TW201441157A

TW201441157A - System and method for recycling in an Andrussow process

Info

Publication number: TW201441157A
Application number: TW102145965A
Authority: TW
Inventors: Stewart Forsyth; Martin J Renner; Aiguo Liu; Brent J Stahlman
Original assignee: Invista Tech Sarl
Priority date: 2012-12-18
Filing date: 2013-12-12
Publication date: 2014-11-01
Also published as: CN110372008A; WO2014099561A1; CN103864109A; HK1198995A1

Abstract

A method and a system for utilizing waste produced during production of hydrogen cyanide are described herein.

Description

在安德盧梭(ANDRUSSOW)法中用於回收之系統及方法 System and method for recycling in the ANDRUSSOW method

相關申請案交叉參考Related application cross reference

本申請案主張2012年12月18日提出申請之標題為「SYSTEM AND METHOD FOR RECYCLING IN AN ANDRUSSOW PROCESS」之美國臨時專利申請案第61/738,895號之優先權益，其揭示內容全部以引用方式併入本文中。 This application claims priority to U.S. Provisional Patent Application Serial No. 61/738,895, filed on Dec. In this article.

本發明係關於自甲烷、氨及氧產生氰化氫(HCN)之安德盧梭(Andrussow)法的回收方案。 This invention relates to a recovery scheme for the Andrussow process for the production of hydrogen cyanide (HCN) from methane, ammonia and oxygen.

安德盧梭法用於經含鉑觸媒自甲烷、氨及氧氣相產生氰化氫(HCN)。將氨、甲烷及氧進給至反應器中並在包含鉑之觸媒存在下加熱至反應溫度。可自天然氣供應甲烷，其可經進一步純化。天然氣中可存在具有兩個碳、三個碳或更多個碳之烴。儘管可使用空氣作為氧來源，但亦可利用富集氧之空氣或未經稀釋之氧(例如，氧安德盧梭法)實施反應。可將含有HCN之反應器廢氣輸送穿過氨吸收處理以去除未反應之氨。此可藉由與磷酸銨溶液、磷酸或硫酸接觸以去除氨來達成。可將產物廢氣自氨吸收器輸送穿過HCN吸收器，在HCN吸收器中可添加冷水以夾帶HCN。可將HCN-水混合物輸送至氰化物汽提塔，在汽提塔中可將HCN與水及其他物質分離。 The Andrussow process is used to produce hydrogen cyanide (HCN) from a methane, ammonia and oxygen phase via a platinum-containing catalyst. Ammonia, methane and oxygen are fed to the reactor and heated to the reaction temperature in the presence of a catalyst comprising platinum. Methane can be supplied from natural gas, which can be further purified. Hydrocarbons having two carbons, three carbons or more may be present in the natural gas. Although air can be used as the source of oxygen, the reaction can also be carried out using oxygen-enriched air or undiluted oxygen (for example, oxygen Andrussow process). The reactor off-gas containing HCN can be passed through an ammonia absorption process to remove unreacted ammonia. This can be achieved by contacting the ammonium phosphate solution, phosphoric acid or sulfuric acid to remove ammonia. The product off-gas can be transported from the ammonia absorber through the HCN absorber where cold water can be added to entrain the HCN. The HCN-water mixture can be passed to a cyanide stripper where HCN can be separated from water and other materials.

安德盧梭法之各個態樣闡述於以下文章中：N.V.Trusov,Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method,Rus.J.of Applied Chemistry，第74卷，第10期，第1693-97頁(2001)；Clean Development Mechanism(CDM)Executive Board,United Nations Framework Convention on Climate Change(UNFCCC),Clean Development Mechanism Project Design Document Form(CDM PDD)，第3版，(2006年7月28日)，其可於http：//cdm.unfccc.int/Reference/PDDs_Forms/PDDs/PDD_form04_v03_2.pdf在線獲得；Gary R.Maxwell等人，Assuring process safety in the transfer of hydrogen cyanide manufacturing technology,J.of Hazardous Materials，第142卷，第677-84頁(2007)；Eric.L.Crump,U.S.Environmental Protection Agency,Office of Air Quality Planning and Standards,Economic Impact Analysis For the Proposed Cyanide Manufacturing NESHAP(2000年5月)，其可於http：//nepis.epa.gov/Exe/ZyPDF.cgi？Dockey=P100AHG1.PDF在線獲得，該等文章之揭示內容如同在本文中再現一般以引用方式併入本文中。 The various aspects of the Andrussow process are described in the following article: NVTrusov, Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method , Rus. J. of Applied Chemistry, Vol. 74, No. 10, Page 1693-97 (2001); Clean Development Mechanism (CDM) Executive Board, United Nations Framework Convention on Climate Change (UNFCCC), Clean Development Mechanism Project Design Document Form (CDM PDD) , 3rd edition, (July 2006) 28th), which is available online at http://cdm.unfccc.int/Reference/PDDs_Forms/PDDs/PDD_form04_v03_2.pdf ; Gary R. Maxwell et al., Assuring process safety in the transfer of hydrogen cyanide manufacturing technology , J. Of Hazardous Materials, Vol. 142, pp. 677-84 (2007); Eric.L.Crump, USEnvironmental Protection Agency, Office of Air Quality Planning and Standards, Economic Impact Analysis For the Proposed Cyanide Manufacturing NESHAP (May 2000) , which is available at http://nepis.epa.gov/Exe/ZyPDF.cgi? Dockey = P100AHG1. PDF is available online, and the disclosure of such articles is hereby incorporated by reference in its entirety herein in its entirety.

藉由自產生HCN之反應生成之熱回收能量及自燃燒氣態廢棄物流回收能量來解決或改良安德盧梭法中之廢熱(thermal waste)及材料廢棄物的問題。本發明係關於利用在安德盧梭法期間(例如，在富集氧之安德盧梭法或氧安德盧梭法期間)產生之廢棄物的方法。本發明亦提供可在氰化氫之產生期間操作並且降低在安德盧梭法期間消耗之能量或材料的量之系統。 Solving or improving the problem of thermal waste and material waste in the Andrussow process by recovering energy from the heat generated by the HCN reaction and recovering energy from the combustion gaseous waste stream. The present invention relates to a method of utilizing waste generated during the Andrussow process (for example, during the enrichment of the Andrussow process or the oxygen Andrussow process). The present invention also provides a system that can operate during the production of hydrogen cyanide and reduce the amount of energy or material consumed during the Andrussow process.

使用富集氧或實質上純淨氧進料流之一些問題可容易地理解。例如，富集氧及實質上純淨氧進料流比空氣更為昂貴。富集氧及實質上純淨氧進料流可包括濃縮的氧來源並且產生含有大量氫之廢棄物流。因此，需要多加注意以避免與使用純氧作為氣態氧進料流相關之問題。例如，處理由將氫回收與富集氧之安德盧梭法或氧安德盧梭法組合引起之安全問題可需要在空氣安德盧梭法中通常不使用或不需要之安全顧慮、裝備設計、裝備維護及操作條件。 Some of the problems of using an enriched oxygen or substantially pure oxygen feed stream can be readily understood. For example, enriched oxygen and substantially pure oxygen feed streams are more expensive than air. The enriched oxygen and substantially pure oxygen feed stream can include a concentrated source of oxygen and produce a waste stream containing a significant amount of hydrogen. Therefore, more care needs to be taken to avoid problems associated with the use of pure oxygen as a gaseous oxygen feed stream. For example, the safety issues associated with the combination of hydrogen recovery with enriched oxygen and the Andrussow process may require safety concerns, equipment design, and equipment that are not normally used or required in the air Andrussow process. Maintenance and operating conditions.

存在或已經建造極少富集氧之安德盧梭製造設施或氧安德盧梭製造設施。除與富集氧之安德盧梭製造設施或氧安德盧梭製造設施有關之較容易明白的顧慮(例如彼等上述者)以外，亦存在諸多不容易或未廣泛瞭解之其他問題。 There are or have built very few oxygen-rich Andrussow manufacturing facilities or oxygen Andruss manufacturing facilities. In addition to the more easily understood concerns associated with the oxygen-rich Andrussow manufacturing facility or the oxygen Andruss manufacturing facility (such as those mentioned above), there are other problems that are not easily or widely understood.

例如，富集氧之安德盧梭法或氧安德盧梭法與採用空氣之安德盧梭法相比對反應物濃度之變化更為敏感。反應物之濃度或流速之變化在富集氧之安德盧梭法或氧安德盧梭法中可造成之方法效率之變化大於在空氣安德盧梭法中所觀察到者。富集氧之安德盧梭法或氧安德盧梭法對於進料氣體之熱值(英制熱量單位(British Thermal Units)(BTU))之變化更為敏感；進料流組成之小的變化可引起之反應器中之溫度波動大於對於空氣安德盧梭法中類似進料流組成所觀察到者。與空氣安德盧梭法相比，反應物經過觸媒時濃度之局部變化可造成觸媒床中之溫度變化，例如熱點，此可縮短觸媒之壽命。空氣中存在約78vol%氮在空氣安德盧梭法中用以稀釋氣體混合物並且可降低副產物之產生及對於反應之加強控制之需要。空氣安德盧梭法之氣態廢棄物流(例如，在HCN回收之後的流)具有低熱值，由此流需要供應以燃料氣(例如，天然氣)來完成燃燒。因此，空氣安德盧梭法之氣態廢棄物流作為燃料氣無意義。 For example, the oxygen-rich Andrussow process or the oxygen Andrussow process is more sensitive to changes in reactant concentration than the air-based Andrussow process. Changes in the concentration or flow rate of the reactants can result in a greater change in the efficiency of the method in the oxygen-rich Andrussow process or the oxygen Andrussow process than in the air Andrussow process. The oxygen-rich Andrussow process or the oxygen Andrussow process is more sensitive to changes in the calorific value of the feed gas (British Thermal Units (BTU)); small changes in the composition of the feed stream can cause The temperature fluctuations in the reactor are greater than those observed for the similar feed stream composition in the air Andrussow process. Compared to the air Andrussow process, local changes in the concentration of the reactants through the catalyst can cause temperature changes in the catalyst bed, such as hot spots, which can shorten the life of the catalyst. The presence of about 78 vol% nitrogen in the air is used in the air Andrussow process to dilute the gas mixture and reduce the need for by-product generation and enhanced control of the reaction. The gaseous waste stream of the Air Andrussow process (eg, the stream after HCN recovery) has a low calorific value, whereby the stream needs to be supplied with fuel gas (eg, natural gas) to complete the combustion. Therefore, the gaseous waste stream of the Air Andrussow process is meaningless as a fuel gas.

自富集氧之安德盧梭法或氧安德盧梭法之流出物之熱傳遞所引起之問題多於對於空氣安德盧梭法所觀察到者。來自富集氧之安德盧梭法或氧安德盧梭法之流出物的濃度高於空氣安德盧梭法。儘管最好快速地進行該濃縮流出物之冷卻以阻止反應物形成副產物，但不應將流出物冷卻至HCN冷凝點，此乃因HCN在冷凝時具有更大聚合傾向。 The heat transfer from the effluent of the oxygen-rich Andrussow process or the oxygen Andrussow process is more problematic than that observed for the air Andrussow process. From the enriched oxygen of Andro The concentration of the effluent of the shuttle or oxygen Andrussow process is higher than that of the air Andrussow method. Although it is preferred to rapidly cool the concentrated effluent to prevent reactant formation by-products, the effluent should not be cooled to the HCN condensation point because HCN has a greater tendency to polymerize upon condensation.

與空氣安德盧梭法相比，富集氧之安德盧梭法或氧安德盧梭法傾向於以更高濃度之方式進行。因此，富集氧之安德盧梭法或氧安德盧梭法傾向於生成更高濃度之所有產物，包括副產物。因此，用於富集氧之安德盧梭法或氧安德盧梭法之反應器及相關裝備更易在系統中聚集雜質，該等雜質可更容易地自用於空氣安德盧梭法中之裝備沖洗掉。更大之副產物聚集速率可導致腐蝕速率增加以及該方法之各部分之更頻繁關斷及維護。可受副產物聚集、腐蝕及相關問題顯著影響之裝備包括(例如)熱回收系統、反應器、氨回收系統及HCN回收系統。 The oxygen-rich Andrussow process or the oxygen Andrussow process tends to proceed at a higher concentration than the air Andrussow process. Thus, the oxygen-rich Andrussow process or the oxygen Andrussow process tends to produce higher concentrations of all products, including by-products. Therefore, the reactors and related equipment for the enriched oxygen-based Andrussow process or the oxygen Andrussow process are more likely to accumulate impurities in the system, which can be more easily washed out from the equipment used in the air Andrussow process. . Larger byproduct aggregation rates can result in increased corrosion rates and more frequent shutdowns and maintenance of various parts of the process. Equipment that can be significantly affected by by-product aggregation, corrosion, and related problems include, for example, heat recovery systems, reactors, ammonia recovery systems, and HCN recovery systems.

儘管富集氧之安德盧梭法或氧安德盧梭法與空氣安德盧梭法相比，產生等效量HCN所需之裝備可更加緊湊(即，更小)，但許多製造商會選擇操作空氣安德盧梭法以避免與富集氧之安德盧梭法或氧安德盧梭法有關之問題。與將富集氧之安德盧梭法或氧安德盧梭法與利用在富集氧之安德盧梭法或氧安德盧梭法期間產生之廢棄物組合有關之問題未充分瞭解，並且困難足夠大而使得大多數製造商不會嘗試該組合。 Although the oxygen-rich Andrussow method or the oxygen Andrussow method is more compact (ie, smaller) than the air Andrussow method, many manufacturers choose to operate the air. The Druso method avoids problems associated with the oxygen-rich Andrussow method or the oxygen Andrussow method. The problems associated with combining the oxygen-rich Andrussow process or the oxygen Andrussow process with wastes generated during the enrichment of the Andrussow process or the oxygen Andrussow process are not fully understood and are difficult enough This makes most manufacturers not try this combination.

然而，益處可令人驚奇地大。本發明之各個實例可自在自富集氧之安德盧梭法或氧安德盧梭法產生HCN期間產生之廢棄物(例如廢熱及材料廢棄物)生成能量。例如，可在反應器之後及在HCN回收之後利用汽電共生(co-generation)單元生成電及熱。各個實例可藉由將所產生之熱及電回收回製程中由此使外部供應之能量的量最小化及使材料廢棄物的量最小化來降低在富集氧之安德盧梭法或氧安德盧梭法期間產生HCN之成本。對於富集氧之安德盧梭法或氧安德盧梭法所述之益處在空氣安德盧梭法中似乎不可行。 However, the benefits can be surprisingly large. Various examples of the present invention can generate energy from wastes (e.g., waste heat and material waste) generated during the production of HCN from the oxygen-rich Andrussow process or the oxygen Andrussow process. For example, electricity and heat can be generated using a co-generation unit after the reactor and after HCN recovery. Each example can reduce the oxygen-rich Andrussow process or oxygenation by recycling the heat and electricity generated back into the process thereby minimizing the amount of externally supplied energy and minimizing the amount of material waste. The cost of HCN during the Druso method. The benefits described for the enriched oxygen Andrussow process or the oxygen Andrussow process do not appear to be feasible in the air Andrussow process.

氨及甲烷至HCN之轉化係吸熱反應，但在安德盧梭法中，藉由使用氨、甲烷、氧及適宜觸媒(例如含Pt觸媒)使該反應轉化成放熱催化反應。經由安德盧梭法產生HCN可在大於800℃、例如約800℃至2,500℃或1,000℃至約1,500℃之反應溫度下進行。供應能量以將反應物進料流加熱至反應溫度可能成本較高。另外，若由反應生成之熱不再俘獲並轉化成能量，則所生成之熱可視為廢熱。另外，回收所生成之熱可降低產物流之溫度並防止產物流之組份形成副產物。在各個實例中，本發明可回收一部分熱並生成電及熱，可將其回收回製程中。例如，可利用汽電共生單元生成蒸汽及電。將電及熱回收回製程中可降低外部供應之能量的量，使廢熱的量最小化，並且提高方法之總效率。 The conversion of ammonia and methane to HCN is an endothermic reaction, but in the Andrussow process, the reaction is converted to an exothermic catalytic reaction by the use of ammonia, methane, oxygen and a suitable catalyst such as a Pt-containing catalyst. The production of HCN via the Andrussow process can be carried out at a reaction temperature of greater than 800 ° C, for example from about 800 ° C to 2,500 ° C or from 1,000 ° C to about 1,500 ° C. It may be costly to supply energy to heat the reactant feed stream to the reaction temperature. In addition, if the heat generated by the reaction is no longer captured and converted into energy, the generated heat can be regarded as waste heat. Additionally, recovering the heat generated can reduce the temperature of the product stream and prevent the components of the product stream from forming by-products. In various examples, the present invention recovers a portion of the heat and generates electricity and heat that can be recycled back to the process. For example, steam and electricity can be generated using a cogeneration unit. Recycling electricity and heat back into the process reduces the amount of externally supplied energy, minimizes the amount of waste heat, and increases the overall efficiency of the process.

在各個實例中，可在HCN之產生期間產生材料廢棄物(例如，化學廢棄物)。例如，在氧安德盧梭法中，對於1,000磅(lbs)HCN，可產生約40,000標準立方呎(scf)廢氣，並且可損失235BTU/scf。如本文中所討論，隨著進料氣體中之氧之百分比增加(例如，在氧安德盧梭法)中，氫及其他易燃組份(例如一氧化碳)增加，由此氣態廢棄物流可用作燃料。在各個實例中，本發明可將化學廢棄物轉化成能量。例如，可在來自氧安德盧梭法或富集氧之安德盧梭法之氣態廢棄物流中利用汽電共生單元並產生熱及電。藉由自材料廢棄物回收能量，本發明之各個實例可降低在HCN之產生期間消耗之材料的量並且與其他方法(例如，空氣安德盧梭法)相比可更高效地產生HCN。例如，各個實例可藉由降低外部供應之能量的量並使材料廢棄物的量最小化來降低產生氰化氫之總成本。 In various instances, material waste (eg, chemical waste) can be produced during the production of HCN. For example, in the oxygen Andrussow process, approximately 1,000,000 standard cubic feet (scf) of exhaust gas can be produced for 1,000 pounds (lbs) of HCN, and 235 BTU/scf can be lost. As discussed herein, as the percentage of oxygen in the feed gas increases (eg, in the oxygen Andrussow process), hydrogen and other flammable components (eg, carbon monoxide) increase, whereby the gaseous waste stream can be used as fuel. In various examples, the invention can convert chemical waste into energy. For example, a cogeneration unit can be utilized in a gaseous waste stream from the oxygen Andrussow process or the oxygen-rich Andrussow process and generate heat and electricity. By recovering energy from material waste, various examples of the present invention can reduce the amount of material consumed during the production of HCN and can produce HCN more efficiently than other methods (eg, air Andrussow process). For example, various examples can reduce the overall cost of producing hydrogen cyanide by reducing the amount of externally supplied energy and minimizing the amount of material waste.

在各個實例中，本發明提供利用在氰化氫之產生期間產生之廢棄物的方法。該方法可包括燃燒氣態廢棄物流以供初級能量生成，其中氣態廢棄物流係來自經組態以產生氰化氫之反應器，並且氣態廢棄物流實質上不含氰化氫。該方法可包括使熱回收單元與熱接觸以供次級能量生成，其中熱係在氰化氫之產生期間由反應器生成。在各個實例中，該方法可包括燃燒氣態廢棄物流以供初級能量生成及使熱回收單元與熱接觸以供次級能量生成二者。初級或次級能量生成可包括熱傳遞、蒸汽生成、電生成或其組合。 In various examples, the present invention provides a method of utilizing waste generated during the production of hydrogen cyanide. The method can include burning a gaseous waste stream for primary energy generation, wherein the gaseous waste stream is from a reactor configured to produce hydrogen cyanide, and the gaseous waste is discarded The stream is substantially free of hydrogen cyanide. The method can include contacting the heat recovery unit with heat for secondary energy generation, wherein the heat is generated by the reactor during the production of hydrogen cyanide. In various examples, the method can include burning a gaseous waste stream for primary energy generation and contacting the heat recovery unit with heat for both secondary energy generation. Primary or secondary energy production can include heat transfer, steam generation, electrical generation, or a combination thereof.

在各個實例中，本發明提供經由安德盧梭法產生氰化氫之系統。該系統包括經組態以在包含鉑之觸媒存在下自包含甲烷、氨及氧之反應混合物產生氰化氫之反應器，其中該反應器亦經組態以向反應混合物供應足夠氧，從而在去除氨及回收氰化氫之後生成具有至少59體積%氫之氣態廢棄物流。該系統可包括第一汽電共生單元，其經組態以燃燒作為燃料之氣態廢棄物流以供初級能量生成，其中氣態廢棄物流實質上不含氰化氫。該系統可包括第二汽電共生單元，其經組態以自反應器吸收熱以供次級能量生成。在各個實例中，該系統可包括第一汽電共生單元及第二汽電共生單元二者。 In various examples, the invention provides a system for producing hydrogen cyanide via the Andrussow process. The system includes a reactor configured to produce hydrogen cyanide from a reaction mixture comprising methane, ammonia, and oxygen in the presence of a platinum-containing catalyst, wherein the reactor is also configured to supply sufficient oxygen to the reaction mixture, thereby A gaseous waste stream having at least 59% by volume of hydrogen is produced after removal of ammonia and recovery of hydrogen cyanide. The system can include a first cogeneration unit configured to combust a gaseous waste stream as a fuel for primary energy generation, wherein the gaseous waste stream is substantially free of hydrogen cyanide. The system can include a second cogeneration unit configured to absorb heat from the reactor for secondary energy generation. In various examples, the system can include both a first cogeneration unit and a second cogeneration unit.

在各個實例中，本發明提供方法。該方法可包括調整包含甲烷、氨及氧之反應混合物以向反應混合物提供足夠氧，從而在去除氨及回收氰化氫之後生成在氣態廢棄物流中具有至少59體積%氫之氣態廢棄物流。該方法可進一步包括燃燒氣態廢棄物流以供能量生成。 In various examples, the invention provides methods. The method can include adjusting a reaction mixture comprising methane, ammonia, and oxygen to provide sufficient oxygen to the reaction mixture to produce a gaseous waste stream having at least 59 volume percent hydrogen in the gaseous waste stream after ammonia removal and recovery of hydrogen cyanide. The method can further include combusting the gaseous waste stream for energy production.

本發明方法及器件之該等以及其他實例及特徵將部分地陳述於下文實施方式中。本發明內容意欲提供本發明標的物之概述，且並不意欲提供窮盡性或排他性解釋。下文之實施方式經納入以提供關於本發明系統及方法之更多資訊。 These and other examples and features of the methods and devices of the present invention are set forth in part in the following description. This Summary is provided to provide an overview of the subject matter of the invention and is not intended to The following embodiments are incorporated to provide further information regarding the systems and methods of the present invention.

2‧‧‧進料流/氨(NH₃)流 2‧‧‧feed stream/ammonia (NH ₃ ) flow

4‧‧‧進料流/甲烷(CH₄)流 4‧‧‧feed stream/methane (CH ₄ ) flow

6‧‧‧進料流/氧流 6‧‧‧feed stream/oxygen flow

8‧‧‧HCN合成系統 8‧‧‧HCN Synthesis System

10‧‧‧產物流 10‧‧‧Product stream

11‧‧‧方法 11‧‧‧Method

12‧‧‧廢熱利用系統 12‧‧‧Waste heat utilization system

14‧‧‧溫度降低之產物流 14‧‧‧Products of reduced temperature

16‧‧‧氨回收系統 16‧‧‧Ammonia recovery system

18‧‧‧磷酸流 18‧‧‧Glucose flow

20‧‧‧NH₃回收流 20‧‧‧NH ₃ recovery stream

22‧‧‧廢水流 22‧‧‧ Wastewater flow

24‧‧‧汽提NH₃之HCN流 24‧‧‧HCN flow for stripping NH ₃

26‧‧‧廢水處理系統 26‧‧‧ Wastewater Treatment System

28‧‧‧廢水流 28‧‧‧ Wastewater flow

30‧‧‧HCN回收系統 30‧‧‧HCN recycling system

32‧‧‧經純化HCN產物流 32‧‧‧ Purified HCN product stream

34‧‧‧氣態廢棄物流 34‧‧‧Gaseous waste stream

36‧‧‧材料廢棄物利用系統 36‧‧‧Material waste utilization system

38‧‧‧H₂回收系統 38‧‧‧H ₂ recovery system

40‧‧‧所回收之H₂ 40‧‧‧Recovered H ₂

42‧‧‧燃燒器/燃燒系統 42‧‧‧Burner/combustion system

44‧‧‧管線 44‧‧‧ pipeline

46‧‧‧圖1之方法之一部分 46‧‧‧ part of the method of Figure 1

48‧‧‧圖1之方法之一部分 48‧‧‧ part of the method of Figure 1

50‧‧‧壓縮器 50‧‧‧Compressor

52‧‧‧氣體加熱器 52‧‧‧ gas heater

54‧‧‧NH₃過熱器 54‧‧‧NH ₃ superheater

56‧‧‧氨氣化器 56‧‧‧Ammonia gasifier

58‧‧‧NH₃蒸氣流 58‧‧‧NH ₃ vapor stream

60‧‧‧過熱NH₃蒸氣 60‧‧‧Overheated NH ₃ vapour

62‧‧‧預熱器 62‧‧‧Preheater

64‧‧‧反應混合物 64‧‧‧Reaction mixture

66‧‧‧反應器 66‧‧‧Reactor

68‧‧‧儲存罐 68‧‧‧ storage tank

69‧‧‧流 69‧‧‧ flow

70‧‧‧鍋爐 70‧‧‧Boiler

72‧‧‧蒸汽 72‧‧‧Steam

74‧‧‧汽電共生單元 74‧‧‧Steam symbiosis unit

76‧‧‧蒸汽 76‧‧‧Steam

78‧‧‧發生器 78‧‧‧ Generator

80‧‧‧鍋爐 80‧‧‧Boiler

82‧‧‧發生器 82‧‧‧ Generator

84‧‧‧檢測器 84‧‧‧Detector

86‧‧‧轉向器 86‧‧‧Steering gear

88‧‧‧蒸汽 88‧‧‧Steam

90‧‧‧汽電共生單元 90‧‧‧Steam symbiosis unit

92‧‧‧蒸汽 92‧‧‧Steam

98‧‧‧所回收之氫流 98‧‧‧Recovered hydrogen flow

在未必按比例繪示之圖式中，在全部若干視圖中，相同數字描述實質上類似之組件。該等圖式通常作為實例而非作為限制闡釋本文件中所討論之各個實例。 In the drawings, which are not necessarily to scale, the The drawings are to be considered as illustrative and not restrictive

圖1係根據各個實例經由安德盧梭法產生氰化氫(HCN)之方法之流程圖。 Figure 1 is a flow diagram of a method of producing hydrogen cyanide (HCN) via the Andrussow process according to various examples.

圖2係根據各個實例圖1之方法11之一部分之更詳細的流程圖。 2 is a more detailed flow diagram of a portion of method 11 of FIG. 1 in accordance with various examples.

圖3係根據各個實例用於產生HCN之圖1之方法之一部分之更詳細的流程圖。 3 is a more detailed flow diagram of a portion of the method of FIG. 1 for generating HCN in accordance with various examples.

現將詳細參考所揭示標的物之某些技術方案。儘管所揭示標的物將結合所列舉之技術方案進行闡述，但應理解，該等技術方案並不意欲將所揭示標的物限於該等技術方案。相反，所揭示標的物意欲涵蓋所有可包括在由技術方案所界定之本發明所揭示標的物之範圍內的替代、改進及等效形式。以下詳細說明包括參考附圖，該等附圖構成詳細說明之一部分。該等圖式作為舉例說明來顯示可實踐本發明之具體實例。 Reference will now be made in detail to certain embodiments of the disclosed subject matter. The disclosed subject matter will be described in conjunction with the exemplified embodiments. It should be understood that the invention is not intended to limit the disclosed subject matter. Rather, the disclosed subject matter is intended to cover alternatives, modifications, and equivalents, which are included within the scope of the subject matter disclosed herein. The detailed description below includes reference to the accompanying drawings, which are incorporated in the specification. The drawings are illustrative of the specific examples in which the invention may be practiced.

在本說明書中提及「一個實例(one example、an example)」等表示所述實例可包括特定特徵、結構或特性，但每一實例可不一定包括該特定特徵、結構或特性。而且，該等片語不一定指代相同實例。此外，當結合實例闡述特定特徵、結構或特性時，認為無論是否明確闡述，結合其他實例實現該特徵、結構或特性在熟習此項技術者之知識範圍內。 References to "one example, an example" and the like in this specification are intended to include a particular feature, structure, or characteristic, but each instance may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same examples. In addition, when a particular feature, structure, or characteristic is described in connection with an example, it is believed that the features, structures, or characteristics may be implemented in combination with other examples, whether or not explicitly stated.

術語「約」可容許值或範圍一定程度之可變性，例如在所述值或所述範圍限值之10%以內、5%以內或1%以內。當給出範圍或有序值清單時，除非另外說明，否則亦揭示在該範圍內之任一值或在所給出有序值之間之任一值。 The term "about" may tolerate a certain degree of variability of the value or range, such as within 10%, within 5%, or within 1% of the stated value or the stated range limit. When a list of ranges or ordered values is given, any value within the range or any value between the given ordered values is also disclosed unless otherwise stated.

如本文中所使用之術語「空氣」係指組成與通常在地面取自大氣之氣體之天然組成大致相同之氣體混合物。在一些實例中，空氣係取自周圍環境。空氣具有包括大約78%氮、21%氧、1%氬及0.04%二氧化碳以及少量其他氣體之組成。 The term "air" as used herein refers to a gas mixture that is substantially the same as the natural composition of a gas that is typically taken from the atmosphere on the ground. In some instances, the air is taken from the surrounding environment. Air has approximately 78% nitrogen, 21% oxygen, 1% argon and 0.04% The composition of carbon oxide and a small amount of other gases.

如本文中所使用，空氣安德盧梭法使用空氣作為含氧進料流，其具有大約20.95mol%氧。 As used herein, the air Andrussow process uses air as the oxygen-containing feed stream having about 20.95 mol% oxygen.

富集氧之安德盧梭法使用具有約21mol%氧至約26mol%氧、27mol%氧、28mol%氧、29mol%氧或至約30mol%氧、例如約22mol%氧、23mol%氧、24mol%氧或約25mol%氧之含氧進料流。 The oxygen-rich Andrussow process uses from about 21 mol% oxygen to about 26 mol% oxygen, 27 mol% oxygen, 28 mol% oxygen, 29 mol% oxygen, or to about 30 mol% oxygen, such as about 22 mol% oxygen, 23 mol% oxygen, 24 mol%. Oxygen or an oxygen-containing feed stream of about 25 mol% oxygen.

如本文中所使用，氧安德盧梭法使用具有約26mol%氧、27mol%氧、28mol%氧、29mol%氧或約30mol%氧至約100mol%氧之含氧進料流。氧安德盧梭法亦可使用具有約35mol%氧、40mol%氧、45mol%氧、50mol%氧、55mol%氧、60mol%氧、65mol%氧、70mol%氧、75mol%氧、80mol%氧、85mol%氧、90mol%氧、95mol%氧或約100mol%氧之含氧進料流。 As used herein, the oxygen Andrussow process uses an oxygen-containing feed stream having about 26 mol% oxygen, 27 mol% oxygen, 28 mol% oxygen, 29 mol% oxygen, or about 30 mol% oxygen to about 100 mol% oxygen. The oxygen Andrussow process can also use about 35 mol% oxygen, 40 mol% oxygen, 45 mol% oxygen, 50 mol% oxygen, 55 mol% oxygen, 60 mol% oxygen, 65 mol% oxygen, 70 mol% oxygen, 75 mol% oxygen, 80 mol% oxygen, An oxygen-containing feed stream of 85 mol% oxygen, 90 mol% oxygen, 95 mol% oxygen, or about 100 mol% oxygen.

如本文中所使用之術語「實質上不含」係指小於約1wt%、小於約0.5wt%及小於約0.10wt%。 The term "substantially free" as used herein means less than about 1 wt%, less than about 0.5 wt%, and less than about 0.10 wt%.

本發明闡述利用自安德盧梭法產生氰化氫(HCN)期間產生之廢棄物的方法及系統。本發明之方法及系統可藉由使用本文所述之方法及系統安全地解決來自富集氧之安德盧梭法或氧安德盧梭法之熱及材料之浪費損失問題。該等方法及系統可涉及燃燒氣態廢棄物流以生成能量。本發明之方法及系統亦可涉及自產生HCN之反應放出之熱生成能量。在各個實例中，可使用自廢棄物生成之能量並回收回產生HCN之製程中。因此，本發明之方法及系統可降低安德盧梭法中作為廢棄物之能量或材料的量。 The present invention describes methods and systems for utilizing waste generated during the production of hydrogen cyanide (HCN) from the Andrussow process. The method and system of the present invention can safely address the waste loss problem of heat and materials from the oxygen-rich Andrussow process or the oxygen Andrussow process by using the methods and systems described herein. The methods and systems can involve burning a gaseous waste stream to generate energy. The method and system of the present invention may also involve the generation of energy from the heat evolved by the reaction that produces HCN. In each instance, energy generated from the waste can be used and recycled back to the process that produces the HCN. Thus, the method and system of the present invention can reduce the amount of energy or material used as waste in the Andrussow process.

在安德盧梭法期間，包括氣態氨進料流、氣態甲烷進料流及氣態氧進料流之反應物氣體進料流反應而形成含有氰化氫及水之產物流。如本文中所討論，藉由安德盧梭法合成氰化氫(例如，參見Ullmann's Encyclopedia of Industrial Chemistry，第8卷，VCH Verlagsgesellschaft,Weinheim,1987，第161-162頁)可在氣相中經由包含鉑或鉑合金或其他金屬之觸媒實施。適於實施安德盧梭法之觸媒發現並闡述於作為美國專利第1,934,838號公開之原始安德盧梭專利及別處。在安德盧梭之原作中，其揭示觸媒可選自在約1000℃之工作溫度下不熔(固體)之氧化觸媒；其納入了呈純形式或作為合金之鉑、銥、銠、鈀、鋨、金或銀作為催化活性金屬。其亦注意到，亦可使用例如呈不熔氧化物或磷酸鹽形式之某些卑金屬，例如稀土金屬、釷、鈾及其他，且注意到觸媒可形成為網(篩網)或沈積於耐熱性固體載體(例如矽石或氧化鋁)上。 During the Andrussow process, a reactant gas feed stream comprising a gaseous ammonia feed stream, a gaseous methane feed stream, and a gaseous oxygen feed stream is reacted to form a product stream comprising hydrogen cyanide and water. Hydrocyanide is synthesized by the Andrussow process as discussed herein (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 8, VCH). Verlagsgesellschaft, Weinheim, 1987, pp. 161-162) can be carried out in the gas phase via a catalyst comprising platinum or a platinum alloy or other metal. The catalysts found to be suitable for the implementation of the Andrussow process are described and described in the original Andrussow patent as disclosed in U.S. Patent No. 1,934,838. In the original work of Andrussow, it is disclosed that the catalyst can be selected from an oxidizing catalyst that does not melt (solid) at an operating temperature of about 1000 ° C; it incorporates platinum, rhodium, ruthenium, palladium in pure form or as an alloy. Antimony, gold or silver acts as a catalytically active metal. It is also noted that certain barium metals, such as rare earth metals, cerium, uranium and others, may also be used, for example, in the form of infusible oxides or phosphates, and it is noted that the catalyst may be formed into a mesh (mesh) or deposited on Heat resistant solid support (such as vermiculite or alumina).

在後續研發工作中，已因效力及甚至呈絲網或網形式之金屬之耐熱性而選擇含鉑觸媒。例如，可使用鉑-銠合金作為觸媒，其可呈金屬絲網或篩網形式，例如織造或針織絲網片，或其可佈置於載體結構上。在實例中，織造或針織絲網片可形成具有20-80個網目大小之網狀結構，例如，具有約0.18mm至約0.85mm大小之開口。觸媒可包含約85wt%至約90wt%鉑(Pt)及約10wt%至約15wt%銠(Rh)。鉑-銠觸媒亦可包含少量金屬雜質，例如鐵(Fe)、鈀(Pd)、銥(Ir)、釕(Ru)及其他金屬。雜質金屬可以痕量(例如約10ppm或更小)存在。 In subsequent research and development work, platinum-containing catalysts have been selected for their effectiveness and even the heat resistance of metals in the form of mesh or mesh. For example, a platinum-rhodium alloy can be used as the catalyst, which can be in the form of a wire mesh or mesh, such as a woven or knitted mesh sheet, or it can be disposed on a carrier structure. In an example, the woven or knitted mesh sheet can be formed into a mesh structure having a mesh size of 20-80, for example, having an opening of about 0.18 mm to about 0.85 mm. The catalyst may comprise from about 85 wt% to about 90 wt% platinum (Pt) and from about 10 wt% to about 15 wt% rhodium (Rh). The platinum-ruthenium catalyst may also contain small amounts of metallic impurities such as iron (Fe), palladium (Pd), iridium (Ir), ruthenium (Ru), and other metals. The impurity metal may be present in trace amounts (e.g., about 10 ppm or less).

安德盧梭法之寬範圍之可能實施例闡述於德國專利549,055中。在一個實例中，在約800℃至2,500℃、1,000℃至1,500℃或約980℃至1050℃之溫度下使用包含複數個串聯佈置之具有10%銠之Pt之細目絲網的觸媒。例如，觸媒可為市售觸媒，例如購自Johnson Matthey Plc,London,UK之Pt-Rh觸媒絲網或購自Heraeus Precious Metals GmbH & Co.,Hanau,Germany之Pt-Rh觸媒絲網。 A possible embodiment of the wide range of the Andrussow process is described in German Patent 549,055. In one example, a catalyst comprising a plurality of fine-grained screens of 10% bismuth Pt arranged in series is used at a temperature of from about 800 °C to 2,500 °C, from 1,000 °C to 1,500 °C, or from about 980 °C to 1050 °C. For example, the catalyst may be a commercially available catalyst such as Pt-Rh catalyst mesh available from Johnson Matthey Plc, London, UK or Pt-Rh catalyst filament available from Heraeus Precious Metals GmbH & Co., Hanau, Germany. network.

安德盧梭法可使用多種用於氣態氧進料流之來源實施。例如，氣態氧進料流可為純氧、氧與惰性氣體之混合物以及空氣與氧之混合物。通常，氣態氧進料流中之較大百分比之氧將在氣態廢棄物流中產生較大百分比之氫。例如，採用為實質上純淨之氧之氣態氧進料流之安德盧梭法可獲得具有多達70-80vol%氫之氣態廢棄物流。然而，採用空氣作為氣態氧進料流之安德盧梭法在其氣態廢棄物流中具有實質上更少之氫，例如，少至15-18vol%。如本文中所討論，空氣安德盧梭法之未補充燃料氣之氣態廢棄物流通常不可用作燃料氣。因此，在氧進料流中具有大於55vol%氧之富集氧之安德盧梭法或實質上純淨氧之安德盧梭法中燃燒氣態廢棄物流以生成能量可比在空氣安德盧梭法中燃燒氣態廢棄物流更具經濟吸引力。例如，來自空氣安德盧梭法之氣態廢棄物流將需要補充燃料氣以包括足夠燃料用於能量生成(例如，經由汽電共生單元)。 The Andrussow process can be implemented using a variety of sources for gaseous oxygen feed streams. For example, the gaseous oxygen feed stream can be pure oxygen, a mixture of oxygen and an inert gas, and a mixture of air and oxygen. Typically, a larger percentage of the oxygen in the gaseous oxygen feed stream will be produced in the gaseous waste stream. A larger percentage of hydrogen is produced. For example, a gaseous waste stream having up to 70-80 vol% hydrogen can be obtained using the Andrussow process which is a gaseous oxygen feed stream of substantially pure oxygen. However, the Andrussow process using air as the gaseous oxygen feed stream has substantially less hydrogen in its gaseous waste stream, for example, as little as 15-18 vol%. As discussed herein, the gaseous waste stream of the air Andrussow process, which is not replenished with fuel gas, is generally not available as a fuel gas. Thus, the combustion of gaseous waste streams in an oxygen feed stream with an enriched oxygen-rich Andrussow process of greater than 55 vol% oxygen or substantially pure oxygen in the Andrussow process to generate energy comparable to combustion in the air Andrussow process Waste streams are more economically attractive. For example, a gaseous waste stream from the air Andrussow process would require supplemental fuel gas to include sufficient fuel for energy generation (eg, via a cogeneration unit).

如本文中所使用，空氣安德盧梭法使用空氣作為含氧進料流，其具有大約20.95vol%氧。富集氧之安德盧梭法使用具有約21vol%氧至約26vol%氧、27vol%氧、28vol%氧、29vol%氧或至約30vol%氧，例如約22vol%氧、23vol%氧、24vol%氧或約25vol%氧之含氧進料流。 As used herein, the air Andrussow process uses air as the oxygen-containing feed stream having about 20.95 vol% oxygen. The oxygen-rich Andrussow process uses from about 21 vol% oxygen to about 26 vol% oxygen, 27 vol% oxygen, 28 vol% oxygen, 29 vol% oxygen, or to about 30 vol% oxygen, such as about 22 vol% oxygen, 23 vol% oxygen, 24 vol% Oxygen or an oxygen-containing feed stream of about 25 vol% oxygen.

氧安德盧梭法使用具有約26vol%氧、27vol%氧、28vol%氧、29vol%氧或約30vol%氧至約100vol%氧之含氧進料流。氧安德盧梭法亦可使用具有約35vol%氧、40vol%氧、45vol%氧、50vol%氧、55vol%氧、60vol%氧、65vol%氧、70vol%氧、75vol%氧、80vol%氧、85vol%氧、90vol%氧、95vol%氧或約100vol%氧之含氧進料流。 The oxygen Andrussow process uses an oxygen-containing feed stream having about 26 vol% oxygen, 27 vol% oxygen, 28 vol% oxygen, 29 vol% oxygen, or about 30 vol% oxygen to about 100 vol% oxygen. The oxygen Andrussow process can also be used with about 35 vol% oxygen, 40 vol% oxygen, 45 vol% oxygen, 50 vol% oxygen, 55 vol% oxygen, 60 vol% oxygen, 65 vol% oxygen, 70 vol% oxygen, 75 vol% oxygen, 80 vol% oxygen, An oxygen-containing feed stream of 85 vol% oxygen, 90 vol% oxygen, 95 vol% oxygen, or about 100 vol% oxygen.

在各個實例中，可藉由以下方式生成富集氧之安德盧梭法或利用具有小於100vol%氧之含氧進料流之氧安德盧梭法中之含氧進料流：混合空氣與氧、混合氧與任一適宜氣體或氣體組合或自含氧氣體組合物(例如空氣)去除一或多種氣體。 In various examples, an oxygen-enriched Andrussow process or an oxygen-containing feed stream in an oxygen Andrussow process having an oxygen-containing feed stream of less than 100 vol% oxygen can be generated by mixing air and oxygen. The mixed oxygen is combined with any suitable gas or gas or one or more gases are removed from the oxygen containing gas composition (eg, air).

圖1係根據多個實例經由安德盧梭法產生氰化氫(HCN)之方法11 之流程圖。在實例方法11中，HCN合成系統8包括一或多個經組態以產生HCN之單元操作。在各個實例中，向HCN合成系統8供應氨(NH₃)流2、甲烷(CH₄)流4及氧流6(其包括氧氣(O₂))。將三個進料流2、4、6混合且在複數個反應器中在適宜觸媒存在下根據反應式1反應以轉化成氰化氫及水：2 NH₃+2 CH₄+3 O₂ → 2 HCN+6 H₂O [1] 1 is a flow diagram of a method 11 of producing hydrogen cyanide (HCN) via the Andrussow process according to various examples. In the example method 11 , the HCN synthesis system 8 includes one or more unit operations configured to generate HCN. In each instance, the supply of ammonia to HCN synthesis system 8 (NH ₃₎ flow 2, methane (CH ₄₎ and stream 4 6 oxygen stream (which include oxygen (O _2)). Mixing three feed streams 2 , 4 , 6 and reacting according to reaction formula 1 in a plurality of reactors in the presence of a suitable catalyst to convert to hydrogen cyanide and water: 2 NH ₃ + 2 CH ₄ + 3 O ₂ → 2 HCN+6 H ₂ O [1]

可將來自HCN合成系統8之所得產物流10進給至廢熱利用系統12(在圖2中進一步詳細討論)中。使用安德盧梭法產生HCN之反應式1之反應係放熱的並且生成熱。若熱未被再俘獲，則所生成之熱可被視為廢熱。另外，藉由自產物流10去除熱，方法11可使副產物形成的量最小化。廢熱利用系統12可包括一或多個經組態以利用廢熱並生成能量之單元操作。在各個實例中，藉由廢熱利用系統12生成之能量可包括熱傳遞、蒸汽生成、電生成或其組合。在一個實例中，廢熱利用系統12生成蒸汽。所生成之蒸汽可用於以同流換熱方式(recuperatively)預熱一或多個反應物進料流，例如，流2、4及6，此可降低將進料流2、4及6之溫度升高至反應溫度之外部供應之熱的量。在一個實例中，廢熱利用系統12生成電。所生成之電可用於補充用於產生HCN之方法11之電需求。 The resulting product stream 10 from the HCN synthesis system 8 can be fed to the waste heat utilization system 12 (discussed in further detail in Figure 2 ). The reaction of Reaction Scheme 1 which produces HCN using the Andrussow process is exothermic and generates heat. If heat is not captured again, the heat generated can be considered waste heat. Additionally, by removing heat from product stream 10 , method 11 minimizes the amount of by-product formation. Waste heat utilization system 12 may include one or more unit operations configured to utilize waste heat and generate energy. In various examples, the energy generated by the waste heat utilization system 12 can include heat transfer, steam generation, electrical generation, or a combination thereof. In one example, waste heat utilization system 12 generates steam. The generated steam can be used to recuperatively preheat one or more reactant feed streams, for example, streams 2 , 4, and 6 , which can reduce the temperature of feed streams 2 , 4, and 6 The amount of heat supplied to the outside of the reaction temperature. In one example, waste heat utilization system 12 generates electricity. The generated electricity can be used to supplement the electrical requirements of method 11 for generating HCN.

在自產物流10去除熱之後，可將所得溫度降低之產物流14進給至氨回收系統16中。流14與流10之組成實質上相同，但流14之溫度低於流10。氨回收系統16可包括一或多個經組態以回收未反應之NH₃之單元操作。可藉由與可自產物流10吸收NH₃之磷酸(H₃PO₄)、硫酸(H₂SO₄)及磷酸銨溶液中之一或多者接觸吸收NH₃來回收氨。在圖1中所示之實例中，將磷酸流18添加至氨回收系統16以吸收NH₃。在H₃PO₄溶液之情況下，可使用一或多個汽提塔將NH₃與H₃PO₄分離自所得磷酸銨溶液去除氨。可經由NH₃回收流20使NH₃回收回NH₃進給流 2。H₃PO₄及其他廢棄物可作為廢水流22進行吹掃，同時可將汽提NH₃之HCN流24進給至HCN回收系統30。 After the heat is removed from product stream 10 , the resulting reduced temperature product stream 14 can be fed to ammonia recovery system 16 . Stream 14 is substantially identical in composition to stream 10 , but stream 14 has a lower temperature than stream 10 . Ammonia recovery system 16 may include a plurality of configured or to recover the unreacted NH ₃ of the operation unit. Ammonia can be recovered by contacting and absorbing NH ₃ with one or more of phosphoric acid (H ₃ PO ₄ ), sulfuric acid (H ₂ SO ₄ ), and ammonium phosphate solutions that can absorb NH ₃ from product stream 10 . In the example shown in FIG. 1, the phosphoric acid stream 18 added to the ammonia recovery system 16 to absorb NH _3. In the case of the solution of H ₃ PO _4, you may use one or more of the NH ₃ stripping column with H ₃ PO ₄ solution was separated from the resulting ammonium removal of ammonia. 20 can be recovered so that NH ₃ NH ₃ NH ₃ recovery flow back through the feed stream 2. H ₃ PO ₄ and other waste can be purged as wastewater stream 22 while the HCN stream 24 of stripped NH ₃ can be fed to HCN recovery system 30 .

HCN回收系統30可包括一或多個單元操作，該等操作經組態以自汽提NH₃之HCN流24分離並純化HCN。作為HCN回收系統30之結果，產生經純化HCN產物流32。HCN回收系統30亦可產生氣態廢棄物流34及廢水流28。可將來自HCN回收系統30之廢水流28進給至廢水處理系統26中。廢水處理系統26可藉由例如進一步處理、儲存或處置而進一步處理廢水流22、28。在進給至廢水處理系統26之前，可將廢水流22及28中之任一者或兩者進行處理以回收額外氨，可將其回收回氨回收系統16。 HCN recovery system 30 may include one or more unit operations, such operation was configured to self-stripping NH HCN ₃ isolated and purified stream of HCN 24. As a result of the HCN recovery system 30 , a purified HCN product stream 32 is produced. The HCN recovery system 30 can also produce a gaseous waste stream 34 and a wastewater stream 28 . The wastewater stream 28 from the HCN recovery system 30 can be fed to the wastewater treatment system 26 . Wastewater treatment system 26 may further treat wastewater streams 22, 28 by, for example, further processing, storage, or disposal. Either or both of the wastewater streams 22 and 28 may be treated to recover additional ammonia prior to being fed to the wastewater treatment system 26 , which may be recycled back to the ammonia recovery system 16 .

在各個實例中，方法11可包括自廢棄物生成能量之材料廢棄物利用系統36。氣態廢棄物流34可包括多種氣體，包括氫、未反應之甲烷、二氧化碳、一氧化碳、水、氮、多種有機腈及痕量HCN。燃燒氣態廢棄物流34較為浪費並且產生材料廢棄物。 In various examples, method 11 can include a material waste utilization system 36 that generates energy from waste. The gaseous waste stream 34 can include a variety of gases including hydrogen, unreacted methane, carbon dioxide, carbon monoxide, water, nitrogen, various organic nitriles, and trace amounts of HCN. The combustion of gaseous waste stream 34 is wasteful and produces material waste.

在各個實例中，可將氣態廢棄物流34進給至材料廢棄物利用系統36、H₂回收系統38、燃燒器(flare)42或其組合。在各個實例中，可將氣態廢棄物流34全部或部分自材料廢棄物利用系統36轉向而進入H₂回收系統38及/或燃燒器42。在各個實例中，可將氣態廢棄物流34在材料廢棄物利用系統36、H₂回收系統38及燃燒器42之間轉向。在各個實例中，可將在H₂回收系統38中的水藉由管線44饋入廢水處理系統26中。 In each instance, the gaseous waste stream 34 may be fed to the waste materials using the system 36, H ₂ recovery system 38, a combustor (flare) 42, or a combination thereof. In each instance, the gaseous waste stream 34 may be all or part of the waste material from the use of the steering system 36 into the H ₂ recovery system 38 and / or burner 42. In each instance, the gaseous waste stream 34 may be 36, the waste material 42 between the steering system using the H ₂ recovery system 38 and burner. In each instance, it can be fed by line 44 into the waste water treatment system 26 in the water recovery system 38 H _2.

在各個實例中，材料廢棄物利用系統36可經組態以燃燒氣態廢棄物流34並生成能量。所生成之能量可包括電生成、蒸汽生成、熱傳遞及其組合。在生成電之實施例中，所生成之電可用於補充用於產生HCN之電之外部供應。在各個實例中，材料廢棄物利用系統36可俘獲一部分自燃燒氣態廢棄物流34生成之熱，並將其回收以預熱進料流反應物。 In various examples, material waste utilization system 36 can be configured to combust gaseous waste stream 34 and generate energy. The generated energy can include electrical generation, steam generation, heat transfer, and combinations thereof. In an embodiment of generating electricity, the generated electricity can be used to supplement the external supply of electricity used to generate the HCN. In various examples, material waste utilization system 36 can capture a portion of the heat generated from combustion gaseous waste stream 34 and recover it to preheat the feed stream reactants.

H₂回收系統38可經組態以自氣態廢棄物流34回收氫。所回收之 H₂ 40可儲存或進一步進行處理。例如，所回收之H₂ 40可用於氫化。如本文中所討論，可將一部分氣態廢棄物流34輸送至燃燒器42。燃燒器42可用於消滅任何所產生之多餘氣體。然而，如本文中所討論，各個實例使燃燒最小化且由此使HCN產生期間產生之材料廢棄物最小化。 H ₂ recovery system 38 may be configured in a gaseous waste stream 34 from hydrogen recovery. The recovered H ₂ 40 can be stored or further processed. For example, the recovered H ₂ 40 can be used for hydrogenation. A portion of the gaseous waste stream 34 can be delivered to the combustor 42 as discussed herein. Burner 42 can be used to extinguish any excess gas produced. However, as discussed herein, various examples minimize combustion and thereby minimize material waste generated during HCN production.

圖2係根據多個實例圖1之方法11之一部分46之更詳細的流程圖。如圖2中所示，出於簡明起見，僅圖解說明一個反應器66。然而，複數個反應器66可串聯連接並用於產生HCN。反應器66可包括觸媒床。觸媒床可包含能夠催化反應1之觸媒材料，例如包含鉑(Pt)之觸媒。在實施例中，觸媒床包含鉑及銠(Rh)觸媒，例如包含約85wt%至約95wt% Pt及約5wt%至約15wt% Rh，例如85/15 Pt/Rh、90/10 Pt/Rh或95/5 Pt/Rh之觸媒。觸媒床之觸媒亦可包含少量金屬雜質，例如鐵(Fe)、鈀(Pd)、銥(Ir)、釕(Ru)及其他金屬。雜質金屬可以痕量(例如約10百萬份數(ppm)或更小)存在。 2 is a more detailed flow diagram of a portion 46 of method 11 of FIG. 1 in accordance with a plurality of examples. As shown in FIG. 2, for simplicity, only one reactor 66 is illustrated. However, a plurality of reactors 66 can be connected in series and used to produce HCN. Reactor 66 can include a catalyst bed. The catalyst bed may comprise a catalytic material capable of catalyzing reaction 1, such as a catalyst comprising platinum (Pt). In an embodiment, the catalyst bed comprises platinum and rhodium (Rh) catalyst, for example comprising from about 85 wt% to about 95 wt% Pt and from about 5 wt% to about 15 wt% Rh, such as 85/15 Pt/Rh, 90/10 Pt /Rh or 95/5 Pt/Rh catalyst. The catalyst bed catalyst may also contain small amounts of metallic impurities such as iron (Fe), palladium (Pd), iridium (Ir), ruthenium (Ru), and other metals. The impurity metal may be present in trace amounts (e.g., about 10 parts per million (ppm) or less).

觸媒床可利用觸媒(例如上述Pt-Rh觸媒)在載體結構(例如織造或針織絲網片)、波形觸媒結構或支撐性觸媒結構上形成。在實例中，織造或針織絲網片可形成具有20-80個網目大小之網狀結構，例如，具有約0.18mm至約0.85mm大小之開口。存在於觸媒床中之觸媒的量可取決於進給至反應器66之反應混合物64的進給速率。在實施例中，觸媒床中之觸媒之質量係每進給至反應器66之反應混合物之進給速率(磅/小時)約0.4克(g)至約0.6g。觸媒床之觸媒可為市售觸媒，例如購自Johnson Matthey Plc,London,UK之Pt-Rh觸媒絲網或購自Heraeus Precious Metals GmbH & Co.,Hanau,GERMANY之Pt-Rh觸媒絲網。 The catalyst bed can be formed on a support structure (e.g., a woven or knitted mesh sheet), a waved catalyst structure, or a supporting catalyst structure using a catalyst such as the Pt-Rh catalyst described above. In an example, the woven or knitted mesh sheet can be formed into a mesh structure having a mesh size of 20-80, for example, having an opening of about 0.18 mm to about 0.85 mm. The amount of catalyst present in the catalyst bed can depend on the feed rate of the reaction mixture 64 fed to the reactor 66 . In the embodiment, the mass of the catalyst in the catalyst bed is from about 0.4 grams (g) to about 0.6 g per feed rate (lbs per hour) of the reaction mixture fed to reactor 66 . The catalyst of the catalyst bed may be a commercially available catalyst such as Pt-Rh catalyst mesh available from Johnson Matthey Plc, London, UK or Pt-Rh contact available from Heraeus Precious Metals GmbH & Co., Hanau, GERMANY. Media screen.

HCN合成系統8(在圖1中圖解說明)可包括欲在期望條件下製備每一進料流(例如，NH₃流2、CH₄流4及氧流6)以根據反應式1實現反應並產生HCN之操作。例如，可作為液體進給之NH₃進料流2可藉由氨氣化器56氣化，氨氣化器56可將液體NH₃流2氣化成NH₃蒸氣流58。NH₃蒸氣流58可在NH₃過熱器54中進一步加熱以形成過熱NH₃蒸氣60。 HCN synthesis system 8 (illustrated in FIG. 1) may comprise at desired conditions to be prepared for each feed stream (e.g., NH ₃ flow 2, CH ₄ and 4 oxygen stream stream 6) to effect a reaction according to reaction formula 1 and The operation of generating HCN. For example, as a liquid feed stream of NH ₃ 2 can feed of ammonia by the gasifier 56, 56 may be of ammonia liquid stream 2 NH ₃ NH ₃ vaporized into a vapor stream 58. The NH ₃ vapor stream 58 can be further heated in the NH ₃ superheater 54 to form superheated NH ₃ vapor 60 .

在各個實例中，CH₄流4可作為包含天然氣、生質物氣體、實質上純淨之甲烷或其混合物之烴進料提供。在一個實施例中，CH₄流4係呈天然氣進料之形式。天然氣進料之組成可為大部分CH₄及較小百分比之其他烴。在實施例中，天然氣進料4可為約90wt%至約97wt% CH₄、約3wt%至約10wt%乙烷(C₂H₆)、約0wt%至約5wt%丙烷(C₃H₈)、約0wt%至約1wt%丁烷(C₄H₁₀，其呈異丁烯、正丁烷或其組合之形式)以及痕量高級烴及其他氣體。天然氣進料亦可經純化以包含更純之甲烷來源。在實施例中，經純化天然氣進料可包含約99.9% CH₄及小於約0.1wt%之其他烴(其主要為乙烷)。天然氣進料可藉由氣體加熱器52加熱。 In each instance, CH ₄ may be provided as stream 4 comprising natural gas, biomass gas, substantially pure hydrocarbons or mixtures of the methane feed. In one embodiment, CH ₄ flow line 4 in the form of natural gas feed. The composition of the feed gas may be most other _{hydrocarbons. 4} and a smaller percentage of CH. In an embodiment, the natural gas feed may be from about 4 to about 90wt% 97wt% CH _4, from about 3wt% to about 10wt% ethane (C ₂ H _6), from about 0 wt% to about 5wt% propane (C ₃ H ₈ ), from about 0% by weight to about 1% by weight of butane (C ₄ H ₁₀ in the form of isobutylene, n-butane or a combination thereof) and traces of higher hydrocarbons and other gases. The natural gas feed can also be purified to include a more pure source of methane. In an embodiment, the purified natural gas feed may comprise from about 99.9% CH ₄ and other hydrocarbons, less than about 0.1wt% of (mainly ethane). The natural gas feed can be heated by a gas heater 52 .

氧流6可利用(例如)壓縮器50(例如，空氣壓縮器)加壓。氧流6可作為富集氧或實質上純淨氧之進料流提供。例如，該氧流6可含有至少約25vol%氧、至少約30vol%氧、至少約40vol%氧、至少約50vol%氧、至少約60vol%氧、至少約70vol%氧、至少約80vol%氧、至少約90vol%氧、至少約95%氧、至少約98%氧。實質上純淨之氧亦可用作氧流6。 The oxygen stream 6 can be pressurized using, for example, a compressor 50 (e.g., an air compressor). Oxygen stream 6 can be provided as a feed stream enriched in oxygen or substantially pure oxygen. For example, the oxygen stream 6 can contain at least about 25 vol% oxygen, at least about 30 vol% oxygen, at least about 40 vol% oxygen, at least about 50 vol% oxygen, at least about 60 vol% oxygen, at least about 70 vol% oxygen, at least about 80 vol% oxygen, At least about 90 vol% oxygen, at least about 95% oxygen, and at least about 98% oxygen. Substantially pure oxygen can also be used as the oxygen stream 6 .

三個進料流2、4、6可在預熱器62中合併，其中預熱器62可幫助將反應混合物加熱至反應溫度。在各個實例中，預熱器62可包括氣體混合器，其經組態以形成包含氣態氨、甲烷及氧氣之反應混合物進料流64。在各個實例中，預熱器62可使三個進料流2、4及6中之一或多者在形成反應混合物進料流64之前與使用來自反應器66之廢熱自汽電共生單元74生成之熱(例如，蒸汽72)接觸。如方法11中所圖解說明，進料流2、4、6在進入反應器66之前合併。在一些實例中，混合可在反應器66之混合區內在進入反應器66之反應器區之前發生。在一些實例中，可將離開反應器66之產物流10之一部分回收於儲存罐68中並藉由流69輸送回預熱器62。 The three feed streams 2 , 4 , 6 can be combined in a preheater 62 , wherein the preheater 62 can help heat the reaction mixture to the reaction temperature. In various examples, preheater 62 can include a gas mixer configured to form a reaction mixture feed stream 64 comprising gaseous ammonia, methane, and oxygen. In each instance, three pre-heater 62 allows the feed stream 2, and 4 to 6, one or more of the reaction mixture formed in the feed stream with the use of waste heat from the reactor before the 6466's from the cogeneration unit 74 The generated heat (eg, steam 72 ) is in contact. As illustrated in Method 11 , feed streams 2 , 4 , 6 were combined prior to entering reactor 66 . In some examples, mixing can occur prior to entering the reactor zone of reactor 66 in the mixing zone of reactor 66 . In some examples, a portion of product stream 10 exiting reactor 66 may be partially recovered in storage tank 68 and sent back to preheater 62 by stream 69 .

如本文中所討論，可回收由離開反應器66之產物流10所具有之熱之一部分並使其回收。在各個實例中，廢熱利用系統12可包括汽電共生單元74，汽電共生單元74包括鍋爐70及發生器78(例如，熱激活發生器)並且經組態以生成電及熱。產物流10可進入鍋爐70，並且在產物流10中所含有之熱能可用於產生蒸汽。例如，可使產物流10所生成之熱與水接觸以產生蒸汽。 As discussed herein, a portion of the heat of the product stream 10 exiting reactor 66 can be recovered and recovered. In each instance, the waste heat utilization system 12 may include a cogeneration unit 74, the cogeneration unit 74 includes a generator 78 and boiler 70 (e.g., heat-activated generators) and configured to generate electricity and by heat. Product stream 10 can enter boiler 70 and the thermal energy contained in product stream 10 can be used to generate steam. For example, the heat generated by product stream 10 can be contacted with water to produce steam.

如本文中所討論，預熱器62可接收自鍋爐70所生成之蒸汽72之一部分以加熱進料流2、4、6。如圖2中所圖解說明，將三個進料流2、4、6在預熱器62內混合並加熱。與不包括預熱器62之方法相比，預熱器62可降低將進料流加熱至反應溫度之外部供應之能量的量。 As discussed herein, the preheater 62 can receive a portion of the steam 72 generated from the boiler 70 to heat the feed streams 2 , 4 , 6 . As illustrated in FIG. 2, the three feed streams 2, 4, 6 are mixed in the preheater 62 and heated. The preheater 62 can reduce the amount of energy supplied to the external supply of the feed stream to the reaction temperature as compared to a method that does not include the preheater 62 .

廢熱利用系統12之汽電共生單元74可包括發生器78(例如，熱激活發生器)，其經組態以自由鍋爐70生成之熱生成電。可將蒸汽76之一部分進給至發生器78以生成電。電可用於產生HCN之方法11中，此降低外部供應之能量的量。 The steam cogeneration unit 74 of the waste heat utilization system 12 can include a generator 78 (e.g., a heat activated generator) configured to generate heat from the heat generated by the boiler 70 . A portion of the steam 76 can be fed to the generator 78 to generate electricity. Electricity can be used in method 11 of generating HCN, which reduces the amount of energy supplied externally.

在各個實例中，來自反應器66之產物流10可具有第一溫度。在產物流10通過汽電共生單元74之後，溫度降低之產物流14可具有第二溫度，其中第二溫度低於第一溫度。在各個實例中，第一溫度可為約1000℃至約1300℃，並且溫度降低之產物流14之第二溫度可為約450℃至約240℃。如本文中所討論，汽電共生單元74可快速吸收熱並減少產物流10之熱以最少化副產物。 In various examples, product stream 10 from reactor 66 can have a first temperature. After the product stream 10 passes through the vapor-electric co-generation unit 74 , the temperature-decreasing product stream 14 can have a second temperature, wherein the second temperature is lower than the first temperature. In various examples, the first temperature can range from about 1000 °C to about 1300 °C, and the second temperature of the reduced temperature product stream 14 can range from about 450 °C to about 240 °C. As discussed herein, the vapor-electricity symbiosis unit 74 can quickly absorb heat and reduce the heat of the product stream 10 to minimize by-products.

如圖2中所圖解說明，使用單一鍋爐70及發生器78生成蒸汽及電。在一些實例中，可使用另一鍋爐(未顯示)在溫度降低之產物流14進入氨回收系統16之前自其去除額外熱。例如，溫度降低之產物流14 可進入另一鍋爐，該另一鍋爐可產生額外蒸汽，可將額外蒸汽再循環回製程中。在各個實例中，熱生成可比電更有利。在該實例中，可利用鍋爐70在不存在發生器78下產生蒸汽。 As illustrated in Figure 2, a single boiler 70 and the steam generator 78 and generate electricity. In some examples, another boiler (not shown) may be used to remove additional heat from the temperature-decreasing product stream 14 before it enters the ammonia recovery system 16 . For example, the reduced temperature product stream 14 can enter another boiler that can generate additional steam that can be recycled back to the process. In various examples, heat generation can be more advantageous than electricity. In this example, boiler 70 can be utilized to generate steam in the absence of generator 78 .

廢熱利用系統12可用於空氣安德盧梭法、富集氧之安德盧梭法及氧安德盧梭法中。然而，在富集氧之安德盧梭法或氧安德盧梭法中利用廢熱利用系統12可更有利，此乃因易燃組份之濃度增加。因此，使產物流12著火或在產物流中產生副產物之風險降低。 The waste heat utilization system 12 can be used in the air Andrussow process, the oxygen-rich Andrussow process, and the oxygen Andrussow process. However, it may be advantageous to utilize the waste heat utilization system 12 in an oxygen-rich Andrussow process or an oxygen Andrussow process because of the increased concentration of flammable components. Thus, the risk of product stream 12 igniting or producing by-products in the product stream is reduced.

圖3係根據多個實例用於產生HCN之圖1之方法之一部分48之更詳細的流程圖。如本文中所討論，在氨回收系統16(在圖1中圖解說明)中去除氨之後，使汽提NH₃之HCN流24進入HCN回收系統30。HCN回收系統30可使流24與水接觸以夾帶HCN。可將HCN-水混合物輸送至氰化物汽提塔，在氰化物汽提塔中自液體去除多餘廢棄物。另外，亦可將HCN-水混合物輸送穿過分餾器以濃縮HCN。可將HCN產物流32儲存在罐中或直接用於合成其他化合物。 3 is a more detailed flow diagram of a portion 48 of the method of FIG. 1 for generating HCNs in accordance with various examples. As discussed herein, after removal of ammonia ammonia recovery system 16 (illustrated in FIG. 1) of the NH HCN ₃ stripping stream 24 enters the HCN recovery system 30. The HCN recovery system 30 can contact the stream 24 with water to entrain the HCN. The HCN-water mixture can be passed to a cyanide stripper to remove excess waste from the liquid in a cyanide stripper. Alternatively, the HCN-water mixture can be passed through a fractionator to concentrate the HCN. The HCN product stream 32 can be stored in a tank or used directly to synthesize other compounds.

在自安德盧梭產物流10(如圖1中所圖解說明)去除氨及氰化氫後，殘留氣態廢產物流34含有多種氣體，包括氫、未反應之甲烷、二氧化碳、一氧化碳、水、氮、多種有機腈及痕量HCN。氣態廢棄物流34應不存在任何可檢測到之氨。氣態廢棄物流34中之該等氣體之量可端視安德盧梭反應條件而變化。可影響氣態廢棄物流34之組成之變量包括安德盧梭反應中氧之量、甲烷對氨之比率、反應器之溫度、觸媒有效性、進入及穿過安德盧梭反應器之流速及諸如此類。例如，當使用純氧作為安德盧梭法之反應物並將反應條件一般地最佳化時，在氣態廢棄物流中可存在至多約75vol%氫，但當採用空氣作為安德盧梭反應之氧來源時，在廢棄物產物流中僅可存在約1.5vol%氫。 Since the Andrussow product stream 10 (as illustrated in FIG. 1) removing ammonia and hydrogen cyanide, residual waste gaseous product stream 34 contains a variety of gases, including hydrogen, unreacted methane, the carbon dioxide, carbon monoxide, water, nitrogen , a variety of organic nitriles and traces of HCN. The gaseous waste stream 34 should be free of any detectable ammonia. The amount of such gases in the gaseous waste stream 34 can vary depending on the Andrussow reaction conditions. Variables that can affect the composition of the gaseous waste stream 34 include the amount of oxygen in the Andrussow reaction, the ratio of methane to ammonia, the temperature of the reactor, the effectiveness of the catalyst, the flow rate into and through the Andrussow reactor, and the like. For example, when pure oxygen is used as the reactant for the Andrussow process and the reaction conditions are generally optimized, up to about 75 vol% hydrogen may be present in the gaseous waste stream, but when air is used as the oxygen source for the Andrussow reaction. Only about 1.5 vol% hydrogen may be present in the waste product stream.

氣態廢棄物流34可有利地含有低於空氣中存在之氮量。例如，氣態廢棄物流34可含有小於約60%氮、小於約50%氮、小於約40% 氮、小於約30%氮、小於約20%氮或小於約10%氮。 The gaseous waste stream 34 can advantageously contain less than the amount of nitrogen present in the air. For example, gaseous waste stream 34 can contain less than about 60% nitrogen, less than about 50% nitrogen, less than about 40% nitrogen, less than about 30% nitrogen, less than about 20% nitrogen, or less than about 10% nitrogen.

如本文中所討論，具有含有大於55vol%氧之氧流6之安德盧梭法(如圖1中所圖解說明)可產生氣態廢棄物流34，氣態廢棄物流34具有能夠在不向氣態廢棄物流34補充燃料氣下使氣態廢棄物流34在可產生蒸汽之溫度下燃燒之熱值。因此，本文揭示之方法及系統在氣態廢棄物流34包括具有大於182BTU/scf之熱值之能量富集組份(例如氫及一氧化碳)時可尤其有利。例如，本發明之方法及系統可藉由利用氣態廢棄物流34之能量富集組份生成能量(例如，熱及電)。在實例中，當使用純氧作為氧流6時，氣態廢棄物流34可包括約78vol%氫及11vol%一氧化碳。通常，氣態廢棄物流34將僅含有殘留量之HCN。通常實質上完全去除HCN，不僅為了使有價值之HCN不損失至廢水中，而且亦出於健康及環境考慮，並且由於大量HCN可使廢水之處理變複雜。 As discussed herein, having an oxygen containing more than 55vol% of oxygen flow of 6 Andrew Andrussow process (as illustrated in FIG. 1) can produce a gaseous waste stream 34, the gaseous waste stream 34 can be performed without having to gaseous waste stream 34 The calorific value of the gaseous waste stream 34 that is combusted at a temperature at which steam can be produced under supplemental fuel gas. Accordingly, the methods and systems disclosed herein may be particularly advantageous when the gaseous waste stream 34 includes energy-enriched components (eg, hydrogen and carbon monoxide) having a calorific value greater than 182 BTU/scf. For example, the methods and systems of the present invention can generate energy (e.g., heat and electricity) by utilizing the energy enrichment component of the gaseous waste stream 34 . In an example, when pure oxygen is used as the oxygen stream 6 , the gaseous waste stream 34 can include about 78 vol% hydrogen and 11 vol% carbon monoxide. Typically, the gaseous waste stream 34 will only contain residual amounts of HCN. HCN is generally substantially completely removed, not only to make valuable HCN not lost to the wastewater, but also for health and environmental considerations, and the treatment of wastewater can be complicated by the large amount of HCN.

材料廢棄物利用系統36可包括汽電共生單元90。在一個實例中，汽電共生單元90可包括鍋爐80及發生器82(例如，發電機)，其經組態以燃燒廢棄物流出物並生成能量(例如，熱及電)。可採用其他汽電共生單元。在一些實例中，材料廢棄物利用系統36亦可包括水提取單元(未顯示)，其經組態以在氣態廢棄物流34作為燃料在汽電共生單元90中燃燒之前自氣態廢棄物流34去除液體水。 Material waste utilization system 36 may include a steam and electricity cogeneration unit 90 . In one example, the cogeneration unit 90 can include a boiler 80 and a generator 82 (eg, a generator) configured to combust waste effluent and generate energy (eg, heat and electricity). Other cogeneration units can be used. In some examples, material waste utilization system 36 may also include a water extraction unit (not shown) configured to remove liquid from gaseous waste stream 34 prior to combustion of gaseous waste stream 34 as fuel in gas-electricity compositing unit 90 . water.

汽電共生單元90可接收氣態廢棄物流34並使其作為燃料燃燒以產生熱能。例如，鍋爐80可接收氣態廢棄物流34並使其燃燒。可使自氣態廢棄物流34燃燒生成之熱與水接觸以生成熱(例如，蒸汽)。可使蒸汽88之一部分再循環回製程中。可將蒸汽92之一部分進給至發生器82以自熱能生成電。發生器82可將熱能轉換成可產生電之轉動能。電可用於產生HCN之方法11中。 The cogeneration unit 90 can receive the gaseous waste stream 34 and combust it as a fuel to generate thermal energy. For example, boiler 80 can receive gaseous waste stream 34 and combust it. The heat generated from the combustion of the gaseous waste stream 34 can be contacted with water to generate heat (eg, steam). A portion of the steam 88 can be recycled back to the process. A portion of the steam 92 can be fed to the generator 82 to generate electricity from thermal energy. Generator 82 converts thermal energy into rotational energy that produces electricity. Electricity can be used in method 11 for producing HCN.

材料廢棄物利用系統36可包括一或多個經組態以定量氣態廢棄物流34中之氰化氫、甲烷、氫、一氧化碳或其組合之含量的檢測器84。材料廢棄物利用系統36亦可包括在材料廢棄物利用系統36、氫回收系統38及燃燒系統42之間引導氣態廢棄物流34之轉向器86。檢測器84可監測能量富集組份，例如氫及一氧化碳。在各個實例中，轉向器86可在氫濃度低於臨限值時使氣態廢棄物流34自汽電共生單元90轉向。例如，當氫濃度等於或小於氣態廢棄物流34之約55vol%時，轉向器86可使氣態廢棄物流自汽電共生單元90轉向。在氫濃度等於或小於55vol%之實例中，氣態廢棄物流34所具有之熱值不能在不添加補充燃料氣下生成蒸汽。因此，轉向器86可將氣態廢棄物流34引導至氫回收系統38及/或燃燒器42。在一些實例中，轉向器86可將氣態廢棄物流34分流，以使得一部分進入汽電共生單元90、氫回收38及燃燒器42，同時可使輸送至燃燒器之量最小化。 Material waste utilization system 36 may include one or more detectors 84 configured to quantify the amount of hydrogen cyanide, methane, hydrogen, carbon monoxide, or combinations thereof in gaseous waste stream 34 . Material waste utilization system 36 may also include a diverter 86 that directs gaseous waste stream 34 between material waste utilization system 36 , hydrogen recovery system 38, and combustion system 42 . Detector 84 can monitor energy enriched components such as hydrogen and carbon monoxide. In various examples, diverter 86 can divert gaseous waste stream 34 from cogeneration unit 90 when the hydrogen concentration is below a threshold. For example, when the hydrogen concentration is equal to or less than about 55 vol% of the gaseous waste stream 34 , the diverter 86 can steer the gaseous waste stream from the oxyhydrogenic unit 90 . In the example where the hydrogen concentration is equal to or less than 55 vol%, the calorific value of the gaseous waste stream 34 cannot generate steam without the addition of supplemental fuel gas. Thus, the diverter 86 can direct the gaseous waste stream 34 to the hydrogen recovery system 38 and/or the combustor 42 . In some examples, diverter 86 may split gaseous waste stream 34 such that a portion enters cogeneration unit 90 , hydrogen recovery 38, and combustor 42 while minimizing the amount delivered to the combustor.

在採用材料廢棄物利用系統70之一個實例中，氧流6可包括大於55vol%氧。在採用材料廢棄物利用系統70之其他實例中，氧流6包括至少65vol%氧至約100vol%氧。如本文中所討論，包括大於55vol%氧之氧流6可生成氣態廢棄物流34，氣態廢棄物流34之熱值足夠大，以致於能夠在不向氣態廢棄物流34補充燃料氣下燃燒時生成蒸汽。 In one example employing a material waste utilization system 70 , the oxygen stream 6 can include greater than 55 vol% oxygen. In other examples employing material waste utilization system 70 , oxygen stream 6 includes at least 65 vol% oxygen to about 100 vol% oxygen. Steam is generated as discussed herein, including greater than the oxygen flow 55vol% of oxygen of 6 to generate a gaseous waste stream 34, the gaseous waste stream heating value of 34, is sufficiently large, so that can be burned without stream 34 supplementary fuel gas into the gaseous waste time .

多個因素可決定是否將氣態廢棄物流34之全部或一部分輸送至汽電共生單元90、氫回收38及或燃燒器42。例如，氫需求可決定是否將氣態廢棄物流34之一部分輸送至氫回收38。例如，至少，輸送至氫回收34之氣態廢棄物流34部分應足以滿足氫需求。在其他實例中，可將更多氣態廢棄物流34輸送至氫回收38並且可儲存所回收之氫。其他因素包括氫、蒸汽及電之成本。例如，可比較氫回收38對汽電共生90之成本分析。 A number of factors may determine whether all or a portion of the gaseous waste stream 34 is delivered to the cogeneration unit 90 , the hydrogen recovery 38, and or the combustor 42 . For example, the hydrogen demand may determine whether a portion of the gaseous waste stream 34 is delivered to the hydrogen recovery 38 . For example, at least, the waste gas fed to hydrogen recovery portion 34 of stream 34 should be sufficient to meet the hydrogen demand. In other examples, more gaseous waste stream 34 can be sent to hydrogen recovery 38 and the recovered hydrogen can be stored. Other factors include the cost of hydrogen, steam, and electricity. For example, a cost analysis of hydrogen recovery 38 versus cogeneration collateral 90 can be compared.

在採用燃燒器42之實例中，要求流向燃燒器42之流動最小化。本發明之方法及系統可使超過所要求最小量流動之任何量最小化。例如，較佳將大部分氣態廢棄物流34輸送至氫回收38、汽電共生單元或其組合。因此，本發明方法及系統可藉由將材料廢棄物轉化成能量(例如，熱及/或電)或回收一部分材料來減少材料廢棄物。在其他實例中，可使用氣態廢棄物流34作為引火氣體(pilot gas)(未顯示)。引火氣體不需要非常高的熱值，此乃因其僅用於維持燃燒。 In the example in which the burner 42 is employed, the flow to the combustor 42 is required to be minimized. The method and system of the present invention minimizes any amount beyond the required minimum amount of flow. For example, most of the gaseous waste stream 34 is preferably delivered to a hydrogen recovery 38, a cogeneration unit, or a combination thereof. Thus, the methods and systems of the present invention can reduce material waste by converting material waste into energy (eg, heat and/or electricity) or by recovering a portion of the material. In other examples, gaseous waste stream 34 can be used as a pilot gas (not shown). The pilot gas does not require a very high calorific value because it is only used to sustain combustion.

在實例中，可將一部分或全部氣態廢棄物流34引導至氫回收系統38。所回收之氫流98可儲存用於將來處理或銷售，輸送至其他氫處理單元，回收至上游或下游之點，用於補充燃燒器42，氫化反應或其組合，如下文進一步討論。然而，若氣態廢棄物流34具有小於約40vol%氫，則氫回收系統42可為不經濟的。 In an example, some or all of the gaseous waste stream 34 can be directed to a hydrogen recovery system 38 . The recovered hydrogen stream 98 can be stored for future processing or sale, sent to other hydrogen processing units, recycled to upstream or downstream points for supplementing the combustor 42 , hydrogenation reaction, or a combination thereof, as discussed further below. However, if the gaseous waste stream 34 has less than about 40 vol% hydrogen, the hydrogen recovery system 42 can be uneconomical.

實例Instance

藉由參考以下實例可更好地理解本發明，該等實例係以舉例方式提供。本發明並不限於本文給出之實例。 The invention may be better understood by reference to the following examples, which are provided by way of example. The invention is not limited to the examples given herein.

比較實例1：空氣安德盧梭法及氧安德盧梭法之廢氣組成之比較Comparative Example 1: Comparison of exhaust gas composition of air Andrussow method and oxygen Andrussow method

此實例說明，使用高度富集之氧來源之安德盧梭法通常產生氫含量高於採用空氣作為氧來源之安德盧梭法之廢棄物流。 This example illustrates that the Andrussow process using a highly enriched oxygen source typically produces a waste stream with a higher hydrogen content than the Andrussow process using air as the source of oxygen.

使用內部具有陶瓷隔熱襯裏之4英吋內徑不銹鋼反應器進行中試規模(pilot scale)測試。加載40個來自Johnson Matthey(USA)之90wt% Pt/10wt% Rh 40網目絲網片作為觸媒床。使用穿孔氧化鋁瓦片支撐觸媒片。將總流速設定為2532SCFH(標準立方呎每小時)。經由兩種單獨的安德盧梭法產生氰化氫。一種方法係氧安德盧梭法，其採用包括35vol%甲烷、38vol%氨及27vol%實質上純淨之氧之氣態反應混合物。另一種方法係空氣安德盧梭法，其採用約17vol%甲烷、19vol%氨及64vol%空氣。兩種方法皆使用含鉑觸媒。 A pilot scale test was conducted using a 4 inch inner diameter stainless steel reactor with a ceramic thermal insulation lining. A 40 wt% Pt/10 wt% Rh 40 mesh screen from Johnson Matthey (USA) was loaded as a catalyst bed. The catalyst sheets were supported using perforated alumina tiles. Set the total flow rate to 2532 SCFH (standard cubic per hour). Hydrogen cyanide is produced via two separate Andrussow processes. One method is the oxygen Andrussow process, which employs a gaseous reaction mixture comprising 35 vol% methane, 38 vol% ammonia, and 27 vol% substantially pure oxygen. Another method is the air Andrussow process, which employs about 17 vol% methane, 19 vol% ammonia, and 64 vol% air. Both methods use a platinum-containing catalyst.

在涉及吸收至磷酸銨流中之方法中自每一產物流單獨地去除氨。然後在涉及酸化水之方法中自氨空乏產物流去除氰化氫，藉此單獨地生成每一方法之氰化氫產物及氣態廢棄物流。 Ammonia is removed separately from each product stream in a process involving absorption into an ammonium phosphate stream. The hydrogen cyanide is then removed from the ammonia depleted product stream in a process involving acidified water, whereby The hydrogen cyanide product and gaseous waste stream of each process are generated separately.

在去除氨及HCN後來自氧法及空氣法之氣態廢棄物流之組成顯示於下表1中。 The composition of the gaseous waste stream from the oxygen and air processes after removal of ammonia and HCN is shown in Table 1 below.

如所說明，採用高度富集之氧作為含氧進料流之來源之安德盧梭法生成的氫顯著高於採用空氣作為含氧進料流之來源之安德盧梭法。 As illustrated, the Andrussow process using highly enriched oxygen as the source of the oxygen-containing feed stream produces significantly higher hydrogen than the Andrussow process using air as the source of the oxygen-containing feed stream.

比較實例2：在氧安德盧梭法期間生成之廢棄物Comparative Example 2: Waste generated during the oxygen Andrussow process

此實例可說明在氰化氫產生期間生成之廢棄物的量。 This example illustrates the amount of waste generated during the production of hydrogen cyanide.

氰化氫係經由安德盧梭法在鉑觸媒存在下自包括35vol%甲烷、 38vol%氨及27vol%實質上純淨之氧之氣態反應混合物產生。將甲烷進料流、氨進料流及氧進料流進給至含有鉑觸媒之反應器中。使用內部具有陶瓷隔熱襯裏之4英吋內徑不銹鋼反應器進行中試規模測試。加載40個來自Johnson Matthey(USA)之90wt% Pt/10wt% Rh 40網目絲網片作為觸媒床。使用穿孔氧化鋁瓦片支撐觸媒片。將總流速設定為2532SCFH(標準立方呎每小時)。 Hydrogen cyanide self-contains 35 vol% methane in the presence of platinum catalyst via the Andrussow process. A gaseous reaction mixture of 38 vol% ammonia and 27 vol% substantially pure oxygen is produced. The methane feed stream, the ammonia feed stream, and the oxygen feed stream are fed to a reactor containing a platinum catalyst. Pilot scale testing was conducted using a 4 inch inner diameter stainless steel reactor with a ceramic thermal insulation lining. A 40 wt% Pt/10 wt% Rh 40 mesh screen from Johnson Matthey (USA) was loaded as a catalyst bed. The catalyst sheets were supported using perforated alumina tiles. Set the total flow rate to 2532 SCFH (standard cubic per hour).

隨著反應進行，持續產生含有氰化氫、未反應之氨、廢氣及其他產物之氣態廢棄物流。在去除氰化氫及未反應之氨後，不含氰化氫之氣態廢棄物流可含有氣體之混合物，例如氫、未反應之甲烷、二氧化碳、一氧化碳、水、氮、多種有機腈及痕量HCN，且因此包括能量富集氣體，例如氫、甲烷及一氧化碳。在實例中，可將氣態廢棄物流輸送至燃燒器以徹底處置氣態廢棄物流之組份。在此實例中，對於1,000lbs HCN，產生大約40,000scf廢氣。另外，在HCN回收後損失258BTU/scf。 As the reaction proceeds, a gaseous waste stream containing hydrogen cyanide, unreacted ammonia, waste gases, and other products is continuously produced. After removal of hydrogen cyanide and unreacted ammonia, the gaseous waste stream containing no hydrogen cyanide may contain a mixture of gases such as hydrogen, unreacted methane, carbon dioxide, carbon monoxide, water, nitrogen, various organic nitriles and traces of HCN. And thus include energy enriched gases such as hydrogen, methane and carbon monoxide. In an example, a gaseous waste stream can be delivered to a combustor to completely dispose of the components of the gaseous waste stream. In this example, approximately 40,000 scf of exhaust gas is produced for 1,000 lbs of HCN. In addition, 258 BTU/scf was lost after HCN recovery.

實例1：氣態廢棄物流中之氫含量Example 1: Hydrogen content in a gaseous waste stream

此實例說明氣態廢棄物流之氫含量在使用具有不同量之氧之反應物含氧進料流之安德盧梭法中如何變化。 This example illustrates how the hydrogen content of the gaseous waste stream varies in the Andrussow process using a reactant oxygenated feed stream having varying amounts of oxygen.

氰化氫係經由一系列如針對比較實例1所述實施之獨立安德盧梭法產生。然而，每一方法係使用不同的反應物含氧進料流實施，其中進料流中之氧含量在約20.9vol%至約100vol%氧之間變化，如表2中所示。 Hydrogen cyanide was produced via a series of independent Andrussow processes as described for Comparative Example 1. However, each process was carried out using a different reactant oxygenated feed stream wherein the oxygen content in the feed stream varied from about 20.9 vol% to about 100 vol% oxygen, as shown in Table 2.

在涉及吸收至磷酸銨流中之方法中自每一產物流個別地去除氨。然後在涉及酸化水之方法中自氨空乏產物流去除氰化氫，藉此個別地生成每一方法之氰化氫產物及氣態廢棄物流。 Ammonia is removed individually from each product stream in a process involving absorption into an ammonium phosphate stream. The hydrogen cyanide is then removed from the ammonia depleted product stream in a process involving acidified water whereby the hydrogen cyanide product and gaseous waste stream of each process are separately produced.

來自利用具有不同氧含量之含氧進料流運行之安德盧梭法之氣態廢棄物流的組成顯示於下表2中。 The composition of the gaseous waste stream from the Andrussow process operating with an oxygen-containing feed stream having different oxygen contents is shown in Table 2 below.

在表2中，廢氣流係指在去除氨及HCN之後廢棄物流中氫之體積%。另外，「有價值的」係指廢氣流是否能夠用作燃料氣(例如，燃燒)以在不添加天然氣下生成蒸汽。 In Table 2, the exhaust gas flow refers to the volume % of hydrogen in the waste stream after removal of ammonia and HCN. In addition, "valuable" refers to whether the exhaust stream can be used as a fuel gas (eg, combustion) to generate steam without the addition of natural gas.

實例2：利用能量再俘獲系統之氧安德盧梭法Example 2: Oxygen Andrussow Method Using Energy Recapture System

本實例說明在經由氧安德盧梭法產生氰化氫期間操作之包括廢熱利用系統及材料廢棄物利用系統之能量再俘獲系統之組態。 This example illustrates the configuration of an energy recapture system including a waste heat utilization system and a material waste utilization system that operates during the production of hydrogen cyanide via the oxygen Andrussow process.

使用內部具有陶瓷隔熱襯裏之4英吋內徑不銹鋼反應器進行中試規模測試。加載40個來自Johnson Matthey(USA)之90wt% Pt/10wt% Rh 40網目片作為觸媒床。使用穿孔氧化鋁瓦片支撐觸媒片。將總流速設定為2532SCFH(標準立方呎每小時)。氰化氫係經由安德盧梭法在含鉑觸媒存在下自包括35vol%甲烷、38vol%氨及27vol%實質上純淨之氧之氣態反應混合物產生。使產物流與汽電共生單元接觸並生成電及蒸汽。可將一部分蒸汽再循環回去以預熱反應混合物進料流，從而使外部供應之熱的量最小化。另外，可將電再循環回製程中並使外部供應之電的量最小化。 Pilot scale testing was conducted using a 4 inch inner diameter stainless steel reactor with a ceramic thermal insulation lining. 40 90 wt% Pt/10 wt% Rh 40 mesh sheets from Johnson Matthey (USA) were loaded as a catalyst bed. The catalyst sheets were supported using perforated alumina tiles. Total flow The speed is set to 2532 SCFH (standard cube 呎 hour). Hydrogen cyanide is produced via the Andrussow process in the presence of a platinum-containing catalyst from a gaseous reaction mixture comprising 35 vol% methane, 38 vol% ammonia, and 27 vol% substantially pure oxygen. The product stream is contacted with a cogeneration unit to generate electricity and steam. A portion of the steam can be recycled back to preheat the reaction mixture feed stream to minimize the amount of externally supplied heat. In addition, electricity can be recycled back into the process and the amount of externally supplied electricity is minimized.

隨著反應進行，持續產生含有氰化氫、未反應之氨、廢氣及其他產物之氣態廢棄物流。在去除氨及氰化氫後，生成氣態廢棄物流。在此實例中，使輸送至燃燒器之量最小化。另外，氣態廢棄物流具有大於258BTU/scf之熱值並輸送至材料廢棄物利用系統之汽電共生單元。在此實例中，在回收HCN之後在氣態廢棄物流中回收大約258BTU/scf。在最佳操作條件期間，該等能量俘獲單元(例如廢熱利用系統及材料廢棄物利用系統)可生成大於100%之藉由所述方法製造氰化氫所需要之能量。 As the reaction proceeds, a gaseous waste stream containing hydrogen cyanide, unreacted ammonia, waste gases, and other products is continuously produced. After removal of ammonia and hydrogen cyanide, a gaseous waste stream is produced. In this example, the amount delivered to the burner is minimized. In addition, the gaseous waste stream has a calorific value greater than 258 BTU/scf and is delivered to the cogeneration unit of the material waste utilization system. In this example, approximately 258 BTU/scf was recovered in the gaseous waste stream after recovery of the HCN. During optimal operating conditions, the energy capture units (e.g., waste heat utilization systems and material waste utilization systems) can generate greater than 100% of the energy required to produce hydrogen cyanide by the method.

以上實施方式意欲具有說明性而非限制性。例如，上述實例(或其一或多個要素)可彼此組合使用。例如，熟習此項技術者可在審查以上說明後使用其他實例。此外，可將各種特徵或要素集合在一起以精簡揭示內容。此不應解釋為意指未主張之揭示特徵對任一技術方案必不可少。而是，發明性標的物可在於少於特定所揭示實施例之所有特徵。因此，在此將以下申請專利範圍併入實施方式中，其中每一技術方案獨立地作為單獨實施例。本發明之範圍應參照所附申請專利範圍連同授權於申請專利範圍之等效物的整個範圍一起來確定。 The above embodiments are intended to be illustrative and not restrictive. For example, the above examples (or one or more of the elements thereof) can be used in combination with each other. For example, those skilled in the art can use other examples after reviewing the above description. In addition, various features or elements can be grouped together to streamline the disclosure. This should not be construed as meaning that the disclosed features are not essential to any technical solution. Rather, the inventive subject matter may lie in less than all features of the particular disclosed embodiments. Accordingly, the scope of the following claims is hereby incorporated by reference in its entirety in its entirety in its entirety herein The scope of the invention should be determined with reference to the appended claims and the scope of the claims

若此文件與任何以引用方式併入之文件之間之使用不一致，則以此文件之使用為準。 In the event of any inconsistency between this document and any document incorporated by reference, the use of this document will prevail.

在此文件中，如在專利文件中常見，使用術語「一(a或an)」來包括一者或一者以上，此獨立於「至少一者」或「一或多者」之任何其他情形或使用。在此文件中，除非另有指示，否則使用術語「或」來指示非排他性，或使得「A或B」包括「A但非B」、「B但非A」及「A及B」。在此文件中，術語「包括(including)」及「其中(in which)」用作各別術語「包含(comprising)」及「其中(wherein)」之通俗英語等效形式。同樣，在下文申請專利範圍中，術語「包括(including)」及「包含(comprising)」為開放式的，即，包括除列於技術方案中之此一術語之後的彼等要素以外之要素之系統、器件、物件、組合物、調配物或方法仍視為歸屬於該技術方案之範圍內。此外，在下文申請專利範圍中，術語「第一」、「第二」及「第三」等僅用作標記，且並不意欲對其對象施加數字要求。 In this document, as commonly found in patent documents, the term "a" or "an" is used to include one or more, and is independent of any of "at least one" or "one or more" Other situations or use. In this document, the term "or" is used to indicate non-exclusiveness, or "A or B" includes "A but not B", "B but not A" and "A and B" unless otherwise indicated. In this document, the terms "including" and "in which" are used in the plain English equivalents of the respective terms "comprising" and "wherein". Also, in the scope of the claims below, the terms "including" and "comprising" are open-ended, that is, include elements other than those listed after the term in the technical solution. Systems, devices, articles, compositions, formulations or methods are still considered to fall within the scope of the technical solution. Moreover, in the scope of the following claims, the terms "first," "second," and "third," and the like are used merely as labels, and are not intended to impose numerical requirements on the subject.

本文所述之方法實例可至少部分地為機器或電腦實施的。一些實例可包括編碼有指令之電腦可讀媒體或機器可讀媒體，該等指令可操作以將電子器件組態為實施如在上文實例中所述之方法或方法步驟。此等方法或方法步驟之實施方案可包括程式碼，例如微程式碼、組合語言程式碼、較高階語言程式碼或諸如此類。此程式碼可包括用於實施各種方法之電腦可讀指令。該程式碼可形成電腦程式產品之部分。此外，在實例中，例如在執行期間或在其他時間，該程式碼可有形地儲存於一或多個揮發性、非暫時性或非揮發性有形電腦可讀媒體上。該等有形電腦可讀媒體之實例可包括(但不限於)硬碟片、可移式磁碟、可移式光碟(例如，壓縮碟片及數位視訊碟片)、磁帶盒、記憶卡或記憶條、隨機存取記憶體(RAM)、唯讀記憶體(ROM)及諸如此類。 Examples of methods described herein can be implemented at least in part for a machine or computer. Some examples may include a computer readable medium or machine readable medium encoded with instructions operable to configure an electronic device to implement a method or method step as described in the above examples. Implementations of such methods or method steps can include code, such as microcode, combined language code, higher order language code, or the like. This code can include computer readable instructions for implementing various methods. This code forms part of a computer program product. Moreover, in an example, such as during execution or at other times, the code may be tangibly stored on one or more volatile, non-transitory or non-volatile tangible computer readable media. Examples of such tangible computer readable media may include, but are not limited to, hard disks, removable disks, removable optical disks (eg, compressed disks and digital video disks), magnetic tape cartridges, memory cards, or memories. Bars, random access memory (RAM), read only memory (ROM), and the like.

提供本摘要以符合37 C.F.R.§1.72(b)，從而容許讀者快速確定本技術揭示內容之本質。提交本摘要係基於以下理解：其並非用於解釋或限制申請專利範圍之範圍或含義。 This abstract is provided to comply with 37 C.F.R. § 1.72(b), to allow the reader to quickly ascertain the nature of the present disclosure. The Abstract is submitted with the understanding that it is not intended to limit or limit the scope or meaning of the claims.

儘管已參照實例性實例闡述了本發明，但熟習此項技術者應認識到，可在形式及細節上作出改變，此並不背離本發明之精神及範圍。 Although the invention has been described with reference to example examples, those skilled in the art should recognize It is to be understood that changes may be made in form and detail without departing from the spirit and scope of the invention.

下文所提供之具體列舉之聲明[1]至[31]僅用於說明目的，且並不以其他方式限制如申請專利範圍所界定所揭示標的物之範圍。該等所列舉之聲明涵蓋其中所述之所有組合、次組合及多層引用(例如，多層依賴性)組合。 The following detailed description of the disclosures [1] to [31] are provided for illustrative purposes only and are not intended to limit the scope of the subject matter as defined by the claims. These recited statements encompass all combinations, sub-combinations, and multi-layered (e.g., multi-layered) combinations described therein.

聲明statement

[1.]一種利用在經由安德盧梭法產生氰化氫期間產生之廢棄物的方法，其包含：(a)燃燒氣態廢棄物流以供初級能量生成，其中該氣態廢棄物流係來自經組態以產生氰化氫之反應器，並且該氣態廢棄物流實質上不含氰化氫；(b)使熱回收單元與熱接觸以供次級能量生成，其中該熱係在該氰化氫之產生期間由反應器生成；或(c)其組合。 [1.] A method of utilizing waste generated during the production of hydrogen cyanide by the Andrussow process, comprising: (a) burning a gaseous waste stream for primary energy generation, wherein the gaseous waste stream is from a configuration a reactor for generating hydrogen cyanide, and the gaseous waste stream is substantially free of hydrogen cyanide; (b) contacting the heat recovery unit with heat for secondary energy generation, wherein the heat is generated by the hydrogen cyanide Generated by the reactor during the period; or (c) a combination thereof.

[2.]如聲明[1]之方法，其中該初級或次級能量生成包含熱傳遞、蒸汽生成、電生成或其組合。 [2] The method of claim [1], wherein the primary or secondary energy generation comprises heat transfer, steam generation, electrical generation, or a combination thereof.

[3.]如聲明[1]或[2]之方法，其中該初級或次級能量生成係蒸汽生成及電生成。 [3] The method of [1] or [2], wherein the primary or secondary energy generation system is steam generation and electrogeneration.

[4.]如聲明[1]至[3]中任一項之方法，其進一步包含在燃燒該氣態廢棄物流之前，調整包含甲烷、氨及氧之反應混合物以向反應混合物提供足夠氧，從而在去除氨及回收氰化氫後在該氣態廢棄物流中生成至少約59體積%氫。 [4] The method of any one of [1] to [3], further comprising adjusting a reaction mixture comprising methane, ammonia, and oxygen to provide sufficient oxygen to the reaction mixture prior to burning the gaseous waste stream, thereby At least about 59% by volume hydrogen is produced in the gaseous waste stream after removal of ammonia and recovery of hydrogen cyanide.

[5.]如聲明[4]之方法，其中該足夠氧係作為包含大於55體積%氧之含氧進料流供應。 [5] The method of claim [4], wherein the sufficient oxygen is supplied as an oxygen-containing feed stream comprising greater than 55 vol% oxygen.

[6.]如聲明[1]至[5]中任一項之方法，其中該氣態廢棄物流包含約60體積%氧至約78體積%氧及約10體積%一氧化碳至約15體積%一氧化碳。 [6] The method of any one of [1] to [5] wherein the gaseous waste stream comprises About 60% by volume of oxygen to about 78% by volume of oxygen and about 10% by volume of carbon monoxide to about 15% by volume of carbon monoxide.

[7.]如聲明[1]至[6]中任一項之方法，其中該氣態廢棄物流包含小於約50體積%氮。 [7] The method of any one of [1] to [6] wherein the gaseous waste stream comprises less than about 50% by volume nitrogen.

[8.]如聲明[1]至[7]中任一項之方法，其中該氣態廢棄物流包含大於182英制熱量單位每標準立方呎(BTU/scf)之熱值。 [8] The method of any one of [1] to [7] wherein the gaseous waste stream comprises a calorific value greater than 182 British thermal units per standard cubic inch (BTU/scf).

[9.]如聲明[1]至[8]中任一項之方法，其中該氣態廢棄物流包含約205BTU/scf至約260BTU/scf之熱值。 [9] The method of any one of [1] to [8] wherein the gaseous waste stream comprises a calorific value of from about 205 BTU/scf to about 260 BTU/scf.

[10.]如聲明[1]至[9]中任一項之方法，其中未向該氣態廢棄物流補充燃料氣。 [10] The method of any one of [1] to [9], wherein the gaseous waste stream is not replenished with fuel gas.

[11.]如聲明[1]至[10]中任一項之方法，其中燃燒該氣態廢棄物流包括使該氣態廢棄物流與第一汽電共生單元接觸。 [11] The method of any one of [1] to [10] wherein burning the gaseous waste stream comprises contacting the gaseous waste stream with a first vapor-electricity commencing unit.

[12.]如聲明[11]之方法，其中該第一汽電共生單元包含第一鍋爐及發電機，該第一鍋爐經組態以生成蒸汽並且該發電機經組態以生成電。 [12] The method of claim [11], wherein the first cogeneration unit comprises a first boiler and a generator, the first boiler being configured to generate steam and the generator configured to generate electricity.

[13.]如聲明[1]至[12]中任一項之方法，其中該熱回收單元係第二汽電共生單元。 [13] The method of any one of [1] to [12] wherein the heat recovery unit is a second gas-electricity symbiosis unit.

[14.]如聲明[13]之方法，其中該第二汽電共生單元包括第二鍋爐及熱激活發生器，該第二鍋爐經組態以生成蒸汽並且該熱激活發生器經組態以生成電。 [14] The method of claim [13], wherein the second steam symbiosis unit comprises a second boiler and a heat activated generator, the second boiler configured to generate steam and the heat activated generator is configured Generate electricity.

[15.]如聲明[13]之方法，其中使該熱回收單元與熱接觸進一步包括使來自該反應器之產物流與該第二汽電共生單元接觸，其中該產物流在與該第二汽電共生單元接觸之前具有第一溫度，並且該產物流在與該第二汽電共生單元接觸之後具有第二溫度，該第一溫度高於該第二溫度。 [15] The method of claim [13], wherein contacting the heat recovery unit with the thermal contact further comprises contacting a product stream from the reactor with the second vapor-electric co-generation unit, wherein the product stream is in the second The vapor co-existing unit has a first temperature prior to contacting, and the product stream has a second temperature after contact with the second vapor-electric co-generation unit, the first temperature being higher than the second temperature.

[16.]如聲明[1]至[15]中任一項之方法，其中該氰化氫係在甲烷、氨及氧之反應混合物中在包含鉑之觸媒存在下產生，其中該反應混合物具有大於約55體積%氧。 [16] The method of any one of [1] to [15] wherein the hydrogen cyanide is in The reaction mixture of alkane, ammonia and oxygen is produced in the presence of a catalyst comprising platinum, wherein the reaction mixture has greater than about 55% by volume oxygen.

[17.]如聲明[16]之方法，其中該甲烷係在含有甲烷之烴進料中提供。 [17] The method of claim [16], wherein the methane is provided in a hydrocarbon feed containing methane.

[18.]如聲明[16]或[17]之方法，其中該甲烷係作為包含天然氣、生質物氣體、實質上純淨之甲烷或其混合物之烴進料提供。 [18] The method of [16] or [17], wherein the methane is provided as a hydrocarbon feed comprising natural gas, biomass gas, substantially pure methane or a mixture thereof.

[19.]如聲明[16]至[18]中任一項之方法，其中該甲烷係作為天然氣提供。 [19] The method of any one of [16] to [18] wherein the methane is provided as natural gas.

[20.]如聲明[16]至[19]中任一項之方法，其中該甲烷係作為實質上純淨之甲烷提供。 [20] The method of any one of [16] to [19] wherein the methane is provided as substantially pure methane.

[21.]如聲明[16]至[20]中任一項之方法，其中該氧係作為富集氧之進料、實質上純淨之氧進料或其任一組合提供。 [21.] The method of any one of [16] to [20] wherein the oxygen is provided as an oxygen-enriched feed, a substantially pure oxygen feed, or any combination thereof.

[22.]如聲明[1]至[21]中任一項之方法，其中氨實質上已自該氣態廢棄物流去除。 [22] The method of any one of [1] to [21] wherein ammonia is substantially removed from the gaseous waste stream.

[23.]如聲明[1]至[22]中任一項之方法，其中水實質上已自該氣態廢棄物流去除。 [23] The method of any one of [1] to [22] wherein water is substantially removed from the gaseous waste stream.

[24.]如聲明[1]至[23]中任一項之方法，其中該氣態廢棄物流包含氫、甲烷或其混合物。 [24] The method of any one of [1] to [23] wherein the gaseous waste stream comprises hydrogen, methane or a mixture thereof.

[25.]一種經由安德盧梭法產生氰化氫之系統，其包含：(a)反應器，其經組態以在包含鉑之觸媒存在下自包含甲烷、氨及氧之反應混合物產生氰化氫，其中該反應器亦經組態以向該反應混合物供應足夠氧，從而在去除氨及回收氰化氫後生成具有至少59體積%氫之氣態廢棄物流；(b)第一汽電共生單元，其經組態以燃燒作為燃料之該氣態廢棄物流以供初級能量生成，其中該氣態廢棄物流實質上不含氰化氫；及/或 (c)第二汽電共生單元，其經組態以自該反應器吸收熱以供次級能量生成。 [25.] A system for producing hydrogen cyanide via the Andrussow process, comprising: (a) a reactor configured to produce a reaction mixture comprising methane, ammonia, and oxygen in the presence of a catalyst comprising platinum. Hydrogen cyanide, wherein the reactor is also configured to supply sufficient oxygen to the reaction mixture to produce a gaseous waste stream having at least 59 vol% hydrogen after removal of ammonia and recovery of hydrogen cyanide; (b) first steam a commensal unit configured to combust the gaseous waste stream as a fuel for primary energy generation, wherein the gaseous waste stream is substantially free of hydrogen cyanide; and/or (c) a second steam symbiosis unit configured to absorb heat from the reactor for secondary energy generation.

[26.]如聲明[25]之系統，其中該足夠氧係作為包含大於55體積%氧之含氧進料流供應。 [26.] The system of claim [25], wherein the sufficient oxygen is supplied as an oxygen-containing feed stream comprising greater than 55 volume percent oxygen.

[27.]如聲明[25]或[26]中任一項之系統，其中該氣態廢棄物流包含約60體積%氧至約78體積%氧及約10體積%一氧化碳至約15體積%一氧化碳。 [27] The system of any one of [25] or [26] wherein the gaseous waste stream comprises from about 60% by volume oxygen to about 78% by volume oxygen and from about 10% by volume carbon monoxide to about 15% by volume carbon monoxide.

[28.]如聲明[25]至[27]中任一項之系統，其中該氣態廢棄物流包含小於約50體積%氮。 [28] The system of any one of [25] to [27] wherein the gaseous waste stream comprises less than about 50% by volume nitrogen.

[29.]如聲明[25]至[28]中任一項之系統，其中該氣態廢棄物流包含大於182BTU/scf之熱值。 [29] The system of any one of [25] to [28] wherein the gaseous waste stream comprises a calorific value greater than 182 BTU/scf.

[30.]如聲明[25]至[29]中任一項之系統，其中該氣態廢棄物流包含約205BTU/scf至約260BTU/scf之熱值。 [30] The system of any one of [25] to [29] wherein the gaseous waste stream comprises a calorific value of from about 205 BTU/scf to about 260 BTU/scf.

[31.]如聲明[25]至[30]中任一項之系統，其中未向該氣態廢棄物流補充燃料氣。 [31] The system of any one of [25] to [30] wherein the gaseous waste stream is not replenished with fuel gas.

[32.]如聲明[25]至[31]中任一項之系統，其進一步包含：(d)第一熱傳遞系統，其經組態以自該第一汽電共生單元吸收熱並使該熱回收；及/或(e)第二熱傳遞系統，其經組態以自該第二汽電共生單元吸收熱並使該熱回收以加熱進給至該反應器中之該甲烷、氨及氧中之至少一者。 [32] The system of any one of clauses [25] to [31] further comprising: (d) a first heat transfer system configured to absorb heat from the first vapor-electricity symbiosis unit and The heat recovery; and/or (e) a second heat transfer system configured to absorb heat from the second vapor-electricity commencing unit and recover the heat to heat the methane, ammonia fed to the reactor And at least one of oxygen.

[33.]如聲明[25]至[32]中任一項之系統，其進一步包含用於定量該氣態廢棄物流中之氰化氫、甲烷、氫、一氧化碳或其組合之含量的檢測器。 [33] The system of any one of [25] to [32], further comprising a detector for quantifying the amount of hydrogen cyanide, methane, hydrogen, carbon monoxide or a combination thereof in the gaseous waste stream.

[34.]如聲明[33]之系統，其進一步包含可操作地連接至該檢測器之閥，其中該閥經組態以在該氣態廢棄物流中檢測到低於臨限值之氫濃度時使該氣態廢棄物流自該第一汽電共生單元轉向。 [34] The system of claim [33], further comprising a valve operatively coupled to the detector, wherein the valve is configured to detect a threshold below the threshold in the gaseous waste stream The gaseous waste stream is diverted from the first steam-electric symbiosis unit at a hydrogen concentration.

[35.]如聲明[33]之系統，其進一步包含可操作地連接至該檢測器之閥，其中該閥經組態以在易燃組份之設定值低於臨限值時使該氣態廢棄物流自該第一汽電共生單元轉向。 [35] The system of claim [33], further comprising a valve operatively coupled to the detector, wherein the valve is configured to cause the gaseous state when a set value of the flammable component is below a threshold The waste stream is diverted from the first cogeneration unit.

[36.]如聲明[35]之系統，其中該臨限值係基於該氣態廢棄物流之熱含量值。 [36.] The system of claim [35], wherein the threshold is based on a heat content value of the gaseous waste stream.

[37.]如聲明[33]之系統，其中該甲烷係包含天然氣、合成氣、生質物氣體、實質上純淨之甲烷或其混合物之烴進料。 [37] The system of claim [33], wherein the methane is a hydrocarbon feed comprising natural gas, syngas, biomass gas, substantially pure methane, or a mixture thereof.

[38].如聲明[33]之系統，其中該甲烷係天然氣。 [38]. The system of claim [33], wherein the methane is natural gas.

[39.]如聲明[33]之系統，其中該甲烷係實質上純淨之甲烷。 [39] The system of claim [33], wherein the methane is substantially pure methane.

[40].如聲明[33]之系統，其中該氧係作為富集氧之進料、實質上純淨之氧進料或其任一組合提供。 [40]. The system of claim [33], wherein the oxygen is provided as an oxygen enriched feed, a substantially pure oxygen feed, or any combination thereof.

[41.]如聲明[25]至[40]中任一項之系統，其中氨實質上已自該氣態廢棄物流去除。 [41] The system of any one of [25] to [40] wherein ammonia is substantially removed from the gaseous waste stream.

[42.]如聲明[25]至[41]中任一項之系統，其中水實質上已自該氣態廢棄物流去除。 [42] The system of any one of [25] to [41] wherein the water has substantially been removed from the gaseous waste stream.

[43.]如聲明[25]至[42]中任一項之系統，其中該廢棄物流出物包含氫、甲烷或其混合物。 [43] The system of any one of [25] to [42] wherein the waste effluent comprises hydrogen, methane or a mixture thereof.

[44.]一種方法，其包含：(a)調整包含甲烷、氨及氧之反應混合物以向該反應混合物提供足夠氧，從而在去除氨及回收氰化氫之後生成在氣態廢棄物流中具有至少59體積%氫之該氣態廢棄物流；及(b)燃燒該氣態廢棄物流以供能量生成。 [44.] A method comprising: (a) adjusting a reaction mixture comprising methane, ammonia, and oxygen to provide sufficient oxygen to the reaction mixture to produce at least a portion of the gaseous waste stream after removal of ammonia and recovery of hydrogen cyanide 59% by volume of the gaseous waste stream; and (b) burning the gaseous waste stream for energy production.

[45.]如聲明[44]之方法，其中該能量生成包含蒸汽生成、電生成或其組合。 [45] The method of claim [44], wherein the energy generation comprises steam generation, electrical generation, or a combination thereof.

[46.]如聲明[44]之方法，其中該能量生成包含經由汽電共生單元之蒸汽生成及電生成。 [46.] The method of claim [44], wherein the energy generation comprises symbiosis via steam and electricity Steam generation and electricity generation of the unit.

[47.]如聲明[44]至[46]中任一項之方法，其中該足夠氧係作為包含大於55體積%氧之含氧進料流供應。 [47] The method of any one of [44] to [46] wherein the sufficient oxygen is supplied as an oxygen-containing feed stream comprising greater than 55 vol% oxygen.

[48.]如聲明[44]至[47]中任一項之方法，其中該氣態廢棄物流包含約59體積%氫至約78體積%氫、約12體積%一氧化碳至約15體積%一氧化碳、約0.7體積%二氧化碳至約1.5體積%二氧化碳、約3體積%氮至約5體積%氮、約1體積%甲烷至約2.0體積%甲烷、約0.01體積%有機腈至約0.1體積%有機腈、約0.01體積% HCN至約0.05體積% HCN、約3體積%水至約5體積%水及其組合。 [48] The method of any one of [44], wherein the gaseous waste stream comprises from about 59% by volume hydrogen to about 78% by volume hydrogen, from about 12% by volume carbon monoxide to about 15% by volume carbon monoxide, About 0.7% by volume of carbon dioxide to about 1.5% by volume of carbon dioxide, about 3% by volume of nitrogen to about 5% by volume of nitrogen, about 1% by volume of methane to about 2.0% by volume of methane, about 0.01% by volume of organic nitrile to about 0.1% by volume of organic nitrile, From about 0.01% by volume HCN to about 0.05% by volume HCN, from about 3% by volume water to about 5% by volume water, and combinations thereof.

[49.]如聲明[44]至[48]中任一項之方法，其中該氣態廢棄物流包含小於約50體積%氮。 [49] The method of any one of [44] to [48] wherein the gaseous waste stream comprises less than about 50% by volume nitrogen.

[50.]如聲明[44]至[49]中任一項之方法，其中該氣態廢棄物流包含大於182BTU/scf之熱值。 [50] The method of any one of [44] to [49] wherein the gaseous waste stream comprises a calorific value greater than 182 BTU/scf.

[51.]如聲明[44]至[50]中任一項之方法，其中該氣態廢棄物流包含約205BTU/scf至約260BTU/scf之熱值。 [51] The method of any one of [44] to [50] wherein the gaseous waste stream comprises a calorific value of from about 205 BTU/scf to about 260 BTU/scf.

[52.]如聲明[44]至[51]中任一項之方法，其中未向該氣態廢棄物流補充燃料氣。 [52] The method of any one of [44] to [51] wherein the gaseous waste stream is not replenished with fuel gas.

2‧‧‧進料流/氨(NH₃)流 2‧‧‧feed stream/ammonia (NH ₃ ) flow

6‧‧‧進料流/氧流 6‧‧‧feed stream/oxygen flow

8‧‧‧HCN合成系統 8‧‧‧HCN Synthesis System

10‧‧‧產物流 10‧‧‧Product stream

11‧‧‧方法 11‧‧‧Method

12‧‧‧廢熱利用系統 12‧‧‧Waste heat utilization system

14‧‧‧溫度降低之產物流 14‧‧‧Products of reduced temperature

16‧‧‧氨回收系統 16‧‧‧Ammonia recovery system

18‧‧‧磷酸流 18‧‧‧Glucose flow

20‧‧‧NH₃回收流 20‧‧‧NH ₃ recovery stream

22‧‧‧廢水流 22‧‧‧ Wastewater flow

24‧‧‧汽提NH₃之HCN流 24‧‧‧HCN flow for stripping NH ₃

26‧‧‧廢水處理系統 26‧‧‧ Wastewater Treatment System

28‧‧‧廢水流 28‧‧‧ Wastewater flow

30‧‧‧HCN回收系統 30‧‧‧HCN recycling system

32‧‧‧經純化HCN產物流 32‧‧‧ Purified HCN product stream

34‧‧‧氣態廢棄物流 34‧‧‧Gaseous waste stream

38‧‧‧H₂回收系統 38‧‧‧H ₂ recovery system

40‧‧‧所回收之H₂ 40‧‧‧Recovered H ₂

42‧‧‧燃燒器/燃燒系統 42‧‧‧Burner/combustion system

Claims

一種利用在經由安德盧梭法產生氰化氫期間產生之廢棄物的方法，其包含：(a)燃燒氣態廢棄物流以供初級能量生成，其中該氣態廢棄物流係來自經組態以產生氰化氫之反應器，並且該氣態廢棄物流實質上不含氰化氫；(b)使熱回收單元與熱接觸以供次級能量生成，其中該熱係在該氰化氫之產生期間由反應器生成；或(c)其組合。 A method of utilizing waste generated during the production of hydrogen cyanide via the Andrussow process, comprising: (a) burning a gaseous waste stream for primary energy generation, wherein the gaseous waste stream is configured to produce cyanidation a reactor of hydrogen, and the gaseous waste stream is substantially free of hydrogen cyanide; (b) contacting the heat recovery unit with heat for secondary energy generation, wherein the heat is generated by the reactor during the production of the hydrogen cyanide Generate; or (c) a combination thereof.

如請求項1之方法，其中該初級或次級能量生成包含熱傳遞、蒸汽生成、電生成或其組合。 The method of claim 1, wherein the primary or secondary energy generation comprises heat transfer, steam generation, electrical generation, or a combination thereof.

如請求項1或2之方法，其中該初級或次級能量生成係蒸汽生成及電生成。 The method of claim 1 or 2, wherein the primary or secondary energy generation is steam generation and electrical generation.

如請求項1至3中任一項之方法，其進一步包含：在燃燒該氣態廢棄物流之前，調整包含甲烷、氨及氧之反應混合物以向反應混合物提供足夠氧，從而在去除氨及回收氰化氫後在該氣態廢棄物流中生成至少約59體積%氫。 The method of any one of claims 1 to 3, further comprising: adjusting a reaction mixture comprising methane, ammonia, and oxygen to provide sufficient oxygen to the reaction mixture prior to burning the gaseous waste stream to remove ammonia and recover cyanide At least about 59% by volume of hydrogen is produced in the gaseous waste stream after hydrogenation.

如請求項4之方法，其中該足夠氧係作為包含大於55體積%氧之含氧進料流供應。 The method of claim 4, wherein the sufficient oxygen is supplied as an oxygen-containing feed stream comprising greater than 55 vol% oxygen.

如請求項1至5中任一項之方法，其中該氣態廢棄物流包含約60體積%氧至約78體積%氧及約10體積%一氧化碳至約15體積%一氧化碳。 The method of any one of claims 1 to 5, wherein the gaseous waste stream comprises from about 60% by volume oxygen to about 78% by volume oxygen and from about 10% by volume carbon monoxide to about 15% by volume carbon monoxide.

如請求項1至6中任一項之方法，其中該氣態廢棄物流包含小於約50體積%氮。 The method of any one of claims 1 to 6, wherein the gaseous waste stream comprises less than about 50% by volume nitrogen.

如請求項1至7中任一項之方法，其中該氣態廢棄物流包含大於 182英制熱量單位(British Thermal Unit)每標準立方呎(BTU/scf)之熱值。 The method of any one of claims 1 to 7, wherein the gaseous waste stream comprises greater than The thermal value of a standard thermal unit (BTU/scf) of 182 British Thermal Units.

如請求項1至8中任一項之方法，其中該氣態廢棄物流包含約205BTU/scf至約260BTU/scf之熱值。 The method of any one of claims 1 to 8, wherein the gaseous waste stream comprises a calorific value of from about 205 BTU/scf to about 260 BTU/scf.

如請求項1至9中任一項之方法，其中未向該氣態廢棄物流補充燃料氣。 The method of any one of claims 1 to 9, wherein the gaseous waste stream is not replenished with fuel gas.

如請求項1至10中任一項之方法，其中燃燒該氣態廢棄物流包括使該氣態廢棄物流與第一汽電共生單元接觸。 The method of any one of claims 1 to 10, wherein burning the gaseous waste stream comprises contacting the gaseous waste stream with a first vapor-electric cogeneration unit.

如請求項11之方法，其中該第一汽電共生單元包含第一鍋爐及發電機，該第一鍋爐經組態以生成蒸汽並且該發電機經組態以生成電。 The method of claim 11, wherein the first cogeneration unit comprises a first boiler and a generator, the first boiler being configured to generate steam and the generator configured to generate electricity.

如請求項1至12中任一項之方法，其中該熱回收單元係第二汽電共生單元。 The method of any one of claims 1 to 12, wherein the heat recovery unit is a second steam symbiosis unit.

如請求項13之方法，其中該第二汽電共生單元包括第二鍋爐及熱激活發生器，該第二鍋爐經組態以生成蒸汽並且該熱激活發生器經組態以生成電。 The method of claim 13, wherein the second cogeneration unit comprises a second boiler and a heat activated generator, the second boiler being configured to generate steam and the heat activated generator configured to generate electricity.

如請求項13之方法，其中使該熱回收單元與熱接觸進一步包括：使來自該反應器之產物流與該第二汽電共生單元接觸，其中該產物流在與該第二汽電共生單元接觸之前具有第一溫度，並且該產物流在與該第二汽電共生單元接觸之後具有第二溫度，該第一溫度高於該第二溫度。 The method of claim 13 wherein the contacting the thermal recovery unit with the thermal further comprises contacting the product stream from the reactor with the second vapor-electric co-generation unit, wherein the product stream is in communication with the second vapor-electricity unit There is a first temperature prior to contacting, and the product stream has a second temperature after contact with the second vapor-electric co-generation unit, the first temperature being higher than the second temperature.

如請求項1至15中任一項之方法，其中該氰化氫係在甲烷、氨及氧之反應混合物中在包含鉑之觸媒存在下產生，其中該反應混合物具有大於約55體積%氧。 The method of any one of claims 1 to 15, wherein the hydrogen cyanide is produced in a reaction mixture of methane, ammonia and oxygen in the presence of a catalyst comprising platinum, wherein the reaction mixture has greater than about 55 vol% oxygen .

如請求項16之方法，其中該甲烷係在含有甲烷之烴進料中提供。 The method of claim 16, wherein the methane is extracted from a hydrocarbon feed containing methane for.

如請求項16或17之方法，其中該甲烷係作為包含天然氣、生質物氣體、實質上純淨之甲烷或其混合物之烴進料提供。 The method of claim 16 or 17, wherein the methane is provided as a hydrocarbon feed comprising natural gas, biomass gas, substantially pure methane or a mixture thereof.

如請求項16至18中任一項之方法，其中該甲烷係作為天然氣提供。 The method of any one of claims 16 to 18, wherein the methane is provided as natural gas.

如請求項16至19中任一項之方法，其中該甲烷係作為實質上純淨之甲烷提供。 The method of any one of claims 16 to 19, wherein the methane is provided as substantially pure methane.

如請求項16至20中任一項之方法，其中該氧係作為富集氧之進料、實質上純淨之氧進料或其任一組合提供。 The method of any one of claims 16 to 20, wherein the oxygen is provided as an oxygen-enriched feed, a substantially pure oxygen feed, or any combination thereof.

如請求項1至21中任一項之方法，其中氨實質上已自該氣態廢棄物流去除。 The method of any one of claims 1 to 21, wherein the ammonia has substantially been removed from the gaseous waste stream.

如請求項1至22中任一項之方法，其中水實質上已自該氣態廢棄物流去除。 The method of any one of claims 1 to 22, wherein the water has substantially been removed from the gaseous waste stream.

如請求項1至23中任一項之方法，其中該氣態廢棄物流包含氫、甲烷或其混合物。 The method of any one of claims 1 to 23, wherein the gaseous waste stream comprises hydrogen, methane or a mixture thereof.

一種經由安德盧梭法產生氰化氫之系統，其包含：(a)反應器，其經組態以在包含鉑之觸媒存在下自包含甲烷、氨及氧之反應混合物產生氰化氫，其中該反應器亦經組態以向該反應混合物供應足夠氧，從而在去除氨及回收氰化氫後生成具有至少59體積%氫之氣態廢棄物流；(b)第一汽電共生單元，其經組態以燃燒作為燃料之該氣態廢棄物流以供初級能量生成，其中該氣態廢棄物流實質上不含氰化氫；及/或(c)第二汽電共生單元，其經組態以自該反應器吸收熱以供次級能量生成。 A system for producing hydrogen cyanide via the Andrussow process, comprising: (a) a reactor configured to produce hydrogen cyanide from a reaction mixture comprising methane, ammonia, and oxygen in the presence of a catalyst comprising platinum, Wherein the reactor is also configured to supply sufficient oxygen to the reaction mixture to produce a gaseous waste stream having at least 59% by volume of hydrogen after removal of ammonia and recovery of hydrogen cyanide; (b) a first gas-electricity symbiosis unit, Configuring to burn the gaseous waste stream as a fuel for primary energy generation, wherein the gaseous waste stream is substantially free of hydrogen cyanide; and/or (c) a second gas-electricity symbiosis unit configured to The reactor absorbs heat for secondary energy generation.

如請求項25之系統，其中該足夠氧係作為包含大於55體積%氧之含氧進料流供應。 The system of claim 25, wherein the sufficient oxygen is included as comprising more than 55 vol% oxygen Oxygen-containing feed stream supply.

如請求項25或26中任一項之系統，其中該氣態廢棄物流包含約60體積%氧至約78體積%氧及約10體積%一氧化碳至約15體積%一氧化碳。 The system of any one of claims 25 or 26, wherein the gaseous waste stream comprises from about 60% by volume oxygen to about 78% by volume oxygen and from about 10% by volume carbon monoxide to about 15% by volume carbon monoxide.

如請求項25至27中任一項之系統，其中該氣態廢棄物流包含小於約50體積%氮。 The system of any one of claims 25 to 27, wherein the gaseous waste stream comprises less than about 50% by volume nitrogen.

如請求項25至28中任一項之系統，其中該氣態廢棄物流包含大於182BTU/scf之熱值。 The system of any one of claims 25 to 28, wherein the gaseous waste stream comprises a calorific value greater than 182 BTU/scf.

如請求項25至29中任一項之系統，其中該氣態廢棄物流包含約205BTU/scf至約260BTU/scf之熱值。 The system of any one of claims 25 to 29, wherein the gaseous waste stream comprises a calorific value of from about 205 BTU/scf to about 260 BTU/scf.

如請求項25至30中任一項之系統，其中未向該氣態廢棄物流補充燃料氣。 The system of any one of claims 25 to 30, wherein the gaseous waste stream is not replenished with fuel gas.

如請求項25至31中任一項之系統，其進一步包含：(d)第一熱傳遞系統，其經組態以自該第一汽電共生單元吸收熱並使該熱回收；及/或(e)第二熱傳遞系統，其經組態以自該第二汽電共生單元吸收熱並使該熱回收以加熱進給至該反應器中之該甲烷、氨及氧中之至少一者。 The system of any one of claims 25 to 31, further comprising: (d) a first heat transfer system configured to absorb heat from the first cogeneration unit and recover the heat; and/or (e) a second heat transfer system configured to absorb heat from the second vapor-electricity commencing unit and recover the heat to heat at least one of the methane, ammonia, and oxygen fed to the reactor .

如請求項25至32中任一項之系統，其進一步包含用於定量該氣態廢棄物流中之氰化氫、甲烷、氫、一氧化碳或其組合之含量的檢測器。 The system of any one of claims 25 to 32, further comprising a detector for quantifying the amount of hydrogen cyanide, methane, hydrogen, carbon monoxide or a combination thereof in the gaseous waste stream.

如請求項33之系統，其進一步包含可操作地連接至該檢測器之閥，其中該閥係經組態以在該氣態廢棄物流中檢測到低於臨限值之氫濃度時使該氣態廢棄物流自該第一汽電共生單元轉向。 The system of claim 33, further comprising a valve operatively coupled to the detector, wherein the valve is configured to discard the gaseous state when a concentration of hydrogen below a threshold is detected in the gaseous waste stream The flow is diverted from the first cogeneration unit.

如請求項33之系統，其進一步包含可操作地連接至該檢測器之閥，其中該閥係經組態以在易燃組份之設定值低於臨限值時使該氣態廢棄物流自該第一汽電共生單元轉向。 The system of claim 33, further comprising a valve operatively coupled to the detector, wherein the valve is configured to cause a set value of the flammable component to be below a threshold value The gaseous waste stream is diverted from the first cogeneration unit.

如請求項35之系統，其中該臨限值係基於該氣態廢棄物流之熱含量值。 The system of claim 35, wherein the threshold is based on a heat content value of the gaseous waste stream.

如請求項33之系統，其中該甲烷係包含天然氣、合成氣、生質物氣體、實質上純淨之甲烷或其混合物之烴進料。 The system of claim 33, wherein the methane is a hydrocarbon feed comprising natural gas, syngas, biomass gas, substantially pure methane, or a mixture thereof.

如請求項33之系統，其中該甲烷係天然氣。 The system of claim 33, wherein the methane is natural gas.

如請求項33之系統，其中該甲烷係實質上純淨之甲烷。 The system of claim 33, wherein the methane is substantially pure methane.

如請求項33之系統，其中該氧係作為富集氧之進料、實質上純淨之氧進料或其任一組合提供。 The system of claim 33, wherein the oxygen is provided as an oxygen enriched feed, a substantially pure oxygen feed, or any combination thereof.

如請求項25至40中任一項之系統，其中氨實質上已自該氣態廢棄物流去除。 The system of any one of clauses 25 to 40, wherein the ammonia has substantially been removed from the gaseous waste stream.

如請求項25至41中任一項之系統，其中水實質上已自該氣態廢棄物流去除。 The system of any one of clauses 25 to 41, wherein the water has substantially been removed from the gaseous waste stream.

如請求項25至42中任一項之系統，其中該廢棄物流出物包含氫、甲烷或其混合物。 The system of any one of claims 25 to 42, wherein the waste effluent comprises hydrogen, methane or a mixture thereof.

一種方法，其包含：(a)調整包含甲烷、氨及氧之反應混合物以向該反應混合物提供足夠氧，從而在去除氨及回收氰化氫之後生成在氣態廢棄物流中具有至少59體積%氫之該氣態廢棄物流；及(b)燃燒該氣態廢棄物流以供能量生成。 A method comprising: (a) adjusting a reaction mixture comprising methane, ammonia, and oxygen to provide sufficient oxygen to the reaction mixture to produce at least 59 vol% hydrogen in the gaseous waste stream after removal of ammonia and recovery of hydrogen cyanide The gaseous waste stream; and (b) burning the gaseous waste stream for energy production.

如請求項44之方法，其中該能量生成包含蒸汽生成、電生成或其組合。 The method of claim 44, wherein the energy generation comprises steam generation, electrical generation, or a combination thereof.

如請求項44之方法，其中該能量生成包含經由汽電共生單元之蒸汽生成及電生成。 The method of claim 44, wherein the energy generation comprises steam generation and electrogeneration via a cogeneration unit.

如請求項44至46中任一項之方法，其中該足夠氧係作為包含大於55體積%氧之含氧進料流供應。 The method of any one of claims 44 to 46, wherein the sufficient oxygen is supplied as an oxygen-containing feed stream comprising greater than 55 vol% oxygen.

如請求項44至47中任一項之方法，其中該氣態廢棄物流包含約59體積%氫至約78體積%氫、約12體積%一氧化碳至約15體積%一氧化碳、約0.7體積%二氧化碳至約1.5體積%二氧化碳、約3體積%氮至約5體積%氮、約1體積%甲烷至約2.0體積%甲烷、約0.01體積%有機腈至約0.1體積%有機腈、約0.01體積% HCN至約0.05體積% HCN、約3體積%水至約5體積%水及其組合。 The method of any one of claims 44 to 47, wherein the gaseous waste stream comprises from about 59% by volume hydrogen to about 78% by volume hydrogen, from about 12% by volume carbon monoxide to about 15% by volume carbon monoxide, about 0.7% by volume carbon dioxide to about 1.5% by volume of carbon dioxide, about 3% by volume of nitrogen to about 5% by volume of nitrogen, about 1% by volume of methane to about 2.0% by volume of methane, about 0.01% by volume of organic nitrile to about 0.1% by volume of organic nitrile, about 0.01% by volume of HCN to about 0.05 vol% HCN, about 3 vol% water to about 5% vol% water, and combinations thereof.

如請求項44至48中任一項之方法，其中該氣態廢棄物流包含小於約50體積%氮。 The method of any one of claims 44 to 48, wherein the gaseous waste stream comprises less than about 50% by volume nitrogen.

如請求項44至49中任一項之方法，其中該氣態廢棄物流包含大於182BTU/scf之熱值。 The method of any one of claims 44 to 49, wherein the gaseous waste stream comprises a calorific value greater than 182 BTU/scf.

如請求項44至50中任一項之方法，其中該氣態廢棄物流包含約205BTU/scf至約260BTU/scf之熱值。 The method of any one of claims 44 to 50, wherein the gaseous waste stream comprises a calorific value of from about 205 BTU/scf to about 260 BTU/scf.

如請求項44至51中任一項之方法，其中未向該氣態廢棄物流補充燃料氣。 The method of any one of claims 44 to 51, wherein the gaseous waste stream is not replenished with fuel gas.