TWM496522U - Reaction assembly for preparing hydrogen cyanide - Google Patents

Abstract

A static mixer is disclosed for a hydrogen cyanide reaction process that thoroughly mixes the reactant gases to form a ternary gas mixture that has a coefficient of variation of less than 0.1 across the diameter of the catalyst bed. The static mixer comprises tabs that are inserted through non-continuous slots in the conduit and the tabs are secured to the external wall of the conduit.

Description

用於製備氰化氫之反應總成Reaction assembly for preparing hydrogen cyanide 相關申請案交叉參考Related application cross reference

本申請案主張優先於2012年12月18日提出申請之美國申請案第61/738,706號，其全部內容及揭示內容併入本文中。The present application claims priority to U.S. Application Serial No. 61/738,706, filed on Dec.

本實用新型係關於製造氰化氫之方法且更具體而言係關於用於製造充分混合之與觸媒接觸之三元氣體的靜式混合器，且係關於使用該靜式混合器之方法。The present invention relates to a method of making hydrogen cyanide and more particularly to a static mixer for making a well-mixed ternary gas in contact with a catalyst, and to a method of using the static mixer.

習慣上，氰化氫(「HCN」)係根據安德盧梭(Andrussow)法或BMA法以工業規模製造。(例如，參見Ullman’s Encyclopedia of Industrial Chemistry，第A8卷，Weinheim 1987，第161-163頁)。例如，在安德盧梭法中，HCN可藉由在升高溫度下在反應器中在適宜觸媒存在下使氨與含甲烷氣體及含氧氣體反應來商業製造(美國專利第1,934,838號及第6,596,251號)。硫化合物及甲烷之高級同系物可對甲烷之氧化氨解參數具有效應。例如，參見Trusov,Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method,Russian J.Applied Chemistry,74：10(2001)，第1693-1697頁)。藉由使反應器流出物氣體流與磷酸銨水溶液在氨吸收器中接觸來分離未反應之氨與HCN。將經分離氨純化並濃縮以供再循環用於HCN轉化。通常藉由吸收至水中自經處理反應 器流出物氣體流回收HCN。經回收HCN可用進一步精製步驟處理以產生經純化HCN。清潔發展機制項目設計文件表格(Clean Development Mechanism Project Design Document Form)(CDM PDD，第3版)，2006示意性地解釋了安德盧梭HCN製造方法。經純化HCN可用於氫氰化，例如含烯烴基團之氫氰化，或例如1,3-丁二烯及戊烯腈之氫氰化，其可用於製造己二腈(「ADN」)。在BMA法中，HCN係在實質上不存在氧下且在鉑觸媒存在下自甲烷及氨合成，從而產生HCN、氫、氮、殘餘氨及殘餘甲烷。(例如，參見Ullman’s Encyclopedia of Industrial Chemistry，第A8卷，Weinheim 1987，第161-163頁)。商業操作人員需要進行方法安全性管理以處置氰化氫之有害性質。(參見Maxwell等人Assuring process safety in the transfer of hydrogen cyanide manufacturing technology,JHazMat 142(2007),677-684)。另外，來自製造設施之HCN製造過程排放物可能要服從於規章，此可影響製造HCN之經濟性。(參見Crump,Economic Impact Analysis For The Proposed Cyanide Manufacturing NESHAP,EPA，2000年5月)。Conventionally, hydrogen cyanide ("HCN") is manufactured on an industrial scale according to the Andrussow process or the BMA process. (See, for example, Ullman's Encyclopedia of Industrial Chemistry, Vol. A8, Weinheim 1987, pp. 161-163). For example, in the Andrussow process, HCN can be produced commercially by reacting ammonia with a methane-containing gas and an oxygen-containing gas in an elevated temperature in a reactor in the presence of a suitable catalyst (U.S. Patent No. 1,934,838 and 6,596,251). Sulfur compounds and higher homologues of methane have an effect on the oxidative aminolysis parameters of methane. See, for example, Trusov, Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method, Russian J. Applied Chemistry, 74: 10 (2001), pp. 1693-1697). Unreacted ammonia and HCN are separated by contacting the reactor effluent gas stream with an aqueous ammonium phosphate solution in an ammonia absorber. The separated ammonia is purified and concentrated for recycle for HCN conversion. Usually treated by absorption into water The effluent gas stream recovers HCN. The recovered HCN can be treated with a further purification step to produce purified HCN. The Clean Development Mechanism Project Design Document Form (CDM PDD, 3rd Edition), 2006 schematically explains the Andrussow HCN manufacturing process. Purified HCN can be used for hydrocyanation, such as hydrocyanation of olefin-containing groups, or hydrocyanation of, for example, 1,3-butadiene and pentenenitrile, which can be used to make adiponitrile ("ADN"). In the BMA process, HCN is synthesized from methane and ammonia in the substantial absence of oxygen and in the presence of a platinum catalyst to produce HCN, hydrogen, nitrogen, residual ammonia, and residual methane. (See, for example, Ullman's Encyclopedia of Industrial Chemistry, Vol. A8, Weinheim 1987, pp. 161-163). Commercial operators need to conduct method safety management to dispose of the harmful properties of hydrogen cyanide. (See Maxwell et al. Assuring process safety in the transfer of hydrogen cyanide manufacturing technology, JHaz Mat 142 (2007), 677-684). In addition, HCN manufacturing process emissions from manufacturing facilities may be subject to regulations that may affect the economics of manufacturing HCN. (See Crump, Economic Impact Analysis For The Proposed Cyanide Manufacturing NESHAP, EPA, May 2000).

在製造HCN時，混合氨氣、含甲烷氣體及含氧氣體以形成進給至反應器之三元氣體混合物。由於HCN方法涉及若干反應性氣體，因此在與觸媒接觸之前混合該等反應性氣體可能有益。然而，當實施反應性氣體之預混合時，與氣體反應性相關之風險可變得顯而易見。美國專利第2,803,522號揭示用於含氧氣體及氨之混合器。美國專利第3,063,803號揭示連接至反應器之可拆卸安裝之氣體混合室。美國專利第3,215,495號揭示用以混合反應物氣體之氣體混合室內之內部擋板。內部擋板可與相對較高之壓力降相關。最近，已提出將混合室置於反應器內，如美國公開案第2011/0171101號中所述。此組態在反應器內需要透氣層及若干混合板。In the manufacture of HCN, ammonia gas, methane-containing gas, and oxygen-containing gas are mixed to form a ternary gas mixture fed to the reactor. Since the HCN process involves several reactive gases, it may be beneficial to mix the reactive gases prior to contact with the catalyst. However, when performing premixing of reactive gases, the risks associated with gas reactivity can become apparent. A mixer for an oxygen-containing gas and ammonia is disclosed in U.S. Patent No. 2,803,522. U.S. Patent No. 3,063,803 discloses a detachably mounted gas mixing chamber connected to a reactor. U.S. Patent No. 3,215,495 discloses an internal baffle in a gas mixing chamber for mixing reactant gases. The internal baffle can be associated with a relatively high pressure drop. Recently, it has been proposed to place a mixing chamber in a reactor as described in U.S. Publication No. 2011/0171101. This configuration requires a gas permeable layer and several mixing plates in the reactor.

該等用於製造HCN之先前混合室不足以產生充分混合之三元氣 體且因此導致生產率損失並增加反應物氣體與HCN之分離。These previous mixing chambers used to make HCN are not sufficient to produce a fully mixed triad And thus cause a loss of productivity and increase the separation of reactant gases from HCN.

美國專利第8,133,458號揭示用於將甲烷、氨及氧以及鹼金屬或鹼土金屬氫氧化物轉化成鹼金屬氰化物或鹼土金屬氰化物之反應器，該轉化係藉由包含具有氣體入口之第一級之兩級反應達成，其中該第一級係藉由具有在觸媒材料上提供均勻氣體分佈之分佈板之錐體來形成，其中該等分佈板位於反應器之氣體入口與觸媒材料之間且分佈板穿有多個孔，其中分佈板在氣體流動方向上彼此間隔開，第一分佈板主要發揮分佈氣體之功能，而最後分佈板作為熱輻射屏蔽及作為面向觸媒材料之分佈板起作用，且其中該觸媒材料係以藉由觸媒重量固定之觸媒絲網形式存在。U.S. Patent No. 8,133,458 discloses a reactor for converting methane, ammonia and oxygen and an alkali metal or alkaline earth metal hydroxide to an alkali metal cyanide or alkaline earth metal cyanide by including a first gas inlet. A two-stage reaction is achieved in which the first stage is formed by a cone having a distribution plate that provides a uniform gas distribution over the catalyst material, wherein the distribution plates are located at the gas inlet and catalytic material of the reactor. The distribution plate is provided with a plurality of holes, wherein the distribution plates are spaced apart from each other in the flow direction of the gas, the first distribution plate mainly functions as a distribution gas, and the last distribution plate serves as a heat radiation shield and a distribution plate as a catalyst-oriented material. Functioning, and wherein the catalyst material is in the form of a catalyst mesh fixed by the weight of the catalyst.

已使用其他靜式混合器來混合反應物氣體。美國專利第4,929,088號揭示適於***流體流中之靜式混合器件，該流體流相對於閉合導管具有主要流動方向，該閉合導管包含至少兩個在流動方向上以與導管之表面呈介於10°與45°之間之預選仰角傾斜之凸耳。美國專利第6,000,841號揭示包含具有凸耳之縱向細長導管之靜式混合器導管，該等凸耳配置有毗鄰導管壁之各別第一邊緣及與導管壁向內徑向間隔之各別對置第二邊緣。通常，靜式混合器足以使流體流穿過，同時維持與紊流相關之相對平坦之速度剖面，但難以安裝及維護。Other static mixers have been used to mix the reactant gases. U.S. Patent No. 4,929,088 discloses a static mixing device adapted to be inserted into a fluid stream having a main flow direction relative to a closed conduit containing at least two in the flow direction to be 10 with the surface of the conduit. A lug that is inclined at a preselected elevation angle between 45° and 45°. U.S. Patent No. 6,000,841 discloses a static mixer conduit comprising longitudinal elongated tubes having lugs disposed with respective first edges adjacent the conduit walls and respective radially spaced apart from the conduit walls radially inwardly The second edge. Typically, a static mixer is sufficient to allow fluid flow therethrough while maintaining a relatively flat velocity profile associated with turbulence, but is difficult to install and maintain.

因此，業內需要適於製造HCN之反應物氣體之改進混合，其亦容易安裝及維持。本實用新型提供有利之解決方案以快速且充分地混合反應物氣體，同時使混合期間之壓力降最小化並避免不期望之副反應，例如氧化及爆燃。Accordingly, there is a need in the industry for improved mixing of reactant gases suitable for the manufacture of HCN, which are also easy to install and maintain. The present invention provides an advantageous solution to quickly and sufficiently mix reactant gases while minimizing pressure drop during mixing and avoiding undesirable side reactions such as oxidation and deflagration.

在第一實施例中，本實用新型係關於用於製備氰化氫之反應總成，其包含：(a)包含細長導管之混合容器，該細長導管具有位於該細長導管近端之出口；第一入口埠及第二入口埠，其各自用於將至少 一種選自由含甲烷氣體、含氨氣體、含氧氣體及其混合物組成之群之反應物氣體引入至該混合容器中，其中該第二入口埠位於該第一入口埠下游；包含一或多個第一列不連續狹縫之第一靜式混合區，一或多個相應凸耳穿過該等不連續狹縫***且緊固至該細長導管之外表面，且其中該第一靜式混合區毗鄰該第一入口埠；包含一或多個第二列不連續狹縫之第二靜式混合區，一或多個相應凸耳穿過該等不連續狹縫***且緊固至該細長導管之外表面，且其中該第二靜式混合區毗鄰該第二入口埠，其中每一相應凸耳具有在流動方向上成角度之上游面，其中該等第一及第二靜式混合區提供至少一種反應物氣體之交叉流混合以產生三元氣體；及(b)反應器容器，其包含反應器入口，該反應器入口操作性地耦合至出口以接收三元氣體混合物；及觸媒床，其含有用於產生氰化氫流之觸媒。第一靜式混合區中之列數可為1至10且第二靜式混合區中之列數可為1至10。第一列及第二列中之每一者可含有1至10個不連續狹縫。第二靜式混合區中之列數可大於或等於第一靜式混合區中之列數。相應凸耳可與導管之內壁具有5°至45°之角度。反應總成可進一步包含一或多個位於第一靜式混合區上游用於對準至少一種反應物氣體之流動之整流器，其中該一或多個整流器各自具有中心主體。反應總成可進一步包含一或多個位於第二靜式混合區上游用於對準至少一種反應物氣體之流動之整流器，其中該一或多個整流器各自具有中心主體。不連續狹縫可為l-形、I-形、T-形、U-形或V-形。兩個或更多個第一列之不連續狹縫可橫向對準。兩個或更多個第二列之不連續狹縫可橫向對準。細長導管內每一相應凸耳可不平行於流動方向。每一相應凸耳可具有角度為30°至90°之後邊緣。每一相應凸耳可具有0°至7°之傾斜度。每一相應凸耳可具有50cm² 至250cm² 之表面積。每一相應凸耳可包含310SS或316SS。In a first embodiment, the present invention is directed to a reaction assembly for preparing hydrogen cyanide comprising: (a) a mixing vessel comprising an elongated conduit having an outlet at a proximal end of the elongated conduit; An inlet port and a second inlet port, each for introducing at least one reactant gas selected from the group consisting of a methane-containing gas, an ammonia-containing gas, an oxygen-containing gas, and a mixture thereof, into the mixing vessel, wherein the second An inlet port is located downstream of the first inlet port; a first static mixing zone comprising one or more first rows of discontinuous slits through which one or more corresponding lugs are inserted and fastened An outer surface of the elongated conduit, and wherein the first static mixing zone is adjacent to the first inlet port; a second static mixing zone comprising one or more second rows of discontinuous slits, one or more corresponding lugs Inserted through the discontinuous slits and secured to the outer surface of the elongated conduit, and wherein the second static mixing zone abuts the second inlet bore, wherein each respective lug has an angle in the flow direction Upstream, where the first and A two-chamber mixing zone provides cross-flow mixing of at least one reactant gas to produce a ternary gas; and (b) a reactor vessel including a reactor inlet operatively coupled to the outlet to receive a ternary gas a mixture; and a catalyst bed containing a catalyst for generating a hydrogen cyanide stream. The number of columns in the first static mixing zone may range from 1 to 10 and the number of columns in the second static mixing zone may range from 1 to 10. Each of the first column and the second column may contain from 1 to 10 discrete slits. The number of columns in the second static mixing zone may be greater than or equal to the number of columns in the first static mixing zone. The respective lugs can have an angle of from 5 to 45 with the inner wall of the catheter. The reaction assembly can further comprise one or more rectifiers upstream of the first static mixing zone for aligning the flow of the at least one reactant gas, wherein the one or more rectifiers each have a central body. The reaction assembly can further comprise one or more rectifiers upstream of the second static mixing zone for aligning the flow of the at least one reactant gas, wherein the one or more rectifiers each have a central body. The discontinuous slits may be l-shaped, I-shaped, T-shaped, U-shaped or V-shaped. The discontinuous slits of the two or more first columns may be laterally aligned. The discontinuous slits of the two or more second columns may be laterally aligned. Each respective lug within the elongated conduit may not be parallel to the direction of flow. Each respective lug may have an edge that is angled from 30[deg.] to 90[deg.]. Each respective lug may have an inclination of 0° to 7°. Each respective lug may have a surface area of 50cm ² of ² to 250cm. Each respective lug may comprise 310SS or 316SS.

本實用新型之第二實施例係關於用於製備氰化氫之反應總成，其包含(a)包含細長導管之混合容器，該細長導管具有位於該細長導 管近端之出口；第一入口埠及第二入口埠，其各自用於將至少一種選自由含甲烷氣體、含氨氣體、含氧氣體及其混合物組成之群之反應物氣體引入至該混合容器中，其中該第二入口埠鄰近該第一入口埠；包含一或多個第一列不連續狹縫之第一靜式混合區，一或多個具有第一角度之相應凸耳穿過該等第一列不連續狹縫***且緊固至該細長導管之外表面，且其中該第一靜式混合區毗鄰該第一入口埠；包含一或多個第二列不連續狹縫之第二靜式混合區，一或多個具有第二角度之相應凸耳穿過該等第二列不連續狹縫***且緊固至該細長導管之外表面，且其中該第二靜式混合區毗鄰該第二入口埠及/或鄰近該第二入口埠，其中該第一角度不同於該第二角度，其中該等第一及第二靜式混合區提供至少一種反應物氣體之交叉流混合以產生三元氣體；及(b)反應器容器，其包含反應器入口，該反應器入口操作性地耦合至出口以接收三元氣體混合物；及觸媒床，其含有用於產生氰化氫流之觸媒。第一角度和第二角度可為5°至45°。第一角度為30°且可大於第二角度。第一角度為30°且可小於第二角度。A second embodiment of the present invention relates to a reaction assembly for preparing hydrogen cyanide, comprising: (a) a mixing vessel comprising an elongated conduit having the elongated guide a proximal end of the tube; a first inlet port and a second inlet port, each for introducing at least one reactant gas selected from the group consisting of a methane-containing gas, an ammonia-containing gas, an oxygen-containing gas, and a mixture thereof to the mixture In the container, wherein the second inlet port is adjacent to the first inlet port; the first static mixing zone comprising one or more first rows of discontinuous slits, and one or more corresponding lugs having the first angle pass through The first row of discontinuous slits are inserted and secured to the outer surface of the elongated conduit, and wherein the first static mixing zone is adjacent to the first inlet port; and includes one or more second rows of discontinuous slits a second static mixing zone, one or more corresponding lugs having a second angle inserted through the second row of discrete slits and secured to the outer surface of the elongated conduit, and wherein the second static mixing a region adjacent to the second inlet port and/or adjacent to the second inlet port, wherein the first angle is different from the second angle, wherein the first and second static mixing regions provide a cross flow of at least one reactant gas Mixing to produce a ternary gas; and (b) reactor vessel And comprising a reactor inlet operatively coupled to the outlet to receive the ternary gas mixture; and a catalyst bed containing a catalyst for generating a hydrogen cyanide stream. The first angle and the second angle may be 5° to 45°. The first angle is 30° and may be greater than the second angle. The first angle is 30° and may be less than the second angle.

100‧‧‧HCN合成系統100‧‧‧HCN Synthesis System

102‧‧‧反應總成102‧‧‧Reaction assembly

104‧‧‧混合容器104‧‧‧Mixed container

106‧‧‧反應器容器106‧‧‧Reactor vessel

108‧‧‧含氧氣體進料流108‧‧‧Oxygen-containing gas feed stream

110‧‧‧含甲烷氣體進料流110‧‧‧Methane-containing gas feed stream

112‧‧‧含氨氣體進料流112‧‧‧Ammonia-containing gas feed stream

114‧‧‧三元氣體混合物114‧‧‧Ternary gas mixture

116‧‧‧粗製氰化氫產物116‧‧‧ crude hydrogen cyanide product

118‧‧‧觸媒床118‧‧‧Tactile bed

120‧‧‧分佈器板120‧‧‧Distributor board

122‧‧‧氨回收區段122‧‧‧Ammonia recovery section

124‧‧‧管線124‧‧‧ pipeline

126‧‧‧HCN精製區段126‧‧‧HCN refining section

128‧‧‧壓力釋放調控器128‧‧‧Pressure release regulator

130‧‧‧細長導管130‧‧‧Slim catheter

132‧‧‧第一入口埠/上部入口132‧‧‧First entrance/upper entrance

134‧‧‧第二入口埠/下部入口134‧‧‧Second entrance/lower entrance

136‧‧‧第一靜式混合區136‧‧‧First static mixing zone

138‧‧‧第二靜式混合區138‧‧‧Second static mixing zone

140‧‧‧列140‧‧‧

142‧‧‧不連續狹縫142‧‧‧discontinuous slit

144‧‧‧出口144‧‧‧Export

146‧‧‧空白空間146‧‧‧ blank space

148‧‧‧支撐件148‧‧‧Support

150‧‧‧凸耳150‧‧‧ lugs

152‧‧‧上游表面152‧‧‧ upstream surface

154‧‧‧下游表面154‧‧‧ downstream surface

156‧‧‧斜邊緣156‧‧‧ oblique edges

158‧‧‧內壁158‧‧‧ inner wall

160‧‧‧排氣管線160‧‧‧Exhaust line

162‧‧‧堆疊162‧‧‧Stacking

170‧‧‧氧進料準備系統170‧‧‧Oxygen feed preparation system

172‧‧‧甲烷進料準備系統172‧‧‧Methane feed preparation system

174‧‧‧新鮮氨進料準備系統174‧‧‧Fresh ammonia feed preparation system

176‧‧‧含氧來源176‧‧‧Oxygen source

178‧‧‧含甲烷來源178‧‧‧Methane source

180‧‧‧經處理新鮮氨流180‧‧‧Processed fresh ammonia flow

182‧‧‧再循環氨進料準備系統182‧‧‧Recycled ammonia feed preparation system

圖1係根據目前所主張實用新型之實施例之HCN合成系統的簡化圖。1 is a simplified diagram of an HCN synthesis system in accordance with an embodiment of the presently claimed invention.

圖2係根據目前所主張實用新型之實施例之混合容器的剖視圖。2 is a cross-sectional view of a mixing container in accordance with an embodiment of the presently claimed invention.

圖3係根據目前所主張實用新型之實施例之***混合容器中之凸耳的詳細剖視圖。3 is a detailed cross-sectional view of a lug inserted into a mixing container in accordance with an embodiment of the presently claimed invention.

圖4A-4C係根據目前所主張實用新型之實施例之凸耳的視圖。4A-4C are views of lugs in accordance with embodiments of the presently claimed invention.

圖5係根據目前所主張實用新型之實施例之具有反應物進料流純化之HCN合成系統的簡化示意性流程圖。Figure 5 is a simplified schematic flow diagram of a HCN synthesis system with reactant feed stream purification in accordance with an embodiment of the presently claimed invention.

本文所用術語僅用於闡述特定實施例之目的而並非意欲限制本實用新型。除非上下文另有明確指示，否則本文所用單數形式「一 (a、an)」及「該」亦意欲包括複數形式。應進一步理解，當本說明書中使用術語「包括(comprises及/或comprising)」時，其係指明存在所述特徵、整數、步驟、操作、元件及/或組件，但並不排除存在或添加一或多個其他特徵、整數、步驟、操作、元件群、組件及/或其群。The terminology used herein is for the purpose of the description of the particular embodiments Unless the context clearly indicates otherwise, the singular form " (a, an) and "the" are also intended to include plural forms. It will be further understood that when the term "comprises and/or "comprising" is used in the specification, it is intended to mean the presence of the features, integers, steps, operations, components and/or components, but does not exclude the presence or addition of a Or a plurality of other features, integers, steps, operations, component groups, components, and/or groups thereof.

諸如「包括(including)」、「包含(comprising)」、「具有(having)」、「含有(containing)」或「涉及(involving)」及其變化形式等用語意欲具有廣泛含義且涵蓋下文所列示之標的物，以及等效形式及未列舉之其他標的物。此外，每當組合物、元件群、製程或方法步驟或任一其他表述前面有過渡性片語「包含(comprising)」、「包括(including)」或「含有(containing)」時，應理解，本文中亦涵蓋在列舉組合物、元件群、製程或方法步驟或任一其他表述之前具有過渡性片語「基本上由……組成」、「由……組成」或「選自由……組成之群」之相同組合物、元件群、製程或方法步驟或任一其他表述。Terms such as "including", "comprising", "having", "containing" or "involving" and variations thereof are intended to have a broad meaning and are The subject matter, as well as equivalents and other objects not listed. In addition, whenever a transitional phrase "comprising", "including" or "containing" is used in the context of a composition, component group, process or method step or any other expression, it should be understood that Also included herein is a transitional phrase "consisting essentially of", "consisting of" or "selected from" before enumerating a composition, component group, process or method step, or any other expression. The same composition, group of elements, process or method steps, or any other expression.

申請專利範圍中所有構件或步驟附加功能元件之相應結構、材料、動作及等效形式意欲包括任一用於組合所具體主張之其他主張元件實施功能之結構、材料或動作。本實用新型之說明已出於例示及說明之目的加以呈現，但並不意欲具有窮盡性或限定於呈所揭示形式之本實用新型。熟習此項技術者將明瞭許多修改及變化形式，此並不背離本實用新型之範圍及精神。選擇及闡述該(等)實施例以便最佳地解釋本實用新型之原理及實際應用，且使其他熟習此項技術者能夠理解本實用新型，從而得出具有適於所涵蓋之具體用途之各種修改之各種實施例。因此，儘管已依照實施例對本實用新型進行了闡述，但熟習此項技術者將認識到，本實用新型可在修改的情況下實施且在隨附申請專利範圍之精神及範疇內。The corresponding structures, materials, acts, and equivalents of all of the components or steps of the functional elements in the claims are intended to include any structure, material, or action for the purpose of combining the claimed embodiments. The description of the present invention has been presented for purposes of illustration and description, and is not intended to Many modifications and variations will be apparent to those skilled in the art without departing from the scope of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the embodiments of the invention Various embodiments of the modifications. Therefore, while the invention has been described in terms of the embodiments, it will be understood by those skilled in the art

現在將詳細地參考某些所揭示標的物。儘管將結合所列舉之申 請專利範圍來闡述所揭示標的物，但應理解，其並不意欲將所揭示標的物限定於彼等申請專利範圍。相反，所揭示標的物意欲涵蓋可包括在如由申請專利範圍所界定之目前所揭示標的物之範圍內的所有替代形式、修改及等效形式。Reference will now be made in detail to certain disclosed subject matter. Although will combine the listed claims The scope of the invention is to be construed as being limited by the scope of the invention, and it is understood that it is not intended to limit the scope of the disclosure. Rather, the invention is to cover all alternatives, modifications, and equivalents, which are included within the scope of the presently disclosed subject matter.

氰化氫(「HCN」)係根據安德盧梭法或藉由BMA法以工業規模製造。在安德盧梭法中，使含甲烷、氨及氧之原材料在高於1000℃之溫度下在觸媒存在下反應以產生包含HCN、氫、一氧化碳、二氧化碳、氮、殘餘氨、殘餘甲烷及水之粗製氰化氫產物。通常使用天然氣作為甲烷來源，同時可使用空氣、富集氧之空氣或純氧作為氧來源。觸媒通常為金屬絲網鉑/銠合金或金屬絲網鉑/銥合金。可使用其他觸媒組合物且包括(但不限於)鉑族金屬、鉑族金屬合金、受支撐之鉑族金屬或受支撐之鉑族金屬合金。亦可使用其他觸媒組態且包括(但不限於)多孔結構、絲網、小片、團塊、單塊、發泡體、浸漬塗層及洗滌塗層。在BMA法中，使用如美國專利第7,429,370號中所述且以引用方式併入本文中之鉑觸媒使甲烷及氨反應。Hydrogen cyanide ("HCN") is manufactured on an industrial scale according to the Andrussow process or by the BMA process. In the Andrussow process, a raw material containing methane, ammonia and oxygen is reacted in the presence of a catalyst at a temperature higher than 1000 ° C to produce HCN, hydrogen, carbon monoxide, carbon dioxide, nitrogen, residual ammonia, residual methane and water. Crude hydrogen cyanide product. Natural gas is commonly used as a source of methane, while air, oxygen-enriched air or pure oxygen can be used as a source of oxygen. The catalyst is usually a wire mesh platinum/rhodium alloy or a wire mesh platinum/rhodium alloy. Other catalyst compositions can be used and include, but are not limited to, platinum group metals, platinum group metal alloys, supported platinum group metals, or supported platinum group metal alloys. Other catalyst configurations can also be used and include, but are not limited to, porous structures, screens, tablets, agglomerates, monoliths, foams, dip coatings, and washcoats. In the BMA process, a platinum catalyst, as described in U.S. Patent No. 7,429,370, incorporated herein by reference, which is incorporated herein by reference in its entirety, is incorporated herein by reference.

通常，圖1顯示HCN合成系統100。通常，HCN係在包括混合容器104及反應器容器106之反應總成102中產生。在安德盧梭法中，將包括含氧氣體進料流108、含甲烷氣體進料流110及含氨氣體進料流112之反應物氣體引入至混合容器104中。應注意，圖1中所示之進料位置係示意性的且並不意欲顯示將反應物進給至混合容器104之順序。在一些實施例中，含甲烷氣體進料流110及含氨氣體進料流112可在引入至混合容器104中之前組合。在BMA法中，反應物氣體包括引入至混合容器104中之含甲烷氣體進料流110及含氨氣體進料流112。在一個實施例中，混合容器104可含有一或多個用於產生充分混合之三元氣體混合物114之靜式混合區。Generally, Figure 1 shows an HCN synthesis system 100. Typically, HCN is produced in a reaction assembly 102 that includes a mixing vessel 104 and a reactor vessel 106. In the Andrussow process, a reactant gas comprising an oxygen-containing gas feed stream 108, a methane-containing gas feed stream 110, and an ammonia-containing gas feed stream 112 is introduced into the mixing vessel 104. It should be noted that the feed locations shown in FIG. 1 are schematic and are not intended to show the order in which reactants are fed to the mixing vessel 104. In some embodiments, the methane-containing gas feed stream 110 and the ammonia-containing gas feed stream 112 can be combined prior to introduction into the mixing vessel 104. In the BMA process, the reactant gases include a methane-containing gas feed stream 110 and an ammonia-containing gas feed stream 112 that are introduced into the mixing vessel 104. In one embodiment, the mixing vessel 104 can contain one or more static mixing zones for producing a well-mixed ternary gas mixture 114.

三元氣體混合物114排出混合容器104並接觸反應器容器106內所 含觸媒以形成含有HCN之粗製氰化氫產物116。觸媒可在觸媒床118內。在一個實施例中，可使用分佈器板120來將三元氣體混合物114運輸至反應器容器106中。分佈器板120亦可用來均勻地分佈三元氣體混合物及視需要進一步混合三元氣體混合物。氨可在氨回收區段122中自粗製氰化氫產物116回收並經由管線124返回。HCN可進一步在HCN精製區段126中精製至期望用途所需純度。在一些實施例中，HCN可為含有小於100重量ppm之水之高純度HCN。The ternary gas mixture 114 exits the mixing vessel 104 and contacts the reactor vessel 106. A catalyst is included to form the crude hydrogen cyanide product 116 containing HCN. The catalyst can be within the catalyst bed 118. In one embodiment, the distributor plate 120 can be used to transport the ternary gas mixture 114 into the reactor vessel 106. The distributor plate 120 can also be used to evenly distribute the ternary gas mixture and further mix the ternary gas mixture as needed. Ammonia may be recovered from the crude hydrogen cyanide product 116 in the ammonia recovery section 122 and returned via line 124. The HCN can be further refined in the HCN refining section 126 to the desired purity for the desired use. In some embodiments, the HCN can be a high purity HCN containing less than 100 ppm by weight water.

用於本實用新型目的之充分混合之三元氣體具有跨越觸媒床之直徑小於0.1或較佳小於0.05且更佳小於0.01之變動係數(CoV)。就範圍而言，CoV可為0.001至0.1或較佳0.001至0.05。低CoV有益地增加轉化成HCN之反應物之生產率。CoV定義為標準偏差σ 對平均值μ之 比率。理想地，CoV會儘可能低，例如小於0.1，例如，0.05。HCN單元可在高於0.1之CoV下操作，且0.2之CoV並不異常，即，在0.01至0.2或0.02至0.15範圍內。然而，在高於0.1之CoV下，操作成本較高且HCN產率較低，例如低2%至7%，此表現為在連續商業操作下每年可能損失數百萬美元。充分混合之三元氣體有利地增加HCN之生產率並回報較高HCN產率。性能改良可藉由跨越觸媒床達成實質上均一之床溫度來獲得。The well-mixed ternary gas for the purposes of the present invention has a coefficient of variation (CoV) that is less than 0.1 or preferably less than 0.05 and more preferably less than 0.01 across the diameter of the catalyst bed. In terms of range, the CoV may be from 0.001 to 0.1 or preferably from 0.001 to 0.05. Low CoV beneficially increases the productivity of the reactants converted to HCN. CoV is defined as the ratio of the standard deviation σ to the average μ . Ideally, the CoV will be as low as possible, for example less than 0.1, for example, 0.05. The HCN unit can operate at a CoV above 0.1, and the CoV of 0.2 is not abnormal, ie, in the range of 0.01 to 0.2 or 0.02 to 0.15. However, at CoV above 0.1, the operating costs are higher and the HCN yield is lower, such as 2% to 7% lower, which is manifested by the potential loss of millions of dollars per year under continuous commercial operation. The well-mixed ternary gas advantageously increases the productivity of HCN and returns a higher HCN yield. Performance improvements can be obtained by achieving a substantially uniform bed temperature across the catalyst bed.

當CoV超過0.1時，反應物氣體之濃度可超出觸媒床之安全操作範圍。例如，當在三元氣體中在較高氧濃度下操作時，較大CoV可產生導致回火之氧增加。另外，當CoV較大時，觸媒床可暴露於較多甲烷，此可導致碳沈積物之聚集。碳沈積物可縮短觸媒壽命並降低性能。因此，對於較大CoV可能具有較高原材料消耗。When the CoV exceeds 0.1, the concentration of the reactant gas can exceed the safe operating range of the catalyst bed. For example, when operating at higher oxygen concentrations in a ternary gas, a larger CoV can produce an increase in oxygen that causes tempering. In addition, when the CoV is large, the catalyst bed can be exposed to more methane, which can result in the accumulation of carbon deposits. Carbon deposits reduce catalyst life and reduce performance. Therefore, it is possible to have a higher raw material consumption for a larger CoV.

混合容器可在50℃至120℃之溫度下操作。可在對反應物氣體進行預熱之混合容器中使用較高溫度，如本文所述。在一個實施例中，混合容器較佳在低於反應器容器之溫度下操作。混合容器之操作壓力 可在130kPa至400kPa且更佳130kPa至300kPa之間廣泛地變化。通常，混合容器可在與反應器容器類似之壓力下操作。The mixing vessel can be operated at a temperature of from 50 °C to 120 °C. Higher temperatures can be used in the mixing vessel that preheats the reactant gases, as described herein. In one embodiment, the mixing vessel is preferably operated at a temperature below the reactor vessel. Operating pressure of the mixing vessel It can vary widely from 130 kPa to 400 kPa and more preferably from 130 kPa to 300 kPa. Typically, the mixing vessel can be operated at a pressure similar to that of the reactor vessel.

在使混合容器內之壓力降最小化之條件下混合反應物氣體。在一個實施例中，混合容器中之壓力降小於35kPa，較佳小於25kPa。使壓力降最小化可降低三元氣體之最大壓力且因此降低在***事件中之潛在壓力。降低壓力降亦使與混合相關之能量(即，壓縮能量)最小化。The reactant gases are mixed under conditions that minimize the pressure drop within the mixing vessel. In one embodiment, the pressure drop in the mixing vessel is less than 35 kPa, preferably less than 25 kPa. Minimizing the pressure drop reduces the maximum pressure of the ternary gas and thus reduces the potential pressure during an explosion event. Reducing the pressure drop also minimizes the energy associated with mixing (ie, compression energy).

將反應物氣體供應至混合容器以提供具有1.2至1.6(例如，1.3至1.5)之氨對氧之莫耳比、1至1.5(例如，1.1至1.45)之氨對甲烷之莫耳比及1至1.25(例如，1.05至1.15)之甲烷對氧之莫耳比的三元氣體混合物。例如，三元氣體混合物可具有1.3之氨對氧及1.2之甲烷對氧之莫耳比。在另一實例性實施例中，三元氣體混合物可具有1.5之氨對氧及1.15之甲烷對氧之莫耳比。三元氣體混合物中之氧濃度可端視該等莫耳比而變化。因此，在一些實施例中，三元氣體混合物包含至少25vol.%氧，例如，至少28vol.%氧。在一些實施例中，三元氣體混合物包含25Vol.%至32vol.%氧，例如，26vol.%至30vol.%氧。可使用各種控制系統來調控反應物氣體流。例如，可使用量測反應物氣體進料流之流動速率、溫度及壓力並且允許控制系統向操作人員及/或控制裝置提供壓力及溫度補償流動速率之「即時」回饋的流量計。The reactant gas is supplied to the mixing vessel to provide a molar ratio of ammonia to oxygen of from 1.2 to 1.6 (eg, 1.3 to 1.5), a molar ratio of ammonia to methane of from 1 to 1.5 (eg, 1.1 to 1.45), and A ternary gas mixture of methane to oxygen molar ratio to 1.25 (eg, 1.05 to 1.15). For example, the ternary gas mixture can have an ammonia to oxygen ratio of 1.3 and a methane to oxygen molar ratio of 1.2. In another exemplary embodiment, the ternary gas mixture may have an ammonia to oxygen ratio of 1.5 and a methane to oxygen molar ratio of 1.15. The concentration of oxygen in the ternary gas mixture can vary depending on the molar ratio. Thus, in some embodiments, the ternary gas mixture comprises at least 25 vol.% oxygen, for example, at least 28 vol.% oxygen. In some embodiments, the ternary gas mixture comprises from 25 Vol.% to 32 vol.% oxygen, for example, 26 vol.% to 30 vol.% oxygen. Various control systems can be used to regulate the reactant gas flow. For example, a flow meter that measures the flow rate, temperature, and pressure of the reactant gas feed stream and allows the control system to provide an "instant" feedback of pressure and temperature compensated flow rates to the operator and/or control device.

熟悉此項技術者應瞭解，上述功能及/或過程可體現為系統、方法或電腦程式產品。例如，功能及/或製程可作為記錄在電腦可讀儲存裝置中之電腦可執行程式指令實施，該裝置在由電腦處理器擷取並執行時，控制計算系統以實施本文所述實施例之功能及/或製程。在實施例中，電腦系統可包括一或多個中央處理單元、電腦記憶體(例如，唯讀記憶體、隨機存取記憶體)及資料儲存器件(例如，硬磁碟機)。電腦可執行指令可使用任一適宜之電腦程式設計語言(例如， C++、JAVA等)編碼。因此，本實用新型之態樣可呈完全為軟體之實施例(包括韌體、常駐軟體、微程式碼等)或組合軟體與硬體態樣之實施例之形式。Those skilled in the art should appreciate that the above-described functions and/or processes may be embodied as a system, method or computer program product. For example, the functions and/or processes may be implemented as computer executable program instructions recorded in a computer readable storage device that, when retrieved and executed by a computer processor, controls the computing system to perform the functions of the embodiments described herein And / or process. In an embodiment, the computer system can include one or more central processing units, computer memory (eg, read-only memory, random access memory), and data storage devices (eg, a hard disk drive). Computer executable instructions can be in any suitable computer programming language (for example, C++, JAVA, etc.) coding. Thus, aspects of the present invention can be in the form of an entirely software embodiment (including firmware, resident software, microcode, etc.) or a combination of software and hardware aspects.

在一個實施例中，當混合反應物氣體時，期望避免混合容器中之副反應。副反應可包括甲烷或氨之氧化。亦應藉由在混合容器中維持大於三元氣體之火焰前緣之流動速度在混合容器中避免在不利操作條件下爆燃或***之風險及影響。本文所用術語「爆燃」係指燃燒波相對於火焰正前方之不燃氣體以次音速速度傳播。「***」係指燃燒波相對於火焰正前方之不燃氣體以超音速速度傳播。爆燃通常引起中等壓力升高，而***可引起異常壓力升高。本實用新型提供有利之解決方案以快速且充分地混合反應物氣體，同時使混合期間之壓力降最小化並避免不期望之副反應，例如氧化及爆燃。In one embodiment, it is desirable to avoid side reactions in the mixing vessel when mixing the reactant gases. Side reactions can include oxidation of methane or ammonia. The risk and impact of deflagration or explosion under adverse operating conditions should also be avoided in the mixing vessel by maintaining the flow rate of the flame front of the ternary gas in the mixing vessel. As used herein, the term "deflagration" refers to the propagation of a combustion wave at a subsonic speed relative to a non-combustible gas directly in front of the flame. "Explosion" means that the combustion wave propagates at a supersonic speed with respect to the non-combustible gas directly in front of the flame. Deflagration usually causes an intermediate pressure rise, and an explosion can cause an abnormal pressure rise. The present invention provides an advantageous solution to quickly and sufficiently mix reactant gases while minimizing pressure drop during mixing and avoiding undesirable side reactions such as oxidation and deflagration.

在圖2中，顯示混合容器104之剖視圖。混合容器104產生具有小於0.1之CoV之三元氣體混合物114，該三元氣體混合物經由近端(例如下游端)排出並進入HCN反應器容器106中。在混合容器104之遠端，例如，上游端，提供壓力釋放調控器128，其更全面地論述於本文中。混合容器104包含細長導管130，該細長導管可在三元氣體之流動方向上延伸至反應器容器中。在一個實施例中，存在第一入口埠132，其亦稱為上部入口，用於引入至少一種選自由含甲烷氣體、含氨氣體、含氧氣體及其混合物組成之群之反應物氣體。較佳地，經由第一入口埠132引入含甲烷氣體110及含氨氣體112。亦可經由第二入口埠134(亦稱為下部入口)將額外反應物氣體引入至導管130中。在一個實施例中，經由第二入口埠134引入之反應物氣體可選自由含甲烷氣體、含氨氣體、含氧氣體及其混合物組成之群。較佳地，可經由第二入口埠134引入含氧氣體流108。如圖2中所示，第二入口埠134鄰近第一入口埠132。由於直至引入含氧氣體才形成三元氣體混合物，因 此較佳在導管130中下游引入含氧氣體流108以減小三元氣體混合物之體積。In Figure 2, a cross-sectional view of the mixing vessel 104 is shown. The mixing vessel 104 produces a ternary gas mixture 114 having a CoV of less than 0.1, which is discharged via a proximal end (e.g., a downstream end) and into the HCN reactor vessel 106. At the distal end of the mixing vessel 104, for example, the upstream end, a pressure release regulator 128 is provided, which is more fully discussed herein. The mixing vessel 104 includes an elongated conduit 130 that can extend into the reactor vessel in the direction of flow of the ternary gas. In one embodiment, there is a first inlet port 132, also referred to as an upper inlet, for introducing at least one reactant gas selected from the group consisting of a methane-containing gas, an ammonia-containing gas, an oxygen-containing gas, and mixtures thereof. Preferably, the methane-containing gas 110 and the ammonia-containing gas 112 are introduced via the first inlet port 132. Additional reactant gases may also be introduced into the conduit 130 via a second inlet port 134 (also referred to as a lower inlet). In one embodiment, the reactant gas introduced via the second inlet port 134 may be selected from the group consisting of a methane-containing gas, an ammonia-containing gas, an oxygen-containing gas, and mixtures thereof. Preferably, the oxygen-containing gas stream 108 can be introduced via the second inlet port 134. As shown in FIG. 2, the second inlet port 134 is adjacent to the first inlet port 132. Since the ternary gas mixture is formed until the introduction of the oxygen-containing gas, This preferably introduces an oxygen-containing gas stream 108 downstream of the conduit 130 to reduce the volume of the ternary gas mixture.

細長導管130進一步包含一或多個用於產生充分混合之三元氣體之靜式混合區。在一個實施例中，存在至少一個靜式混合區136，其毗鄰第一入口埠132定位。靜式混合區136提供含甲烷氣體110與含氨氣體112之混合，然後與含氧氣體108混合。靜式混合區136可形成甲烷及氨之二元氣體。亦存在至少一個靜式混合區138，其毗鄰或鄰近第二入口埠134定位。靜式混合區138混合含氧氣體與其他反應物氣體以產生三元氣體混合物。具體而言，靜式混合區138應實際上儘可能靠近反應器容器106中之反應器觸媒床(未顯示)安裝以使混合容器104中之三元氣體混合物之體積及停留時間最小化。The elongated conduit 130 further includes one or more static mixing zones for producing a well-mixed ternary gas. In one embodiment, there is at least one static mixing zone 136 positioned adjacent to the first inlet bore 132. The static mixing zone 136 provides a mixture of the methane-containing gas 110 and the ammonia-containing gas 112 and is then mixed with the oxygen-containing gas 108. The static mixing zone 136 can form a binary gas of methane and ammonia. There is also at least one static mixing zone 138 positioned adjacent to or adjacent to the second inlet weir 134. The static mixing zone 138 mixes the oxygen containing gas with the other reactant gases to produce a ternary gas mixture. In particular, the static mixing zone 138 should be mounted as close as possible to the reactor catalyst bed (not shown) in the reactor vessel 106 to minimize the volume and residence time of the ternary gas mixture in the mixing vessel 104.

儘管在圖2中對於埠132及134顯示一個入口，但在一個實施例中可存在複數個第一入口埠及第二入口埠。圍繞細長導管130之整個圓周可存在多個進料入口。每一進料入口可與三元氣體混合物之流動方向呈5至90。之角度。主反應物進料管線可連接至環繞複數個第一入口埠及/或第二入口埠之環形區(未顯示)。可存在複數個孔(未顯示)，其界定入口埠並將進料自環形區輸入細長導管130中。不受理論限制，當將反應物進給至混合容器104時，複數個孔可防止旋轉，即渦漩。Although one entry is shown for 埠132 and 134 in FIG. 2, in one embodiment there may be a plurality of first entry ports and second entry ports. There may be multiple feed inlets around the entire circumference of the elongated conduit 130. Each feed inlet can be from 5 to 90 in the direction of flow of the ternary gas mixture. The angle. The main reactant feed line can be connected to an annular zone (not shown) that surrounds the plurality of first inlet ports and/or second inlet ports. There may be a plurality of holes (not shown) that define the inlet enthalpy and feed the feed from the annular zone into the elongated conduit 130. Without being bound by theory, when the reactants are fed to the mixing vessel 104, the plurality of holes prevent rotation, i.e., vortexing.

在另一實施例中，第一入口埠132及第二入口埠136可延伸至細長導管130之空腔中。此可允許將反應物引入至細長導管130之中部中。不受理論限制，經延伸入口可防止反應物穿過混合容器104而不接觸凸耳150。較佳地，進給含氧氣體108之第二入口埠138延伸至導管130之中部中。In another embodiment, the first inlet port 132 and the second inlet port 136 can extend into the cavity of the elongated conduit 130. This may allow the reactants to be introduced into the middle of the elongated conduit 130. Without being bound by theory, the extended inlet prevents the reactants from passing through the mixing vessel 104 without contacting the lug 150. Preferably, the second inlet port 138 feeding the oxygen-containing gas 108 extends into the middle of the conduit 130.

靜式混合區136及138各自包含一或多列140不連續狹縫142。每一靜式混合區136及138可包含1至10列不連續狹縫142。在一個實施例中，第二靜式混合區138中之列數可大於或等於第一靜式混合區136中 之列數。例如，第二靜式混合區138可具有1至3列。每列140可包含1至10個不連續狹縫142，且較佳包括2至6個不連續狹縫142。在每一列140內，不連續狹縫142較佳圍繞導管130之圓周均勻地間隔且不連續。當列數及/或每列中之凸耳150數增加時，混合容器104中之壓力降亦會增加。因此，期望使用列與凸耳之組合，其提供充分混合，同時維持小於35kPa之壓力降。在一個態樣中，混合容器之不連續狹縫142及因此凸耳150之總數可為4至24，例如，8至20或10至16。The static mixing zones 136 and 138 each include one or more columns 140 of discontinuous slits 142. Each of the static mixing zones 136 and 138 can include from 1 to 10 rows of discontinuous slits 142. In one embodiment, the number of columns in the second static mixing zone 138 can be greater than or equal to the first static mixing zone 136. The number of columns. For example, the second static mixing zone 138 can have from 1 to 3 columns. Each column 140 can include from 1 to 10 discrete slits 142, and preferably includes from 2 to 6 discrete slits 142. Within each column 140, the discontinuous slits 142 are preferably evenly spaced and discontinuous about the circumference of the conduit 130. As the number of columns and/or the number of lugs 150 in each column increases, the pressure drop in the mixing vessel 104 also increases. Therefore, it is desirable to use a combination of columns and lugs that provide for adequate mixing while maintaining a pressure drop of less than 35 kPa. In one aspect, the total number of discontinuous slits 142 and thus the lugs 150 of the mixing container can range from 4 to 24, for example, 8 to 20 or 10 to 16.

鄰近第二靜式混合區138且在混合容器104之出口144之前，可存在空白空間146。空白空間146為三元氣體混合物留出非混合區域。空白空間146可具有0.1*d至10*d之高度，其中d係細長導管130之內徑。A blank space 146 may be present adjacent to the second static mixing zone 138 and prior to the outlet 144 of the mixing vessel 104. Blank space 146 leaves a non-mixed zone for the ternary gas mixture. The blank space 146 can have a height of 0.1*d to 10*d, where d is the inner diameter of the elongated conduit 130.

在一個實施例中，不連續狹縫142可與三元氣體之流動方向對準或可呈l-形、I-形、T-形、U-形或V-形。如圖4A-4C中所示，支撐件148係條，例如，l-形或I-形，且延伸經過上游表面152之平面。在其他實施例中，當每一凸耳150具有一個以上支撐件148時，可使用V-形或U-形不連續狹縫142。In one embodiment, the discontinuous slit 142 may be aligned with the flow direction of the ternary gas or may be in the shape of a l-shape, an I-shape, a T-shape, a U-shape, or a V-shape. As shown in Figures 4A-4C, the support member 148 is tying, e.g., 1- or I-shaped, and extends through the plane of the upstream surface 152. In other embodiments, a V-shaped or U-shaped discontinuous slit 142 can be used when each lug 150 has more than one support member 148.

凸耳150包含斜邊緣156，如圖4B中所示，該斜邊緣在不連續狹縫142上方延伸且緊靠細長導管130之內壁158，如圖3中所示。斜邊緣156亦可在支撐件148上方延伸。較佳地，斜邊緣156不接觸另一毗鄰列140之凸耳150。斜邊緣156之角度可由上游表面152之角度確定。The lug 150 includes a beveled edge 156 that extends over the discontinuous slit 142 and abuts against the inner wall 158 of the elongated conduit 130, as shown in Figure 4B, as shown in Figure 3. The beveled edge 156 can also extend over the support 148. Preferably, the beveled edge 156 does not contact the lug 150 of the other adjacent column 140. The angle of the beveled edge 156 can be determined by the angle of the upstream surface 152.

凸耳150可由諸如310SS及316SS等不銹鋼材料構築。The lug 150 can be constructed from stainless steel materials such as 310SS and 316SS.

支撐件148可向凸耳150提供剛性以使得凸耳150在壓力變化下不變形。由於不連續狹縫142及凸耳150之配置及在細長導管130之內表面上缺乏黏合劑或焊接，因此凸耳150可具有剛性以在細長導管130中壓力變化後保持一定角度。當細長導管130內存在壓力變化時，該等凸耳可比表面焊接至導管130內部之彎曲圓角焊接混合凸耳更強。出於本實用新型之目的，凸耳在超過5MPa(例如，較佳超過13MPa)之 壓力變化下不變形。在壓力條件恢復至正常操作條件後，凸耳保持其原來角度。因此，混合容器104在此等壓力變化下不發生混合效率降低。The support 148 can provide rigidity to the lug 150 such that the lug 150 does not deform under pressure changes. Due to the configuration of the discontinuous slits 142 and lugs 150 and the lack of adhesive or weld on the inner surface of the elongated conduit 130, the lugs 150 can be rigid to maintain a certain angle after pressure changes in the elongated conduit 130. When there is a change in pressure within the elongated conduit 130, the lugs may be stronger than the curved fillet weld mixing lugs that are surface welded to the interior of the conduit 130. For the purposes of the present invention, the lugs are above 5 MPa (eg, preferably over 13 MPa) No deformation under pressure changes. The lug maintains its original angle after the pressure condition returns to normal operating conditions. Therefore, the mixing container 104 does not suffer from a decrease in mixing efficiency under such pressure changes.

不連續狹縫142係穿過導管130之開口，其中未進給反應物氣體。不連續狹縫142可機械加工至導管130中。凸耳150係穿過不連續狹縫142***且凸耳150延伸至導管130之空腔中。延伸經過上游表面之平面之支撐件148可滑動地咬合至來自細長導管130之內部空腔之不連續狹縫142中。凸耳150可稱為透切式(through-cut)混合凸耳。將凸耳150緊固至導管130之外壁。較佳地，在***凸耳150後，藉由黏合劑或焊接自導管130之外部緊固凸耳150。在緊固凸耳150後，沒有氣體洩漏穿過不連續狹縫142。與難以適當地對準及緊固之內部焊接不同，此顯著地提高將凸耳150定位在導管130內之效率及精確度。另外，其藉由允許自導管外部而非自導管內操作允許容易地***凸耳。The discontinuous slit 142 is passed through the opening of the conduit 130 where the reactant gases are not fed. The discontinuous slit 142 can be machined into the catheter 130. The lug 150 is inserted through the discontinuous slit 142 and the lug 150 extends into the cavity of the catheter 130. A support member 148 extending through the plane of the upstream surface slidably engages into a discontinuous slit 142 from the internal cavity of the elongated conduit 130. The lug 150 can be referred to as a through-cut hybrid lug. The lug 150 is fastened to the outer wall of the catheter 130. Preferably, after insertion of the lug 150, the lug 150 is secured from the exterior of the catheter 130 by adhesive or welding. After the lug 150 is tightened, no gas leaks through the discontinuous slit 142. This is a significant improvement in the efficiency and precision of positioning the lug 150 within the catheter 130, unlike internal welds that are difficult to properly align and fasten. In addition, it allows for easy insertion of the lugs by allowing operation from outside the catheter rather than from within the catheter.

當使每一靜式混合區之各列定位時，可在導管之外表面上研磨出凹槽且使不連續狹縫穿過該凹槽。在***凸耳150後，凹槽可用焊接金屬填充以緊固凸耳150。凸耳150可自導管內部***且凸耳150及支撐件148可延伸穿過導管以在外部緊固凸耳150。When the columns of each of the static mixing zones are positioned, the grooves can be ground on the outer surface of the conduit and the discontinuous slits can be passed through the grooves. After the lug 150 is inserted, the groove can be filled with a weld metal to secure the lug 150. The lug 150 can be inserted from within the catheter and the lug 150 and the support 148 can extend through the catheter to secure the lug 150 externally.

在一個實施例中，凸耳150具有在流動方向上成角度之上游表面152。自導管之內壁量測凸耳150之角度。角度可在5°至45°且更佳20°至35°之間變化。下游表面154可與上游表面具有類似角度。一列內之凸耳可具有實質上類似之角度，例如在±5°內。毗鄰列之間以及不同混合區之間之凸耳之角度可有所變化。在具有多列之混合區中，下游列之凸耳之角度可小於上游列中之凸耳之角度。在一個實例性實施例中，第一混合區136之凸耳可具有30°之角度且第二混合區138之凸耳可具有25°之角度。在另一實例性實施例中，第一混合區136之凸耳可具有30°之角度且第二混合區138之凸耳可具有45°之角度。限制每一 凸耳150之表面152上游之表面積以防止壓力降增加且其通常可在50cm² 至250cm² (例如，75cm² 至150cm² )範圍內，此取決於凸耳及列之數量。當所有凸耳150之總表面積增加時，壓力降亦可增加。In one embodiment, the lug 150 has an upstream surface 152 that is angled in the direction of flow. The angle of the lug 150 is measured from the inner wall of the catheter. The angle may vary from 5° to 45° and more preferably from 20° to 35°. The downstream surface 154 can have a similar angle to the upstream surface. The lugs in a row can have substantially similar angles, for example within ±5°. The angle of the lugs between adjacent columns and between different mixing zones may vary. In a mixing zone having multiple columns, the angle of the lugs of the downstream columns may be less than the angle of the lugs in the upstream column. In an exemplary embodiment, the lugs of the first mixing zone 136 can have an angle of 30° and the lugs of the second mixing zone 138 can have an angle of 25°. In another exemplary embodiment, the lugs of the first mixing zone 136 can have an angle of 30° and the lugs of the second mixing zone 138 can have an angle of 45°. The surface area upstream of the surface 152 of each lug 150 is limited to prevent an increase in pressure drop and it can typically range from 50 cm ² to 250 cm ² (eg, 75 cm ² to 150 cm ² ) depending on the number of lugs and columns. As the total surface area of all of the lugs 150 increases, the pressure drop can also increase.

另外，凸耳150無傾斜度，即未扭曲，且在導管130之內壁上對準而實質上與三元氣體混合物之流動平行。在一個實施例中，凸耳150之傾斜度係0°至7°，例如，0°至3°或0°至1°。具有大於8°之輕微傾斜度可導致差混合性能，此可導致床溫度變化增加及/或不合意之壓力降增加。因此，本實用新型之透切式不連續狹縫允許凸耳具有降低之傾斜度及降低床溫度變動之改良之性能。在一個實施例中，跨越床之床溫度變動可為15℃至25℃。Additionally, the lug 150 has no inclination, i.e., is not twisted, and is aligned on the inner wall of the conduit 130 to be substantially parallel to the flow of the ternary gas mixture. In one embodiment, the inclination of the lug 150 is 0° to 7°, for example, 0° to 3° or 0° to 1°. Having a slight slope of greater than 8° can result in poor mixing performance, which can result in increased bed temperature variations and/or undesirable pressure drop increases. Thus, the through-cut discontinuous slit of the present invention allows the lug to have reduced slope and improved performance in reducing bed temperature variations. In one embodiment, the bed temperature variation across the bed can range from 15 °C to 25 °C.

在反應器中之壓力失衡(upset)下，凸耳150定位於透切物內以耐受扭曲且在壓力失衡下不變形。此避免了以高代價延遲進行修復。若存在任一損壞，則可容易地去除受損凸耳並用新凸耳替換，該替換係藉由將新凸耳穿過不連續狹縫***並自細長導管之外表面焊接來達成。Under the pressure upset in the reactor, the lug 150 is positioned within the perforate to withstand distortion and does not deform under pressure imbalance. This avoids repairs with high cost delays. If any damage is present, the damaged lugs can be easily removed and replaced with new lugs by inserting new lugs through the discontinuous slits and welding from the outer surface of the elongate conduit.

另外，靜式混合區內之凸耳可具有實質上類似之角度。對於不同靜式混合區中之不同列及凸耳，可使用不同角度。在實例性實施例中，第一靜式混合區136中之凸耳之角度不同於第二靜式混合區138內之凸耳之角度。增加角度可增加混合，但壓力降會有相應不合意之增加。細長導管130內之每一凸耳150不平行於流動方向。換言之，在導管130之空腔內，凸耳150不具有實質上平行於導管130之壁之表面。支撐件148可實質上平行於流動方向，但支撐件148位於下游表面154上且對混合不具有顯著影響。而是，將凸耳150及支撐件148穿過不連續狹縫142***，將凸耳150緊固至導管130之外壁。沿著導管130之外壁，凸耳150可具有實質上平行於外壁之表面。Additionally, the lugs in the static mixing zone can have substantially similar angles. Different angles can be used for different columns and lugs in different static mixing zones. In an exemplary embodiment, the angle of the lugs in the first static mixing zone 136 is different than the angle of the lugs in the second static mixing zone 138. Increasing the angle increases the mixing, but the pressure drop has an undesired increase. Each lug 150 within the elongated conduit 130 is not parallel to the flow direction. In other words, within the cavity of the catheter 130, the lug 150 does not have a surface that is substantially parallel to the wall of the catheter 130. The support 148 can be substantially parallel to the flow direction, but the support 148 is located on the downstream surface 154 and does not have a significant impact on mixing. Rather, the lug 150 and the support member 148 are inserted through the discontinuous slit 142 to secure the lug 150 to the outer wall of the catheter 130. Along the outer wall of the catheter 130, the lug 150 can have a surface that is substantially parallel to the outer wall.

每一凸耳150可具有0.1至2.5cm(例如，0.5cm至1.5cm)之適宜 厚度，以維持凸耳150之剛性。凸耳之後邊緣係凸耳自導管之內壁最遠延伸至混合區域中之邊緣。凸耳之後邊緣可視需要為圓形、錐形或正方形以提供必要混合。在一個實施例中，凸耳之後邊緣可為銳邊緣，例如刀形邊緣，具有30°至90°(例如，45°至90°)之角度。銳邊緣可增加混合容器104內之混合。具有小於30°之角度之鈍邊緣可不合意地增加混合容器內之壓力降。Each lug 150 may have a suitable fit of 0.1 to 2.5 cm (eg, 0.5 cm to 1.5 cm) The thickness is to maintain the rigidity of the lug 150. The edge of the lug is extended from the inner wall of the catheter to the edge of the mixing zone as far as the edge. The trailing edge of the lug may be circular, tapered or square as needed to provide the necessary mixing. In one embodiment, the trailing edge of the lug may be a sharp edge, such as a knife edge, having an angle of 30° to 90° (eg, 45° to 90°). Sharp edges can increase mixing within the mixing vessel 104. A blunt edge having an angle of less than 30° may undesirably increase the pressure drop within the mixing vessel.

導管130內之凸耳150作為流體箔操作，在反應物氣體流動穿過混合容器104之情況下，針對其上游表面152表現之流體壓力較大且針對其下游表面154表現之流體壓力降低。每一凸耳150之相互對置毗鄰面上之此流體壓力差使在每一凸耳150上方並經過每一凸耳150之縱向流重新定向，由此增加穿過導管130之流體之縱向流的徑向交叉流分量。每一凸耳之邊緣上方之流體流因成角度之上游面而使該流向內及向上偏轉，從而生成數對位於每一凸耳頂端之相對旋轉之主要為順流的渦流及與由單一凸耳生成之毗鄰順流渦流互連之下游髮夾式渦流。每一此對之渦流沿著兩個邊界表面之間之環形空間繞著大體沿縱向順流流體流動方向定向之旋轉軸具有相互對置之旋轉。由靜式混合區136、138生成之紊流混合產生具有小於0.1之CoV之充分混合之三元氣體混合物。The lug 150 within the conduit 130 operates as a fluid foil with the fluid pressure exhibited for its upstream surface 152 being greater and the fluid pressure exhibited for its downstream surface 154 decreasing as the reactant gas flows through the mixing vessel 104. This fluid pressure differential across the opposing faces of each lug 150 redirects the longitudinal flow over each lug 150 and through each lug 150, thereby increasing the longitudinal flow of fluid through conduit 130. Radial cross-flow component. The fluid flow above the edge of each lug deflects the flow inwardly and upwardly due to the angled upstream face, thereby creating a plurality of pairs of vortexes that are primarily downstream of the relative rotation of the top end of each lug and with a single lug A downstream hairpin vortex is generated adjacent to the downstream vortex interconnect. Each of the pair of vortices has mutually opposite rotations along an annular space between the two boundary surfaces about an axis of rotation oriented generally in the direction of longitudinal fluid flow. The turbulent mixing produced by the static mixing zones 136, 138 produces a well-mixed ternary gas mixture having a CoV of less than 0.1.

在一個實施例中，當靜式混合區136、138包含超過兩列140時，來自每列之凸耳150可與毗鄰列橫向對準以達成期望混合效應。在一些實施例中可使用橫向偏位凸耳150，即「交錯」。In one embodiment, when the static mixing zone 136, 138 includes more than two columns 140, the lugs 150 from each column can be laterally aligned with adjacent columns to achieve the desired mixing effect. Lateral offset lugs 150, i.e., "staggered", may be used in some embodiments.

凸耳150之上游表面152之形狀可包括梯形、正方形、平行四邊形、半橢圓形、圓角正方形或矩形。可使用錐形凸耳，例如梯形凸耳。另外，凸耳可輕微彎曲或折彎。在一個實施例中，在主順流流之方向上，凸耳之縱長尺寸不超過凸耳寬度之兩倍。The shape of the upstream surface 152 of the lug 150 can include a trapezoidal shape, a square shape, a parallelogram shape, a semi-elliptical shape, a rounded square shape, or a rectangular shape. Tapered lugs can be used, such as trapezoidal lugs. In addition, the lugs can be slightly bent or bent. In one embodiment, the longitudinal dimension of the lug does not exceed twice the width of the lug in the direction of the main downstream flow.

混合容器104之尺寸可廣泛地變化且將在很大程度上取決於反應 器容器106之容量。在本文所揭示之本實用新型之一個實例性實施例中，混合容器104之外部長度對直徑之比率在2至20(例如2至10)範圍內。混合容器之大小可有所變化，但可具有1m至5m(例如，1.2m至2.5m)之長度及5cm至60cm(例如，10cm至35cm)之內徑。The size of the mixing vessel 104 can vary widely and will depend to a large extent on the reaction The capacity of the container 106. In an exemplary embodiment of the invention disclosed herein, the ratio of the outer length to the diameter of the mixing vessel 104 is in the range of 2 to 20 (e.g., 2 to 10). The size of the mixing vessel may vary, but may have a length of from 1 m to 5 m (eg, 1.2 m to 2.5 m) and an inner diameter of from 5 cm to 60 cm (eg, from 10 cm to 35 cm).

儘管存在圖2中所示之兩個入口埠及兩個靜式混合區，但在其他實施例中，可存在一個入口埠，具有一個靜式混合器。另外，可存在兩個入口埠，具有一個鄰近下部入口埠定位之靜式混合器。可在本實用新型範圍內使用入口埠及靜式混合器之其他組態。Although there are two inlet ports and two static mixing zones as shown in Figure 2, in other embodiments there may be one inlet port with a static mixer. Additionally, there may be two inlet ports with a static mixer positioned adjacent the lower inlet port. Other configurations of inlet ports and static mixers can be used within the scope of the present invention.

三元氣體混合物114可自混合容器104進入反應器容器106之入口埠中。在一個實施例中，可存在一或多個用於在觸媒床上提供均勻分佈之三元氣體混合物之分佈器板120。消焰器亦可與分佈器板組合使用以在觸媒床上分佈三元氣體。較佳地，分佈器板不應在反應器容器中引起大於35kPa之壓力降，例如更佳小於25kPa之壓力降。在一個實施例中，存在一個在反應器容器內佈置於入口下游及消焰器上游之分佈器板。分佈器板之直徑可大於入口埠且小於反應器容器之最大直徑。分佈器板具有由一或多個孔形成之空隙區域，該空隙區域係分佈器板之面積之至少50%至80%。空隙區域可在上游表面上具有凸起之圓錐形特徵以擴散三元氣體混合物。分佈器板亦可包含與入口埠之中心點對準、較佳同心對準之實心區域。在一個實施例中，分佈器板可為金屬絲網材料。The ternary gas mixture 114 can enter the inlet port of the reactor vessel 106 from the mixing vessel 104. In one embodiment, there may be one or more distributor plates 120 for providing a uniformly distributed ternary gas mixture over the catalyst bed. The flame arrester can also be used in combination with a distributor plate to distribute the ternary gas on the catalyst bed. Preferably, the distributor plate should not cause a pressure drop greater than 35 kPa in the reactor vessel, such as a pressure drop of less than 25 kPa. In one embodiment, there is a distributor plate disposed downstream of the inlet and upstream of the flame arrestor within the reactor vessel. The distributor plate may have a diameter greater than the inlet enthalpy and less than the largest diameter of the reactor vessel. The distributor plate has a void region formed by one or more apertures that is at least 50% to 80% of the area of the distributor plate. The void region may have a convex conical feature on the upstream surface to diffuse the ternary gas mixture. The distributor plate may also include a solid region that is aligned with the center point of the inlet weir, preferably concentrically aligned. In one embodiment, the distributor plate can be a wire mesh material.

用於混合容器及凸耳之構築材料可有所變化且可為任一與三元氣體混合物相容之材料，其能夠耐受混合容器中之設計溫度及壓力而不會顯著降解，且不會促進三元氣體混合物中之氣體之反應。已使用包括310SS及316SS之不銹鋼構築材料獲得滿意結果。The construction material for the mixing container and the lug can vary and can be any material compatible with the ternary gas mixture, which can withstand the design temperatures and pressures in the mixing vessel without significant degradation and will not Promotes the reaction of gases in the ternary gas mixture. Satisfactory results have been obtained using stainless steel construction materials including 310SS and 316SS.

在一個實施例中，藉由拋光彼等暴露於氣體流之表面以減小內表面之比表面積(粗糙度)來降低混合器之內表面之催化活性。例如， 將一定內徑之混合容器機械加工成約125微英吋(3.2微米)之表面粗糙度(rms)顯著地降低催化活性。In one embodiment, the catalytic activity of the inner surface of the mixer is reduced by polishing them to the surface of the gas stream to reduce the specific surface area (roughness) of the inner surface. E.g, Machining a certain inner diameter mixing vessel to a surface roughness (rms) of about 125 microinch (3.2 microns) significantly reduces the catalytic activity.

混合容器104可提供有一或多個用於量測排出第一靜式混合區136及/或第二靜式混合區138之甲烷及氨之濃度的適宜分析器。此等在線及離線分析器為業內所熟知。此等分析器之非限制性實例包括紅外線分析器、傅立葉(Fourier)變換紅外線分析器、氣體層析分析器及質譜分析器。同樣，第二靜式混合區138可提供有一或多個用於量測三元氣體混合物中之氧濃度之適宜分析器。The mixing vessel 104 can provide one or more suitable analyzers for measuring the concentration of methane and ammonia exiting the first static mixing zone 136 and/or the second static mixing zone 138. These online and offline analyzers are well known in the art. Non-limiting examples of such analyzers include an infrared analyzer, a Fourier transform infrared analyzer, a gas chromatography analyzer, and a mass spectrometer. Likewise, the second static mixing zone 138 can provide one or more suitable analyzers for measuring the concentration of oxygen in the ternary gas mixture.

在圖2中未顯示之可選實施例中，上部及下部入口132及134提供有具有自動閥之鈍氣連接件，以使得可在需要時吹掃連接至混合容器104之管線中之反應物，例如用於維護關斷或反應器關斷。In an alternative embodiment not shown in FIG. 2, the upper and lower inlets 132 and 134 are provided with a blunt gas connection with an automatic valve to allow the reactants in the line connected to the mixing vessel 104 to be purged when needed. For example, for maintenance shutdown or reactor shutdown.

在一個實施例中，混合容器104亦可包含一或多個整流器(未顯示)。整流器可具有在氣體進料流接觸靜式混合區之前對準流之組態。此外，整流器跨越整流器維持實質上均一之速度剖面。整流器亦可圍繞導管130之整個區域分佈氣體並防止反應物氣體向下直接穿過混合容器104之中部。In one embodiment, the mixing vessel 104 can also include one or more rectifiers (not shown). The rectifier can have a configuration that aligns the flow before the gas feed stream contacts the static mixing zone. In addition, the rectifier maintains a substantially uniform velocity profile across the rectifier. The rectifier can also distribute gas around the entire area of the conduit 130 and prevent reactant gases from passing directly down the interior of the mixing vessel 104.

整流器在使用時可在第一入口埠132及/或第二入口埠134鄰近(例如，下游)定位。較佳地，整流器分別直接位於第一靜式混合區136中之第一列凸耳上游及第二靜式混合區138上游。The rectifier can be positioned adjacent (eg, downstream) of the first inlet port 132 and/or the second inlet port 134 when in use. Preferably, the rectifiers are located directly upstream of the first column of lugs in the first static mixing zone 136 and upstream of the second static mixing zone 138.

在一個實施例中，整流器可具有複數個在中部連接之徑向板。一些整流器可在中部具有中心主體以防止反應物氣體向下穿過細長導管之中部。中心主體可為圓錐形或角錐形。中心主體通常經定位以與混合容器之中心管線至少部分地重疊。中心主體藉由拒絕穿過混合容器之中部之流動來有利地改良混合並迫使三元氣體混合物接觸自內壁延伸之凸耳。當防止氣體穿過混合容器之中部時，可改良每一靜式混合區中之三元氣體混合物之混合。In one embodiment, the rectifier can have a plurality of radial plates joined in the middle. Some rectifiers may have a central body in the middle to prevent reactant gases from passing down the middle of the elongated conduit. The center body can be conical or pyramidal. The center body is typically positioned to at least partially overlap the centerline of the mixing vessel. The central body advantageously improves mixing by rejecting flow through the middle of the mixing vessel and forces the ternary gas mixture into contact with the lugs extending from the inner wall. The mixing of the ternary gas mixture in each of the static mixing zones can be improved when gas is prevented from passing through the middle of the mixing vessel.

緊急壓力釋放調控器128(例如破裂盤)可安裝在混合容器104之排氣管線160中。壓力釋放調控器128限制細長導管130中之壓力且因此限制於第一靜式混合區136與觸媒床(未顯示)之間所含之總質量及位能，由此降低在不利操作條件下爆燃之影響或***之風險及影響。在一個實施例中，壓力釋放調控器128具有混合容器104之110%至115%操作壓力之壓力釋放設定點。An emergency pressure release regulator 128 (eg, a rupture disk) can be installed in the exhaust line 160 of the mixing vessel 104. The pressure release regulator 128 limits the pressure in the elongated conduit 130 and is thus limited to the total mass and potential energy contained between the first static mixing zone 136 and the catalyst bed (not shown), thereby reducing under adverse operating conditions. The impact of explosion or the risk and impact of an explosion. In one embodiment, the pressure release regulator 128 has a pressure relief set point for the 110% to 115% operating pressure of the mixing vessel 104.

當壓力釋放調控器128支撐於第一靜式混合區136遠端上以與可延伸至堆疊162之排氣管線160連通時，獲得良好結果。因此，在混合容器104中存在過量壓力聚集時，壓力釋放調控器128打開且經加熱氣體自反應容器106及混合容器104排出。可使用氮吹掃流來吹掃穿過壓力釋放調控器128之蒸氣體積。Good results are obtained when the pressure release regulator 128 is supported on the distal end of the first static mixing zone 136 to communicate with the exhaust line 160 that can extend to the stack 162. Therefore, when there is excessive pressure build-up in the mixing vessel 104, the pressure release regulator 128 is opened and discharged from the reaction vessel 106 and the mixing vessel 104 via the heated gas. A nitrogen purge stream can be used to purge the vapor volume through the pressure release regulator 128.

在製造HCN時，反應物氣體各自分別經由適宜之進料準備系統170、172及174處理，如圖5中所示。各別反應物氣體之來源可經由業內已知之任一適宜遞送系統(例如管線、卡車、船或軌道及諸如此類)遞送至每一各別進料準備系統。In the manufacture of HCN, the reactant gases are each treated separately via suitable feed preparation systems 170, 172, and 174, as shown in FIG. The source of the individual reactant gases can be delivered to each individual feed preparation system via any suitable delivery system known in the art, such as lines, trucks, boats or rails, and the like.

如圖5中所示，含氧來源176可自氧進料準備系統170供應，該氧進料準備系統包括用以調控引入至該方法中之含氧來源176之壓力之裝備，及用以自未過濾之含氧來源176去除細粒子之過濾器。增加含氧來源176之氧含量可有利於增加反應產率及減小處理裝備之大小。增加空氣之氧含量亦增加通常在空氣中可燃之物質之可燃性。進料流中夾帶之金屬粒子(例如鐵或鋼)及/或其他污染物及副產物若不去除，則可引起氧管路火災。可使用任一適宜機制自未過濾之含氧來源176去除夾帶之金屬粒子及其他污染物，例如，過濾、旋風分離器、聚結器、除濕器及除霧器。當含氧進料氣體之來源需要壓縮時，使用熟習此項技術者已知之無油壓縮器及密封設計亦可減小污染。對於富集氧之空氣而言，可能需要壓縮器。As shown in FIG. 5, the oxygen-containing source 176 can be supplied from an oxygen feed preparation system 170 that includes equipment for regulating the pressure of the oxygen-containing source 176 introduced into the method, and for The unfiltered oxygen-containing source 176 removes the filter of fine particles. Increasing the oxygen content of the oxygen-containing source 176 can be beneficial to increase the reaction yield and reduce the size of the processing equipment. Increasing the oxygen content of the air also increases the flammability of materials that are normally flammable in air. If the metal particles (such as iron or steel) and/or other contaminants and by-products entrained in the feed stream are not removed, it can cause an oxygen line fire. The entrained metal particles and other contaminants can be removed from the unfiltered oxygen containing source 176 using any suitable mechanism, such as filtration, cyclone separators, coalescers, dehumidifiers, and mist eliminators. When the source of the oxygen-containing feed gas requires compression, the use of oil-free compressors and seal designs known to those skilled in the art can also reduce contamination. For oxygen enriched air, a compressor may be required.

本文所用術語「空氣」係指組成與取自通常在地面高度之大氣之氣體之天然組成大致相同的氣體混合物。在一些實例中，空氣取自周圍環境。空氣之組成包括約78vol.%氮、約21vol.%氧、約1vol.%氬及約0.04vol.%二氧化碳以及少量其他氣體。As used herein, the term "air" refers to a gas mixture that is substantially identical in composition to the natural composition of a gas taken from the atmosphere at ambient altitude. In some instances, air is taken from the surrounding environment. The composition of the air includes about 78 vol.% nitrogen, about 21 vol.% oxygen, about 1 vol.% argon, and about 0.04 vol.% carbon dioxide, and a small amount of other gases.

本文所用術語「富集氧之空氣」係指組成包含超過存於空氣中之氧的氣體混合物。富集氧之空氣之組成包括大於21vol.%之氧、小於78vol.%之氮、小於1vol.%之氬及小於0.04vol.%之二氧化碳。在一些實施例中，富集氧之空氣包含至少28vol.%氧，例如，至少80vol.%氧、至少95vol.%氧或至少99vol.%氧。As used herein, the term "enriched air" means a composition comprising a gas mixture that exceeds the oxygen present in the air. The composition of the oxygen-enriched air includes greater than 21 vol.% oxygen, less than 78 vol.% nitrogen, less than 1 vol.% argon, and less than 0.04 vol.% carbon dioxide. In some embodiments, the oxygen-enriched air comprises at least 28 vol.% oxygen, for example, at least 80 vol.% oxygen, at least 95 vol.% oxygen, or at least 99 vol.% oxygen.

在含氧來源176中使用高氧濃度(即，低濃度之惰性物質，例如氮)提供降低原本為處理大量惰性氮所需之下游裝備之大小及操作成本之機會。在一個實施例中，含氧氣體包含大於21vol.%之氧，例如大於28vol.%之氧、大於80vol.%、大於90vol.%、大於95vol.%或大於99vol.%之氧。在本文中為清楚起見，每當使用術語「富集氧之空氣」時，該術語皆意欲涵蓋大於21vol.%直至且包括100vol.%(即，純氧)之氧含量。每當使用術語「含氧氣體進料流」時，該術語皆意欲涵蓋21vol.%直至且包括100vol.%(即，純氧)之氧含量。The use of high oxygen concentrations (i.e., low concentrations of inert materials, such as nitrogen) in the oxygen-containing source 176 provides an opportunity to reduce the size and operating cost of the downstream equipment that would otherwise be required to handle large amounts of inert nitrogen. In one embodiment, the oxygen containing gas comprises greater than 21 vol.% oxygen, such as greater than 28 vol.% oxygen, greater than 80 vol.%, greater than 90 vol.%, greater than 95 vol.%, or greater than 99 vol.% oxygen. For the sake of clarity herein, the term is intended to encompass greater than 21 vol.% up to and including 100 vol.% (ie, pure oxygen) oxygen content whenever the term "oxygen enriched air" is used. Whenever the term "oxygen-containing gas feed stream" is used, the term is intended to cover 21 vol.% up to and including the oxygen content of 100 vol.% (ie, pure oxygen).

當含氧來源176之氧含量增加時，可更小心地控制含甲烷來源178之純度。如熟習此項技術者應瞭解，甲烷之來源可變且可自可再生來源(例如垃圾、農場、來自發酵或化石燃料(例如天然氣)之生物氣體、油附隨氣體、煤氣及氣體水合物)獲得，如下文中進一步闡述：VN Parmon,「Source of Methane for Sustainable Development」，第273-284頁；及Derouane編輯Sustainable Strategies for the Upgrading of Natural Gas：Fundamentals,Challenges,and Opportunities(2003)。出於本實用新型之目的，含甲烷來源178之甲烷純度及一致組成非常重要。甲烷可以純化狀態、以半純化狀態或以不純狀態遞送至HCN合成 系統100。The purity of the methane-containing source 178 can be more carefully controlled as the oxygen content of the oxygen-containing source 176 is increased. Those skilled in the art should appreciate that methane sources are variable and can be derived from renewable sources (eg, garbage, farms, biogas from fermentation or fossil fuels (eg, natural gas), oil-associated gases, gas, and gas hydrates). Obtained, as further explained below: VN Parmon, "Source of Methane for Sustainable Development", pp. 273-284; and Derouane ed. Sustainable Strategies for the Upgrading of Natural Gas: Fundamentals, Challenges, and Opportunities (2003). For the purposes of the present invention, the methane purity and uniform composition of the methane-containing source 178 is very important. Methane can be purified, delivered to HCN synthesis in a semi-purified state or in an impure state System 100.

例如，天然氣係甲烷之不純狀態。亦即，天然氣係實質上含甲烷之氣體，其可用於提供在本實用新型方法中製造之HCN之碳元素。然而，除甲烷以外，天然氣亦可能含有污染物，例如硫化氫、二氧化碳、氮、水及較高分子量烴，例如乙烷、丙烷、丁烷、戊烷等，所有該等污染物在存在時皆對HCN之製造有害。天然氣組成可隨來源而顯著變化。由管線提供之天然氣之組成亦可隨時間且甚至在短時間間隔內顯著改變，此乃因來源係承接自管線並自管線引出。此組成變動導致難以維持最佳且穩定之處理性能。當經由含氧來源176之氧富集降低惰性物質負載時，HCN合成方法對於該等變動之敏感性變得更嚴重。For example, natural gas is an impure state of methane. That is, natural gas is a gas containing substantially methane which can be used to provide the carbon elements of HCN produced in the process of the present invention. However, in addition to methane, natural gas may also contain contaminants such as hydrogen sulfide, carbon dioxide, nitrogen, water and higher molecular weight hydrocarbons such as ethane, propane, butane, pentane, etc., all of which are present when present. Harmful to the manufacture of HCN. Natural gas composition can vary significantly from source to source. The composition of the natural gas provided by the pipeline can also vary significantly over time and even over short intervals, since the source is taken from the pipeline and taken from the pipeline. This compositional variation makes it difficult to maintain optimal and stable processing performance. The sensitivity of the HCN synthesis process to these changes becomes more severe when the inerts loading is reduced via oxygen enrichment of the oxygen-containing source 176.

參考圖5，含甲烷來源178可自甲烷進料準備系統172供應，該甲烷進料準備系統包括用於以下目的之裝備：濃縮甲烷，自天然氣去除較高分子量烴、二氧化碳、硫化氫及水，並過濾天然氣以去除細粒子。例如，天然氣之純化提供甲烷高度濃縮且組成及燃料值之可變性顯著降低之含甲烷氣體進料流110。與使用未純化之含甲烷氣體進料流相比，經純化含甲烷氣體110在與含氧氣體108及含氨氣體112混合時，在HCN合成期間提供以較高預測性反應之三元氣體混合物。含甲烷氣體之更一致之純化及控制穩定製程並允許測定及控制甲烷/氧及氨/氧之最佳莫耳比，此進而產生HCN之較高產率。Referring to Figure 5, a methane-containing source 178 can be supplied from a methane feed preparation system 172 that includes equipment for the purpose of concentrating methane, removing higher molecular weight hydrocarbons, carbon dioxide, hydrogen sulfide, and water from natural gas. The natural gas is filtered to remove fine particles. For example, purification of natural gas provides a methane-containing gas feed stream 110 that is highly concentrated in methane and that has significantly reduced composition and fuel value variability. The purified methane-containing gas 110, when mixed with the oxygen-containing gas 108 and the ammonia-containing gas 112, provides a ternary gas mixture with a higher predictive response during HCN synthesis, as compared to the use of an unpurified methane-containing gas feed stream. . A more consistent purification and control stabilization process for methane-containing gases allows for the determination and control of the optimal molar ratio of methane/oxygen and ammonia/oxygen, which in turn produces higher yields of HCN.

使用經純化天然氣獲得含甲烷氣體進料流110(即，含實質上純淨之甲烷者)以產生HCN亦增加觸媒壽命及HCN之產率。具體而言，使用含實質上純淨之甲烷之氣體110：(1)降低諸如硫、CO₂ 及H₂ O等雜質之濃度，該等雜質具有有害下游效應或不具有製程益處；(2)將剩餘組成穩定於一致水準，從而(a)允許將下游HCN合成最佳化及(b)藉由緩解HCN合成步驟之大的溫度偏差使得能夠使用含高度富集之氧 或純氧之氣體，該等偏差通常與高級烴含量變動有關且對最佳產率及可操作性有害(例如損壞觸媒、互鎖及損失可操作時間)，及(3)減少高級烴(即，C₂ 及高級烴)以使合成反應中之高級腈(例如乙腈、丙烯腈及丙腈)之形成及去除腈期間HCN之相關產率損失最小化。The use of purified natural gas to obtain a methane-containing gas feed stream 110 (i.e., containing substantially pure methane) to produce HCN also increases catalyst life and HCN yield. Specifically, a gas containing substantially pure methane is used 110: (1) reducing the concentration of impurities such as sulfur, CO ₂ and H ₂ O, which have harmful downstream effects or have no process benefits; (2) The remaining composition is stable to a consistent level such that (a) allows optimization of downstream HCN synthesis and (b) enables the use of highly enriched oxygen or pure oxygen gas by mitigating large temperature deviations of the HCN synthesis step, Equal deviations are usually associated with higher hydrocarbon content fluctuations and are detrimental to optimum yield and operability (eg, damage to catalysts, interlocks, and loss of operational time), and (3) reduction of higher hydrocarbons (ie, C ₂ and higher hydrocarbons) To minimize the associated yield loss of HCN during the formation of the nitrile (eg, acetonitrile, acrylonitrile, and propionitrile) in the synthesis reaction and removal of the nitrile.

另外，使用含實質上純淨之甲烷之氣體110(1)消除或最小化原料之可變性(即，其穩定碳及氫含量以及燃燒值)且由此穩定整個HCN合成系統100，從而允許測定及控制用於穩定操作之最佳甲烷對氧及氨對氧莫耳比及最有效之HCN產率；(2)消除或最小化相關溫度峰值及所致觸媒損壞；及(3)使二氧化碳最小化，由此降低在氨回收製程及來自氨回收製程之回收或再循環氨流中發現之二氧化碳的量，該氨回收製程可在反應器容器106下游。消除或最小化此一氨回收製程及回收或再循環氨流中之二氧化碳降低胺基甲酸鹽形成之可能性，該形成引起管道及其他處理裝置之堵塞及/或結垢。In addition, the use of substantially pure methane gas 110(1) eliminates or minimizes the variability of the feedstock (i.e., its stable carbon and hydrogen content and combustion value) and thereby stabilizes the entire HCN synthesis system 100, allowing for determination and Controls the optimum methane to oxygen and ammonia to oxygen molar ratio for stable operation and the most effective HCN yield; (2) eliminates or minimizes the associated temperature peaks and causing catalyst damage; and (3) minimizes carbon dioxide Thereby, thereby reducing the amount of carbon dioxide found in the ammonia recovery process and the recovered or recycled ammonia stream from the ammonia recovery process, which can be downstream of the reactor vessel 106. Eliminating or minimizing this ammonia recovery process and recovering or recycling carbon dioxide in the ammonia stream reduces the likelihood of urethane formation, which causes blockage and/or fouling of pipes and other processing equipment.

在混合容器104中與含氧氣體108及含甲烷氣體110混合之前，經由新鮮氨進料準備系統174處理「補充」或新鮮之氨流180。通常，新鮮氨進料準備系統174之主要功能係在將含氨氣體112引入至混合容器104中之前自新鮮氨流180去除諸如水、油及鐵等污染物。含氨氣體112之污染物可縮短觸媒壽命，從而導致差反應產率。新鮮氨進料準備系統174可包括處理裝備，例如氣化器及過濾器，用於「補充」或新鮮之氨流180以提供經處理新鮮氨流112。The "supplemented" or fresh ammonia stream 180 is processed via the fresh ammonia feed preparation system 174 prior to mixing with the oxygen-containing gas 108 and the methane-containing gas 110 in the mixing vessel 104. Typically, the primary function of the fresh ammonia feed preparation system 174 is to remove contaminants such as water, oil, and iron from the fresh ammonia stream 180 prior to introducing the ammonia containing gas 112 into the mixing vessel 104. The contaminants of the ammonia-containing gas 112 can shorten the life of the catalyst, resulting in poor reaction yield. The fresh ammonia feed preparation system 174 can include processing equipment, such as a gasifier and filter, for "supplementing" or fresh ammonia stream 180 to provide a treated fresh ammonia stream 112.

例如，市售液氨可在氣化器中處理以提供部分純化之氨蒸氣流及含有水、鐵、鐵微粒及其他不揮發雜質之第一液體流。可使用氨分離器(例如除氨器(ammonia demister))來分離存於部分純化之氨蒸氣流中之雜質及任一液體以產生經處理新鮮氨流(實質上純淨之氨蒸氣流)及含有存於部分純化之氨蒸氣流中之夾帶之雜質及任一液氨的第二液體流。For example, commercially available liquid ammonia can be processed in a gasifier to provide a partially purified ammonia vapor stream and a first liquid stream containing water, iron, iron particles, and other non-volatile impurities. An ammonia separator (eg, an ammonia demister) can be used to separate the impurities and any liquid present in the partially purified ammonia vapor stream to produce a treated fresh ammonia stream (substantially pure ammonia vapor stream) and contain An entrained impurity present in the partially purified ammonia vapor stream and a second liquid stream of any liquid ammonia.

在一個實施例中，將含有水、鐵、鐵微粒及其他不揮發雜質之第一液體流進給至第二氣化器，其中將一部分液體流氣化以產生部分純化之第二氨蒸氣流及含有水、鐵、鐵微粒及其他不揮發雜質之更高濃度之第二液體流，該第二液體流可作為吹掃或廢物流經進一步處理。可將部分純化之第二氨蒸氣流進給至氨分離器。在另一實施例中，將含有水、鐵、鐵微粒及其他不揮發雜質之更高濃度之第二液體流進給至第三氣化器以進一步降低氨含量，然後作為吹掃或廢物流處理。In one embodiment, a first liquid stream comprising water, iron, iron particles, and other non-volatile impurities is fed to a second gasifier, wherein a portion of the liquid stream is gasified to produce a partially purified second ammonia vapor stream and A higher concentration second liquid stream containing water, iron, iron particles, and other non-volatile impurities that can be further treated as a purge or waste stream. A partially purified second ammonia vapor stream can be fed to the ammonia separator. In another embodiment, a second liquid stream containing a higher concentration of water, iron, iron particles, and other non-volatile impurities is fed to the third gasifier to further reduce the ammonia content and then act as a purge or waste stream. deal with.

氣化器中之泡沫形成可限制氨之氣化速率並降低所產生氨蒸氣之純度。通常藉由將消泡劑直接引入至氣化器中或引入至氣化器進料流中延遲泡沫形成。消泡劑屬於能夠消除或顯著降低液體及/或液體與氣體之混合物形成泡沫之能力的一大類聚合材料及溶液。消泡劑藉由降低溶液表面張力來抑制攪拌液體中形成氣泡。消泡劑之實例包括聚矽氧、有機磷酸酯及醇。在一個實施例中，將足量消泡劑添加至新鮮氨流以在新鮮氨流180中維持在2mpm至20mpm範圍內之消泡劑濃度。消泡劑之非限制實例係由Unichem of Hobbs,NM製造之UNICHEM 7923。Foam formation in the gasifier limits the rate of ammonia gasification and reduces the purity of the ammonia vapor produced. The foam formation is typically retarded by introducing the antifoaming agent directly into the gasifier or into the gasifier feed stream. Defoamers are a large class of polymeric materials and solutions that are capable of eliminating or significantly reducing the ability of liquids and/or mixtures of liquids and gases to form foams. The antifoaming agent suppresses the formation of bubbles in the agitating liquid by reducing the surface tension of the solution. Examples of antifoaming agents include polyoxyxides, organic phosphates, and alcohols. In one embodiment, a sufficient amount of antifoaming agent is added to the fresh ammonia stream to maintain an antifoam concentration in the fresh ammonia stream 180 in the range of 2 mpm to 20 mpm. A non-limiting example of an antifoaming agent is UNICHEM 7923 manufactured by Unichem of Hobbs, NM.

新鮮氨進料準備系統174亦可提供有過濾系統，用於自經處理新鮮氨流180去除微粒以防止反應器容器106中之觸媒中毒。過濾系統可為單個過濾器或複數個過濾器。The fresh ammonia feed preparation system 174 may also be provided with a filtration system for removing particulates from the treated fresh ammonia stream 180 to prevent catalyst poisoning in the reactor vessel 106. The filtration system can be a single filter or a plurality of filters.

亦在氨回收區段182中作為再循環氨流124分離並回收氨，該再循環氨流可在再循環氨進料準備系統182中單獨地處理。再循環氨進料準備系統182可包括用於過濾及加熱再循環氨流182以產生經處理再循環氨流112之處理裝備。加熱攜載再循環氨流124之管道有助於防止在管道壁內部上沈積。經處理再循環氨流124可與經處理新鮮氨流112組合。Ammonia is also separated and recovered as a recycle ammonia stream 124 in the ammonia recovery section 182, which may be separately processed in the recycle ammonia feed preparation system 182. The recycle ammonia feed preparation system 182 can include processing equipment for filtering and heating the recycle ammonia stream 182 to produce a treated recycle ammonia stream 112. Heating the conduit carrying the recycle ammonia stream 124 helps prevent deposition on the interior of the conduit wall. The treated recycle ammonia stream 124 can be combined with the treated fresh ammonia stream 112.

發生於反應容器106中之HCN合成反應係在1000℃至1250℃範圍中之反應溫度及100kPa至400kPa範圍中之壓力下進行之吸熱反應。觸媒通常為金屬絲網鉑/銠合金或金屬絲網鉑/銥合金。在一個態樣中，85/15鉑/銠合金可在平坦觸媒支撐件上使用。90/10鉑/銠合金可與相比於平坦觸媒支撐件具有增加之表面積之波紋支撐件一起使用。可使用其他觸媒組合物且包括(但不限於)鉑族金屬、鉑族金屬合金、受支撐之鉑族金屬或受支撐之鉑族金屬合金。亦可使用其他觸媒組態且包括(但不限於)多孔結構、絲網、小片、團塊、單塊、發泡體、浸漬塗層及洗滌塗層。在反應容器中將觸媒加載至在0.7至1.4(g觸媒)/(kg進料氣體/hr)範圍中之觸媒負載。使三元氣體混合物與反應容器中之觸媒接觸以提供含有氰化氫之反應產物，例如，粗製氰化氫產物。The HCN synthesis reaction occurring in the reaction vessel 106 is an endothermic reaction carried out at a reaction temperature in the range of 1000 ° C to 1250 ° C and a pressure in the range of 100 kPa to 400 kPa. The catalyst is usually a wire mesh platinum/rhodium alloy or a wire mesh platinum/rhodium alloy. In one aspect, the 85/15 platinum/rhodium alloy can be used on a flat catalyst support. The 90/10 platinum/rhodium alloy can be used with a corrugated support having an increased surface area compared to a flat catalyst support. Other catalyst compositions can be used and include, but are not limited to, platinum group metals, platinum group metal alloys, supported platinum group metals, or supported platinum group metal alloys. Other catalyst configurations can also be used and include, but are not limited to, porous structures, screens, tablets, agglomerates, monoliths, foams, dip coatings, and washcoats. The catalyst was loaded in the reaction vessel to a catalyst loading in the range of 0.7 to 1.4 (g catalyst) / (kg feed gas / hr). The ternary gas mixture is contacted with a catalyst in a reaction vessel to provide a reaction product comprising hydrogen cyanide, for example, a crude hydrogen cyanide product.

在一個實施例中，能夠將經加熱三元氣體轉化成HCN之觸媒床係由支撐件總成支撐，該支撐件總成係由能夠減少矽化鉑形成並將反應器之管道之抗熱應力性及結垢最佳化的材料形成。觸媒支撐件總成實質上毗鄰觸媒床佈置。消焰器在空間上佈置於觸媒床上方以在二者之間提供間隔。消焰器淬滅因內反應室內之回火所致之任一上游燃燒。陶瓷發泡體沿界定內反應室之外殼之至少一部分內壁及觸媒佈置。當關斷反應器時，陶瓷發泡體使得因觸媒收縮所致之進料氣體繞行最小化。佈置於觸媒床上方之陶瓷發泡體發揮功能以使三元氣體體積最小化，降低壓力降並淬滅反應器操作期間形成之自由基。套管佈置在外殼之每一出口中且在觸媒床與廢熱鍋爐之上部之間提供流體連通。具有實質上呈窩組態以降低跨越底部支撐件(undersupport)之壓力降的底部支撐件實質上毗鄰觸媒支撐件之下部表面佈置。In one embodiment, the catalyst bed capable of converting the heated ternary gas to HCN is supported by a support assembly that is resistant to thermal stress by the formation of deuterated platinum and the reactor tubes. Sex and scale optimized material formation. The catalyst support assembly is disposed substantially adjacent to the catalyst bed. The flame arrestor is spatially disposed on the bed of the catalyst to provide a space therebetween. The flame arrester quenches any upstream combustion due to tempering within the inner reaction chamber. The ceramic foam is disposed along at least a portion of the inner wall of the outer casing defining the inner reaction chamber and the catalyst. When the reactor is shut down, the ceramic foam minimizes feed gas bypass due to catalyst shrinkage. The ceramic foam disposed on the bed of the catalyst functions to minimize the volume of the ternary gas, reduce the pressure drop and quench the free radicals formed during operation of the reactor. A sleeve is disposed in each outlet of the outer casing and provides fluid communication between the catalyst bed and the upper portion of the waste heat boiler. A bottom support having a substantially nested configuration to reduce the pressure drop across the bottom undersupport is disposed substantially adjacent the lower surface of the catalyst support.

消焰器可由業內已知之任一適宜材料製得，只要消焰器能夠實施任一以下功能即可：(1)在來自觸媒床之回火事件中淬滅上游燃 燒；(2)用作流動分佈器以確保跨越觸媒床之均勻流動及消除可能回火之低氣體速度區域；(3)用作空間填充物以減小反應器中反應物之體積，從而使其中之位能最小化；及/或在熱觸媒床與在反應器上部中之三元氣體混合物之間提供熱絕緣。所用消焰器可由以下材料製造：(1)具有最小催化效應，(2)在用於製造HCN之溫度下熱穩定，(3)不會分解氨且(4)不會起始氧化。可用於構築消焰器之材料之實例係任一適宜形式之陶瓷耐火材料，包括(但不限於)：陶瓷丸、陶瓷發泡體、陶瓷纖維毯、氧化鋁-矽石耐火非織造毯、其組合及諸如此類。適宜陶瓷耐火材料組合物之非限制性實例包括90wt%氧化鋁及95wt%氧化鋁。另外，當使用丸作為構築消焰器中之材料時，丸之大小及形狀可有所變化，前提為用於消焰器中之丸能夠實施上文所提及之功能。The flame arrester can be made of any suitable material known in the art as long as the flame arrester can perform any of the following functions: (1) quenching the upstream combustion in a tempering event from the catalyst bed (2) used as a flow distributor to ensure uniform flow across the catalyst bed and to eliminate areas of low gas velocity that may temper; (3) as a space filler to reduce the volume of reactants in the reactor, thereby Minimizing the position therein; and/or providing thermal insulation between the thermal catalyst bed and the ternary gas mixture in the upper portion of the reactor. The flame arrester used can be made of (1) having a minimal catalytic effect, (2) being thermally stable at the temperature used to make the HCN, (3) not decomposing ammonia, and (4) not starting oxidation. Examples of materials that can be used to construct the flame arrester are any suitable form of ceramic refractory material, including but not limited to: ceramic pellets, ceramic foams, ceramic fiber blankets, alumina-xorite refractory nonwoven carpets, Combinations and the like. Non-limiting examples of suitable ceramic refractory compositions include 90 wt% alumina and 95 wt% alumina. In addition, when pellets are used as the material in the construction of the flame arrester, the size and shape of the pellets may vary, provided that the pellets used in the flame arrester are capable of performing the functions mentioned above.

應注意，使用消焰器實質上降低經加熱三元氣體混合物經由自爆燃轉變成***而變得可***之可能性。例如，若測定三元氣體混合物在304kPa及100℃下之火焰速度係1.2m/sec，則預熱三元氣體混合物穿過消焰器(例如，含有3/8-英吋(9.5mm)直徑丸之丸床)之表觀速度應實質上大於1.2m/sec，由此防止火焰前進穿過丸床。儘管用於丸床中之丸之大小可廣泛地變化，但丸之直徑大小通常為1/8英吋至1/2英吋(3mm至13mm)。It should be noted that the use of a flame arrester substantially reduces the likelihood that the heated ternary gas mixture will become explosive by transitioning from a deflagration to an explosion. For example, if the flame velocity of the ternary gas mixture at 304 kPa and 100 ° C is 1.2 m/sec, the preheated ternary gas mixture passes through the flame arrester (for example, contains a 3/8-inch (9.5 mm) diameter. The apparent velocity of the pill's pill bed should be substantially greater than 1.2 m/sec, thereby preventing the flame from advancing through the pill bed. Although the size of the pellets used in the pill bed can vary widely, the diameter of the pellets is typically from 1/8 inch to 1/2 inch (3 mm to 13 mm).

選擇消焰器之特性(例如丸床之深度)以平衡三元氣體混合物之增加之速度及消焰器與觸媒床之間之減小之開放空間與預熱三元氣體混合物跨越消焰器之壓力降，由此使爆燃中可能釋放之能量最小化，而不會實質上損害向混合容器中之壓力釋放器件之回流。在一個實施例中，丸床之深度係至少0.4m。Selecting the characteristics of the flame arrester (eg depth of the pill bed) to balance the increased rate of the ternary gas mixture and the reduced open space between the flame arrester and the catalytic bed and the preheated ternary gas mixture across the flame arrester The pressure drop thereby minimizes the energy that may be released during detonation without substantially compromising the backflow to the pressure relief device in the mixing vessel. In one embodiment, the depth of the pill bed is at least 0.4 m.

根據上文闡述，可明瞭本實用新型非常適於實施目標及獲得本文所提及之優點以及目前所提供揭示內容中固有之優點。儘管已出於 本實用新型之目的闡述本實用新型之較佳實施例，但應理解，可做出熟習此項技術者可容易地想到且在本實用新型精神內達成之變化。In view of the foregoing, it will be apparent that the present invention is well adapted to the embodiments and the advantages of the present invention and the advantages of the present disclosure. Even though it is out of The present invention has been described with reference to the preferred embodiments of the present invention, but it should be understood that modifications may be readily made by those skilled in the art.

可藉由參考以下實例來進一步理解本實用新型。The invention can be further understood by reference to the following examples.

實例1Example 1

如圖2中所圖解說明，將複數個具有l-形支撐件之凸耳穿過細長導管上之相應不連續狹縫***以形成第一靜式混合區中之一列四個凸耳及第二靜式混合區中之三列四個凸耳，從而形成混合容器。第一靜式混合區定位於含有甲烷及氨之氣體之入口埠之間且第二靜式混合區定位於含氧氣體之入口埠與出口埠之間。除第二靜式混合區中之底部列(其中凸耳具有25°±1°之角度)外，每一凸耳皆具有30°±1°之角度。每一凸耳具有約77.5cm² 之表面積。將每一凸耳自細長導管內部***且焊接至細長導管之外表面。來自一列之凸耳與毗鄰列對準且來自第一混合區之凸耳與來自第二混合區之凸耳對準。凸耳之傾斜度係0°至3°。此形成實例性混合容器以產生三元氣體混合物。As illustrated in Figure 2, a plurality of lugs having l-shaped supports are inserted through respective discontinuous slits in the elongate conduit to form one of the four lugs and the second in the first static mixing zone. Three columns of four lugs in the static mixing zone form a mixing vessel. The first static mixing zone is positioned between the inlet ports of the gas containing methane and ammonia and the second static mixing zone is positioned between the inlet and outlet ports of the oxygen-containing gas. Each lug has an angle of 30° ± 1° except for the bottom row in the second static mixing zone (where the lugs have an angle of 25° ± 1°). Each lug has a surface area of about 77.5 cm ² . Each lug is inserted from the interior of the elongate catheter and welded to the outer surface of the elongate catheter. The lugs from one row are aligned with the adjacent columns and the lugs from the first mixing zone are aligned with the lugs from the second mixing zone. The inclination of the lugs is 0° to 3°. This forms an exemplary mixing vessel to produce a ternary gas mixture.

混合容器亦具有安裝在排氣管線中之破裂盤。具有四個徑向板及一個中心主體之整流器定位於第一靜式混合區上游。具有四個徑向板及一個中心主體之第二整流器定位於第二靜式混合區上游及含氧氣體入口下游。The mixing vessel also has a rupture disk mounted in the vent line. A rectifier having four radial plates and a central body is positioned upstream of the first static mixing zone. A second rectifier having four radial plates and a central body is positioned upstream of the second static mixing zone and downstream of the oxygen-containing gas inlet.

比較實例AComparison example A

比較靜式混合器與實例1中之實例性混合容器具有相同凸耳數量及列組態，只是凸耳焊接至細長導管之內表面。比較靜式混合器無不連續狹縫。凸耳之傾斜度大於8°，此導致靜式混合器中之旋轉增加及差的混合。The comparative static mixer has the same number of lugs and column configuration as the example mixing container of Example 1, except that the lugs are welded to the inner surface of the elongated conduit. The static mixer has no discontinuous slits. The inclination of the lugs is greater than 8°, which results in increased rotation and poor mixing in the static mixer.

實例2Example 2

將含甲烷及氨之反應物氣體進給至第一靜式混合區且將含氧反應物氣體進給至第二靜式混合區。以1.2之甲烷對氧之比率及1：1.5之 氨對氧之比率進給反應物氣體，以產生含有約28.5vol.%氧之三元氣體混合物。然後將三元氣體混合物進給至在平坦觸媒床上具有85/15鉑/銠觸媒之反應器容器。反應溫度係1000℃至1200℃。使用實例1之實例性混合容器，三元氣體混合物將具有跨越觸媒床小於0.1之變動係數(CoV)。靜式混合器之操作壓力可在130kPa至400kPa之間變化。另外，實例1之實例性混合容器內之壓力降小於35kPa。The reactant gas containing methane and ammonia is fed to the first static mixing zone and the oxygen-containing reactant gas is fed to the second static mixing zone. The ratio of methane to oxygen of 1.2 and 1:1.5 The ratio of ammonia to oxygen is fed to the reactant gas to produce a ternary gas mixture containing about 28.5 vol.% oxygen. The ternary gas mixture was then fed to a reactor vessel having 85/15 platinum/ruthenium catalyst on a flat catalyst bed. The reaction temperature is from 1000 ° C to 1200 ° C. Using the exemplary mixing vessel of Example 1, the ternary gas mixture will have a coefficient of variation (CoV) of less than 0.1 across the catalyst bed. The operating pressure of the static mixer can vary from 130 kPa to 400 kPa. Additionally, the pressure drop within the exemplary mixing vessel of Example 1 was less than 35 kPa.

實例3Example 3

使用實例1之實例性混合容器且在與實例2類似之反應條件下，觸媒床具有跨越床15℃至25℃之床溫度變動。此床溫度變動將指示充分混合之三元氣體混合物。相反，在與實例2類似之反應條件下，比較A之靜式混合器產生將導致跨越床35℃至100℃之床溫度變動之三元氣體混合物。比較A之靜式混合器之差混合可歸因於難以藉由焊接至細長導管之內部對準凸耳。Using the exemplary mixing vessel of Example 1 and under similar reaction conditions as in Example 2, the catalyst bed had bed temperature variations across the bed at 15 °C to 25 °C. This bed temperature change will indicate a well mixed ternary gas mixture. In contrast, under the reaction conditions similar to those of Example 2, the static mixer of Comparative A produced a ternary gas mixture which would result in a bed temperature change across the bed from 35 °C to 100 °C. The poor mixing of the static mixer of Comparative A can be attributed to the difficulty of welding to the inner alignment lugs of the elongated conduit.

實例4Example 4

使用實例1之實例性混合容器且在與實例2類似反應條件下，反應器失衡引起估計大於13MPa之急劇壓力增加，此會衝破破裂盤。實例1之實例性混合容器中之凸耳耐受壓力失衡且不變形。凸耳維持其形狀且傾斜度保持為0°至3°。相反，比較A之靜式混合器之凸耳不能經受壓力失衡且會變形。此需要替換受損凸耳及/或替換混合容器，從而產生製造HCN中之停機時間。Using the exemplary mixing vessel of Example 1 and under similar reaction conditions to Example 2, the reactor imbalance caused an abrupt pressure increase of greater than 13 MPa, which would break the rupture disk. The lugs in the exemplary mixing vessel of Example 1 were pressure tolerant and not deformed. The lugs maintain their shape and the inclination is maintained at 0° to 3°. In contrast, the lugs of the static mixer of Comparative A cannot withstand pressure imbalance and can deform. This necessitates replacement of the damaged lugs and/or replacement of the mixing vessel, resulting in downtime in the manufacture of the HCN.

實例5Example 5

測試實例1之實例性混合容器以測定在***凸耳並焊接後是否有任何含氧氣體、含甲烷氣體或含氨氣體洩漏穿過16個不連續狹縫。將該等氣體進給至混合容器且將混合容器密封並加壓。使用檢測器來測定是否有任何氣體正自混合容器洩漏。預計不會報導洩漏。An exemplary mixing vessel of Example 1 was tested to determine if any oxygen-containing gas, methane-containing gas, or ammonia-containing gas leaked through the 16 discrete slits after insertion of the lugs and welding. The gases are fed to the mixing vessel and the mixing vessel is sealed and pressurized. A detector is used to determine if any gas is leaking from the mixing vessel. It is not expected to report a leak.

實例6Example 6

將複數個具有l-形支撐件之凸耳穿過細長導管上之相應不連續狹縫***以形成靜式混合區中之四列四個凸耳，該靜式混合區定位於含氧氣體之入口埠與出口埠之間。與實例1不同，沒有凸耳定位於含甲烷氣體及含氨氣體之入口埠之間。除底部列(其中凸耳具有25°±1°之角度)外，每一凸耳皆具有30°±1°之角度。每一凸耳具有約77.5cm² 之表面積。自細長導管內部***每一凸耳且自細長導管之外表面焊接。來自一列之凸耳與毗鄰列對準。凸耳之傾斜度係0°至3°。此形成實例性混合容器以產生三元氣體混合物。在與實例2類似之反應條件下，CoV高於實例2，從而指示降低之混合效率。Inserting a plurality of lugs having an l-shaped support member through respective discontinuous slits in the elongated conduit to form four rows of four lugs in the static mixing zone, the static mixing zone being positioned in the oxygen-containing gas Between the entrance 埠 and the exit 埠. Unlike Example 1, no lugs were positioned between the methane-containing gas and the inlet enthalpy of the ammonia-containing gas. Each lug has an angle of 30° ± 1° except for the bottom row (where the lugs have an angle of 25° ± 1°). Each lug has a surface area of about 77.5 cm ² . Each lug is inserted from inside the elongated catheter and welded from the outer surface of the elongated catheter. The lugs from one column are aligned with the adjacent columns. The inclination of the lugs is 0° to 3°. This forms an exemplary mixing vessel to produce a ternary gas mixture. Under the reaction conditions similar to Example 2, the CoV was higher than that of Example 2, indicating a reduced mixing efficiency.

100‧‧‧HCN合成系統100‧‧‧HCN Synthesis System

102‧‧‧反應總成102‧‧‧Reaction assembly

104‧‧‧混合容器104‧‧‧Mixed container

106‧‧‧反應器容器106‧‧‧Reactor vessel

108‧‧‧含氧氣體進料流108‧‧‧Oxygen-containing gas feed stream

110‧‧‧含甲烷氣體進料流110‧‧‧Methane-containing gas feed stream

112‧‧‧含氨氣體進料流112‧‧‧Ammonia-containing gas feed stream

114‧‧‧三元氣體混合物114‧‧‧Ternary gas mixture

116‧‧‧粗製氰化氫產物116‧‧‧ crude hydrogen cyanide product

118‧‧‧觸媒床118‧‧‧Tactile bed

120‧‧‧分佈器板120‧‧‧Distributor board

122‧‧‧氨回收區段122‧‧‧Ammonia recovery section

124‧‧‧管線124‧‧‧ pipeline

126‧‧‧HCN精製區段126‧‧‧HCN refining section

Claims (15)

一種用於製備氰化氫之反應總成，其包含：(a)包含細長導管之混合容器，該細長導管具有位於該細長導管近端之出口，第一入口埠及第二入口埠，其各自用於將至少一種選自由含甲烷氣體、含氨氣體、含氧氣體及其混合物組成之群之反應物氣體引入至該混合容器中，其中該第二入口埠係位於該第一入口埠下游，包含一或多個第一列不連續狹縫之第一靜式混合區，一或多個相應凸耳穿過該等不連續狹縫***且緊固至該細長導管之外表面，且其中該第一靜式混合區毗鄰該第一入口埠，包含一或多個第二列不連續狹縫之第二靜式混合區，一或多個相應凸耳穿過該等不連續狹縫***且緊固至該細長導管之該外表面，且其中該第二靜式混合區毗鄰該第二入口埠，其中每一相應凸耳具有在流動方向上成角度之上游面，其中該等第一及第二靜式混合區提供該至少一種反應物氣體之交叉流混合以產生三元氣體；及(b)反應器容器，其包含反應器入口，該反應器入口操作性地耦合至該出口以接收該三元氣體混合物；及觸媒床，其含有用於產生氰化氫流之觸媒。A reaction assembly for preparing hydrogen cyanide, comprising: (a) a mixing vessel comprising an elongated conduit having an outlet at a proximal end of the elongated conduit, a first inlet port and a second inlet port, each of which And introducing at least one reactant gas selected from the group consisting of a methane-containing gas, an ammonia-containing gas, an oxygen-containing gas, and a mixture thereof, wherein the second inlet system is located downstream of the first inlet port, a first static mixing zone comprising one or more first rows of discontinuous slits through which one or more respective lugs are inserted and secured to an outer surface of the elongated conduit, and wherein a first static mixing zone adjacent the first inlet port, including a second static mixing zone of one or more second rows of discontinuous slits through which one or more corresponding lugs are inserted and Fastened to the outer surface of the elongated conduit, and wherein the second static mixing zone is adjacent to the second inlet bore, wherein each respective lug has an upstream face that is angled in the flow direction, wherein the first and a second static mixing zone providing the at least a cross-flow of reactant gases to produce a ternary gas; and (b) a reactor vessel comprising a reactor inlet operatively coupled to the outlet to receive the ternary gas mixture; and a catalyst A bed containing a catalyst for generating a hydrogen cyanide stream. 如請求項1之反應總成，其中該第一靜式混合區中之列數為1至10且該第二靜式混合區中之該列數為1至10。The reaction assembly of claim 1, wherein the number of columns in the first static mixing zone is from 1 to 10 and the number of columns in the second static mixing zone is from 1 to 10. 如請求項1之反應總成，其中該等第一列及第二列中之每一者含有1至10個該等不連續狹縫。The reaction assembly of claim 1, wherein each of the first and second columns contains from 1 to 10 such discontinuous slits. 如請求項1之反應總成，其中該第二靜式混合區中之列數大於或 等於該第一靜式混合區中之該列數。The reaction assembly of claim 1, wherein the number of columns in the second static mixing zone is greater than or Equal to the number of columns in the first static mixing zone. 如請求項1之反應總成，其中該等相應凸耳與該導管之內壁具有5°至45°之角度。The reaction assembly of claim 1, wherein the respective lugs have an angle of from 5 to 45 with the inner wall of the conduit. 如請求項1之反應總成，其進一步包含一或多個位於該第一靜式混合區上游用於對準該至少一種反應物氣體之流動之整流器，其中該一或多個整流器各自具有中心主體。The reaction assembly of claim 1 further comprising one or more rectifiers upstream of the first static mixing zone for aligning the flow of the at least one reactant gas, wherein the one or more rectifiers each have a center main body. 如請求項1之反應總成，其進一步包含一或多個位於該第二靜式混合區上游用於對準該至少一種反應物氣體之流動之整流器，其中該一或多個整流器各自具有中心主體。The reaction assembly of claim 1, further comprising one or more rectifiers upstream of the second static mixing zone for aligning the flow of the at least one reactant gas, wherein the one or more rectifiers each have a center main body. 如請求項1之反應總成，其中該等不連續狹縫係呈l-形、I-形、T-形、U-形或V-形。The reaction assembly of claim 1, wherein the discontinuous slits are in the form of a 1-shape, an I-shape, a T-shape, a U-shape or a V-shape. 如請求項1之反應總成，其中兩個或更多個第一列之該等不連續狹縫係橫向對準。The reaction assembly of claim 1, wherein the discontinuous slits of the two or more first columns are laterally aligned. 如請求項1之反應總成，其中兩個或更多個第二列之該等不連續狹縫係橫向對準。The reaction assembly of claim 1, wherein the discontinuous slits of the two or more second columns are laterally aligned. 如請求項1之反應總成，其中該細長導管內之該等相應凸耳中之每一者不平行於該流動方向。The reaction assembly of claim 1 wherein each of the respective lugs within the elongated conduit are not parallel to the flow direction. 如請求項1之反應總成，其中該等相應凸耳中之每一者具有角度為30°至90°之後邊緣。The reaction assembly of claim 1, wherein each of the respective lugs has an edge of an angle of 30° to 90°. 如請求項1之反應總成，其中該等相應凸耳中之每一者具有0°至7°之傾斜度。The reaction assembly of claim 1, wherein each of the respective lugs has a slope of 0° to 7°. 如請求項1之反應總成，其中該等相應凸耳中之每一者具有50cm² 至250cm² 之表面積。The requested item of the reaction assembly 1, wherein the that corresponding lugs each having a surface area of 50cm ² of ² to 250cm. 如請求項1之反應總成，其中該等相應凸耳中之每一者包含310SS或316SS。The reaction assembly of claim 1, wherein each of the respective lugs comprises 310SS or 316SS.