxide gas stream 307 and a raw hydrogen stream 309. A typical carbon monoxide separation unit that may be used may include a cold box, a membrane system, or a pressure swing adsorption unit. 最 The most suitable one of the carbon oxide separation units may be selected. The exhaust gas stream 318 of the carbon monoxide separation unit 3E can be recycled and used as a fuel for the hydrocarbon conversion unit 3B. • The exhaust gas stream 3丨9 can contain a product of a fuel that is supplied to the hydrocarbon conversion unit 3B. The carbon monoxide separation unit 3E can be produced. The carbon monoxide 307 is directed to the nanocarbon material manufacturing unit 3F. The waste carbon dioxide gas stream 311 from the nanocarbon material manufacturing unit can be directed to the carbon dioxide compression unit 3H and then the compressed gas stream can be directed to the hydrocarbon conversion reactor 3B. 8 containing a solid ί. nanocarbon product and may, for example, comprise a solid-nanocarbon material deposited on a screen or filter, or may comprise an effluent gas stream (such as carbon monoxide, enriched in a nanocarbon material product, Carbon dioxide, etc.) The nanocarbon manufacturing unit 3F may include several subunits (not shown), Such as nano-sparing reactors, means for separating solid nanocarbon products from the effluent stream, means for separating and recycling unreacted feed gases, and possibly for unwanted by-products A device for separating from a carbon dioxide by-product gas stream. 132047.doc 200911687 The raw hydrogen stream 309 can enter a pressure swing adsorption device 3G that typically includes an adsorbent material. Typically, the adsorbent material is activated carbon or zeolite 5 adsorbent material. The product may be hydrogen at a high pressure which will exit the unit 3G as a gas stream. The remaining gas present in the gas stream will open the unit 3G' via line 31 and may be used as a fuel gas for hydrocarbon conversion. There are many changes to the above methods. For example, the heat required for the reformer can be generated by burning a portion of the hydrogen product from the reformer. In addition, hydrogen products are commercially available and natural gas can be used to refuel the reformer. Alternatively, the heat released by the exothermic reaction in the nanocarbon material reactor unit 317 can be used to preheat the feed to the reformer, thereby reducing the amount of fuel required for the process. In an embodiment, an additional amount of carbon dioxide can be input from an external source and mixed with the feed to the reformer to achieve additional advantages. When the hydrocarbon feed to the reformer is decane, up to an equivalent amount of external carbon dioxide can also be fed to the reactor via gas stream 320. Under these conditions the 'total process' can be schematically illustrated by the total reaction (V). Adding input carbon dioxide to the reformer reduces the amount of hydrogen by-products produced by the process. This process provides the consumption of carbon dioxide and thus prevents its release into the atmosphere. Carbon monoxide is considered an important contributor to global warming in large oxygen because the total reaction (V) is exothermic and the individual unit operations of the process are effective. Integrated, so the combination of carbon nanotubes and external carbon dioxide can be isolated with little or no additional fossil fuel combustion. All of the method integration processes discussed above can help eliminate virtually all CO2 emissions from the nanofiber manufacturing process. It is also possible to enter II 132047.doc -22- 200911687 Carbon oxide for use as part of the feed to the process. Therefore, the integrated method can be used as an effective method for isolating carbon dioxide in the form of valuable products (nanocarbon materials). It will be appreciated that the methods and apparatus described herein are merely exemplary and that modifications and variations can be made without departing from the spirit and scope of the disclosure. All such changes and modifications are intended to be included within the scope of the disclosure as described above. In addition, all representative examples disclosed are not necessarily optional, as the various aspects can be combined to provide the desired results. Therefore, our disclosure is limited only by the scope of the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic illustration of an apparatus for manufacturing a nanocarbon material according to an embodiment of the present invention. Figure 2 is a schematic illustration of an apparatus for making a nanocarbon material in accordance with another embodiment of the present invention. μ Fig. 3 schematically illustrates an apparatus for manufacturing a nanocarbon material according to another embodiment of the present invention. 〇 [Main component symbol description] 1 Hydrocarbon 2 Oxygen flow 2Α Pretreatment reactor 2Β Hydrocarbon conversion reactor 2C Heat recovery unit, which contains a treatment heat boiler, various heat exchangers and cooling of the gas stream 204 to the required downstream temperature. Tower 2D first stage membrane unit 132047.doc. 200911687 2E second stage membrane unit 2F nanocarbon material manufacturing unit, which may comprise several subunits 2G compression unit 2H compression unit 3 pipeline / hydrocarbon gas stream 3 A pretreatment reactor 3B Hydrocarbon conversion reactor 3C heat recovery apparatus, which comprises a treatment heat boiler, various heat exchangers, and a cooling tower 3D carbon dioxide removal unit 3E that cools the gas stream 304. The carbon monoxide separation unit 3F nanocarbon material manufacturing unit may include several subunits. 3G pressure swing adsorption unit, which typically includes an adsorbent material 3 二氧化碳 carbon dioxide compression unit 4 line/gas stream containing hydrogen, carbon monoxide, carbon dioxide, unreacted oxygen, unreacted hydrocarbons (such as methane), and water 5 gas stream 6 line 7 a material having a relatively high pressure of one carbon oxide enriched gas stream 8 nanocarbon material manufacturing unit G, which is One of the purity oxidized carbon gas streams 9 carbon dioxide by-product gas stream from the nanocarbon manufacturing unit G 10 osmotic exhaust gas stream 132047.doc -24- 200911687 11 recycle gas stream 201 hydrocarbon 202 part of the untreated hydrocarbon gas stream 203 pipeline / hydrocarbon gas stream 204 gas stream, It comprises hydrogen, carbon monoxide, unreacted steam, unreacted carbon dioxide, and unreacted hydrocarbon 205 gas stream having the same chemical composition as gas stream 204 but at a lower temperature than * gas stream 204, 206 mainstream, which contains most of the Carbon oxide charcoal together with a portion of unreacted carbon dioxide and a portion of unreacted hydrocarbons. 207 Higher purity one carbon oxide gas stream 208 Solid nanocarbon material product 209 Waste carbon dioxide gas stream 210 from nanocarbon material manufacturing unit 2F Gas stream 211 Enrichment of carbon dioxide permeation Gas stream 212 Line C; 213 Water ^ 214 Output steam 215 from water 213 Steam 216 Infiltrated exhaust stream, which mainly contains hydrogen along with most of the unreacted dioxide 217 vent stream 218 Stream 301 Hydrocarbon I32047.doc -25 - 200911687 302 Part of the hydrocarbon stream 303 pipeline / hydrocarbon stream 304 pipeline / gas flow ' The gas stream comprises hydrogen, carbon monoxide, carbon dioxide, and unreacted hydrocarbons, such as a methane 305 gas stream, which has the same chemical composition as stream 304 but a lower temperature than gas stream 304, 306 depleted carbon dioxide gas stream 307, which is produced in carbon monoxide separation unit 3E. a carbon monoxide 308 gas stream comprising a solid nanocarbon product and which may, for example, comprise a solid nanocarbon material deposited on a screen or filter or may comprise an exhaust gas stream enriched in the nanocarbon material product. Gas stream 311 waste carbon dioxide gas stream 312 from nanocarbon material manufacturing unit 3F carbon dioxide gas stream 313 recycled carbon dioxide gas stream 314 water 315 output steam 316 from water 3 14 steam 317 line 318 exhaust gas stream leaving carbon monoxide separation unit 3E 319 exhaust gas stream 320 gas stream A pretreatment reactor 132047.doc · 26. 200911687 B hydrocarbon conversion reactor C deoxygenation unit D compression unit E first stage membrane unit F second stage membrane unit G nano carbon material manufacturing unit, which contains several subunits 132047. Doc -27-

Claims (1)

200911687 十、申請專利範圍·· ι· 一種製造碳奈米管之方法，其包含： (a) 產生包含一氧化碳、二氧化碳' 氫及烴之合成 氣； (b) 將該氫及該烴自該合成氣分離以產生具有一氧化 碳及二氧化碳之產物氣流以及具有氫及該烴之副產物氣 ^ 流； ^ (C)使用該產物氣流中之一氧化碳製造碳奈米管；及 () (d)將來自該產物氣流及來自該碳奈米管之製造之二 氧化碳再循環。 2.如請求項1之方法，其中產生合成氣包含： (a) 將煙氣流與二氧化碳氣流組合以形成組合氣流； (b) 將該組合氣流轉化以形成該合成氣。 3·如请求項2之方法’其中將該組合氣流轉化包含在7〇〇。〇 與1，000°C之間的溫度下及高達15〇個大氣壓之壓力下乾 重整。 G 4·如叫求項3之方法，其中將該組合氣流轉化另外包含蒸 汽重整。 — 长員3之方法’其中重整係在鉑、把、姥或鎳之觸 ' 媒存在下進行。 6. 如請求 0 + +、4_ ^ 之方法’其另外包含預處理該烴氣流以移除 雜質。 7. 如叫求項2之方法，其中該烴為甲烷。 月长項1之方法’其中對產生合成氣而言，其包含： 132047.doc 200911687 (a)將·、j·孩产 &氣流、二氧化碳氣流及氧氣流組合以形成組 合氣流； (b )另等* 5亥組合氣流轉化以形成包含一氧化碳、二氧化 碳、氫、i C： + 禾反應之烴及未反應之氧之轉化氣流；及 t $轉化氣流脫氧以移除該未反應之氧且形成該 合成氣。 9. 如請求項父 巧8之方法，其中將該組合氣流轉化包含在7〇〇°C 1 4 〇 Q 0「 /、’ L之間的溫度下及高達150個大氣壓之壓力下， 、姥或鎳之觸媒存在下進行該烴之催化重整。 10. 如請求項P夕 7 <方法’其另外包含預處理該烴氣流以移除 雜質。 η.如請求項8之方法，其中該烴為甲烷。 i2·如明求項丨之方法其另外包含將該產物氣流分離成一 氧化碳氣流及二氧化碳氣流。 如叫求項!之方法，其另外包含將該副產物氣流中之氫 純化且回收純氫。200911687 X. Patent Application Range·· ι· A method for manufacturing a carbon nanotube comprising: (a) producing a synthesis gas comprising carbon monoxide, carbon dioxide 'hydrogen and hydrocarbons; (b) synthesizing the hydrogen and the hydrocarbon therefrom Gas separation to produce a product gas stream having carbon monoxide and carbon dioxide and a by-product gas stream having hydrogen and the hydrocarbon; ^ (C) using the carbon monoxide in the product gas stream to produce a carbon nanotube; and () (d) from The product gas stream and carbon dioxide from the manufacture of the carbon nanotubes are recycled. 2. The method of claim 1 wherein generating syngas comprises: (a) combining a flue gas stream with a carbon dioxide gas stream to form a combined gas stream; (b) converting the combined gas stream to form the syngas. 3. The method of claim 2 wherein the combined gas stream is converted to 7 Torr.干 Dry reforming at a temperature between 1,000 ° C and a pressure of up to 15 ° atmosphere. G. The method of claim 3, wherein the converting the combined gas stream further comprises steam reforming. — Method of the member 3' wherein the reforming is carried out in the presence of a catalyst of platinum, rhodium, ruthenium or nickel. 6. A method of requesting 0 + +, 4_ ^, which additionally comprises pretreating the hydrocarbon gas stream to remove impurities. 7. The method of claim 2, wherein the hydrocarbon is methane. The method of month length item 1 wherein, for the production of syngas, it comprises: 132047.doc 200911687 (a) combines the gas stream, the carbon dioxide gas stream and the oxygen stream to form a combined gas stream; (b) In addition, a 5 liter combined gas stream is converted to form a reformed gas stream comprising carbon monoxide, carbon dioxide, hydrogen, i C: + and reacted hydrocarbons and unreacted oxygen; and t $ converted gas stream is deoxygenated to remove the unreacted oxygen and form The syngas. 9. The method of claim 2, wherein the combined gas stream conversion is carried out at a temperature between 7 ° C 1 4 〇 Q 0 " /, ' L and at a pressure of up to 150 atmospheres, 姥Catalytic reforming of the hydrocarbon in the presence of a nickel catalyst. 10. The method of claim 7, wherein the method further comprises pretreating the hydrocarbon gas stream to remove impurities. η. The method of claim 8, wherein The hydrocarbon is methane. The method of the present invention further comprises separating the product gas stream into a carbon monoxide gas stream and a carbon dioxide gas stream. The method of claim 2, further comprising purifying the hydrogen in the by-product gas stream and Recovery of pure hydrogen. 14. 一種製造碳奈米管之設備其包含： 知⑷合成氣製造單元，其用於製造包含—氧化碳、二 氧化碳、氫及烴之合成氣； (b)分離單元，其用於將氫及該烴自該合成氣分離以 =具有—氧化碳及二氧化碳之產物氣流以及具有氮及 該烴之副產物氣流； ⑷碳奈米管製造單元，其使用該產物氣流中 化碳製造碳奈米管；及 132047.doc 200911687 (d)二氧化碳再循環裝置，其用於將來自該碳奈米管 製造單元之二氧化碳再循環至該合成氣製造單元。 15.如請求項14之設備，其中該合成氣製造單元包含二氧化 碳氣體來源、烴氣體來源、將二氧化碳氣體及烴氣體組 合成組合氣流之組合構件，及用於將該組合氣流轉化以 形成該合成氣之轉化反應。 1 6.如請求項1 5之設備，其中該轉化反應器為乾重整器單元 或乾重整器單元與蒸汽重整器單元之組合。 17. 如請求項15之設備，其中該烴為曱烷。 18. 如請求項14之設備，其中該合成氣製造單元包含二氧化 碳氣體來源；烴氣體來源；氧氣來源；將二氧化碳氣 體、烴氣體及氧氣組合成組合氣流之組合構件；及用於 將該組合氣流轉化以形成包含一氧化碳、二氧化碳、 氫、未反應之烴及未反應之氧之轉化氣流的轉化反應； 及將該未反應之氧自該轉化氣流中移除且形成該合成氣 之脫氧單元。 1 9.如請求項1 8之設備，其中該轉化反應器為具有鉑、鈀、 铑或鎳之觸媒之催化重整器單元。 20. 如請求項1 8之設備，其中該烴為甲烷。 21. 如請求項14之設備，其中該分離單元為膜分離器、變壓 吸附單元或低溫分離器。 22. 如請求項14之設備，其另外包含用於將該產物氣流分離 成一氧化碳氣流及二氧化碳氣流之純化單元，其中該純 化單元為膜分離器、變壓吸附單元或低溫分離器。 132047.doc 200911687 2 3 .如請求項14之設備’其另外包含用於自該副產物氣流純 化及回收氫之精煉單元。 C ί 132047.doc14. An apparatus for manufacturing a carbon nanotube comprising: (4) a syngas manufacturing unit for producing a syngas comprising carbon monoxide, carbon dioxide, hydrogen, and a hydrocarbon; (b) a separation unit for using hydrogen and The hydrocarbon is separated from the synthesis gas to have a product gas stream having carbon monoxide and carbon dioxide, and a by-product gas stream having nitrogen and the hydrocarbon; (4) a carbon nanotube manufacturing unit, which uses the product gas stream to produce carbon nanotubes And 132047.doc 200911687 (d) A carbon dioxide recycling unit for recycling carbon dioxide from the carbon nanotube manufacturing unit to the syngas manufacturing unit. 15. The apparatus of claim 14, wherein the syngas manufacturing unit comprises a carbon dioxide gas source, a hydrocarbon gas source, a combination of carbon dioxide gas and a hydrocarbon gas into a combined gas stream, and for converting the combined gas stream to form the synthesis Gas conversion reaction. 1 6. The apparatus of claim 15 wherein the conversion reactor is a dry reformer unit or a combination of a dry reformer unit and a steam reformer unit. 17. The apparatus of claim 15 wherein the hydrocarbon is decane. 18. The apparatus of claim 14, wherein the syngas manufacturing unit comprises a source of carbon dioxide gas; a source of hydrocarbon gas; a source of oxygen; a combination of carbon dioxide gas, hydrocarbon gas, and oxygen into a combined gas stream; and A conversion reaction to form a reformed gas stream comprising carbon monoxide, carbon dioxide, hydrogen, unreacted hydrocarbons, and unreacted oxygen; and a deoxygenation unit that removes unreacted oxygen from the reformed gas stream and forms the syngas. 1 9. The apparatus of claim 18, wherein the conversion reactor is a catalytic reformer unit having a catalyst of platinum, palladium, rhodium or nickel. 20. The apparatus of claim 18, wherein the hydrocarbon is methane. 21. The apparatus of claim 14, wherein the separation unit is a membrane separator, a pressure swing adsorption unit, or a cryogenic separator. 22. The apparatus of claim 14 additionally comprising a purification unit for separating the product gas stream into a carbon monoxide gas stream and a carbon dioxide gas stream, wherein the purification unit is a membrane separator, a pressure swing adsorption unit or a cryogenic separator. 132047.doc 200911687 2 3. The apparatus of claim 14 which additionally comprises a refining unit for purifying and recovering hydrogen from the by-product gas stream. C ί 132047.doc
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