TW201341609A - Methods and system for forming carbon nanotubes - Google Patents

Methods and system for forming carbon nanotubes Download PDF

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TW201341609A
TW201341609A TW101143104A TW101143104A TW201341609A TW 201341609 A TW201341609 A TW 201341609A TW 101143104 A TW101143104 A TW 101143104A TW 101143104 A TW101143104 A TW 101143104A TW 201341609 A TW201341609 A TW 201341609A
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gas
reactor
feed
heat exchanger
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Robert Dean Denton
Dallas Noyes
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Exxonmobil Upstream Res Co
Solid Carbon Prod Llc
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Abstract

Systems and a method for forming carbon nanotubes are described. A method includes forming carbon nanotubes in a first reactor, using a feed gas. The carbon nanotubes are separated from a reactor effluent to form a waste stream. The feed gas, a dry waste stream, or both, are heated with waste heat from the waste stream. The waste stream is chilled in an ambient temperature heat exchanger to condense water vapor, forming a dry waste stream.

Description

用於形成碳奈米管之方法及系統 Method and system for forming carbon nanotubes 相關申請案 Related application

本臨時申請案與Noyes之美國專利申請案第13/263,311號(標題為「藉由還原碳氧化物製造固態碳之方法(Method for Producing Solid Carbon by Reducing Carbon Oxides)」，其係於2011年10月6日提出)相關，該案主張Noyes之國際專利申請案PCT/US2010/029934號(標題為「藉由還原碳氧化物製造固態碳之方法(Method for Producing Solid Carbon by Reducing Carbon Oxides)」之優先權，其係於2010年4月5日提出)，後者又主張美國臨時專利申請案61/170,199號(2009年4月17日提出，且標題為「藉由還原碳氧化物製造固態碳之方法(Method for Producing Solid Carbon by Reducing Carbon Oxides)」)之優先權，該等專利案之揭示均以引用之方式併入本文中。 U.S. Patent Application Serial No. 13/263,311, entitled "Method for Producing Solid Carbon by Reducing Carbon Oxides", No. 10, 2011, which is incorporated herein by reference. In the case of the International Patent Application No. PCT/US2010/029934, entitled "Method for Producing Solid Carbon by Reducing Carbon Oxides", No. Priority, which was filed on April 5, 2010), which in turn advocates U.S. Provisional Patent Application No. 61/170,199 (issued April 17, 2009, entitled "Solution of Solid Carbon by Reduction of Carbon Oxide" The method of Producing Solid Carbon by Reducing Carbon Oxides, the disclosure of which is incorporated herein by reference.

本技術係關於用於形成碳纖維及碳奈米材料之工業規模方法。 This technology relates to industrial scale processes for forming carbon fiber and carbon nanomaterials.

本章節意欲介紹本技術各種不同實施樣態，其可與本技術之範例具體實例相關聯。一般認為該討論有助於提供框架以促進本技術特定實施樣態之更佳理解。因此，應暸 解應從該角度閱讀本章節，而不一定需經先前技術容許。 This section is intended to introduce various embodiments of the present technology, which may be associated with example embodiments of the present technology. This discussion is generally believed to help provide a framework to facilitate a better understanding of the particular implementation of the technology. Therefore, it should be The explanation should be read from this point of view without necessarily having to be allowed by the prior art.

多年來，主要由固態或元素碳所形成之材料已用於眾多產品。例如，碳黑為高碳含量材料，其係用作顏料以及橡膠及塑膠產品(諸如車胎)中之強化化合物。碳黑經常藉由將烴(諸如甲烷)或重質芳族油不完全熱解而形成。藉由天然氣之熱解所形成的熱碳黑其中包括包含大型未黏聚粒子，例如大小在200-500 nm範圍內之粒子。藉由重質油之熱解所形成的爐黑包括黏聚或膠黏遠遠較小之粒子，其大小10-100 nm範圍內，該等粒子黏聚在一起而形成結構。二者情況中，粒子可從具有開放式末端或邊緣之石墨烯薄片的層形成。就化學上來說，開放式邊緣形成可用於吸收、結合至基質等之反應性區域。 Materials that have been formed primarily from solid or elemental carbon have been used in many products for many years. For example, carbon black is a high carbon content material that is used as a reinforcing compound in pigments and in rubber and plastic products such as tires. Carbon black is often formed by incomplete pyrolysis of a hydrocarbon such as methane or a heavy aromatic oil. Thermal carbon black formed by pyrolysis of natural gas includes large non-agglomerated particles, such as particles having a size in the range of 200-500 nm. Furnace blacks formed by pyrolysis of heavy oils include particles that are much less cohesive or tacky, ranging from 10 to 100 nm, and the particles stick together to form a structure. In either case, the particles may be formed from a layer of graphene sheets having open ends or edges. Chemically, open edges form reactive regions that can be used to absorb, bind to substrates, and the like.

已發展更新近的元素碳形式(諸如富勒體(fullerene))，且開始在商業應用中之發展。與碳黑之更開放式結構相反的是，富勒體係從呈封閉式石墨烯結構(即，其中之邊緣係結合至其他邊緣以形成球體、管等)的碳形成。兩個結構(碳奈米纖維及碳奈米管)具有眾多潛在應用，從電池及電子設備至用於營造業之混凝土的用途。碳奈米材料可具有石墨烯之單層壁或石墨烯之多重巢狀壁，或從堆疊之薄片組形成呈杯或板形式之纖維結構。碳奈米管之末端經常覆蓋半球形結構，呈類富勒體狀構造。與碳黑不同的是，尚未實現碳奈米材料之大規模製造方法。然而，已對於許多已提出之製造方法進行研究。 Recent renewed elemental carbon forms, such as fullerene, have been developed and are beginning to evolve in commercial applications. In contrast to the more open structure of carbon black, the Fuller system is formed from carbon in a closed graphene structure (i.e., where the edge bonds are bonded to other edges to form spheres, tubes, etc.). Two structures (carbon nanofibers and carbon nanotubes) have many potential applications, from batteries and electronic equipment to the use of concrete for the construction industry. The carbon nanomaterial may have a single layer of graphene or multiple nested walls of graphene, or form a fiber structure in the form of a cup or plate from a stacked sheet group. The end of the carbon nanotube tube often covers a hemispherical structure and has a Fuller-like structure. Unlike carbon black, a large-scale manufacturing method of carbon nanomaterials has not yet been realized. However, research has been conducted on many of the proposed manufacturing methods.

以電弧為基礎、以雷射為基礎之剝蝕技術以及化學氣 相沉積典型地用於從碳表面產生碳奈米管。例如，在Karthikeyan等人之「大規模合成碳奈米管(Large Scale Synthesis of Carbon Nanotubes)」(E-Journal of Chemistry,2009,6(1),1-12)中評述用以產生碳奈米管之技術。在所述之一項技術當中，在金屬觸媒存在下使用電弧以使石墨從電極汽化時，獲致約1克/分鐘之生產率。所述之其他技術在惰性氣體流中使用雷射剝蝕以使碳從標靶電極汽化。然而，雷射技術使用高純度石墨及高功率雷射，但提供低碳奈米管產率，使其對於大規模合成而言不實用。這些作者所述之第三種技術係以化學氣相沉積(CVD)為基礎，其中於觸媒存在下將烴熱分解。在一些研究中，該等技術在70%純度水準下已獲致高達數公斤/小時之生產率。然而，所述方法當中無一能實際用於大規模商業生產。 Arc-based, laser-based ablation technology and chemical gas Phase deposition is typically used to produce carbon nanotubes from carbon surfaces. For example, in Karthikeyan et al., "Large Scale Synthesis of Carbon Nanotubes" (E-Journal of Chemistry, 2009, 6(1), 1-12), it is used to produce carbon nanotubes. The technology of the tube. In one of the techniques described, an arc is used in the presence of a metal catalyst to achieve a productivity of about 1 gram per minute when the graphite is vaporized from the electrode. Other techniques described use laser ablation in an inert gas stream to vaporize carbon from the target electrode. However, laser technology uses high purity graphite and high power lasers, but provides low carbon nanotube yields that make it impractical for large scale synthesis. The third technique described by these authors is based on chemical vapor deposition (CVD) in which hydrocarbons are thermally decomposed in the presence of a catalyst. In some studies, these techniques have achieved productivity of up to several kilograms per hour at 70% purity. However, none of the methods can be practically used for large-scale commercial production.

烴熱解係用於製造碳黑及各種碳奈米管以及富勒體產物。存在經由使用溫度、壓力及存在觸媒以支配所形成之固態碳形態以熱解烴而產生及獲得不同形式之固態碳的各種不同方法。例如，Kauffman等人(美國專利2,796,331)揭示用於在剩餘氫存在下使用硫化氫作為觸媒而從烴製造各種形式之纖維狀碳的方法，及用於將該等纖維狀碳集中在固體表面上之方法。Kauffman亦主張使用煉焦爐氣作為烴來源。 Hydrocarbon pyrolysis is used to make carbon black and various carbon nanotubes as well as fullerene products. There are various different methods of producing and obtaining different forms of solid carbon by pyrolysis of hydrocarbons by using temperature, pressure, and presence of a catalyst to dominate the solid carbon form formed. For example, Kauffman et al. (U.S. Patent 2,796,331) discloses a method for producing various forms of fibrous carbon from hydrocarbons using hydrogen sulfide as a catalyst in the presence of residual hydrogen, and for concentrating the fibrous carbons on a solid surface. The method above. Kauffman also advocates the use of coke oven gas as a source of hydrocarbons.

在其他研究中，以焰製為基礎之技術係描述於Vander Wal,R.L.等人之「單層壁碳奈米管及奈米纖維之焰製合成 (Flame Synthesis of Single-Walled Carbon Nanotubes and Nanofibers)」(Microgravity Combustion and Chemically Reacting Systems第7屆國際研討會，2003年8月，73-76(NASA Research Publication：NASA/CP-2003-212376/REV1))。該技術將CO或CO/C2H2混合物與觸媒一起引入火焰中，以形成碳奈米管。該等作者注意到可使用用於製造碳黑之以焰製為基礎的技術獲致高生產力。然而，作者們注意到縮放焰製合成規模呈現諸多挑戰。具體而言，觸媒粒子形成、碳奈米管開始形成及碳奈米管生長的總時間限制在約100 ms。 In other studies, the flame-based technology is described in Vander Wal, RL et al., "Flame Synthesis of Single-Walled Carbon Nanotubes and Nanofibers." (Microgravity Combustion and Chemically Reacting Systems, 7th International Symposium, August 2003, 73-76 (NASA Research Publication: NASA/CP-2003-212376/REV1)). This technique introduces a CO or CO/C 2 H 2 mixture with a catalyst into a flame to form a carbon nanotube. The authors noted that high efficiency can be achieved using flame based technology for the manufacture of carbon black. However, the authors note that scaling the scale of synthetic flames presents many challenges. Specifically, the total time for catalyst particle formation, carbon nanotube formation, and carbon nanotube growth is limited to about 100 ms.

Noyes之國際專利申請公開案WO/2010/120581揭示一種藉由在觸媒存在下使用還原劑還原碳氧化物而製造各種形態之固態碳產物的方法。該等碳氧化物通常為一氧化碳或二氧化碳。還原劑通常為烴氣或氫。所希望之固態碳產物的形態可受特殊觸媒、反應條件及該還原反應中所使用之隨意的添加劑控制。該方法係在低壓下進行，並使用低溫急冷程序以從進料流去除水。 International Patent Application Publication No. WO/2010/120581 to Noyes discloses a process for producing various forms of solid carbon products by reducing carbon oxides using a reducing agent in the presence of a catalyst. The carbon oxides are typically carbon monoxide or carbon dioxide. The reducing agent is usually a hydrocarbon gas or hydrogen. The morphology of the desired solid carbon product can be controlled by the particular catalyst, the reaction conditions, and the optional additives used in the reduction. The process is carried out at low pressure and a low temperature quenching procedure is used to remove water from the feed stream.

雖然所描述之技術均可用以形成碳奈米管，但該等方法無一提出用於大量或工業規模製造的實際可行方法。具體而言，形成之量及製程效率二者均低。 While the techniques described can be used to form carbon nanotubes, none of these methods suggest practical methods for mass or industrial scale manufacturing. Specifically, both the amount formed and the process efficiency are low.

本文所揭示之具體實例提出一種用於製造碳奈米管之系統。該系統包括經構置以經構置以使用來自廢氣流之廢 熱加熱進料氣體進料氣體加熱器及經構置以從該進料氣體形成碳奈米管之反應器。一分離器係經構置以使該等碳奈米管從該反應器流出物流分離，形成廢氣流。該系統包括水移除系統，該水移除系統具有周圍溫度熱交換器及經構置以將大量水從該廢氣流分離以形成乾燥廢氣流之分離器。 The specific examples disclosed herein propose a system for making carbon nanotubes. The system includes a configuration configured to use waste from the exhaust stream The feed gas feed gas heater is thermally heated and a reactor configured to form a carbon nanotube from the feed gas. A separator is configured to separate the carbon nanotubes from the reactor effluent stream to form an exhaust stream. The system includes a water removal system having an ambient temperature heat exchanger and a separator configured to separate a quantity of water from the exhaust stream to form a dry exhaust stream.

另一具體實例提出用於形成碳奈米管之方法。該方法包括在第一反應器中使用進料進料氣體形成碳奈米管，且從反應器流出物分離出該等碳奈米管以形成廢棄流。該進料氣體、乾燥廢氣流或二者係使用來自該廢棄流之廢熱加熱。在周圍溫度熱交換器中使該廢棄流急冷以凝結水蒸氣，形成乾燥廢氣流。 Another specific example proposes a method for forming a carbon nanotube. The method includes forming a carbon nanotube using a feedstock feed gas in a first reactor and separating the carbon nanotubes from the reactor effluent to form a waste stream. The feed gas, dry exhaust stream, or both are heated using waste heat from the waste stream. The waste stream is quenched in an ambient temperature heat exchanger to condense water vapor to form a dry exhaust stream.

另一具體實例提出用於形成碳奈米管之反應系統。該反應系統包括二或多個經構置以從包含甲烷及二氧化碳之氣體流形成碳奈米管的反應器。該反應系統中，將最終反應器之前的各反應器之流出物用作下游反應器之進料流，且來自該最終反應器之流出物流包含反應物耗乏之廢棄流。分離系統位於各反應器下游，其中各分離系統係經構置以從來自該反應器之流出物移除碳奈米管。進料加熱器位於各分離系統下游，其中各進料加熱器包含經構置以使用來自該反應器之流出物的廢熱加熱用於後續之反應器的進料氣體流的熱交換器，且其中該最終反應器下游之進料加熱器係經構置以加熱用於第一反應器之氣體流。周圍溫度熱交換器位於各進料加熱器下游，其中各周圍溫度熱交 換器係經構置以從該流出物移除水，形成用於後續反應器之進料流。壓縮機係經構置以提高該反應物耗乏之廢棄流的壓力。位於該壓縮機下游之周圍溫度熱交換器係經構置以從該反應物耗乏之廢棄流移除水。氣體分餾系統經構置以將該反應物耗乏之廢棄流分離成富含甲烷流及富含二氧化碳流。混合機係經構置以將該富含甲烷流或該富含二氧化碳流摻合至初始進料流。 Another specific example proposes a reaction system for forming a carbon nanotube. The reaction system includes two or more reactors configured to form a carbon nanotube from a gas stream comprising methane and carbon dioxide. In the reaction system, the effluent from each reactor prior to the final reactor is used as a feed stream to the downstream reactor, and the effluent stream from the final reactor contains a spent stream of reactant waste. A separation system is located downstream of each reactor, wherein each separation system is configured to remove carbon nanotubes from the effluent from the reactor. A feed heater is located downstream of each separation system, wherein each feed heater includes a heat exchanger configured to heat the feed gas stream for subsequent reactors using waste heat from the effluent from the reactor, and wherein The feed heater downstream of the final reactor is configured to heat the gas stream for the first reactor. The ambient temperature heat exchanger is located downstream of each feed heater, wherein each ambient temperature is hot The exchanger is configured to remove water from the effluent to form a feed stream for subsequent reactors. The compressor is configured to increase the pressure of the spent stream that is depleted of the reactants. An ambient temperature heat exchanger located downstream of the compressor is configured to remove water from the waste stream from which the reactants are depleted. The gas fractionation system is configured to separate the waste stream from which the reactants are depleted into a methane-rich stream and a carbon dioxide-rich stream. The mixer is configured to blend the methane-rich stream or the carbon dioxide-rich stream to the initial feed stream.

在以下詳細描述章節中，茲描述本技術之特定具體實例。然而，至以下描述之本技術特定具體實例或特定用途範圍，希望只用作為範例且只提供範例具體實例之描述。因此，該等技術不局限於以下描述之特定具體實例，而是包括在附錄申請專利範圍之精神與範疇內的所有代替方案、修改及同等物。 In the following detailed description sections, specific specific examples of the present technology are described. However, to the specific embodiments of the present technology or the specific scope of the application described below, it is intended to be used as an example only and the description of the specific examples are provided. Therefore, the present invention is not limited to the specific embodiments described below, but includes all alternatives, modifications, and equivalents within the spirit and scope of the appended claims.

首先，為容易參考，茲說明本申請案中所使用之特定用語及其於內容中之意義。在本文所使用之術語於下文未予界定的情況下，應如同至少一印刷出版品及已頒發專利所反映，給予相關技術之技術人士所給予該術語的最廣定義。此外，本技術不受以下所示之用語限制，此係因所有等效物、同義字、新發展及用於相同或類似目的之用語或技術被視為在該等申請專利範圍之範疇內。 First, for ease of reference, the specific terms used in the present application and their meanings in the content are explained. To the extent that the terms used herein are not defined below, the broadest definition of the term is given to a person skilled in the art, as reflected in at least one printed publication and issued patent. In addition, the present technology is not limited by the terms of the following description, and all equivalents, synonymous, new developments, and terms or techniques for the same or similar purposes are considered to be within the scope of the claims.

碳纖維、奈米纖維及奈米管為具有圓柱形奈米結構之碳的異形體。碳奈米纖維及奈米管為富勒體結構族之成 員，該富勒體結構族包括被稱為「富勒體」之球形碳球。碳奈米管之壁係從呈石墨烯結構之碳薄片所形成。如本文中所使用，奈米管可包括任意長度之單層壁奈米管及多層壁奈米管。可暸解本文及申請專利範圍中所使用之「碳奈米管」用語包括碳之其他富勒體異形體，諸如碳纖維、碳奈米纖維及其他碳奈米結構。 The carbon fiber, the nanofiber, and the nanotube are isomorphs of carbon having a cylindrical nanostructure. Carbon nanofibers and nanotubes are a family of fullerite structures The Fowler structure family includes a spherical carbon sphere called the "Fullite Body". The wall of the carbon nanotube is formed from a carbon sheet having a graphene structure. As used herein, a nanotube can include a single layer of wall nanotubes of any length and a multilayer wall nanotube. It is to be understood that the term "carbon nanotubes" as used herein and in the scope of the patent application includes other fullerene bodies of carbon, such as carbon fibers, carbon nanofibers, and other carbon nanostructures.

「壓縮機」為用於壓縮工作氣體(包括氣體-蒸氣混合物或廢氣)之裝置，且包括泵、渦輪壓縮機、往復式壓縮機、活塞壓縮機、轉葉式或螺旋式壓縮機，以及能壓縮工作氣體之裝置及組合。在一些具體實例中，以特定類型之壓縮機為佳，諸如渦輪壓縮機。本文中可使用活塞壓縮機以包括螺旋式壓縮機、轉葉式壓縮機等。 "Compressor" is a device for compressing a working gas (including a gas-vapor mixture or exhaust gas) and includes a pump, a turbo compressor, a reciprocating compressor, a piston compressor, a rotary vane or a screw compressor, and Apparatus and combination for compressing working gases. In some embodiments, a particular type of compressor is preferred, such as a turbo compressor. Piston compressors may be used herein to include screw compressors, rotary vane compressors, and the like.

如本文所使用之「設備」係處理或輸送化學或能量產物的實體裝備之集合。最廣義來說，用語「設備」適用於可用以產生能量或形成化學產物之任何裝備。設施之實例包括聚合設備、碳黑設備、天然氣處理設備及發電設備。 A "device" as used herein is a collection of physical equipment that processes or transports chemical or energy products. In the broadest sense, the term "device" applies to any equipment that can be used to generate energy or form a chemical product. Examples of facilities include polymerization equipment, carbon black equipment, natural gas processing equipment, and power generation equipment.

「烴」為主要包括元素氫及碳，惟亦可存在少量氮、硫、氧、金屬或任何數量之其他元素的有機化合物。如本文所使用，烴通常係指在天然氣、油或化學處理設施中發現的組分。 "Hydrocarbon" is an organic compound mainly comprising elemental hydrogen and carbon, but may also be present in a small amount of nitrogen, sulfur, oxygen, metals or any other element of any amount. As used herein, hydrocarbon generally refers to a component found in natural gas, oil, or chemical processing facilities.

如本文所使用之用語「天然氣」係指從原油井或從地下含氣層所獲得之多組分氣體。天然氣之組成及壓力可顯著變化。一般天然氣流含有甲烷(CH4)作為主要組分，即天然氣流之超過50莫耳%為甲烷。天然氣流亦可含有乙 烷(C2H6)、高分子量烴(例如C3-C20烴)、一或多種酸氣(例如硫化氫)或其任何組合。天然氣亦可含有少量污染物，諸如水、氮、硫化鐵、蠟、原油或其任何組合。天然氣流可在用於具體實例之前實質上經純化，以去除可能作為毒物之化合物。 As used herein, the term "natural gas" means a multicomponent gas obtained from a crude oil well or from a subterranean gas zone. The composition and pressure of natural gas can vary significantly. Usually the natural gas stream contains methane (CH 4) as a main component, i.e., the natural gas stream is more than 50 mole% methane. The natural gas stream may also contain ethane (C 2 H 6 ), high molecular weight hydrocarbons (eg, C 3 -C 20 hydrocarbons), one or more acid gases (eg, hydrogen sulfide), or any combination thereof. Natural gas may also contain minor amounts of contaminants such as water, nitrogen, iron sulfide, waxes, crude oil or any combination thereof. The natural gas stream can be substantially purified prior to use in the specific examples to remove compounds that may act as poisons.

「低BTU天然氣」為從儲氣層採收時包括相當大比例之CO2的氣體。例如低BTU天然氣除了烴及其他組分之外可包括10莫耳%或更多之CO2。在一些情況下，低BTU天然氣可大部分包括CO2。 "Low BTU natural gas" is a gas that includes a significant proportion of CO 2 when recovered from a gas storage layer. For example, low BTU natural gas may include 10 moles or more of CO 2 in addition to hydrocarbons and other components. In some cases, low BTU natural gas may mostly include CO 2 .

當「相當大」用以指材料之數量或量，或其特殊特徵時，係指足以影響原本欲提供之材料或特徵的量。在某些例中，偏離之確切可容許程度視具體內容而定。 When "substantially" is used to mean the quantity or amount of material, or its particular characteristics, it refers to an amount sufficient to affect the material or feature that is intended to be provided. In some instances, the exact allowable degree of deviation depends on the specific content.

概述 Overview

本文所述之具體實例提出用於以工業規模使用其中可包括二氧化碳及甲烷之接近化學計量混合物的原料製造碳纖維、奈米纖維及奈米管(CNT)之系統及方法。在一些具體實例中，原料之CH4較多，而在其他具體實例中，原料之CO2較多。該方法係在使用Bosch反應之高溫及壓力條件下進行，如圖2所討論。該方法可為能量中性至稍微吸熱。可收集至少一部分來自該反應之熱以用於加熱進料氣體，而提供一部分於連續操作期間該方法所使用的熱。由於使用高壓方法，周圍溫度熱交換器足以從產物流去除水蒸氣，而不使用低溫冷卻器。在將反應期間所形成的產 物與水分開之後，使用氣體分餾系統從廢氣混合物分離出任何殘留量之限量試劑，且將該試劑再循環至該程序。 The specific examples described herein suggest systems and methods for producing carbon fibers, nanofibers, and nanotubes (CNTs) on a commercial scale using materials that can include near stoichiometric mixtures of carbon dioxide and methane. In some embodiments, the CH 4 of the feedstock is more, while in other embodiments, the feedstock has more CO 2 . The process is carried out under high temperature and pressure conditions using a Bosch reaction, as discussed in Figure 2. The method can be energy neutral to slightly endothermic. At least a portion of the heat from the reaction can be collected for heating the feed gas to provide a portion of the heat used by the process during continuous operation. Due to the use of the high pressure process, the ambient temperature heat exchanger is sufficient to remove water vapor from the product stream without the use of a cryocooler. After separating the product formed during the reaction from the water, any residual amount of the limited reagent is separated from the exhaust gas mixture using a gas fractionation system and the reagent is recycled to the process.

如本文所使用，周圍溫度熱交換器可包括水急冷器、空氣冷卻器或與處於實質上為周圍溫度之來源熱交換之任何其他冷卻系統。可暸解周圍溫度實質上為設施之位置的外部空氣之溫度，例如從約-40℃至約+40℃，視該設施之位置而定。此外，可視當前周圍溫度而使用不同類型之周圍溫度熱交換器。例如，在夏季使用水急冷器之設施在冬季可能使用空氣冷卻器。可暸解可在本文描述周圍溫度熱交換器之任何點使用適當類型之周圍溫度熱交換器。整個設備中之周圍溫度熱交換器的類型可視所需之冷卻量而改變。 As used herein, ambient temperature heat exchangers can include water quenchers, air coolers, or any other cooling system that is in heat exchange with a source that is substantially ambient temperature. It can be appreciated that the ambient temperature is substantially the temperature of the outside air at the location of the facility, for example from about -40 ° C to about +40 ° C, depending on the location of the facility. In addition, different types of ambient temperature heat exchangers can be used depending on the current ambient temperature. For example, a facility that uses a water chiller during the summer may use an air cooler during the winter. It can be appreciated that a suitable type of ambient temperature heat exchanger can be used at any point of the ambient temperature heat exchanger described herein. The type of ambient temperature heat exchanger in the entire plant can vary depending on the amount of cooling required.

本文所述之具體實例可使用碳氧化物作為主要碳來源以製造工業數量之碳產物，尤其是諸如富勒體、碳奈米管、碳奈米纖維、碳纖維石墨、碳黑及石墨烯。可能產物之平衡可藉由用於反應之條件而調整，該等條件包括觸媒組成、溫度、壓力、原料等。在反應器系統中，碳氧化物係經催化轉化成固態固態碳及水。該等碳氧化物可從眾多來源獲得，包括大氣、燃燒氣體、製程廢氣、井氣及其他天然及工業來源。 Specific examples described herein may use carbon oxides as the primary carbon source to produce industrial quantities of carbon products, particularly such as fullereere, carbon nanotubes, carbon nanofibers, carbon fiber graphite, carbon black, and graphene. The balance of possible products can be adjusted by the conditions used for the reaction, including catalyst composition, temperature, pressure, starting materials, and the like. In a reactor system, carbon oxides are catalytically converted to solid solid carbon and water. These carbon oxides are available from a variety of sources, including the atmosphere, combustion gases, process gases, well gases and other natural and industrial sources.

本發明方法使用兩種原料：碳氧化物，例如二氧化碳(CO2)；及還原劑，例如甲烷(CH4)。還原劑可包括其他烴氣、氫(H2)或其混合物。烴氣可兼用作額外碳來源以及用作碳氧化物之還原劑。其他氣體(諸如合成氣) 可能產生在該方法中作為中間化合物或包含在進料中，且亦可用作還原劑。合成氣包括一氧化碳(CO)及氫(H2)，如此在單一混合物中包含碳氧化物及還原劑。合成氣可用作進料氣體之全部或一部分。 The process of the invention uses two starting materials: a carbon oxide such as carbon dioxide (CO 2 ); and a reducing agent such as methane (CH 4 ). The reducing agent may include other hydrocarbon gases, hydrogen (H 2 ), or a mixture thereof. Hydrocarbon gas can serve as both an additional carbon source and as a reducing agent for carbon oxides. Other gases, such as syngas, may be produced as intermediate compounds in the process or included in the feed, and may also be used as a reducing agent. Syngas includes carbon monoxide (CO) and hydrogen (H 2 ), thus comprising carbon oxides and reducing agents in a single mixture. Syngas can be used as all or part of the feed gas.

碳氧化物(尤其是二氧化碳)係可從廢氣、低BTU井氣及從一些製程廢氣提取之豐沛氣體。雖然二氧化碳亦可從空氣提取，但其他來源經常具有遠遠較高之濃度，且為採收二氧化碳之更經濟來源。此外二氧化碳可作為發電的副產物而獲得。使用來自該等來源之CO2可藉由將一部分CO2轉化成碳產物而降低二氧化碳之排放。 Carbon oxides (especially carbon dioxide) are abundant gases extracted from exhaust gases, low BTU wells, and from some process gases. Although carbon dioxide can also be extracted from air, other sources often have much higher concentrations and are a more economical source of carbon dioxide. In addition, carbon dioxide can be obtained as a by-product of power generation. The use of CO 2 from such sources can reduce carbon dioxide emissions by converting a portion of the CO 2 to a carbon product.

本文所述之方法可併入發電及用於固存碳氧化物以使其能轉化成固態碳產物的工業方法。例如，可將燃燒或製程廢氣中之碳氧化物分離出且濃縮成為該方法之原料。在一些情況下，該等方法可在無分離及濃縮之情況下直接併入該流程，例如作為多階段燃氣渦輪機發電站中之中間步驟。 The methods described herein can incorporate power generation and industrial processes for sequestering carbon oxides to enable them to be converted to solid carbon products. For example, the carbon oxides in the combustion or process off-gas can be separated and concentrated to become the feedstock for the process. In some cases, such methods can be directly incorporated into the process without separation and concentration, for example as an intermediate step in a multi-stage gas turbine power plant.

圖1為產生碳結構(例如作為二氧化碳固存反應之副產物)的反應系統100之方塊圖。對反應系統100提供進料氣體102，進料氣體102為CO2與CH4之混合物。在一些具體實例中，該反應可用於固存來自發電廠等之廢氣流的CO2。在其他具體實例中，來自天然氣田之低BTU氣體流中的CH4濃度較高。進料氣體102中可存在其他組分，諸如C2H6、C2H4等。在一具體實例中，進料氣體102可經處理以去除該等組分，例如用於作為產物流販售。 1 is a block diagram of a reaction system 100 that produces a carbon structure, such as a by-product of a carbon dioxide sequestration reaction. Providing a feed gas to the reactor system 100, 102, 102 of the feed gas mixture of CO 2 and CH 4 of. In some instances, the reaction may be used to sequester the exhaust gas from power plants and other flow CO 2. In other instances, the higher concentration of CH 4 gas flow from the low BTU gas in the fields. The feed gas 102 may be present in other components, such as C 2 H 6, C 2 H 4 and the like. In one embodiment, the feed gas 102 can be treated to remove such components, for example, for sale as a product stream.

進料氣體102係通過熱交換器104而被加熱以進行反應。於連續操作期間，該加熱係使用從反應所收集的熱106進行。於啟動期間，如下文進一步描述，使用輔助加熱器以提供初始熱。將經加熱之進料氣體108進料至反應器110。 The feed gas 102 is heated by the heat exchanger 104 to carry out the reaction. During continuous operation, the heating is carried out using heat 106 collected from the reaction. During startup, an auxiliary heater is used to provide initial heat as described further below. The heated feed gas 108 is fed to the reactor 110.

在反應器110中，觸媒與一部分該經加熱之進料氣體108反應以形成碳奈米管112。如下文更詳細描述，反應器110可為任何任何數種不同觸媒(包括例如金屬粒、受載觸媒等)之流體化床。從排出反應器110之流動流114分離出碳奈米管112，留下含有過量試劑及水蒸氣之廢氣流116。在流動流114作為廢氣流116進入急冷器之前，將來自流動流114之熱用以形成經加熱進料氣體108。 In reactor 110, a catalyst reacts with a portion of the heated feed gas 108 to form carbon nanotubes 112. As described in more detail below, reactor 110 can be a fluidized bed of any of a variety of different catalysts including, for example, metal particles, supported catalysts, and the like. The carbon nanotubes 112 are separated from the flow stream 114 exiting the reactor 110, leaving an exhaust stream 116 containing excess reagent and water vapor. The heat from the flow stream 114 is used to form the heated feed gas 108 before the flow stream 114 enters the chiller as the exhaust stream 116.

該廢氣流116係通過周圍溫度熱交換器，諸如水急冷器118，該周圍溫度熱交換器凝結出水120。所得之乾燥廢氣流122係用作氣體分餾系統124之進料流。可暸解如本文所使用之乾燥廢氣流具有大量經去除的水，但仍具有少量水蒸氣。例如，乾燥廢氣流之露點可大於約10℃，大於約20℃或更高。乾燥機可用以在氣體分餾之前降低露點，例如，降至-50℃或更低。 The exhaust stream 116 passes through an ambient temperature heat exchanger, such as a water chiller 118, which condenses the effluent 120. The resulting dried exhaust stream 122 is used as a feed stream to the gas fractionation system 124. It will be appreciated that the dry exhaust stream as used herein has a large amount of removed water, but still has a small amount of water vapor. For example, the dry exhaust stream may have a dew point greater than about 10 ° C and greater than about 20 ° C or higher. The dryer can be used to reduce the dew point prior to gas fractionation, for example, to -50 ° C or lower.

氣體分餾系統124移除一部分最低濃度之試劑並將其再循環至該程序，例如藉由將該再循環物126與進料氣體102摻合。可例如藉由販售給下游使用者以處置較高濃度氣體或過量進料128。例如，若CO2為與CH4之摻合物中的最高濃度氣體，該氣體分餾系統124可用以去除殘留在 該廢氣流中之任何CH4，並將其作為再循環物126送回該方法。該方法發揮在試劑與固態碳之間均勻反應的功能，茲參考圖2進一步討論。 The gas fractionation system 124 removes a portion of the lowest concentration reagent and recycles it to the process, for example by blending the recycle 126 with the feed gas 102. The higher concentration gas or excess feed 128 can be disposed of, for example, by a downstream user for sale. For example, if CO 2 is the highest concentration gas in the blend with CH 4 , the gas fractionation system 124 can be used to remove any CH 4 remaining in the exhaust stream and return it as recycle 126. . This method functions as a homogeneous reaction between the reagent and the solid carbon, as further discussed with reference to FIG.

圖2為碳202、氫204及氧206之間的均衡的C-H-O均衡圖200，其表示在各種不同溫度條件下呈均衡之物種。存在涉及這三種元素之反應的範圍，於其中各種不同均衡已被稱為反應。橫貫該圖之在不同溫度下的均衡線顯示將形成固態碳之大概區域。就各溫度而言，固態碳將在相關聯之均衡線上方的區域中形成，但在該均衡線下方之區域中不會形成。 2 is a balanced C-H-O equilibrium diagram 200 between carbon 202, hydrogen 204, and oxygen 206, showing species that are balanced under various temperature conditions. There are ranges of reactions involving these three elements, in which various different equilibriums have been referred to as reactions. The equalization line at different temperatures across the graph shows the approximate area that will form solid carbon. For each temperature, solid carbon will form in the region above the associated equalization line, but will not form in the region below the equalization line.

烴熱解為有利於固態碳製造之氫與碳之間的均衡反應，通常有少許或無氧或水存在，例如，沿從較高氫204含量至較高碳202含量的均衡線208。Boudouard反應(亦稱為一氧化碳歧化反應)為有利於固態碳製造之碳與氧之間的均衡反應，通常有少許或無氫或水存在，例如沿著從較高氧206含量至較高碳202含量之均衡線210。 Hydrocarbon pyrolysis is an equilibrium reaction between hydrogen and carbon that facilitates solid carbon production, typically with little or no oxygen or water present, for example, along an equilibrium line 208 from a higher hydrogen 204 content to a higher carbon 202 content. The Boudouard reaction (also known as carbon monoxide disproportionation) is an equilibrium reaction between carbon and oxygen that facilitates solid carbon production, usually with little or no hydrogen or water present, for example, from a higher oxygen content of 206 to a higher carbon 202. The equilibrium line 210 of the content.

Bosch反應為有利於固態碳製造之碳、氧及氫均存在的均衡反應。在C-H-O均衡圖200中，Bosch反應係位於固態碳與含有各種組合之碳、氫及氧的試劑之間建立均衡的三角形的內部區域中。Bosch反應區中許多點有利於形成CNT及數種固態碳產物之其他形式。反應率及產物可藉由使用觸媒(諸如鐵)加強。觸媒、反應氣體及反應條件之選擇可提供對於所形成之碳類型的控制。如此，該等方法開啟製造諸如CNT之固態碳產物的新途徑。 The Bosch reaction is an equilibrium reaction that favors the production of carbon, oxygen and hydrogen in solid carbon production. In the C-H-O equilibrium map 200, the Bosch reaction is located in a triangular inner region between the solid carbon and the reagents containing various combinations of carbon, hydrogen and oxygen. Many points in the Bosch reaction zone facilitate the formation of CNTs and other forms of several solid carbon products. The reaction rate and product can be enhanced by the use of a catalyst such as iron. The choice of catalyst, reaction gas, and reaction conditions provides control over the type of carbon formed. As such, these methods open up new ways to make solid carbon products such as CNTs.

反應系統 Reaction system

圖3為用於從包含二氧化碳及甲烷之氣體進料製造碳產物的反應系統300之簡化流程圖。如圖所示，該反應系統300可用於CO2含量較高或CH4含量較高之進料氣體302。更具體之反應器系統係圖4所討論之用於較高CO2含量進料氣體者及圖5所討論之用於較高CH4含量進料氣體者。在反應系統300中，進料氣體302係與較少氣體之濃度提高的再循環氣體304結合。此可使用靜態混合器306完成。 3 is a simplified flow diagram of a reaction system 300 for producing a carbon product from a gas feed comprising carbon dioxide and methane. As shown, the higher the reaction system 300 may be used or the CO 2 content higher CH 4 content of the feed gas 302. More specifically, the reactor system of FIG. 4 lines for discussion higher the CO 2 content of the feed to those discussed higher CH 4 content of the feed gas by gas 5 and FIG. In reaction system 300, feed gas 302 is combined with a recycle gas 304 having a reduced concentration of less gas. This can be done using static mixer 306.

結合之氣體流308係通過熱交換器或一組串聯熱交換器310，以藉由反應器流出物流加熱。該經加熱氣體流312之溫度可從約90℉(約32.2℃)升高至約1400℉(約760℃)。該溫度可能足以維持連續操作期間之反應。於啟動期間，可由封裝體加熱器314提供全部或部分該熱。然後將熱氣體流316引入第一流體化床反應器318。參考圖6討論具體實例中可使用之一般流體化床反應器。在第一流體化床反應器318中，碳奈米管係在觸媒粒子上形成。該等觸媒粒子與反應係進一步參考圖7討論。 The combined gas stream 308 is passed through a heat exchanger or a series of series heat exchangers 310 to be heated by the reactor effluent stream. The temperature of the heated gas stream 312 can be raised from about 90 °F (about 32.2 °C) to about 1400 °F (about 760 °C). This temperature may be sufficient to maintain the reaction during continuous operation. All or part of this heat may be provided by the package heater 314 during startup. Hot gas stream 316 is then introduced to first fluidized bed reactor 318. A general fluidized bed reactor that can be used in a specific example is discussed with reference to FIG. In the first fluidized bed reactor 318, a carbon nanotube system is formed on the catalyst particles. These catalyst particles and reaction systems are discussed further with reference to FIG.

碳奈米管係在來自第一流體化床反應器318之反應器流出物流320中運送。該反應器流出物流320可為約1650℉(約899℃)之溫度，且可經冷卻以例如提供用以加熱反應物之部分或全部的熱。在冷卻之前或之後，反應器流出物流320係通過分離裝置，諸如第一鎖定式加料漏 斗322，以移除碳奈米管。所得之廢氣流324係用以在熱交換器326中提供熱。該碳亦可於第二分離裝置(未圖示)中在低於廢氣流324之溫度下予以移除。當可使用並聯之多個熱交換器以冷卻該廢氣流324同時加熱供應至下一反應器336之進料氣體的情況下特別容易完成。通常，所有碳固體係於凝結存在廢氣流324中之任何水蒸氣之前藉由分離裝置予以移除。然後將該經冷卻之廢氣流328通過周圍溫度熱交換器330，該周圍溫度熱交換器330進一步冷卻該經冷凝之廢氣流328，並形成凝結為液體的大量水，然後將該流進料至分離容器332。從該分離容器移除水334，並在第一分離容器332頂部排出約100℉(約38℃)之反應物流336。 The carbon nanotubes are carried in a reactor effluent stream 320 from a first fluidized bed reactor 318. The reactor effluent stream 320 can be at a temperature of about 1650 °F (about 899 °C) and can be cooled to provide, for example, heat to heat some or all of the reactants. Prior to or after cooling, the reactor effluent stream 320 is passed through a separation device, such as a first locked feed leak. Bucket 322 to remove the carbon nanotubes. The resulting exhaust stream 324 is used to provide heat in the heat exchanger 326. The carbon may also be removed in a second separation unit (not shown) at a temperature below the exhaust stream 324. This is particularly easy to accomplish when multiple heat exchangers in parallel can be used to cool the exhaust stream 324 while heating the feed gas supplied to the next reactor 336. Typically, all of the carbon solids are removed by a separation device prior to condensing any water vapor present in the exhaust stream 324. The cooled exhaust stream 328 is then passed through an ambient temperature heat exchanger 330 that further cools the condensed exhaust stream 328 and forms a quantity of water that condenses into a liquid, which is then fed to the stream. The container 332 is separated. Water 334 is removed from the separation vessel and a reactant stream 336 of about 100 °F (about 38 °C) is discharged overhead of the first separation vessel 332.

反應物流336通過熱交換器326且藉由來自從廢氣流324之廢熱加熱。將經加熱之流338進料至第二流體化床反應器340，於其中形成額外碳奈米管。然而，該經加熱流338可能不處於足以在第二流體化床反應器340中形成碳奈米管的充分高之溫度，例如大於約1600℉(約871℃)。為提高該經加熱流338之溫度，可使用第二封裝體加熱器341。在一些具體實例中，第二反應器流出物流342係用以對該第二反應物流336提供熱。然後將第二反應器流出物流342進料至第二鎖定式加料漏斗344，以從該第二反應器流出物流342分離出碳產物。當所得之廢氣流346通過熱交換器310時，其用以對該結合之氣體流308提供熱。 Reaction stream 336 is passed through heat exchanger 326 and heated by waste heat from exhaust stream 324. The heated stream 338 is fed to a second fluidized bed reactor 340 where additional carbon nanotubes are formed. However, the heated stream 338 may not be at a sufficiently high temperature sufficient to form a carbon nanotube in the second fluidized bed reactor 340, such as greater than about 1600 °F (about 871 °C). To increase the temperature of the heated stream 338, a second package heater 341 can be used. In some embodiments, the second reactor effluent stream 342 is used to provide heat to the second reactant stream 336. The second reactor effluent stream 342 is then fed to a second locked feed funnel 344 to separate the carbon product from the second reactor effluent stream 342. When the resulting exhaust stream 346 passes through the heat exchanger 310, it is used to provide heat to the combined gas stream 308.

雖然只顯示兩個流體化床反應器318及340，但反應系統300可視需要含有更多反應器。反應器之數量係根據原料及所希望之各原料的剩餘量而決定。在一些情況下，可使用依序之三、四或更多個反應器，其中來自各反應器之流出物流提供熱給該順序中之下一反應器的進料氣體。此外，該等反應器不一定為流體化床反應器，原因係在具體實例中可使用其他構造。例如，可使用固定床反應器、管式反應器、連續進料反應器或任何數種其他構造。 Although only two fluidized bed reactors 318 and 340 are shown, reaction system 300 may contain more reactors as desired. The number of reactors is determined by the amount of raw materials and the amount of each raw material desired. In some cases, three, four or more reactors may be used, wherein the effluent stream from each reactor provides heat to the feed gas of the next reactor in the sequence. Moreover, the reactors are not necessarily fluidized bed reactors, as other configurations may be used in specific examples. For example, a fixed bed reactor, a tubular reactor, a continuous feed reactor, or any of several other configurations can be used.

在提供熱給該結合氣體流308之後，經冷卻之廢棄流348係通過周圍溫度熱交換器350，然後進料至分離容器352。水354在該分離容器352中沉降，並從底部移除。所得之氣體流356為約100℉(約38℃)且壓力為約540 psia(約3,720 kPa)。在一具體實例中，然後在乾燥機(未圖示)中將該氣體乾燥至低露點。該流進入壓縮機358，該壓縮機358使該氣體流356之壓力提高至約1050 psia(約7,240 kPa)以形成高壓流360，將該高壓流360通過另一周圍溫度熱交換器362。若未使用乾燥機，則從周圍溫度熱交換器362將該高壓流360進料至用於移除任何剩餘水之分離容器364。 After providing heat to the combined gas stream 308, the cooled waste stream 348 passes through the ambient temperature heat exchanger 350 and is then fed to the separation vessel 352. Water 354 settles in the separation vessel 352 and is removed from the bottom. The resulting gas stream 356 is about 100 °F (about 38 °C) and has a pressure of about 540 psia (about 3,720 kPa). In one embodiment, the gas is then dried to a low dew point in a dryer (not shown). The stream enters a compressor 358 that increases the pressure of the gas stream 356 to about 1050 psia (about 7,240 kPa) to form a high pressure stream 360 that passes through another ambient temperature heat exchanger 362. If a dryer is not used, the high pressure stream 360 is fed from ambient temperature heat exchanger 362 to a separation vessel 364 for removing any remaining water.

然後將經乾燥氣體流366送至氣體分餾系統368，該氣體分餾系統368從該再循環氣體304分離出量進料370。在以適當過量CO2為基礎之反應系統300中，過量進料370可主要包含CO2，而再循環氣體可主要包含CH4。在以適當過量CH4為基礎之反應系統300中，過量 進料370可主要包含CO2，而再循環氣體可主要包含CH4。在一些具體實例中，可分接過量進料370、再循環氣體304或二者中之一部分以提供用於該設備的燃料氣體流、沖洗氣體流或二者。 The dried gas stream 366 is then sent to a gas fractionation system 368, from which the gas feed system 368 separates the feed 370. In a suitable excess of the reaction from CO 2 based system 300, 370 may overfeeding comprising predominantly CO 2, mainly recycled gas may comprise CH 4. In an appropriate excess of the reaction CH 4 based system 300, 370 may overfeeding comprising predominantly CO 2, mainly recycled gas may comprise CH 4. In some embodiments, excess feed 370, recycle gas 304, or a portion of both can be tapped to provide a fuel gas stream, a flush gas stream, or both for the apparatus.

所使用之反應條件可導致金屬表面顯著降解，如可包含降解珠之觸媒本身的選擇所顯示。因此，該方法係經設計以減少曝露於該等製程條件之金屬量，茲參考以下圖式進一步討論。 The reaction conditions employed can result in significant degradation of the metal surface as indicated by the choice of the catalyst itself which can comprise degraded beads. Accordingly, the method is designed to reduce the amount of metal exposed to the process conditions and is further discussed with reference to the following figures.

圖4A、4B及4C為用於從包含二氧化碳及甲烷之氣體進料製造碳奈米管的其他反應系統400之簡化流程圖。圖4中，相似數字項目係如圖3所述。該方法中之經編號菱形對應於模擬製程值，如表1所提供之較高CO2含量進料氣體402。第二組模擬值係提供於表2。如第二模擬所示，許多結果顯示在一些條件之下，該整體方法可為稍微吸熱。在該情況下，該第二封裝體加熱器341所提供之額外熱可用於增加碳奈米管產生，同時減少其他產物(諸如非晶形碳)產生。至於圖3，進料氣體402通過靜態混合器306，於該靜態混合器306中與高甲烷之再循環氣體404結合。該結合之氣體流308係通過熱交換器310，例如包括多重外殼熱交換器及管式熱交換器406。該詳細流程圖4與圖3之間的主要差別係在從反應器流出物流320及342分離出CNT之前使用熱交換器冷卻該等反應器流出物流320及342。 4A, 4B and 4C are simplified flow diagrams of other reaction systems 400 for making carbon nanotubes from a gas feed comprising carbon dioxide and methane. In Fig. 4, similar digital items are as shown in Fig. 3. The method of numbered diamond process corresponding to the analog value, the higher the CO 2 content as provided in Table 1, the feed gas 402. The second set of simulated values is provided in Table 2. As shown in the second simulation, many of the results show that under some conditions, the overall process can be slightly endothermic. In this case, the additional heat provided by the second package heater 341 can be used to increase carbon nanotube production while reducing the production of other products, such as amorphous carbon. As for Figure 3, feed gas 402 is passed through static mixer 306 where it is combined with high methane recycle gas 404. The combined gas stream 308 passes through a heat exchanger 310, for example, including a multiple shell heat exchanger and a tube heat exchanger 406. The main difference between this detailed flow chart 4 and Figure 3 is the use of a heat exchanger to cool the reactor effluent streams 320 and 342 prior to separating the CNTs from the reactor effluent streams 320 and 342.

在該具體實例中，經加熱之氣體流312在流經第二熱 交換器之前係在熱交換器310中升高至約800℉(約427℃)之溫度。在該第二熱交換器408中，該經加熱之氣體流312流經第一陶瓷均熱塊熱交換器410，如箭頭412所示。貯存在該第一陶瓷均熱塊熱交換器410中之熱係與該經加熱之氣體流312交換，並可將溫度提高至約1540℉(838℃)。 In this particular example, the heated gas stream 312 is flowing through the second heat. The exchanger was previously raised in heat exchanger 310 to a temperature of about 800 °F (about 427 °C). In the second heat exchanger 408, the heated gas stream 312 flows through the first ceramic soaking block heat exchanger 410 as indicated by arrow 412. The heat stored in the first ceramic soaking block heat exchanger 410 is exchanged with the heated gas stream 312 and the temperature can be raised to about 1540 °F (838 °C).

雖然第一陶瓷均熱塊熱交換器410係用以加熱該經加熱之氣體流312，但第二陶瓷均熱塊加熱器414係用以冷卻第二反應器流出物流342，其係藉由使該流流經該第二陶瓷均熱塊加熱器414而進行，如箭頭416所表示。當該第二陶瓷均熱塊熱交換器414達到選定溫度時，或該第一陶瓷均熱塊熱交換器410降至選定溫度時，改變入口閥418及出口閥420之位置。換言之，將開啟之閥關閉並將關閉之閥開啟。改變該等閥之位置使得藉由來自反應器340之流所加熱為陶瓷均熱塊熱交換器410或414中之何者改變及用以加熱該經加熱之氣體流312為陶瓷均熱塊熱交換器414或410中之何者改變。在流經陶瓷均熱塊熱交換器410或414之後，該流係可圖3所示。 Although the first ceramic soaking block heat exchanger 410 is used to heat the heated gas stream 312, the second ceramic soaking block heater 414 is used to cool the second reactor effluent stream 342 by This flow proceeds through the second ceramic soaking block heater 414 as indicated by arrow 416. When the second ceramic soaking block heat exchanger 414 reaches a selected temperature, or the first ceramic soaking block heat exchanger 410 drops to a selected temperature, the position of the inlet valve 418 and the outlet valve 420 are varied. In other words, the valve that opens is closed and the valve that is closed is opened. Changing the position of the valves causes any of the ceramic soaking block heat exchangers 410 or 414 to be heated by the flow from the reactor 340 and to heat the heated gas stream 312 for ceramic heat block heat exchange. Which of the devices 414 or 410 changes. After flowing through the ceramic soaking block heat exchanger 410 or 414, the flow system can be as shown in FIG.

第二熱交換器326亦可包括殼管式熱交換器422，在該情況下，該殼管式熱交換器422將第二反應物流336之溫度從點11的約100℉(約37.8℃)提高至點12的約715℉(約379.4℃)。然後將第二反應物流336通過另一熱交換器424，該熱交換器424包括兩個陶瓷均熱塊熱交換器426。該等陶瓷均熱塊熱交換器426係經構置以具有 經交換流，如前文討論之第二熱交換器408所示。系統400之其他部分與圖3所述相似，惟製程值可不同，並將該系統之相關製程值示於表1或表2以用於其他模擬。此外，該具體實例中亦可使用超過兩個反應器系統。 The second heat exchanger 326 can also include a shell and tube heat exchanger 422, in which case the shell and tube heat exchanger 422 will have a temperature of the second reactant stream 336 from point 11 of about 100 °F (about 37.8 °C). Increase to about 715 °F (about 379.4 ° C) to point 12. The second reactant stream 336 is then passed through another heat exchanger 424 that includes two ceramic soaking block heat exchangers 426. The ceramic soaking block heat exchangers 426 are configured to have The exchange stream is shown as the second heat exchanger 408 discussed above. Other portions of system 400 are similar to those described in Figure 3, except that process values may vary and the associated process values for the system are shown in Table 1 or Table 2 for other simulations. Furthermore, more than two reactor systems can be used in this specific example.

在該具體實例中，CNT之分離系統426包括旋風分離器428、鎖定式加料漏斗430及過濾器432。在大部分CNT係藉由旋風反應器428移除係沉積在鎖定式加料漏斗430中之後，使用過濾器432從該廢氣流324及346分離出剩餘CNT。此可有助於防止廢氣流324及346中之殘留CNT所造成的阻塞或其他問題。過濾器432尤其可包括袋式過濾器。茲參考圖10更詳細討論CNT分離系統426。 In this particular example, the CNT separation system 426 includes a cyclone separator 428, a locked addition funnel 430, and a filter 432. After most of the CNTs are deposited in the lock-up addition funnel 430 by the cyclone reactor 428, the remaining CNTs are separated from the exhaust streams 324 and 346 using a filter 432. This can help prevent clogging or other problems caused by residual CNTs in the exhaust streams 324 and 346. Filter 432 may especially include a bag filter. The CNT separation system 426 is discussed in more detail with reference to FIG.

在第三分離容器364中從高壓流360去除最後一份水之後，將經乾燥氣體流366送至氣體分餾系統434，該氣體分餾系統434可從CO2廢棄流436分離出高甲烷再循環氣體404。氣體分餾系統434係參考圖3進一步討論。個別流404及436可用以供應該方法之其他氣體。例如，燃 料氣體流438可從高甲烷再循環氣體404分離出並用以對渦輪機、鍋爐或其他裝備供應動力，以例如提供動力至系統400。此外，可從CO2廢棄流436分離出沖洗氣體流440。該沖洗氣體流440可用以冷卻及沖洗CNT，如圖10所述。該沖洗氣體亦可用做該設備中的各種不同清潔功能，諸如當流逆轉時將殘留CNT吹出陶瓷熱交換器410、414或426。 After removal of the last of the high pressure water stream 360 from the third separation vessel 364, 366 to the gas flow fractionation system 434 via the drying gas, the gas fractionation system 434 can be isolated from the high methane recycle gas CO 2 waste stream 436 404. Gas fractionation system 434 is further discussed with reference to FIG. Individual streams 404 and 436 can be used to supply other gases of the process. For example, fuel gas stream 438 may be separated from high methane recycle gas 404 and used to power turbines, boilers, or other equipment to, for example, provide power to system 400. Moreover, CO 2 can be separated from the waste gas stream 436 440 flush. This flushing gas stream 440 can be used to cool and rinse the CNTs as described in FIG. The flushing gas can also be used as a variety of different cleaning functions in the apparatus, such as blowing residual CNTs out of the ceramic heat exchanger 410, 414 or 426 when the flow is reversed.

表1及2所示之製程條件僅意圖作為設備中可發現之條件的實例，如藉由模擬所決定者。實際條件可明顯不同且可大幅改變所示條件。類似設備構造可用於高甲烷進料氣體，如圖5所討論。此外，再循環及流出物廢棄流可含有大量氫及一氧化碳，例如各大於約5莫耳%，各大於約10莫耳%，或甚至各大於20莫耳%。該等組分通常存在進料中且所有非CO2產物流(即再循環甲烷)始終含有一些CO及H2。 The process conditions shown in Tables 1 and 2 are intended only as examples of conditions that can be found in the device, such as those determined by simulation. The actual conditions can vary significantly and the conditions shown can be drastically changed. A similar equipment configuration can be used for high methane feed gas, as discussed in Figure 5. Additionally, the recycle and effluent waste streams can contain significant amounts of hydrogen and carbon monoxide, for example, greater than about 5 mole percent each, greater than about 10 mole percent each, or even greater than 20 mole percent each. These components are typically present in the feed and all non-CO 2 product streams (ie, recycled methane) always contain some CO and H 2 .

圖5A、5B及5C為用於從包含二氧化碳及甲烷之氣體進料製造碳奈米管的其他反應系統500之簡化流程圖。圖5中，相似數字項目係如圖3及圖4所述。此外，未顯示一些數字以簡化該圖。在該具體實例中，該進料氣體的甲烷含量可高於二氧化碳，例如約80莫耳%CH4及20莫耳%CO2，惟可使用任何比率。類似地，再循環氣體504之CO2含量將高於CH4含量，形成可為約51莫耳%CO2及49莫耳%CH4之反應器進料氣體。該方法其餘部分與圖4所討論之系統400類似。然而，由於CH4廢棄流506銷售 至能源市場，故可使用經構置以產生更高純度CH4(例如約99莫耳%CH4或更高者)之氣體分餾系統508。可使用之氣體分餾系統508係參考圖9進一步討論。至於參考圖4討論之系統400，沖洗氣體流510可取自再循環氣體504，而燃料氣體流512可取自CH4廢棄流506。茲將暸解廢棄流僅針對該方法而言。圖5之CH4廢棄流506及圖4之CO2廢棄流436可銷售給例如管線營運商。 5A, 5B, and 5C are simplified flow diagrams of other reaction systems 500 for making carbon nanotubes from a gas feed comprising carbon dioxide and methane. In Fig. 5, similar digital items are as shown in Figs. 3 and 4. In addition, some numbers are not shown to simplify the figure. In this particular example, the feed gas may have a higher methane content than carbon dioxide, such as about 80 mole % CH 4 and 20 mole % CO 2 , although any ratio may be used. Similarly, the recirculation gas to the CO 2 content of greater than 504 CH 4 content of the feed gas can be formed from about 51 mole% CO 2 and 49 mole% CH 4 of the reactor. The remainder of the method is similar to the system 400 discussed in FIG. However, since the waste stream 506 CH 4 energy sold to the market, it can be configured by using the counter to produce a higher purity CH 4 (e.g. about 99 mole% CH 4 or more persons) of the gas fractionation system 508. A gas fractionation system 508 that can be used is further discussed with reference to FIG. For system 400 discussed with respect to FIG. 4, flush gas stream 510 can be taken from recycle gas 504 and fuel gas stream 512 can be taken from CH 4 waste stream 506. It will be appreciated that the waste stream is only for this method. The CH 4 waste stream 506 of Figure 5 and the CO 2 waste stream 436 of Figure 4 can be sold to, for example, a pipeline operator.

可暸解用於形成碳奈米管之系統可包括任何數目之反應器、任何數目之類型，包括所示之流體化床反應器。在一具體實例中，只有單一反應器係用以形成碳奈米管。 It will be appreciated that the system for forming a carbon nanotube can include any number of reactors, any number of types, including the illustrated fluidized bed reactor. In one embodiment, only a single reactor is used to form the carbon nanotubes.

反應器系統 Reactor system

圖6為用於形成碳奈米管602之流體化床反應器600的圖。將熱氣體進料流604通過管線606進料至流體化床反應器600底部。控制閥608可用以調節進入該反應器之熱氣體進料流604的流量。該熱氣體進料流604流經分配器板610，且藉由反應器壁614將位於適當位置之觸媒珠612流體化。如本文所使用之「流體化」意指觸媒珠612流經彼此周圍以使氣泡通過，提供流動狀流之行為。如本文中所討論，反應條件對於任何曝露之金屬表面均非常嚴苛，原因係該金屬表面將作為反應之觸媒。因此，該反應將導致曝露之金屬表面緩慢降解。因此，反應器內表面(包括反應器壁614及頭端615)及分配器板610以及其他部件可由陶瓷材料製成以保護該等表面。 FIG. 6 is a diagram of a fluidized bed reactor 600 for forming a carbon nanotube 602. Hot gas feed stream 604 is fed through line 606 to the bottom of fluidized bed reactor 600. Control valve 608 can be used to regulate the flow of hot gas feed stream 604 into the reactor. The hot gas feed stream 604 flows through the distributor plate 610 and fluidizes the catalyst beads 612 in place by the reactor wall 614. As used herein, "fluidization" means that the catalyst beads 612 flow around each other to pass the bubbles, providing a flow of fluid. As discussed herein, the reaction conditions are very severe for any exposed metal surface because the metal surface will act as a catalyst for the reaction. Therefore, the reaction will cause the exposed metal surface to slowly degrade. Thus, the inner surface of the reactor (including reactor wall 614 and head end 615) and distributor plate 610 and other components can be made of a ceramic material to protect the surfaces.

當熱氣體進料流604流經觸媒粒子612之流體化床時，將從觸媒珠612形成CNT 602。該流動之熱氣體進料流604將CNT 602運送至頂部管線616，於該處從反應器600移出CNT 602。視流率而定，例如控制閥608調整，可將一些量之觸媒珠612或自觸媒珠612碎裂之粒子運送至頂部管線616。因此，觸媒分離器618可用以從反應器流出物流620分離出觸媒珠及較大粒子，且經由再循環管線622將其送返反應器600。任何數目之構造均可用於觸媒分離器618，包括旋風分離器、沉降槽、加料漏斗等。於圖7中更詳細討論在流體化床中發生之反應。 When hot gas feed stream 604 flows through the fluidized bed of catalyst particles 612, CNTs 602 will be formed from catalyst beads 612. The flowing hot gas feed stream 604 carries the CNTs 602 to the overhead line 616 where the CNTs 602 are removed from the reactor 600. Depending on the flow rate, such as control valve 608 adjustment, some amount of catalyst beads 612 or particles fragmented from the contact beads 612 may be transported to the top line 616. Thus, the catalyst separator 618 can be used to separate the catalyst beads and larger particles from the reactor effluent stream 620 and return it to the reactor 600 via the recycle line 622. Any number of configurations can be used for the catalytic separator 618, including cyclones, settling tanks, addition funnels, and the like. The reactions occurring in a fluidized bed are discussed in more detail in Figure 7.

圖7為用於在觸媒珠702上形成碳奈米管之催化反應700的示意圖。熱氣體進料流706中一部分CH4與CO2之間的初始反應704導致形成化學計量數量之CO及H2。過量來源氣體706連續流經該反應器，其有助於流體化該床且帶走CNT 708及觸媒粒子710。 FIG. 7 is a schematic illustration of a catalytic reaction 700 for forming a carbon nanotube on a catalyst bead 702. The hot gas feed stream 706 in the initial reaction between a portion of the CH 4 and CO 2 704 results in the formation of a stoichiometric amount of CO and H 2. Excess source gas 706 is continuously passed through the reactor, which aids in fluidizing the bed and entraining CNT 708 and catalyst particles 710.

形成CNT 708之反應係在觸媒珠702上發生。CNT 708之大小及CNT 708之類型(例如單層壁或多層壁CNT 708)可由顆粒712之大小控制。換言之，在顆粒邊界之具有充分大小的鐵原子核心形成碳產物在觸媒珠702上生長的成核點。通常，較小顆粒712會在CNT 708中形成較少層，且可用以獲得單層壁CNT 708。其他參數亦可用以影響最終產物的形態，其包括反應溫度、壓力及進料氣體流率。 The reaction to form CNTs 708 occurs on the catalyst beads 702. The size of the CNT 708 and the type of CNT 708 (e.g., single layer or multi-wall CNT 708) may be controlled by the size of the particles 712. In other words, a core of iron atoms having a sufficient size at the boundary of the particles forms a nucleation site where the carbon product grows on the catalyst beads 702. Generally, smaller particles 712 will form fewer layers in CNT 708 and can be used to obtain single layer wall CNTs 708. Other parameters can also be used to influence the morphology of the final product, including reaction temperature, pressure, and feed gas flow rate.

CO及H2在顆粒邊界714反應，將活性觸媒粒子716 抬離觸媒珠702，並形成H2O 718及CNT 708之固態碳。CNT 708從觸媒珠702及從觸媒粒子710斷裂。可例如由參考圖6所討論之觸媒分離器618捕獲較大觸媒粒子710並將之送返該反應器，同時非常細微之觸媒粒子710將與CNT 708一起被帶出。最終產物將包含約95莫耳%之固態碳及約5莫耳%之金屬，諸如鐵。CNT 708經常黏聚形成團簇720，其為最終產物的常見形式。一部分CO及H2通過反應器而不反應並且為反應器流出物流中之污染物。 CO and H 2 in the grain boundaries 714 of the reaction, the active catalyst particles are lifted from the catalyst beads 716 702, and forms H 2 O 718 708 and the CNT of solid carbon. The CNTs 708 are broken from the catalyst beads 702 and from the catalytic particles 710. The larger catalyst particles 710 can be captured and returned to the reactor, for example, by the catalyst separator 618 discussed with reference to Figure 6, while very fine catalyst particles 710 will be carried with the CNTs 708. The final product will comprise about 95 mole percent solid carbon and about 5 mole percent metal, such as iron. CNTs 708 are often coagulated to form clusters 720, which are a common form of final product. Portion of the CO and H 2 and passed through the reactor without the reactor effluent stream contaminant of the reactor.

當反應進行時，觸媒珠702降解且最終消耗掉。因此，反應可描述於金屬成塵反應。在一些具體實例中，藉由陶瓷襯料保護金屬表面免受侵襲，原因係該等與反應條件接觸之金屬表面不僅降解，且亦形成適當品質之產物。 As the reaction proceeds, the catalyst beads 702 degrade and eventually become consumed. Therefore, the reaction can be described in a metal dusting reaction. In some embodiments, the metal surface is protected from attack by a ceramic lining because the metal surface in contact with the reaction conditions not only degrades, but also forms a product of suitable quality.

觸媒珠702可包含任何數目之其他金屬，諸如鎳、釕、鈷、釤及其他金屬。然而，觸媒珠702上之催化位置原則上係由鐵原子構成。在一具體實例中，觸媒珠702包括金屬粒，例如可用於噴擊之約25至50篩目的珠。在一具體實例中，觸媒可為不鏽鋼球軸承等。 Catalyst beads 702 can comprise any number of other metals, such as nickel, ruthenium, cobalt, rhodium, and other metals. However, the catalytic position on the catalyst beads 702 is in principle composed of iron atoms. In one embodiment, the catalyst beads 702 comprise metal particles, such as beads of about 25 to 50 mesh that can be used for spraying. In one embodiment, the catalyst can be a stainless steel ball bearing or the like.

氣體分餾系統 Gas fractionation system

圖8為可用於用以製造碳奈米管之反應器系統的氣體製造程序800之簡化流程圖。氣體分餾系統800為可併用諸如圖4所討論之高CO2反應器系統的整體分餾法。在氣體分餾系統800中，將進料氣體802進料至乾燥機804以將露點降至約-70℉(約-56.7℃)或更低。進料氣體802可 對應於圖3至5所討論之經乾燥氣體流366。乾燥機804可為固定或流體化乾燥機床，其含有吸附劑，諸如分子篩、乾燥劑等。亦可使用其他乾燥機技術，諸如低溫乾燥機系統。在一些具體實例中，乾燥機可位於壓縮機358之前，此可消除對於周圍溫度熱交換器362之需求。 Figure 8 is a simplified flow diagram of a gas manufacturing process 800 that can be used in a reactor system for making carbon nanotubes. Gas fractionation system 800, such as may be used in a high overall CO 2 fractional distillation reactor system of FIG. 4 discussed. In gas fractionation system 800, feed gas 802 is fed to dryer 804 to reduce the dew point to about -70 °F (about -56.7 °C) or less. Feed gas 802 may correspond to dried gas stream 366 as discussed in Figures 3-5. Dryer 804 can be a fixed or fluidized drying machine tool that contains an adsorbent such as molecular sieves, desiccants, and the like. Other dryer technologies, such as a low temperature dryer system, can also be used. In some embodiments, the dryer can be located prior to compressor 358, which eliminates the need for ambient temperature heat exchanger 362.

然後將乾燥氣體進料806進料至低溫急冷器808以降低溫度以預備分離。由於CO2在-77℉(約-61℃)下將從該氣體凝結出來，多階段急冷系統810可用以將溫度降至該水準左右。該多階段急冷系統810可包括用以使用來自乾燥進料氣體806的能量813加熱出口氣體的熱收集系統812。 Dry gas feed 806 is then fed to low temperature chiller 808 to lower the temperature to prepare for separation. Since CO 2 at -77 deg.] F (about -61 deg.] C) will condense out of the gas, a multi-stage quench system 810 may be used to level the temperature is reduced to about. The multi-stage quench system 810 can include a heat collection system 812 to heat the outlet gas using energy 813 from the dry feed gas 806.

將經急冷進料816進料至分離容器818以分離出液態流820及蒸氣流822。將蒸氣流822通過膨脹器824以藉由在絕熱膨脹過程中產生機械功而降低溫度。在一具體實例中，機械功826係用以驅動發電機828，該發電機828提供一部分該設備中所使用之電力。在其他具體實例中，機械功826係用以驅動壓縮機，例如用於壓縮多階段急冷系統810之冷凍劑流。該膨脹可形成兩相流830。 The quench feed 816 is fed to a separation vessel 818 to separate the liquid stream 820 and the vapor stream 822. Vapor stream 822 is passed through expander 824 to reduce temperature by creating mechanical work during adiabatic expansion. In one embodiment, mechanical work 826 is used to drive a generator 828 that provides a portion of the power used in the device. In other embodiments, mechanical work 826 is used to drive a compressor, such as a refrigerant stream for compressing a multi-stage quench system 810. This expansion can form a two-phase stream 830.

將該液態流820及該兩相流830進料至分離塔832，例如在沿著分離塔832之不同進料。藉由再沸器834將熱供應至該分離塔832。該再沸器832係藉由來自熱交換器836之流加熱。熱交換器836可為急冷器系統的一部分，其比分離塔832更溫暖，惟低於周圍溫度。塔底流838係通過再沸器834並在加溫之後的部分840再注入。來自再 沸器834之出口流842提供CO2產物844。CO2產物844之一部分846可再循環經過熱交換器836以將能量帶至該再沸器834。 The liquid stream 820 and the two phase stream 830 are fed to a separation column 832, such as at a different feed along the separation column 832. Heat is supplied to the separation column 832 by the reboiler 834. The reboiler 832 is heated by the flow from the heat exchanger 836. Heat exchanger 836 can be part of a chiller system that is warmer than separation column 832, but below ambient temperature. The bottom stream 838 is reinjected through the reboiler 834 and after the warming portion 840. Outlet stream 842 from the reboiler 834 of the product 844 provides CO 2. A portion 846 of the CO 2 product 844 can be recycled through the heat exchanger 836 to bring energy to the reboiler 834.

來自分離塔832塔頂流848為富含甲烷之流，例如包括約73莫耳%CH4及約23莫耳%CO2。如前述，塔頂流848可用於急冷器系統812以冷卻乾燥氣體進料806，將塔頂流848加溫以形成再循環氣體850。可存在該再循環氣體850中之其他組分包括例如約3.5莫耳%CO及H2。若甲烷欲用於販售，諸如在參考圖6所討論之高甲烷反應系統中，可使用較高純度分離系統，如圖9所討論。 The overhead stream 848 from separation column 832 is a methane-rich stream comprising, for example, about 73 mole % CH 4 and about 23 mole % CO 2 . As before, the overhead stream 848 can be used in the chiller system 812 to cool the dry gas feed 806 and the overhead stream 848 to warm to form the recycle gas 850. Other components that may be present in the recycle gas 850 include, for example, about 3.5 mole % CO and H 2 . If methane is to be used for sale, such as in the high methane reaction system discussed with reference to Figure 6, a higher purity separation system can be used, as discussed in Figure 9.

圖9為可用於用以製造碳奈米管之反應器系統的另一氣體製造程序900之簡化流程圖。圖9中，相似編號項目係如圖8所討論。在該氣體分餾製程900中，可將經急冷進料816直接進料至第一分離塔902，該第一分離塔902分離出CO2。該CO2係在塔底產物流904中排出第一分離塔902。將一部分該塔底產物流904通過再沸器906，該再沸器906增加熱。然後將該經加熱流908再注入該第一分離塔902。剩餘之塔底產物流904形成CO2產物910，將其再循環，例如參考圖5所討論作為再循環氣體504。 9 is a simplified flow diagram of another gas production process 900 that can be used in a reactor system for making carbon nanotubes. In Figure 9, similar numbered items are discussed in Figure 8. In the gas fractionation process 900, it may be quenched directly fed 816 fed to the first separation column 902, the first separation column 902 is separated CO 2. The CO 2 is discharged from the first separation column 902 in the bottoms product stream 904. A portion of the bottoms product stream 904 is passed through a reboiler 906 which adds heat. The heated stream 908 is then reinjected into the first separation column 902. The residual bottoms stream 904 CO 2 product 910 is formed, which is recycled, for example as discussed with reference to FIG recycle gas 504.

將來自第一分離塔902之塔頂流912送至第二分離塔914以進一步純化該甲烷產物。來自第二分離塔914之塔底產物流916係藉由泵918加壓且作為回流流920送返該第一分離塔902。來自第二分離塔914之塔頂流922係通過急冷器924，該急冷器924可使用氮冷凍單元926以獲 致遠遠較低之溫度。然後將該經急冷之流驟沸至分離容器928。來自該分離容器928之塔頂流930提供富含CH4之產物。該塔頂流930可用以提供乾燥氣體進料806之冷卻，例如藉由進料通過共用急冷系統812而進行。來自分離容器928之塔底產物流934係藉由泵936加壓且作為回流流938送返該第二分離塔914。 The overhead stream 912 from the first separation column 902 is sent to a second separation column 914 to further purify the methane product. The bottoms product stream 916 from the second separation column 914 is pressurized by pump 918 and returned to the first separation column 902 as reflux stream 920. The overhead stream 922 from the second separation column 914 is passed through a chiller 924 that can use the nitrogen refrigeration unit 926 to achieve a much lower temperature. The quench stream is then aspirated to a separation vessel 928. The overhead stream from the separation vessel 928 930 CH 4 of the enriched product. The overhead stream 930 can be used to provide cooling of the dry gas feed 806, such as by feeding through a shared quench system 812. The bottoms product stream 934 from the separation vessel 928 is pressurized by a pump 936 and returned to the second separation column 914 as a reflux stream 938.

該等參考圖8及9討論之構造及單元僅為範例。可對該等系統進行任何數目之變化。此外，其他氣體分離系統可用於具體實例中，只要可獲致流率及純度水準即可。 The configurations and units discussed with reference to Figures 8 and 9 are merely examples. Any number of changes can be made to these systems. In addition, other gas separation systems can be used in the specific examples as long as the flow rate and purity level can be obtained.

分離系統 Separation system

圖10為可反應器流出物流分離出碳奈米管之分離系統1000的簡化流程圖。分離系統1000與圖4及圖5中所示之鎖定式加料漏斗430重疊，且係用以從該程序分離出CNT以供封裝。在該系統中之各反應器可具有獨立之封裝列1002及1004。由於不同反應器可製造不同量之CNT，故該裝備可定為不同大小，惟功能可相同。例如，在第一模擬中，由第一封裝列1002分離之CNT的量可為約162.7噸/天(148,000公斤/天)，而移除至第二封裝列1004之量可為約57.5噸/天(52,000公斤/天)。 Figure 10 is a simplified flow diagram of a separation system 1000 in which a reactor effluent stream separates carbon nanotubes. The separation system 1000 overlaps the lock-type addition funnel 430 shown in Figures 4 and 5 and is used to separate CNTs from the program for packaging. Each reactor in the system can have separate package columns 1002 and 1004. Since different reactors can produce different amounts of CNTs, the equipment can be sized differently, but the functions can be the same. For example, in the first simulation, the amount of CNTs separated by the first package column 1002 can be about 162.7 tons per day (148,000 kilograms per day), while the amount removed to the second package column 1004 can be about 57.5 tons per volume. Day (52,000 kg / day).

各封裝列1002及1004可具有取樣閥1006以從鎖定式加料漏斗430移除CNT。閥1006可為經構置以使在旋轉回點之一部分期間能令特定量之CNT及氣體通過的旋轉閥。在一些具體實例中，取樣閥1006可為經構置以完 全開啟經選定時間期間以使得在完全關閉之前能令選定量之CNT及氣體通過的球閥。使該CNT及氣體流入桶1008以供沖洗及冷卻。 Each package column 1002 and 1004 can have a sampling valve 1006 to remove CNTs from the locking addition funnel 430. Valve 1006 can be a rotary valve configured to enable passage of a particular amount of CNTs and gases during a portion of the rotational return point. In some embodiments, the sampling valve 1006 can be configured to complete Fully open the ball valve for a selected period of time to allow a selected amount of CNTs and gas to pass before being fully closed. The CNTs and gases are flowed into the barrel 1008 for rinsing and cooling.

在取樣閥1006已關閉之後，可開放沖洗流1010進入桶1008以清出剩餘氣體，諸如CO、H2、H2O及CH4。如前述，沖洗流1010可取自氣體分餾系統之富含CO2側，例如參考圖4討論之沖洗氣體流440，或參考圖5討論之沖洗氣體流510。沖洗出口流1012將運送一些量之CNT及其他細微粒子，且可在作為沖洗送回料1016送回該程序之前通過過濾器1014。該過濾器1014可為袋式過濾器、旋風分離器或任何適用之分離系統。在沖洗完成之後，封裝閥1018將開啟以使CNT流1020流至填充站1022，以封裝成桶或罐以供販售。 After sampling valve 1006 is closed, you can open into the flushing stream 1010 to 1008 clear the tub residual gas, such as CO, H 2, H 2 O and CH 4. As noted above, the flushing stream 1010 can be taken from the CO 2 rich side of the gas fractionation system, such as the flushing gas stream 440 discussed with reference to FIG. 4, or the flushing gas stream 510 discussed with reference to FIG. The rinse outlet stream 1012 will carry some amount of CNTs and other fine particles and may pass through the filter 1014 before being returned to the process as a rinse feed 1016. The filter 1014 can be a bag filter, a cyclone or any suitable separation system. After the flushing is complete, the encapsulation valve 1018 will open to allow the CNT stream 1020 to flow to the fill station 1022 for packaging into a bucket or canister for sale.

上述之分離系統僅為範例。具體實例中可使用任何數目之其他系統。然而，該等CNT具有非常低密度，為低於約0.5 g/cc，其視形態分布而定，且最佳可在經構置以從大氣中將彼等分離出之系統中封裝，以降低損失至設備環境之量。 The above separation system is only an example. Any number of other systems can be used in a specific example. However, such CNTs have a very low density, below about 0.5 g/cc, depending on the morphology distribution, and optimally can be packaged in a system configured to separate them from the atmosphere to reduce The amount lost to the equipment environment.

方法 method

圖11為用於從包含甲烷及二氧化碳之進料氣體產生碳奈米管的方法1100。方法1100從於方塊1102開始，於該處獲得混合之CO2/CH4原料。該原料可從任何數目之來源獲得。如上述，該原料可包括從地下儲氣層採收之天然 氣、來自發電廠之廢氣，或任何數目之來自天然或工廠來源之氣體。 11 is a method 1100 for producing a carbon nanotube from a feed gas comprising methane and carbon dioxide. Method 1100 begins at block 1102 where a mixed CO 2 /CH 4 feedstock is obtained. This material can be obtained from any number of sources. As noted above, the feedstock may include natural gas recovered from an underground gas storage layer, waste gas from a power plant, or any number of gases from natural or plant sources.

在方塊1104，該原料與從該程序中所產生之廢氣獲得之再循環氣體結合。如本文所述，該再循環氣體可藉由低溫氣體分餾以及任何數目之之其他技術而從廢氣獲得。於方塊1106，使用從反應程序收集之廢熱加熱該結合之氣體流。加熱之後，於方塊1108，令該結合之氣體流與金屬觸媒於反應器中反應以形成CNT。於方塊1110，從廢氣分離出該等CNT。於方塊1112，沖洗該等經分離之CNT，並經封裝以送至市場。 At block 1104, the feedstock is combined with the recycle gas obtained from the offgas produced in the process. As described herein, the recycle gas can be obtained from the offgas by cryogenic gas fractionation and any number of other techniques. At block 1106, the combined gas stream is heated using waste heat collected from the reaction sequence. After heating, at block 1108, the combined gas stream is reacted with a metal catalyst in a reactor to form CNTs. At block 1110, the CNTs are separated from the exhaust. At block 1112, the separated CNTs are rinsed and packaged for delivery to the market.

將該廢氣冷卻以去除反應期間所形成的過量水。由於該程序係在高溫及高壓下進行，周圍溫度熱交換器提供充分冷卻以凝結出水蒸氣。將對反應系統中之各依序反應器重複方塊1106至1114所述之程序。 The exhaust gas is cooled to remove excess water formed during the reaction. Since the process is carried out at high temperatures and pressures, the ambient temperature heat exchanger provides sufficient cooling to condense water vapor. The procedures described in blocks 1106 through 1114 will be repeated for each of the sequential reactors in the reaction system.

於方塊1116，將廢氣分餾成富含CO2流及富含CH4流。於方塊1118，可販售任一含有過量試劑之流，同時可將另一流再循環至方塊1104以用於該程序。 At block 1116, the offgas is fractionated into a CO 2 rich stream and a CH 4 rich stream. At block 1118, any stream containing excess reagents may be sold while another stream may be recycled to block 1104 for use in the process.

該主張之主題的其他具體實例可包括以下編號段落所列之要素的任何組合： Other specific examples of the subject matter of the claim may include any combination of the elements listed in the following numbered paragraphs:

1.一種用於製造碳奈米管之系統，其包括：進料氣體加熱器，其經構置以使用來自廢氣流之廢熱加熱進料氣體；反應器，其經構置以從該進料氣體形成碳奈米管；分離器，其經構置以從該反應器流出物流分離出該等 碳奈米管，形成廢氣流；及水移除系統，其包括周圍溫度熱交換器及經構置以從該廢氣流分離出大量水以形成乾燥廢氣流之分離器。 CLAIMS 1. A system for making a carbon nanotube comprising: a feed gas heater configured to heat a feed gas using waste heat from an exhaust stream; a reactor configured to receive from the feed The gas forms a carbon nanotube; a separator configured to separate the effluent stream from the reactor A carbon nanotube tube forms an exhaust stream; and a water removal system comprising an ambient temperature heat exchanger and a separator configured to separate a quantity of water from the exhaust stream to form a dry exhaust stream.

2.如段落1之系統，其中該周圍溫度熱交換器包括水急冷器。 2. The system of paragraph 1, wherein the ambient temperature heat exchanger comprises a water chiller.

3.如段落1或2之系統，其中該周圍溫度熱交換器包括空氣冷卻熱交換器。 3. The system of paragraph 1 or 2, wherein the ambient temperature heat exchanger comprises an air cooled heat exchanger.

4.如段落1、2或3之系統，其包括經構置以加熱用於該系統初始啟動之進料氣體的封裝體加熱器。 4. The system of paragraph 1, 2 or 3, comprising a package heater configured to heat a feed gas for initial startup of the system.

5.如前述段落任一者之系統，其包括：熱交換器，其經構置以使用來自該廢氣流之廢熱加熱該乾燥廢氣流以形成第二進料氣體；第二反應器，其經構置以從該第二進料氣體形成碳奈米管；分離器，其經構置以從來自該第二反應器之流出物流分離出該等碳奈米管，形成第二廢氣流，且其中用於該進料氣體加熱器之廢氣流包括該第二廢氣流；及水移除系統，其經構置以使用周圍溫度熱交換器急冷該第二廢氣流並移除大量水，而從該第二廢氣流分離出水，以形成第二乾燥廢氣流。 5. The system of any of the preceding paragraphs, comprising: a heat exchanger configured to heat the dry exhaust stream to form a second feed gas using waste heat from the exhaust stream; a second reactor Constructed to form a carbon nanotube from the second feed gas; a separator configured to separate the carbon nanotubes from the effluent stream from the second reactor to form a second exhaust stream, and Wherein the exhaust stream for the feed gas heater includes the second exhaust stream; and a water removal system configured to quench the second exhaust stream and remove a large amount of water using an ambient temperature heat exchanger The second exhaust stream separates water to form a second dry exhaust stream.

6.如段落5之系統，其包含壓縮機，其經構置以提高該第二乾燥廢氣流之壓力；及最終水移除系統，其經構置以從該第二廢氣流移除 水。 6. The system of paragraph 5, comprising a compressor configured to increase a pressure of the second dry exhaust stream; and a final water removal system configured to be removed from the second exhaust stream water.

7.如段落5或6之系統，其包括經構置以從該第二廢氣流分離出富含甲烷流與富含CO2流之氣體分餾系統。 7. The system of paragraph 5 or 6, which comprises a counter configured to separate via the second exhaust gas stream from the methane-enriched gas stream and the rich stream of the fractionation system 2 CO.

8.如段落5、6或7之系統，其包括經構置以在該進料氣體加熱器之前將該富含甲烷流混入該進料氣體的混合系統。 8. The system of paragraphs 5, 6 or 7, comprising a mixing system configured to mix the methane-rich stream into the feed gas prior to the feed gas heater.

9.如申請專利範圍第5至8中任一者之系統，其中該氣體分餾系統包括經構置以使在某一溫度下可凝結之氣體與在該溫度下不凝結之氣體分開的低溫凝結系統。 9. The system of any one of claims 5 to 8, wherein the gas fractionation system comprises a low temperature condensation configured to separate a gas condensable at a temperature from a gas that does not condense at the temperature. system.

10.如段落1或5之系統，其中該反應器為使用進料氣體之逆向流將觸媒流體化之流體化床反應器。 10. The system of paragraph 1 or 5, wherein the reactor is a fluidized bed reactor that fluidizes the catalyst using a reverse flow of feed gas.

11.如段落10之系統，其中該觸媒包括金屬噴擊珠。 11. The system of paragraph 10, wherein the catalyst comprises metal spray beads.

12.如段落10或11之系統，其中該觸媒包含包括鐵及鎳、鉻或其任何組合之金屬珠。 12. The system of paragraph 10 or 11, wherein the catalyst comprises metal beads comprising iron and nickel, chromium or any combination thereof.

13.如段落10、11或12之系統，其中該觸媒包括大小介於約25篩目與50篩目之間的金屬珠。 13. The system of paragraph 10, 11 or 12, wherein the catalyst comprises metal beads having a size between about 25 mesh and 50 mesh.

14.如前述段落任一者之系統，其中該反應器襯有經構置以防止金屬殼降解之材料。 The system of any of the preceding paragraphs, wherein the reactor is lined with a material configured to prevent degradation of the metal shell.

15.如前述段落任一者之系統，其中在該反應器與交叉熱交換器之間的管路連接襯有經構置以保護金屬表面免於降解之耐火性材料。 The system of any of the preceding paragraphs, wherein the pipe connection between the reactor and the cross heat exchanger is lined with a refractory material configured to protect the metal surface from degradation.

16.如前述段落任一者之系統其中該進料氣體加熱器包括經構置以用於金屬成塵環境中之熱交換器。 16. The system of any of the preceding paragraphs wherein the feed gas heater comprises a heat exchanger configured for use in a metal dusting environment.

17.一種用於形成碳奈米管之方法，其包括： 在第一反應器中使用進料氣體形成碳奈米管；從反應器流出物分離出該等碳奈米管以形成廢棄流；使用來自該廢棄流之廢熱加熱該進料氣體、乾燥廢氣流或二者；及在周圍溫度熱交換器中使該廢棄流急冷以凝結水蒸氣，形成該乾燥廢氣流。 17. A method for forming a carbon nanotube comprising: Using a feed gas to form a carbon nanotube in the first reactor; separating the carbon nanotubes from the reactor effluent to form a waste stream; heating the feed gas, drying the exhaust stream using waste heat from the waste stream Or both; and quenching the waste stream in an ambient temperature heat exchanger to condense water vapor to form the dry exhaust stream.

18.如段落17之方法，其包含將該乾燥廢棄流進料至第二反應器；在該第二反應器中形成另一部分之碳奈米管；分離出該等碳奈米管以形成第二廢氣流；以來自該第二廢棄流之廢熱加熱該進料；及在周圍溫度熱交換器中使該第二廢棄流急冷以凝結水蒸氣，形成第二乾燥廢棄流。 18. The method of paragraph 17, comprising feeding the dry waste stream to a second reactor; forming another portion of the carbon nanotubes in the second reactor; separating the carbon nanotubes to form a first a waste gas stream; heating the feed with waste heat from the second waste stream; and quenching the second waste stream in an ambient temperature heat exchanger to condense water vapor to form a second dry waste stream.

19.如段落18之方法，其包含壓縮該第二乾燥廢棄流以形成經壓縮氣體；使該經壓縮氣體通過周圍溫度熱交換器以凝結並移除任何殘留之水蒸氣；分餾該經壓縮氣體以分離出甲烷及二氧化碳；及將該甲烷添加至該進料氣體。 19. The method of paragraph 18, comprising compressing the second dry waste stream to form a compressed gas; passing the compressed gas through an ambient temperature heat exchanger to condense and remove any residual water vapor; fractionating the compressed gas To separate methane and carbon dioxide; and to add the methane to the feed gas.

20.一種用於形成碳奈米管之反應系統，其包括：二或多個反應器，其經構置以從包含甲烷及二氧化碳之氣體流形成碳奈米管，其中將最終反應器之前的各反應器之流出物用作下游反應器之進料流，且其中來自該最終反應器之流出物流包含反應物耗乏之廢棄流； 各反應器下游之分離系統，其中該分離系統係經構置以從來自該反應器之流出物移除碳奈米管；各分離系統下游之進料加熱器，其中該進料加熱器包括經構置以使用來自該反應器之流出物的廢熱加熱用於後續之反應器的進料氣體流的熱交換器，且其中該最終反應器下游之進料加熱器係經構置以加熱用於第一反應器之氣體流；各進料加熱器下游之周圍溫度熱交換器，其中該周圍溫度熱交換器係經構置以從該流出物移除水，形成用於後續反應器之進料流；壓縮機，其經構置以提高該反應物耗乏之廢棄流的壓力；該壓縮機下游之周圍溫度熱交換器，其經構置以從該反應物耗乏之廢棄流移除水；氣體分餾系統，其經構置以將該反應物耗乏之廢棄流分離成富含甲烷流及富含二氧化碳流；及混合機，其經構置以將該富含甲烷流或該富含二氧化碳流摻合至初始進料流。 20. A reaction system for forming a carbon nanotube comprising: two or more reactors configured to form a carbon nanotube from a gas stream comprising methane and carbon dioxide, wherein prior to the final reactor The effluent from each reactor is used as a feed stream to the downstream reactor, and wherein the effluent stream from the final reactor comprises a spent stream that is depleted of reactants; a separation system downstream of each reactor, wherein the separation system is configured to remove carbon nanotubes from the effluent from the reactor; a feed heater downstream of each separation system, wherein the feed heater includes A heat exchanger configured to heat a feed gas stream for a subsequent reactor using waste heat from the effluent of the reactor, and wherein the feed heater downstream of the final reactor is configured to be heated for use a gas stream of a first reactor; an ambient temperature heat exchanger downstream of each feed heater, wherein the ambient temperature heat exchanger is configured to remove water from the effluent to form a feed for subsequent reactors a compressor; the compressor configured to increase the pressure of the waste stream that is depleted of the reactant; an ambient temperature heat exchanger downstream of the compressor configured to remove water from the waste stream from which the reactant is depleted; a fractionation system configured to separate the reactant waste-laden waste stream into a methane-rich stream and a carbon dioxide-rich stream; and a mixer configured to incorporate the methane-rich stream or the carbon dioxide-rich stream Into the initial Flow.

21.如段落20之反應系統，其中有一反應器包括使用金屬珠作為觸媒之流體化床反應器。 21. The reaction system of paragraph 20, wherein one of the reactors comprises a fluidized bed reactor using metal beads as a catalyst.

22.如段落20或21之反應系統，其包括各周圍溫度熱交換器下游之分離容器，其中該分離容器係經構置以從氣體流分離出液態水。 22. The reaction system of paragraph 20 or 21, comprising a separation vessel downstream of each ambient temperature heat exchanger, wherein the separation vessel is configured to separate liquid water from the gas stream.

23.如段落20、21或22之反應系統，其包括經構置 以加熱用於設備啟動之初始進料流的封裝體加熱器。 23. The reaction system of paragraph 20, 21 or 22, comprising a configuration A package heater that heats the initial feed stream for equipment startup.

24.如段落20、21、22或23之反應系統，其中該封裝體加熱器係用以加熱供應至後續反應器之進料流。 24. The reaction system of paragraph 20, 21, 22 or 23, wherein the package heater is for heating a feed stream supplied to a subsequent reactor.

25.如段落23或24之反應系統，其中該封裝體加熱器係經構置為現場安裝之加熱器，或係電力加熱器、經構置用於加熱氣體之市售加熱器，或其任何組合。 25. The reaction system of paragraph 23 or 24, wherein the package heater is configured as a field mounted heater, or is an electric heater, a commercially available heater configured to heat the gas, or any combination.

26.如段落23、24或25之反應系統，其中該封裝體加熱器係經構置以在無實質損害情況下加熱還原性氣體流。 26. The reaction system of paragraph 23, 24 or 25, wherein the package heater is configured to heat the reducing gas stream without substantial damage.

雖然本技術可容易進行各種修改及替代形式，但前文所討論之具體實例僅供舉例說明。然而，應再次理解，該等技術無意局限於本文所揭示之特定具體實例。實際上，本技術包括在附錄申請專利範圍之真正精神與範疇的所有替代者、修改及等效物。 While the present invention may be susceptible to various modifications and alternative forms, the specific examples discussed above are illustrative only. However, it should be understood again that such techniques are not intended to be limited to the particular embodiments disclosed herein. In fact, this technology includes all alternatives, modifications, and equivalents of the true spirit and scope of the patent application.

102/302/402/802‧‧‧進料氣體 102/302/402/802‧‧‧ Feed gas

104/310/326/424/836‧‧‧熱交換器 104/310/326/424/836‧‧‧ heat exchanger

106‧‧‧熱 106‧‧‧Hot

108‧‧‧經加熱之進料氣體 108‧‧‧heated feed gas

110‧‧‧反應器 110‧‧‧Reactor

112/602‧‧‧碳奈米管 112/602‧‧‧Carbon nanotubes

114‧‧‧流動流 114‧‧‧current flow

116/324/346‧‧‧廢氣流 116/324/346‧‧‧Exhaust flow

118‧‧‧水急冷器 118‧‧‧Water chiller

120/334/354‧‧‧水 120/334/354‧‧‧ water

122‧‧‧乾燥廢氣流 122‧‧‧Dry waste gas flow

124/368/434/508/800‧‧‧氣體分餾系統 124/368/434/508/800‧‧‧ gas fractionation system

126‧‧‧再循環物 126‧‧‧Recycling

128‧‧‧過量進料 128‧‧‧Excess feed

202‧‧‧碳 202‧‧‧Carbon

204‧‧‧氫 204‧‧‧ hydrogen

206‧‧‧氧 206‧‧‧Oxygen

208/210‧‧‧均衡線 208/210‧‧‧equal line

300/400/500‧‧‧反應系統 300/400/500‧‧‧Reaction system

304/504/850‧‧‧再循環氣體 304/504/850‧‧‧Recycled gas

306‧‧‧靜態混合器 306‧‧‧Static mixer

308‧‧‧結合之氣體流 308‧‧‧Combined gas flow

312‧‧‧經加熱氣體流 312‧‧‧heated gas flow

314/341‧‧‧封裝體加熱器 314/341‧‧‧Package heater

316‧‧‧熱氣體流 316‧‧‧ hot gas flow

318/340/600‧‧‧流體化床反應器 318/340/600‧‧‧ Fluidized Bed Reactor

320/342/620‧‧‧反應器流出物流 320/342/620‧‧‧Reactor effluent logistics

322/344/430‧‧‧鎖定式加料漏斗 322/344/430‧‧‧Locked addition funnel

328‧‧‧經冷卻之廢氣流 328‧‧‧ cooled exhaust gas stream

330/350/362‧‧‧周圍溫度熱交換器 330/350/362‧‧‧ ambient temperature heat exchanger

332/352/364/818/928‧‧‧分離容器 332/352/364/818/928‧‧‧Separation container

336‧‧‧反應物流 336‧‧‧Reaction Logistics

338/908‧‧‧經加熱之流 338/908‧‧‧heated stream

348‧‧‧經冷卻之廢棄流 348‧‧‧ cooled waste stream

356‧‧‧所得之氣體流 356‧‧‧Gas flow

358‧‧‧壓縮機 358‧‧‧Compressor

360‧‧‧高壓流 360‧‧‧High pressure flow

366‧‧‧經乾燥氣體流 366‧‧‧dry gas flow

370‧‧‧過量進料 370‧‧‧Excess feed

402‧‧‧較高CO2含量進料氣體 402‧‧‧High CO 2 content feed gas

404‧‧‧高甲烷之再循環氣體 404‧‧‧High methane recycle gas

406‧‧‧多重外殼與管式熱交換器 406‧‧‧Multiple shell and tube heat exchangers

408‧‧‧第二熱交換器 408‧‧‧second heat exchanger

410/414/426‧‧‧陶瓷均熱塊熱交換器 410/414/426‧‧‧Ceramic soaking block heat exchanger

412/416‧‧‧箭頭 412/416‧‧‧ arrow

418‧‧‧入口閥 418‧‧‧Inlet valve

420‧‧‧出口閥 420‧‧‧Export valve

422‧‧‧殼管式熱交換器 422‧‧‧Shell tube heat exchanger

426/1000‧‧‧分離系統 426/1000‧‧‧Separation system

428‧‧‧旋風分離器 428‧‧‧Cyclone separator

432/1014‧‧‧過濾器 432/1014‧‧‧Filter

436‧‧‧CO2廢棄流 436‧‧‧CO 2 waste stream

438/512‧‧‧燃料氣體流 438/512‧‧‧fuel gas flow

440/510‧‧‧沖洗氣體流 440/510‧‧‧ flushing gas flow

506‧‧‧CH4廢棄流 506‧‧‧CH 4 waste stream

604/706‧‧‧熱氣體進料流 604/706‧‧‧ hot gas feed stream

606‧‧‧管線 606‧‧‧ pipeline

608‧‧‧控制閥 608‧‧‧Control valve

610‧‧‧分配器板 610‧‧‧Distributor board

612/702‧‧‧觸媒珠 612/702‧‧‧ Catalyst beads

614‧‧‧反應器壁 614‧‧‧reactor wall

615‧‧‧頭端 615‧‧‧ head end

616‧‧‧頂部管線 616‧‧‧Top pipeline

618‧‧‧觸媒分離器 618‧‧‧catalyst separator

622‧‧‧再循環管線 622‧‧‧Recycling pipeline

708‧‧‧CNT 708‧‧‧CNT

710‧‧‧觸媒粒子 710‧‧‧catalyst particles

712‧‧‧顆粒 712‧‧‧ granules

714‧‧‧顆粒邊界 714‧‧‧ grain boundaries

716‧‧‧活性觸媒粒子 716‧‧‧Active Catalyst Particles

718‧‧‧H2O 718‧‧‧H 2 O

720‧‧‧團簇 720‧‧‧ cluster

804‧‧‧乾燥機 804‧‧‧Dryer

806‧‧‧乾燥氣體進料 806‧‧‧ Dry gas feed

808‧‧‧低溫急冷器 808‧‧‧Cryogenic chiller

810‧‧‧多階段急冷系統 810‧‧‧Multi-stage quenching system

812‧‧‧熱收集系統 812‧‧‧Heat collection system

813‧‧‧能量 813‧‧‧Energy

816‧‧‧經急冷進料 816‧‧‧Quenched feed

820‧‧‧液態流 820‧‧‧ liquid flow

822‧‧‧蒸氣流 822‧‧‧Vapor flow

824‧‧‧膨脹器 824‧‧‧Expander

826‧‧‧機械功 826‧‧‧Mechanical work

828‧‧‧發電機 828‧‧‧Generator

830‧‧‧兩相流 830‧‧‧Two-phase flow

832/902/914‧‧‧分離塔 832/902/914‧‧‧ separation tower

834/906‧‧‧再沸器 834/906‧‧‧ reboiler

838‧‧‧塔底流 838‧‧‧ bottom stream

840‧‧‧部分 Section 840‧‧‧

842‧‧‧出口流 842‧‧‧Export stream

844/910‧‧‧CO2產物 844/910‧‧‧CO 2 product

846‧‧‧CO2產物844之一部分846 846‧‧‧ Part 846 of the CO 2 product 844

848/912/922/930‧‧‧塔頂流 848/912/922/930‧‧‧ top flow

904/916/934‧‧‧塔底產物流 904/916/934‧‧‧ bottom product stream

918/936‧‧‧泵 918/936‧‧‧ pump

920/938‧‧‧回流流 920/938‧‧‧Return flow

924‧‧‧急冷器 924‧‧‧Quencher

926‧‧‧氮冷凍單元 926‧‧‧Nitrogen Freezer Unit

1002/1004‧‧‧封裝列 1002/1004‧‧‧Package column

1006‧‧‧取樣閥 1006‧‧‧Sampling valve

1008‧‧‧桶 1008‧‧‧ barrel

1010‧‧‧沖洗流 1010‧‧‧ flushing flow

1012‧‧‧沖洗出口流 1012‧‧‧ rinse outlet flow

1016‧‧‧沖洗送回料 1016‧‧‧Washing and returning materials

1018‧‧‧封裝閥 1018‧‧‧Package valve

1020‧‧‧CNT流 1020‧‧‧ CNT flow

1022‧‧‧填充站 1022‧‧‧fill station

藉由參考以下詳細描述及附圖將更暸解本技術之優點。 The advantages of the present technology will be better understood by reference to the following detailed description and drawings.

圖1為產生碳奈米管(例如作為二氧化碳固存反應之副產物)的反應系統之方塊圖；圖2為碳、氫及氧之間的均衡的C-H-O均衡圖，其表示在各種不同溫度條件下呈均衡之物種；圖3為用於從包含二氧化碳及甲烷之氣體進料製造碳奈米管的反應系統之簡化流程圖； 圖4A、4B及4C為用於從包含二氧化碳及甲烷之氣體進料製造碳奈米管的其他反應系統之簡化流程圖；圖5A、5B及5C為用於從包含二氧化碳及甲烷之氣體進料製造碳奈米管的其他反應系統之簡化流程圖；圖6為用於形成碳奈米管之流體化床反應器的圖；圖7為用於在觸媒珠上形成碳奈米管之催化反應的示意圖；圖8為可用於用以製造碳奈米管之反應器系統的氣體製造程序之簡化流程圖；圖9為可用於用以製造碳奈米管之反應器系統的其他氣體製造程序之簡化流程圖；圖10為可反應器流出物流分離出碳奈米管之分離系統的簡化流程圖；及圖11為用於從包含甲烷及二氧化碳之進料氣體產生碳奈米管的方法。 1 is a block diagram of a reaction system for producing a carbon nanotube (for example, as a by-product of a carbon dioxide sequestration reaction); FIG. 2 is a balanced CHO equilibrium diagram between carbon, hydrogen, and oxygen, which is shown at various temperature conditions. a balanced species; Figure 3 is a simplified flow diagram of a reaction system for producing carbon nanotubes from a gas feed comprising carbon dioxide and methane; 4A, 4B and 4C are simplified flow diagrams of other reaction systems for producing carbon nanotubes from a gas feed comprising carbon dioxide and methane; Figures 5A, 5B and 5C are for feeding from a gas comprising carbon dioxide and methane A simplified flow chart of other reaction systems for making carbon nanotubes; Figure 6 is a diagram of a fluidized bed reactor for forming carbon nanotubes; and Figure 7 is a catalyst for forming carbon nanotubes on catalyst beads. Schematic diagram of the reaction; Figure 8 is a simplified flow diagram of a gas manufacturing procedure that can be used in a reactor system for making carbon nanotubes; Figure 9 is another gas manufacturing procedure that can be used in a reactor system for making carbon nanotubes. Simplified flow chart; Figure 10 is a simplified flow diagram of a separation system for separating a carbon nanotube from a reactor effluent stream; and Figure 11 is a method for producing a carbon nanotube from a feed gas comprising methane and carbon dioxide.

302‧‧‧進料氣體 302‧‧‧ Feed gas

310,326‧‧‧熱交換器 310,326‧‧‧ heat exchanger

324,346‧‧‧廢氣流 324,346‧‧‧Exhaust flow

334,354‧‧‧水 334, 354 ‧ water

368‧‧‧氣體分餾系統 368‧‧‧ gas fractionation system

300‧‧‧反應系統 300‧‧‧Reaction system

304‧‧‧再循環氣體 304‧‧‧Recycled gas

306‧‧‧靜態混合器 306‧‧‧Static mixer

308‧‧‧結合之氣體流 308‧‧‧Combined gas flow

312‧‧‧經加熱氣體流 312‧‧‧heated gas flow

314,341‧‧‧封裝體加熱器 314,341‧‧‧Package heater

316‧‧‧熱氣體流 316‧‧‧ hot gas flow

318,340‧‧‧流體化床反應器 318,340‧‧‧Fluidized bed reactor

320,342‧‧‧反應器流出物流 320,342‧‧‧Reactor effluent logistics

322,344‧‧‧鎖定式加料漏斗 322,344‧‧‧Locked addition funnel

328‧‧‧經冷卻之廢氣流 328‧‧‧ cooled exhaust gas stream

330,350,362‧‧‧周圍溫度熱交換器 330,350,362‧‧‧ ambient temperature heat exchanger

332,352,364‧‧‧分離容器 332,352,364‧‧‧Separate container

336‧‧‧反應物流 336‧‧‧Reaction Logistics

338‧‧‧經加熱之流 338‧‧‧heated stream

348‧‧‧經冷卻之廢棄流 348‧‧‧ cooled waste stream

356‧‧‧所得之氣體流 356‧‧‧Gas flow

358‧‧‧壓縮機 358‧‧‧Compressor

360‧‧‧高壓流 360‧‧‧High pressure flow

366‧‧‧經乾燥氣體流 366‧‧‧dry gas flow

Claims (26)

一種用於製造碳奈米管之系統，其包含：進料氣體加熱器，其經構置以使用來自廢氣流之廢熱加熱進料氣體；反應器，其經構置以從該進料氣體形成碳奈米管；分離器，其經構置以從該反應器流出物流分離出該等碳奈米管，形成廢氣流；及水移除系統，其包含周圍溫度熱交換器及經構置以從該廢氣流分離出大量水以形成乾燥廢氣流之分離器。 A system for making a carbon nanotube comprising: a feed gas heater configured to heat a feed gas using waste heat from an exhaust stream; a reactor configured to form from the feed gas a carbon nanotube; a separator configured to separate the carbon nanotubes from the reactor effluent stream to form an exhaust stream; and a water removal system comprising an ambient temperature heat exchanger and configured to A large amount of water is separated from the exhaust stream to form a separator for the dry exhaust stream. 如申請專利範圍第1項之系統，其中該周圍溫度熱交換器包含水急冷器。 The system of claim 1, wherein the ambient temperature heat exchanger comprises a water chiller. 如申請專利範圍第1項之系統，其中該周圍溫度熱交換器包含空氣冷卻熱交換器。 The system of claim 1, wherein the ambient temperature heat exchanger comprises an air cooled heat exchanger. 如申請專利範圍第1項之系統，其包含經構置以加熱用於該系統初始啟動之進料氣體的封裝體加熱器。 A system as claimed in clause 1, which comprises a package heater configured to heat a feed gas for initial startup of the system. 如申請專利範圍第1項之系統，其包含熱交換器，其經構置以使用來自該廢氣流之廢熱加熱該乾燥廢氣流以形成第二進料氣體；第二反應器，其經構置以從該第二進料氣體形成碳奈米管；分離器，其經構置以從來自該第二反應器之流出物流分離出該等碳奈米管，形成第二廢氣流，且其中用於該進料氣體加熱器之廢氣流包含該第二廢氣流；及水移除系統，其經構置以使用周圍溫度熱交換器急冷 該第二廢氣流並移除大量水，而從該第二廢氣流分離出水，以形成第二乾燥廢氣流。 The system of claim 1, comprising a heat exchanger configured to heat the dry exhaust stream to form a second feed gas using waste heat from the exhaust stream; a second reactor configured Forming a carbon nanotube from the second feed gas; a separator configured to separate the carbon nanotubes from the effluent stream from the second reactor to form a second exhaust stream, and wherein The exhaust stream of the feed gas heater includes the second exhaust stream; and a water removal system configured to quench with an ambient temperature heat exchanger The second exhaust stream removes a quantity of water and separates water from the second exhaust stream to form a second dry exhaust stream. 如申請專利範圍第5項之系統，其包含壓縮機，其經構置以提高該第二乾燥廢氣流之壓力；及最終水移除系統，其經構置以從該第二廢氣流移除水。 A system of claim 5, comprising a compressor configured to increase a pressure of the second dry exhaust stream; and a final water removal system configured to be removed from the second exhaust stream water. 如申請專利範圍第6項之系統，其包含經構置以從該第二廢氣流分離出富含甲烷流與富含CO2流之氣體分餾系統。 The patentable scope of application of the system of item 6, comprising a counter configured to separate by the second exhaust gas stream from the methane-enriched gas stream and the rich stream of the fractionation system 2 CO. 如申請專利範圍第7項之系統，其包含經構置以在該進料氣體加熱器之前將該富含甲烷流混入該進料氣體的混合系統。 A system of claim 7, comprising a mixing system configured to mix the methane-rich stream into the feed gas prior to the feed gas heater. 如申請專利範圍第7項之系統，其中該氣體分餾系統包含經構置以使在某一溫度下可凝結之氣體與在該溫度下不凝結之氣體分開的低溫凝結系統(cryogenic condensation system)。 The system of claim 7, wherein the gas fractionation system comprises a cryogenic condensation system configured to separate a gas condensable at a temperature from a gas that does not condense at the temperature. 如申請專利範圍第1項之系統，其中該反應器為使用進料氣體之逆向流將觸媒流體化之流體化床反應器。 The system of claim 1, wherein the reactor is a fluidized bed reactor fluidizing a catalyst using a reverse flow of a feed gas. 如申請專利範圍第10項之系統，其中該觸媒包含金屬噴擊珠。 The system of claim 10, wherein the catalyst comprises metal spray beads. 如申請專利範圍第10項之系統，其中該觸媒包含包括鐵及鎳、鉻或其任何組合之金屬珠。 The system of claim 10, wherein the catalyst comprises metal beads comprising iron and nickel, chromium or any combination thereof. 如申請專利範圍第10項之系統，其中該觸媒包含 大小介於約25篩目與50篩目之間的金屬珠。 For example, the system of claim 10, wherein the catalyst comprises Metal beads having a size between about 25 mesh and 50 mesh. 如申請專利範圍第1項之系統，其中該反應器襯有經構置以防止金屬殼降解之材料。 The system of claim 1, wherein the reactor is lined with a material configured to prevent degradation of the metal shell. 如申請專利範圍第1項之系統，其中在該反應器與交叉熱交換器之間的管路連接襯有經構置以保護金屬表面免於降解之耐火性材料。 The system of claim 1, wherein the pipe connection between the reactor and the cross heat exchanger is lined with a fire resistant material configured to protect the metal surface from degradation. 如申請專利範圍第1項之系統，其中該進料氣體加熱器包含經構置以用於金屬成塵環境中之熱交換器。 The system of claim 1, wherein the feed gas heater comprises a heat exchanger configured for use in a metal dusting environment. 一種用於形成碳奈米管之方法，其包含：在第一反應器中使用進料氣體形成碳奈米管；從反應器流出物分離出該等碳奈米管以形成廢棄流；使用來自該廢棄流之廢熱加熱該進料氣體、乾燥廢氣流或二者；及在周圍溫度熱交換器中使該廢棄流急冷以凝結水蒸氣，形成該乾燥廢氣流。 A method for forming a carbon nanotube comprising: forming a carbon nanotube using a feed gas in a first reactor; separating the carbon nanotubes from the reactor effluent to form a waste stream; The waste heat of the waste stream heats the feed gas, the dry exhaust stream, or both; and quenches the waste stream in an ambient temperature heat exchanger to condense water vapor to form the dry exhaust stream. 如申請專利範圍第17項之方法，其包含將該乾燥廢棄流進料至第二反應器；在該第二反應器中形成另一部分之碳奈米管；分離出該等碳奈米管以形成第二廢氣流；以來自該第二廢棄流之廢熱加熱該進料；及在周圍溫度熱交換器中使該第二廢棄流急冷以凝結水蒸氣，形成第二乾燥廢棄流。 The method of claim 17, comprising: feeding the dry waste stream to a second reactor; forming another portion of the carbon nanotubes in the second reactor; separating the carbon nanotubes to Forming a second exhaust stream; heating the feed with waste heat from the second waste stream; and quenching the second waste stream in an ambient temperature heat exchanger to condense water vapor to form a second dry waste stream. 如申請專利範圍第18項之方法，其包含壓縮該第二乾燥廢棄流以形成經壓縮氣體； 使該經壓縮氣體通過周圍溫度熱交換器以凝結並移除任何殘留之水蒸氣；分餾該經壓縮氣體以分離出甲烷及二氧化碳；及將該甲烷添加至該進料氣體。 The method of claim 18, comprising compressing the second dry waste stream to form a compressed gas; The compressed gas is passed through an ambient temperature heat exchanger to condense and remove any residual water vapor; the compressed gas is fractionated to separate methane and carbon dioxide; and the methane is added to the feed gas. 一種用於形成碳奈米管之反應系統，其包含：二或多個反應器，其經構置以從包含甲烷及二氧化碳之氣體流形成碳奈米管，其中將最終反應器之前的各反應器之流出物用作下游反應器之進料流，且其中來自該最終反應器之流出物流包含反應物耗乏之廢棄流；各反應器下游之分離系統，其中該分離系統係經構置以從來自該反應器之流出物移除碳奈米管；各分離系統下游之進料加熱器，其中該進料加熱器包含經構置以使用來自該反應器之流出物的廢熱加熱用於後續之反應器的進料氣體流的熱交換器，且其中該最終反應器下游之進料加熱器係經構置以加熱用於第一反應器之氣體流；各進料加熱器下游之周圍溫度熱交換器，其中該周圍溫度熱交換器係經構置以從該流出物移除水，形成用於後續反應器之進料流；壓縮機，其經構置以提高該反應物耗乏之廢棄流的壓力；該壓縮機下游之周圍溫度熱交換器，其經構置以從該反應物耗乏之廢棄流移除水；氣體分餾系統，其經構置以將該反應物耗乏之廢棄流 分離成富含甲烷流及富含二氧化碳流；及混合機，其經構置以將該富含甲烷流或該富含二氧化碳流摻合至初始進料流。 A reaction system for forming a carbon nanotube comprising: two or more reactors configured to form a carbon nanotube from a gas stream comprising methane and carbon dioxide, wherein each reaction prior to the final reactor The effluent of the reactor is used as a feed stream to the downstream reactor, and wherein the effluent stream from the final reactor comprises a spent stream of reactant waste; a separation system downstream of each reactor, wherein the separation system is configured to The effluent from the reactor removes the carbon nanotubes; a feed heater downstream of each separation system, wherein the feed heater comprises waste heat that is configured to use the effluent from the reactor for subsequent use a heat exchanger for the feed gas stream of the reactor, and wherein the feed heater downstream of the final reactor is configured to heat the gas stream for the first reactor; ambient temperature heat downstream of each feed heater An exchanger wherein the ambient temperature heat exchanger is configured to remove water from the effluent to form a feed stream for a subsequent reactor; a compressor configured to increase waste of the reactants Pressure; ambient temperature heat exchanger downstream of the compressor, which is configured by opposing waste stream to remove water from the reaction of the lack of material consumption; gas fractionation system configured by opposing to the reaction of the waste stream of spent material consumption Separating into a methane-rich stream and a carbon dioxide-rich stream; and a mixer configured to blend the methane-rich stream or the carbon dioxide-rich stream to the initial feed stream. 如申請專利範圍第20項之反應系統，其中有一反應器包含使用金屬珠作為觸媒之流體化床反應器。 A reaction system according to claim 20, wherein one of the reactors comprises a fluidized bed reactor using metal beads as a catalyst. 如申請專利範圍第20項之反應系統，其包含各周圍溫度熱交換器下游之分離容器，其中該分離容器係經構置以將液態水與氣體流分開。 A reaction system according to claim 20, comprising a separation vessel downstream of each ambient temperature heat exchanger, wherein the separation vessel is configured to separate the liquid water from the gas stream. 如申請專利範圍第20項之反應系統，其包含經構置以加熱用於設備啟動之初始進料流的封裝體加熱器。 A reaction system according to claim 20, comprising a package heater configured to heat an initial feed stream for plant startup. 如申請專利範圍第23項之反應系統，其中該封裝體加熱器係用以加熱供應至後續反應器之進料流。 The reaction system of claim 23, wherein the package heater is for heating a feed stream supplied to a subsequent reactor. 如申請專利範圍第23項之反應系統，其中該封裝體加熱器係經構置為現場安裝之加熱器，或係電力加熱器、經構置用於加熱氣體之市售加熱器，或其任何組合。 The reaction system of claim 23, wherein the package heater is configured as a field-mounted heater, or is an electric heater, a commercially available heater configured to heat the gas, or any thereof combination. 如申請專利範圍第23項之反應系統，其中該封裝體加熱器係經構置以在無實質損害情況下加熱還原性氣體流。 The reaction system of claim 23, wherein the package heater is configured to heat the reducing gas stream without substantial damage.
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