WO2014099606A1

WO2014099606A1 - Hydrogen cyanide production with treated natural gas as source or methane-containing feedstock

Info

Publication number: WO2014099606A1
Application number: PCT/US2013/074653
Authority: WO
Inventors: John C. CATON; Rocky Wang; David W. RABENALDT
Original assignee: Invista Technologies S.A.R.L.
Priority date: 2012-12-18
Filing date: 2013-12-12
Publication date: 2014-06-26
Also published as: CN103864101A; TW201434749A; HK1199005A1; US20160194210A1; TWI510436B; CN103864101B; EP2935113A1

Abstract

The present invention relates to an improved process for producing hydrogen cyanide. More particularly, the present invention relates to a commercially advantageous process for producing hydrogen cyanide at enhanced levels of productivity and yield while using natural gas comprising at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide. The natural gas is purified to be used as a source of methane-containing feedstock.

Description

HYDROGEN CYANIDE PRODUCTION WITH TREATED NATURAL GAS AS SOURCE OF METHANE-CONTAINING FEEDSTOCK

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. App. No. 61/738,717, filed December 18,

2012, the entire contents and disclosures of which are incorporated herein.

FIELD OF THE INVENTION

[0002] The present invention relates to an improved process for producing hydrogen cyanide. More particularly, the invention relates to a commercially advantageous process for producing hydrogen cyanide at enhanced levels of productivity and yield while using natural gas, having been treated in a particular manner, as a source of methane-containing feedstock.

BACKGROUND OF THE INVENTION

[0003] Conventionally, hydrogen cyanide ("HCN") is produced on an industrial scale according to either the Andrussow process or the BMA process. (See e.g., Ullman's Encyclopedia of Industrial Chemistry, Volume A8, Weinheim 1987, pages 161-163). For example, in the Andrussow process, HCN can be commercially produced by reacting ammonia with a methane-containing gas and an oxygen-containing gas at elevated temperatures in a reactor in the presence of a suitable catalyst (U.S. Patent No. 1,934,838 and U.S. Patent No. 6,596,251). Sulfur compounds and higher homologues of methane may have an effect on the parameters of oxidative ammonolysis of methane. See, e.g., Trusov, Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method, Russian J. Applied Chemistry, 74: 10 (2001), pp. 1693-1697). Unreacted ammonia is separated from HCN by contacting the reactor effluent gas stream with an aqueous solution of ammonium phosphate in an ammonia absorber. The separated ammonia is purified and concentrated for recycle to HCN conversion. HCN is recovered from the treated reactor effluent gas stream typically by absorption into water. The recovered HCN may be treated with further refining steps to produce purified HCN. Clean Development Mechanism Project Design Document Form (CDM PDD, Version 3), 2006, schematically explains the Andrussow HCN production process. Purified HCN can be used in hydrocyanation, such as hydrocyanation of an olefin-containing group, or such as hydrocyanation of 1,3 -butadiene and pentenenitrile, which can be used in the manufacture of adiponitrile ("ADN")- In the BMA process, HCN is synthesized from methane and ammonia in the substantial absence of oxygen and in the presence of a platinum catalyst, resulting in the production of HCN, hydrogen, nitrogen, residual ammonia, and residual methane (See e.g., Ullman's Encyclopedia of Industrial Chemistry, Volume A8, Weinheim 1987, pages 161 -163). Commercial operators require process safety management to handle the hazardous properties of hydrogen cyanide. (See Maxwell et al. Assuring process safety in the transfer of hydrogen cyanide manufacturing technology, JHazMat 142 (2007), 677-684). Additionally, emissions of HCN production processes from production facilities may be subject to regulations, which may affect the economics of HCN manufacturing. (See Crump, Economic Impact Analysis For The Proposed Cyanide Manufacturing NESHAP, EPA, May 2000).

SUMMARY OF THE INVENTION

[0004] In one embodiment, the present invention is directed to a process for producing HCN comprising (a) determining methane content of a natural gas stream comprising at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide; (b) supplying a ternary gas mixture comprising at least 25 vol.% oxygen, wherein the ternary gas mixture is formed by combining an oxygen-containing gas, a methane-containing gas and an ammonia-containing gas, wherein the methane in the feed stream is obtained from the natural gas stream, said natural gas stream having been treated in a particular manner; (c) heating at least one of the oxygen-containing gas and the one or more feed streams in a suitable manner, e.g., by indirect heat exchange; (e) mixing the oxygen-containing gas and the one or more feed streams in a mixing zone to form a ternary gas mixture, wherein the rate of flow of the ternary gas mixture through the mixing zone is maintained above burning velocity of the ternary gas mixture, and the residence time of the ternary gas mixture in the mixing zone is less than a flame induction time of the ternary gas mixture; and (e) contacting the ternary gas mixture of step (d) with a catalyst to provide a crude hydrogen cyanide product. The particular manner or process for treatment of the natural gas stream of step (b) comprises contacting the natural gas stream with an amine capable of substantially removing carbon dioxide and hydrogen sulfide from the natural gas stream thereby providing a stream containing methane and at least one C2+ hydrocarbon and a stream containing substantially carbon dioxide and hydrogen sulfide; (ii) recovering and dehydrating the stream containing methane and at least one C2+ hydrocarbon from step (i) to provide a substantially anhydrous methane stream containing at least one C2+ hydrocarbon; (iii) treating the substantially anhydrous methane stream containing at least one C2+ hydrocarbon from step (ii) to provide a stream containing substantially at least one C2+ hydrocarbon and a stream containing purified methane and less than 1 vol.% C2+ hydrocarbon; and (iv) recovering the purified methane stream from step (iii) for use as the feed stream containing methane in the one or more feed streams of step (b).

[0005] Another embodiment of the present invention is directed to a process for producing HCN wherein the amount of C2+ hydrocarbons present in the stream containing purified methane of step (iii) above is less than 0.5 vol.%, or amount of C3+hydrocarbons present in the stream containing purified methane of step (iii) is less than 0.1 vol.%. In another embodiment, the molar ratio of ammonia-to-oxygen in the ternary gas mixture of step (e) above is in the range of from 1.2 to 1.6, and the molar ratio of ammonia-to-methane in the ternary gas mixture of step (e) is in the range of from 1.10 to 1.5. In another embodiment, the oxygen-containing gas of step (b) above is substantially anhydrous. In another embodiment, the catalyst of step (e) above comprises a platinum group metal, platinum group metal alloy, supported platinum group metal or supported platinum group metal alloy. For example, the catalyst of step (e) comprises platinum, rhodium, iridium, platinum/rhodium alloy or platinum/iridium alloy.

[0006] Another embodiment of the present invention is directed to a process for producing HCN comprising (a) determining methane content of a natural gas stream comprising at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide; (b) providing a ternary gas mixture comprising at least 25 vol.% oxygen, wherein the ternary gas mixture is formed by combining an oxygen-containing gas, an ammonia-containing gas, and the methane-containing gas, wherein the methane-containing gas is obtained from the natural gas stream, and wherein the methane containing-gas comprises less than 300 mpm carbon dioxide, less than 1 vol.% C2+ hydrocarbons, less than 2.5 mpm water, and less than 0.01 vol.% hydrogen sulfide; and (c) contacting the ternary gas mixture of step (b) with a catalyst to produce HCN; wherein the methane-containing gas of step (b) is prepared by a particular process. The particular process for preparing the methane-containing gas of step (b) comprises (i) contacting the natural gas stream with an amine capable of removing at least a portion of the carbon dioxide and the hydrogen sulfide from the natural gas stream, thereby providing an intermediate natural gas stream containing methane and at least one C2+ hydrocarbon, and a purge stream containing carbon dioxide and hydrogen sulfide; and (ii) dehydrating and treating the intermediate natural gas stream to provide a C2+ hydrocarbon stream containing at least one C2+ hydrocarbon, and the methane-containing gas of step (b).

[0007] In another embodiment, the present invention is directed to a process for purifying natural gas for hydrogen cyanide production, comprising: determining the methane content of a natural gas stream; contacting the natural gas stream with an amine capable of removing at least a portion of the carbon dioxide and the hydrogen sulfide from the natural gas stream, thereby providing a stream containing methane and at least one C2+ hydrocarbon, and a stream containing carbon dioxide and hydrogen sulfide; recovering and dehydrating the stream containing methane and at least one C2+ hydrocarbon to provide a substantially anhydrous methane stream containing at least one C2+ hydrocarbon; and treating the substantially anhydrous methane stream containing at least one C2+ hydrocarbon to provide a stream containing substantially at least one C2+ hydrocarbon and a stream containing purified methane and less than 300 mpm carbon dioxide, less than 1 vol.% C2+ hydrocarbons, less than 2.5 mpm water, and less than 0.01 vol.% hydrogen sulfide. The amine may be selected from the group consisting of diethylamine, methyldiethanolamine, methylmonoethanolamine, and mixtures thereof. The treating may be performed in a hydrocarbon separator comprising a cryogenic distillation column.

BRIEF DESCRIPTION OF THE DRAWING

[0008] FIG. 1 is a simplified schematic flow diagram of an HCN synthesis system according to an embodiment of the present invention.

[0009] FIG. 2 is a graph of the effect of ethane in the methane gas feed stream feedstock on conversion of ammonia to HCN.

[0010] FIG. 3 is a graph of the effect of ethane in the methane gas feed stream feedstock on ammonia recycle requirements for the production of HCN. [0011] FIG. 4 is a graph of the effect of ethane in the methane gas feed stream feedstock on the methane concentration in the off-gas feed stream of a HCN synthesis reaction.

[0012] FIG. 5 is a graph of the effect of ethane in the methane gas feed stream feedstock on conversion of carbon to HCN.

DETAILED DESCRIPTION OF THE INVENTION

[0013] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, group of elements, components, and/or groups thereof.

[0014] Language such as "including," "comprising," "having," "containing," or

"involving," and variations thereof, is intended to be broad and encompass the subject matter listed thereafter, as well as equivalents, and additional subject matter not recited. Further, whenever a composition, a group of elements, process or method steps, or any other expression is preceded by the transitional phrase "comprising," "including," or "containing," it is understood that it is also contemplated herein the same composition, group of elements, process or method steps or any other expression with transitional phrases "consisting essentially of," "consisting of," or "selected from the group of consisting of," preceding the recitation of the composition, the group of elements, process or method steps or any other expression.

[0015] The corresponding structures, materials, acts, and equivalents of all means or step plus function elements in the claims, if applicable, are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The embodiment(s) described herein was/were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated. Accordingly, while the invention has been described in terms of embodiments, those of skill in the art will recognize that the invention can be practiced with modifications and in the spirit and scope of the appended claims.

[0016] Reference will now be made in detail to certain disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that they are not intended to limit the disclosed subject matter to those claims. On the contrary, the disclosed subject matter is intended to cover all alternatives, modifications, and equivalents, which can be included within the scope of the presently disclosed subject matter as defined by the claims.

[0017] As used herein, "burning velocity" is defined as the velocity of a flame front with respect to unburned gas immediately ahead of the flame. "Detonation" is defined as a combustion wave propagating at supersonic velocity relative to the unburned gas immediately ahead of the flame, i.e., the detonation velocity is greater than the speed of sound in the unburned gas. "Auto-ignition temperature" (AIT) of a gas mixture is defined as the lowest temperature, at a given pressure, for which the gas mixture will spontaneously ignite without an external source of ignition. "Flame Induction Time" (FIT) is defined as the point between the point in time at which a ternary gas mixture attains AIT and the point in time at which actual ignition of the ternary gas mixture occurs.

[0018] In the Andrussow process for forming HCN, methane, ammonia and oxygen- containing raw materials are reacted at temperatures at least 1000°C, e.g. from 1000°C to 1200°C, in the presence of a catalyst to produce a crude hydrogen cyanide product comprising HCN, hydrogen, carbon monoxide, carbon dioxide, nitrogen, residual ammonia, residual methane, and water. Natural gas may be used as the source of methane while air, oxygen- enriched air, or pure oxygen can be used as the source of oxygen. The catalyst is typically a wire mesh platinum/rhodium alloy or a wire mesh platinum/iridium alloy. Other catalyst compositions can be used and include, but are not limited to, a platinum group metal, e.g. ruthenium, rhodium, palladium, osmium, iridium and platinum, or platinum group metal alloy, supported platinum group metal or supported platinum group metal alloy. Other catalyst configurations can also be used and include, but are not limited to, porous structures, wire mesh (e.g. gauze, knitted or woven structures), tablets, pellets, monoliths, foams, impregnated coatings, and wash coatings.

[0019] Natural gas, one source of the methane for the methane-containing gas, is an impure state of methane. That is, natural gas is a substantially methane-containing gas that can be used to provide the carbon element of the HCN produced in the process of the present invention. Natural gas may typically comprise from 60 to 99 vol.% methane, e.g., 70 to 90 vol.%. The remainder of the natural gas may be comprised of contaminants such as hydrogen sulfide (H₂S), carbon dioxide (C0₂), nitrogen (N₂), water (H₂0) and higher molecular weight hydrocarbons, such as ethane, propane, butane, pentane, and higher hydrocarbons. These higher molecular weight hydrocarbons are referred to herein as "C2+ hydrocarbons." As the amount of impurities, on a volumetric percentage, increase, purification may be required. For example, if natural gas comprises above 90 vol.% methane, commercial processes may not purify the natural gas to remove the hydrocarbons. These prior commercial processes allowed larger quantities of C2+ hydrocarbons to enter the process, which causes adverse affects on productivity. Advantageously, the present invention reduces and controls the amount of C2+ hydrocarbons to improve productivity by decreasing unconverted ammonia and/or methane. Preventing unconverted ammonia and/or methane, i.e., "leaking through" the reactor has a significant impact on improving conversions. In some aspects, the methane leakage through the reactor is from 0.05 to 1 vol.%, e.g., from 0.05 to 0.55 vol.% or from 0.2 to 0.3 vol.% The ammonia leakage through the reactor may range from 0.01 to 0.04 vol.%, e.g., from 0.05 to 0.3 vol.% or from 0.1 to 0.3 vol.%). Improving the conversion and overall yield of HCN, even by small amounts of 2% to 7%), may translate into a savings of millions of dollars per year in continuous commercial operation. Additionally, reducing the amount of methane leakage may reduce the buildup of nitriles during the separation of the crude hydrogen cyanide product. This reduction or elimination of a nitriles purge during the separation may also translate into an increased overall yield of HCN and capital savings.

[0020] Natural gas compositions can vary significantly from source to source. For purposes of the present invention, the natural gas used to produce the methane-containing gas comprises at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide. The composition of natural gas provided by pipeline can also change significantly over time and even over short time spans as sources are taken on and off of the pipeline. Such variation in composition, especially with regard to the presence of and amount of C2+ hydrocarbons, leads to difficulty in sustaining optimum and stable process performance. The presence of C2+ hydrocarbons in the natural gas composition is especially troublesome due to 1) their higher heating value than methane, 2) their deactivating effect on the catalyst in the HCN reactor, especially C₃ ⁺ hydrocarbons, and 3) side reactions that may form high nitriles, e.g., acetonitrile, acrylonitrile and propionitrile. The sensitivity of the HCN synthesis process to variations in and large amounts of C2+ hydrocarbons becomes more severe as inert loading is reduced through oxygen enrichment of the oxygen-containing gas.

[0021] Therefore, the present invention is directed to a process for producing HCN using a methane-containing gas derived from a natural gas stream, having been treated in a particular manner, whereby after treatment, the methane-containing gas comprises less than 1 vol.% C2+ hydrocarbons, e.g., less than 0.5 vol.%, less than 0.15 vol.%, or that is substantially free of C2+ hydrocarbons. "Substantially free of C2+ hydrocarbons" includes from 0 to 0.1 vol.% C2+ hydrocarbons. This methane-containing gas may also be referred to herein as "purified natural gas." In some embodiments, the methane-containing gas is substantially free of contaminants. The methane-containing gas preferably comprises less than 0.1 volume % C3+ hydrocarbons, less than 300 mpm carbon dioxide, less than 2.5 mpm water, and less than 0.01 vol.% hydrogen sulfide. Additionally, the methane-containing gas may be considered substantially anhydrous.

[0022] Using purified natural gas as the methane-containing gas in this process increases the catalyst life and yield of HCN. In particular, utilizing the purified natural gas stream stabilizes the remaining composition at a consistent level to allow downstream HCN synthesis to be optimized, and enables the use of highly enriched or pure oxygen feed streams by mitigating large temperature excursions in the HCN synthesis step that are typically related to variation in higher hydrocarbon content and which are detrimental to optimum yield and operability, such as catalyst damage, interlock, and loss of uptime. Using the purified natural gas also minimizes formation of higher nitriles and minimizes the associated yield losses of HCN during removal of nitriles. In addition, use of the purified natural gas as the source of the methane-containing gas minimizes variability in the feed stock by stabilizing the carbon and hydrogen content as well as the fuel values and thereby stabilizes the entire HCN synthesis system allowing for the determination and control of methane-to-oxygen and ammonia-to-oxygen molar ratios for stable operation and more efficient HCN yield. Further, using the purified natural gas minimizes related temperature spikes and resulting catalyst damage.

[0023] In some embodiments, the process may comprise determining methane content of the methane-containing source. Methane content may be determined using gas chromatograph- based measurements, including Raman Spectroscopy. The methane content may be determined continuously in real time or as needed when new sources of methane-containing sources are introduced into the process. When the methane content is less than 90 vol.%, additional purification methods may be used. In addition, to achieve higher purities, the methane-containing source may be purified when the methane content is above 90 vol.%, e.g., from 90 to 95 vol.%. Known purification methods may be used to purify the methane-containing source to remove oil, condensate, water, C2+ hydrocarbons (e.g., ethane, propane, butane, pentane, hexane, and isomers thereof), sulfur, and carbon dioxide.

[0024] Referring now to Fig. 1, shown therein is a process for producing HCN, also referred to as an HCN synthesis system 100. Generally, the HCN is produced in a reaction assembly 150 which includes a mixing vessel 151 and a reactor 152. A methane-containing gas 112 from methane source 110, an oxygen-containing gas 122 from oxygen source 120 and an ammonia-containing gas 132 from ammonia source 130 (sometimes referred to herein as gases 1 12, 122 and 132) are introduced from gas zone 102 into the mixing vessel 151. Each gas 112, 122 and 132 may be independently preheated in preheaters 111, 121, and 131, respectively, to form pre-heated gases 113, 123 and 133, respectively, and then fed to mixing vessel 151. In some embodiments, the ammonia-containing gas and the methane-containing gas may be combined prior to being fed to mixing vessel 151 (not shown). A ternary gas mixture 153 is formed. This ternary gas mixture is flammable, but non-detonable. The ternary gas mixture 153 has a pressure from 200 to 400 kPa, e.g., from 230 to 380 kPa. Unless otherwise indicated, all pressures are absolute. The ternary gas mixture 153 is contacted with a catalyst contained in reactor 152 to form a crude HCN product that is cooled in heat exchanger 154 and which then exits the reaction assembly via line 155 to enter HCN purification zone 103. Ammonia can be recovered from the crude HCN product by separating the crude HCN product into an ammonia stream 162 and an HCN product stream 161 in an ammonia recovery section 160. Ammonia stream 162 may be further processed in ammonia processing zone 165 and the HCN product stream 161 can be further refined in an HCN refining section 170 to a purity required for the desired use. The processed ammonia stream may be combined via line 166 with ammonia- containing gas 132 or preheated ammonia-containing gas 133. Thus, processed ammonia stream 166 may be recycled to the reactor. High purity HCN 171 may contain less than 100 mpm by weight water. One possible use for a high purity HCN is hydrocyanation, such as hydrocyanation of an olefin-containing group. Another possible use for a high purity HCN is in the manufacture of adiponitrile ("ADN") by hydrocyanation of 1,3-butadiene and pentenenitrile to adiponitrile.

[0025] FIG. 1 also shows a purification process 101 to provide methane source 112. Natural gas is fed via line 104 to processing zone 105 to form a purge stream 107 comprising C2+ hydrocarbons and a purified natural gas stream 106. Natural gas 104 comprises less than 90 vol.% methane, at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide. Processing zone 105 includes equipment to treat the natural gas 104 in the particular manner and concentrate the methane, remove higher molecular weight hydrocarbons, carbon dioxide (C0₂), hydrogen sulfide (H₂S) and water (H₂0) from a natural gas stream 104, and filter the natural gas stream 104 in order to remove fine particles. Purification of natural gas stream 104 as required herein provides a methane-containing gas 106 highly concentrated in methane and with greatly reduced variability in the composition and fuel value. The purified methane-containing gas 106, contains less than 1 vol.%, for example, less than 0.5 vol.%, such as less than 0.15 vol.%, C2+ hydrocarbons, when mixed with the oxygen-containing gas 122 and ammonia-containing gas 132, provides the ternary gas mixture 153 that reacts more predictably during the synthesis of HCN compared to use of an unpurified methane-containing gas. Consistent purification and control of the methane-containing gas stabilizes the process and allows determination and control of optimum molar ratios of methane-to-oxygen and ammonia-to-oxygen which, in turn, leads to a higher yield of HCN.

[0026] Processing zone 105 comprises (i) contacting the natural gas stream with an amine capable of substantially removing carbon dioxide and hydrogen sulfide from the natural gas stream, thereby providing a stream containing methane and at least one C2+ hydrocarbon and a stream containing substantially carbon dioxide and hydrogen sulfide, (ii) recovering and dehydrating the stream containing methane and at least one C2+ hydrocarbon from step (i) to provide a substantially anhydrous methane stream containing at least one C2+ hydrocarbon, (iii) treating the substantially anhydrous methane stream containing the at least one C2+ hydrocarbon from step (ii) to provide a stream containing substantially at least one C2+ hydrocarbon and a stream containing purified methane and less than 1 vol.% C2+ hydrocarbon, and (iv) recovering the purified natural gas (methane) stream from step (iii) for use as purified natural gas stream 106.

[0027] Processing zone 105 may use an absoiption process or a cryogenic expansion process to separate C2+ hydrocarbons from the purified natural gas stream. Purified natural gas stream 106 is used as methane source 110. If the absorption process is used, hydrocarbon separator 105 comprises absorption towers containing absorption oil. This absorption oil has an affinity for C2+ hydrocarbons. Once removed from the absorption tower, the C2+ hydrocarbons may be recovered from the absorption oil and used in other processes. If the cryogenic process is used, hydrocarbon separator 105 may comprise a cryogenic expansion turbine to cool the natural gas stream to a temperature of approximately -49°C, and a cryogenic distillation column. Operating at this temperature, the C2+ hydrocarbons are condensed while methane remains in the gas phase. The cryogenic expansion process may be preferred to reduce the ethane content in the natural gas. The absorption process may be preferred to reduce C3+ hydrocarbon content in the natural gas. Thus, the type of hydrocarbon separation process may be chosen depending on the natural gas composition. Existing hydrocarbon separation processes are described in U.S. Pats. 4,022,597; 4,687,499; 4,698,081 and 5,960,644, the entire contents and disclosures of which are incoiporated by reference herein.

[0028] Regardless of whether the absorption method or the cryogenic expansion process is used, the hydrocarbon separator may further comprise a deethanizer, a depropanizer, and a debutanizer to separate ethane, propane and butane from methane. The hydrocarbon separator may further comprise a deisobutanizer to remove isobutane.

[0029] In step (i) above, the natural gas stream 104 is first fed to an amine system (not shown) containing suitable amine, such as for example selected from the group consisting of diethylamine, methylmonoethanolamine, methyldiethanolamine (MDEA) and combinations thereof. The amine system can be provided with an amine contactor for contacting the natural gas stream 104 with a combined lean amine stream formed from combining a first lean amine stream (make-up) with a recycled second lean amine stream. The combined lean amine stream contains 50 vol.% suitable amine, such as for example selected from the group consisting of diethylamine, methylmonoethanolamine, methyldiethanolamine (MDEA) and combinations thereof, and reacts with the natural gas stream 104 to provide the second natural gas stream substantially depleted of carbon dioxide, hydrogen sulfide, and other sulfur compounds, and an amine stream enriched with carbon dioxide, hydrogen sulfide and other sulfur compounds removed from the natural gas stream. The rich amine stream can be fed to an amine separator wherein the carbon dioxide, hydrogen sulfide and other sulfur compounds are separated from the rich amine stream to thereby create the second lean amine stream and a carbon dioxide/hydrogen sulfide amine separator top stream. The carbon dioxide/hydrogen sulfide amine separator top stream can be routed to a flare stack where hydrogen sulfide is burned.

[0030] In another embodiment, the natural gas 104 may be subjected to a zinc oxide treatment system (not shown) prior to being fed to the amine contactor. Prior to being fed to the zinc oxide treatment system (not shown), the natural gas 104 can be heated to at least 100°C and the heated natural gas stream can be contacted with a zinc oxide catalyst. The amount of zinc oxide catalyst used is dependent upon the flow of the natural gas 104. However in one embodiment, the zinc oxide catalyst is supported on a sloped screen and has a catalyst density of 65 pounds per cubic foot. In another alternate embodiment, the zinc oxide treatment system (not shown) can be designed to remove hydrogen sulfide from natural gas with less than 0.2 mpm ("moles per million moles") H₂S leakage. If the natural gas 104 is heated to 100°C, it is calculated that the zinc oxide catalyst can absorb approximately 5 % by weight of sulfur prior to exhaustion. In the event that the natural gas 104 contains organic sulfur, the zinc oxide treatment system (not shown) may also include an activated carbon system (not shown);

[0031] In another embodiment, the amine system includes filters, such as sock filters to remove particulate solids, and activated carbon filters to remove organics from the rich amine stream which can cause foaming in the amine contactor after the rich amine stream is processed in the amine separator and recycled to the amine contactor as the resulting second lean amine stream. The filters can include an activated carbon bed to facilitate removal of the particulate solids and organics found in the rich amine stream.

[0032] In another embodiment, a stream containing antifoaming agent is introduced into the combined lean amine stream prior to introduction of the combined lean amine stream into the amine contactor. The antifoaming agent limits foaming in the amine contactor. A wide range of antifoaming agents can be used such as, for example, polyglycol. The amounts of antifoaming agent or agents vary with the particular foaming agent used and with the operating conditions of the particular process employed.

[0033] The second natural gas stream, substantially depleted of carbon dioxide, hydrogen sulfide, and other sulfur compounds, is taken off the top of the amine contactor and fed to a dehydration system. The dehydration system can include one or more molecular sieve columns for removing water from the second natural gas to prevent ice formation in the hydrocarbon separator contained in processing zone 105. A filter, such as a dust filter, removes from the second natural gas stream any particulate matter, such as dust from the molecular sieve column, to produce a third natural gas stream.

[0034] An embodiment of the presently claimed invention relates to producing HCN by reacting in the presence of a catalyst a ternary gas mixture, wherein the components of the ternary gas mixture include a methane stream derived from natural gas comprising methane having been treated in a particular manner, an ammonia stream, and an oxygen-containing gas containing from 21 to 100 vol.% oxygen gas. More specifically, the methane stream is obtained from a natural gas stream comprising methane, at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide. Still more specifically, the natural gas stream is treated by (i) contacting the natural gas stream with an amine capable of substantially removing carbon dioxide and hydrogen sulfide from the natural gas stream thereby providing a stream containing methane and at least one C2+ hydrocarbon and a stream containing substantially carbon dioxide and hydrogen sulfide; (ii) recovering and dehydrating the stream containing methane and at least one C2+ hydrocarbon from step (i) to provide a substantially anhydrous methane stream containing at least one C2+ hydrocarbon; (iii) treating the substantially anhydrous methane stream containing at least one C2+ hydrocarbon from step (ii) to provide a stream containing substantially at least one C2+ hydrocarbon and a stream containing purified methane and less than 1 vol.% C2+ hydrocarbons; and (iv) recovering the purified methane stream from step (iii) for use as the methane feed stream.

[0035] More specifically, the oxygen-containing gas for use in step (a) may comprise air or air enriched with oxygen or pure oxygen.

[0036] The term "air" as used herein refers to a mixture of gases with a composition approximately identical to the native composition of gases taken from the atmosphere, generally at ground level. In some examples, air is taken from the ambient surroundings. Air has a composition that includes approximately 78 vol.% nitrogen, approximately 21 vol.% oxygen, approximately 1 vol.% argon, and approximately 0.04 vol.% carbon dioxide, as well as small amounts of other gases.

[0037] The term "oxygen-enriched air" as used herein refers to a mixture of gases with a composition comprising more oxygen than is present in air. Oxygen-enriched air has a composition including greater than 21 vol.% oxygen, less than 78 vol.% nitrogen, less than 1 vol.% argon and less than 0.04 vol.% carbon dioxide. In some embodiments, oxygen-enriched air comprises at least 28 vol.% oxygen, e.g., at least 80 vol.% oxygen, at least 95 vol.% oxygen, or at least 99 vol.% oxygen.

[0038] The formation of HCN in the Andrussow process is often represented by the following generalized reaction:

2C¾ + 2NH₃ + 30₂ -» 2HCN + 6H₂0

However, it is understood that the above reaction represents a simplification of a much more complicated kinetic sequence where a portion of the hydrocarbon is first oxidized to produce the thermal energy necessary to support the endothermic synthesis of HCN from the remaining hydrocarbon and ammonia.

[0039] Three basic side reactions also occur during the synthesis of HCN:

CH₄ + H₂0 - CO + 3H₂

2CH₄ + 30₂ 2CO + 4H₂0

4N¾ + 30₂ 2N₂ + 6H₂0

In addition to the amount of nitrogen generated in the side reactions, additional nitrogen may be present in the crude product, depending on the source of oxygen. Although the prior art has suggested that oxygen-enriched air or pure oxygen can be used as the source of oxygen, the advantages of using oxygen-enriched air or pure oxygen have not been fully explored. When using air as the source of oxygen, the crude HCN product comprises the components of air, e.g., 78 vol.% nitrogen, and the nitrogen produced in the ammonia and oxygen side reaction.

[0040] Due to the large amount of nitrogen in air, it is advantageous to use oxygen- enriched air (which contains less nitrogen than air), in the synthesis of HCN because the use of air as the source of oxygen in the production of HCN results in the synthesis being performed in the presence of a large volume of inert gas (nitrogen) necessitating the use of larger equipment in the synthesis step and resulting in a lower concentration of HCN in the product gas. Additionally, because of the presence of the inert nitrogen, more methane is required to be combusted (when air is used, as compared to oxygen-enriched air) in order to raise the temperature of the ternary gas mixture components to a temperature at which HCN synthesis can be sustained. The crude HCN product contains the HCN and also by-product hydrogen, methane combustion byproducts (carbon monoxide, carbon dioxide and water), residual methane, and residual ammonia. However, when using air (i.e., 21 vol.% oxygen), after separation of the HCN and recoverable ammonia from the other gaseous components, the presence of the inert nitrogen renders the residual gaseous stream with a fuel value that may be lower than desirable for energy recovery.

[0041] It has been found that both productivity and production efficiency of HCN can be significantly improved, while maintaining stable operation, in part, by providing an oxygen- containing gas sufficiently enriched in oxygen and by adjusting the molar ratio of ammonia-to- methane to a sufficiently high level. In one embodiment, the ternary gas mixture contains at least 25 vol.% oxygen the molar ratio of ammonia-to-oxygen in the ternary gas mixture is in the range from 1.2 to 1.6, e.g., from 1.3 to 1.5, the molar ratio of ammonia-to-methane in the ternary gas mixture is in the range from 1 to 1.5, e.g., from 1.10 to 1.45, and the molar ratio of methane- to-oxygen is in the range from 1 to 1.25, e.g., from 1.05 to 1.15. In another embodiment, the oxygen-containing gas contains at least 80 vol.% oxygen, the molar ratio of ammonia-to-oxygen in the ternary gas mixture is in a range from 1.2 to 1.6, and the molar ratio of ammonia-to- methane in the ternary gas mixture is in the range from 1.15 to 1.40. In some embodiments, the ternary gas mixture comprises at least 25 vol.% oxygen, e.g., at least 28 vol.% oxygen. In some embodiments, the ternary gas mixture comprises from 25 to 32 vol.% oxygen, e.g., from 26 to 30 vol.% oxygen.

[0042] Prior to being mixed with the oxygen-containing gas 122 and the methane- containing gas 112, the ammonia-containing gas source 130 may be subject to treatment. This treatment may include removing contaminants, such as water, oil, and iron (Fe), from the ammonia-containing gas source 130. Contaminants in the ammonia-containing gas 132 can reduce catalyst life which results in poor reaction yields. The processing may include using processing equipment, such as vaporizers, and filters, to provide a treated ammonia-containing gas 132.

[0043] For example, commercially available liquid ammonia can be processed in a vaporizer to provide a partially purified ammonia vapor stream and a first liquid stream containing water, iron, iron particulate and other nonvolatile impurities. An ammonia separator, such as an ammonia demister, can be used to separate the impurities and any liquid present in the partially purified ammonia vapor stream to produce the treated ammonia-containing gas 132 (a substantially pure ammonia vapor stream) and a second liquid stream containing entrained impurities and any liquid ammonia present in the partially purified ammonia vapor stream.

[0044] In one embodiment, the first liquid ammonia stream containing water, iron, iron particulate and other nonvolatile impurities is fed to a second vaporizer where a portion of the liquid stream is vaporized to create a second partially purified ammonia vapor stream and a second, more concentrated, liquid stream containing water, iron, iron particulate and other nonvolatile impurities which can be further treated as a purge or waste stream. The second partially purified ammonia vapor stream can be fed to the ammonia separator. In another embodiment, the second, more concentrated, liquid stream containing water, iron, iron particulate and other nonvolatile impurities is fed to a third vaporizer to further reduce the ammonia content before treating as a purge or waste stream.

[0045] Foaming in the vaporizers can limit the vaporization rate of ammonia and decrease the purity of the ammonia vapor produced. Foaming is generally limited by the introduction of an antifoaming agent into the vaporizers directly or into the vaporizer feed streams. The antifoaming agents belong to a broad class of polymeric materials and solutions that are capable of eliminating or significantly reducing the ability of a liquid and/or liquid and gas mixture to foam. Antifoaming agents inhibit the formation of bubbles in an agitated liquid by reducing the surface tension of the solutions. Examples of antifoaming agents include silicones, organic phosphates, and alcohols. In one embodiment, a sufficient amount of antifoaming agent is added to the ammonia-containing gas 132 to maintain an antifoaming agent concentration of from 2 to 20 mpm in the ammonia-containing gas 132. A non-limiting example of an antifoaming agent is Unichem 7923 manufactured by Unichem of Hobbs, NM. The processing of the ammonia- containing gas source 130 may also include a filter system for removing micro particulates in order to prevent poisoning of the catalyst in the reactor 152. The filter system can be a single filter or a plurality of filters.

[0046] Using the methane-containing gas 106 obtained from natural gas comprising less than 90 vol.% methane, at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide treated in the particular manner required herein, i.e., one containing less than 1 vol.%, for example, less than 0.5 vol.%, such as less than 0.15 vol.%, C2+ hydrocarbons, to produce HCN also increases the catalyst life and yield of HCN. In particular, utilizing such a substantially pure methane-containing gas 106: (1) reduces the concentration of impurities, such as sulfur, C0₂, and ¾0, that have either a detrimental effect downstream or have no process benefit; (2) stabilizes the remaining composition at a consistent level to (a) allow downstream HCN synthesis to be optimized, and (b) enables the use of highly enriched or pure oxygen feed streams by mitigating large temperature excursions in the HCN synthesis step that are typically related to variation in higher hydrocarbon content and which are detrimental to optimum yield and operability (such as catalyst damage, interlock, and loss of uptime); and (3) reduces higher hydrocarbons to minimize formation of higher nitriles such as acetonitrile, acrylonitrile, and propionitrile in the synthesis reaction, and the associated yield losses of HCN during removal of nitriles. In addition, use of such a substantially pure methane-containing gas (1) eliminates or minimizes variability in the feed stock (i.e., it stabilizes the carbon and hydrogen content as well as the fuel values) and thereby stabilizes the entire HCN synthesis system allowing for the determination and control of methane-to-oxygen and ammonia-to-oxygen molar ratios for stable operation and the most efficient HCN yield; (2) eliminates or minimizes related temperature spikes and resulting catalyst damage; and (3) minimizes carbon dioxide thereby reducing the amount of carbon dioxide found in an ammonia recovery process, such as recovery section 160, and in a recovered or recycled ammonia stream coming from an ammonia recovery process, that may be downstream of the reactor 153. Eliminating or minimizing the carbon dioxide in such an ammonia recovery process and in a recovered or recycled ammonia stream reduces the potential for carbamate formation which causes plugging and/or fouling of the piping and other process apparatus.

[0047] It is desirable that the methane- containing gas 112 has very low concentrations of sulfur-containing compounds. The presence of sulfur actually has several beneficial short term effects, such as: (1) faster catalyst activation; (2) higher catalyst bed temperature; and (3) higher ammonia conversion. However, long term effects due to the presence of sulfur in the methane- containing gas 112 include (1) catalyst bed decomposition; (2) buildup of sulfur compounds in subsequent downstream refining systems; (3) increased mobility of platinum in the catalyst; and (4) extreme restructuring of the catalyst. It has been found that the reduction of sulfur containing compounds in the methane-containing gas 112 has overall beneficial effects on HCN yield as well as on catalyst activity and catalyst longevity.

[0048] Cryogenic demethanizer distillation for use in processing zone 105 may comprise introducing natural gas 104 to a compressor (not shown) to compress the gas to a pressure of up to 420 psig. The temperature of natural gas 104 may be increased up to 60°C in the compressor. The compressed natural gas may then be introduced to a warm gas separator, where the compressed natural gas is cooled and sent to a cold gas separator. The compressed natural gas is cooled to a temperature of -72°C in the cold gas separator, and is then fed to an expander (not shown) and a demethanizer reflux condenser (not shown). The compressed natural gas is separated in the demethanizer reflux condenser to produce a residue comprising C2+ hydrocarbons and a distillate comprising methane.

[0049] The methane-containing gas 1 12 for the present invention contains substantially pure methane and minor amounts, i.e. less than 1 vol.% C2+ hydrocarbons, such as, for example, less than 0.5 vol.%, e.g. less than 0.15 vol.%, C2+ hydrocarbons. Preferably, it will contain less than 300 mpm C0₂, e.g. from 150 to 300, mpm (moles) C0₂; less than 0.5 vol.%, e.g. less than 0.15 vol. % C2+ hydrocarbons; less than 2.5 mpm ¾0, e.g. from less than 0.2 to less than 2.5, mpm H₂0; and less than 0.01 vol.% H₂S. Thus, the methane-containing gas 112 provided to reactor 152 is substantially free of organic and inorganic contaminants, including C2+ hydrocarbons. In another embodiment, the gas, after removal of higher hydrocarbons, is fed to a warm separator to remove residual water and to reduce benzene concentrations to less than 25 parts per million moles (mpmm).

100501 The HCN refining section 170 shown in FIG. 1 is shown for use in the present invention. Broadly, the HCN refining section 170 includes a scrubber, an HCN absorber, an HCN stripper and an HCN enricher.

[0051] As will be appreciated by one skilled in the art, the foregoing functions and/or process may be embodied as a system, method or computer program product. For example, the functions and/or process may be implemented as computer-executable program instructions recorded in a computer-readable storage device that, when retrieved and executed by a computer processor, controls the computing system to perform the functions and/or process of embodiments described herein. In embodiments, the computer system can include one or more central processing units, computer memories (e.g., read-only memory, random access memory), and data storage devices (e.g., a hard disk drive). The computer-executable instructions can be encoded using any suitable computer programming language (e.g., C++, JAVA, etc.). Accordingly, aspects of the present invention may take the form of an entirely software embodiment (including firmware, resident software, micro-code, etc.) or an embodiment combining software and hardware aspects.

10052] From the above description, it is clear that the present invention is well adapted to carry out the objects and to attain the advantages mentioned herein as well as those inherent in the presently provided disclosure. While preferred embodiments of the present invention have been described for purposes of this disclosure, it will be understood that changes may be made which will readily suggest themselves to those skilled in the art and which are accomplished within the spirit of the present invention.

[0053] In order to demonstrate the present process, the following examples are given. It is to be understood that the examples are for illustrative purposes only and not to be construed as limiting the scope of the invention.

Example 1

[0054] Natural gas is obtained from a pipeline and the contents of the natural gas are measured. The natural gas is fed to a hydrocarbon separator to form a purified natural gas. The hydrocarbon separator comprises a cryogenic expansion turbine to remove C2+ hydrocarbons. The hydrocarbon separator further comprises a deethanizer, a depropanizer, a debutanizer, and a deisobutanizer to remove C2+ hydrocarbons from the natural gas. The contents of the natural gas and the purified natural gas are shown in Table 1.

TABLE 1. COMPARISON OF NATURAL CAS AND PURIFIED NATURAL

GAS

Nominal Composition, vol.% Natural Gas Purified Natural Gas

Nitrogen 0.01 to 0.5 <1

Carbon Dioxide 2 to 10 <300 mpm

Methane 70 to 90 at least 99

Ethane 2 to 15 <1500 mpm

Propane 2 to 10 —

Butanes 2 to 7 —

Pentanes and Heavier 0.1 to 3 —

Example 2

[0055] The utilization rates of ammonia in the HCN synthesis system are measured when differing compositions of methane-containing gases are used. Generally, ammonia conversion to HCN utilizing a one-pass synthesis process (i.e., no ammonia was recycled from downstream recycling and/or refining processes) decreases by 5-10% when the methane-containing gas contains approximately 8 vol.% ethane as compared to purified natural gas, referred to as substantially pure methane, as is shown in FIG. 2. The results of the above described experiment are demonstrated in FIG. 2 wherein the ammonia conversion to HCN is plotted against the carbon/air feed ratios for both a substantially pure methane-containing gas stream and a methane-containing gas stream containing 92 vol.% methane/8 vol.% ethane mixture.

[0056] The results shown in FIG. 3 demonstrate a two fold increase in ammonia recycle requirements for any given carbon/air feed ratio when the methane-containing gas contains about 8 vol.% ethane. Since the ammonia conversion decreases at a constant ammonia yield, the ammonia leakage, i.e., the amount of ammonia that is not used/converted during the reaction increases. The presence of ethane in the methane-containing gas also causes a three-fold increase in methane leakage, i.e., the amount of methane that is not used/converted during the reaction as shown in FIG. 4. [0057] Finally, FIG. 5 shows that HCN yield from carbon in the methane-containing gas is 50% using a substantially pure methane-containing gas versus only a maximum of 45% HCN yield using a methane-containing gas containing 8 vol.% ethane and 92 vol.% methane. Thus, the presence of C2+ hydrocarbons in the methane-containing gas provided to the reactor causes (1) a drop in conversion of carbon to HCN; (2) an increase in the amount of ammonia unconverted or "leaking through" the reactor; (3) an increase in the amount of methane unconverted in the reactor; and (4) increased amounts of recycled ammonia required.

Claims

We claim:

1. A process for the manufacture of hydrogen cyanide comprising:

(a) determining methane content of a natural gas stream comprising at least one C2+ hydrocarbon, carbon dioxide, and hydrogen sulfide;

(b) providing a ternary gas mixture comprising at least 25 vol.% oxygen, wherein the ternary gas mixture is formed by combining an oxygen-containing gas, an ammonia-containing gas, and the methane-containing gas, wherein the methane-containing gas is obtained from the natural gas stream, and wherein the natural gas stream is treated by a process comprising:

(i) contacting the natural gas stream with an amine capable of substantially removing carbon dioxide and hydrogen sulfide from the natural gas stream, to form a methane stream comprising methane and at least one C2+ hydrocarbon and a contaminant stream comprising carbon dioxide and hydrogen sulfide,

(ii) recovering and dehydrating the methane stream to provide a substantially anhydrous methane stream containing at least one C2+ hydrocarbon, and

(iii) treating the substantially anhydrous methane stream to provide a stream comprising at least one C2+ hydrocarbon and the methane-containing gas comprising less than 1 vol.% C2+ hydrocarbon; and

(c) contacting the ternary gas mixture with a catalyst to provide a crude hydrogen cyanide product.

2. The process of claim 1, wherein the treating comprises separating the substantially anhydrous methane stream in a hydrocarbon separator to form the stream comprising at least one C2+ hydrocarbon and the methane-containing gas comprising less than 1 vol.% C2+ hydrocarbon.

3. The process of claim 2, wherein the hydrocarbon separator comprises adsorption towers.

4. The process of claim 2, wherein the hydrocarbon separator comprises a cryogenic expansion turbine.

5. The process of claims 2 to 4, wherein the hydrocarbon separator comprises a deethanizer, a depropanizer, a debutanizer, and/or a deisobutanizer.

6. The process of any of the preceding claims, wherein methane-containing gas comprises less than 0.5 vol.% C2+ hydrocarbons, preferably less than 0.15 vol.% C2+ hydrocarbons, wherein the C2+ hydrocarbons are selected from the group consisting of ethane, propane, butane, pentane, isomers thereof, and combinations thereof.

7. The process of any of the preceding claims, wherein methane-containing gas comprises less than 0.1 vol.% C3+ hydrocarbons.

8. The process of any of the preceding claims, wherein the methane-containing gas comprises less than 0.01 vol.% hydrogen sulfide.

9. The process of any of the preceding claims, wherein the methane-containing gas comprises less than 300 mpm carbon dioxide.

10. The process of any of the preceding claims, wherein a molar ratio of ammonia-to-oxygen in the ternary mixture is from 1.2 to 1.6, and a molar ratio of methane-to-oxygen in the ternary gas mixture is from 1 to 1.25.

11. The process of any of the preceding claims, wherein the amine is selected from the group consisting of diethylamine, methyldiethanolamine, methylmonoethanolamine, and mixtures thereof.

12. The process of any of the preceding claims, wherein the methane-containing gas is substantially anhydrous.

13. The process of any of the preceding claims, wherein the oxygen-containing gas is substantially anhydrous.

14. The process of any of the preceding claims, wherein the oxygen-containing gas comprises greater than 80 vol.% oxygen.

15. The process of any of the preceding claims, wherein the oxygen-containing gas is pure oxygen.