CN103864105A - Enhanced methane control for Andrussow process - Google Patents
Enhanced methane control for Andrussow process Download PDFInfo
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- CN103864105A CN103864105A CN201310680715.1A CN201310680715A CN103864105A CN 103864105 A CN103864105 A CN 103864105A CN 201310680715 A CN201310680715 A CN 201310680715A CN 103864105 A CN103864105 A CN 103864105A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/022—Apparatus therefor
- C01C3/0225—Apparatus therefor characterised by the synthesis reactor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
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Abstract
The invention relates to a process for producing hydrogen cyanide and more particularly, to a process for producing a crude hydrogen cyanide product comprising from 0.05 to 1 vol.% methane. The invention also relates to a reactor for producing a crude hydrogen cyanide product having a catalyst bed that is supported by an annular shelf that provides a pass-through area of at least 90% of the area of the cross-sectional area of the reactor and the annular shelf substantially prevents catalyst bed bypass. The invention also relates to a crude hydrogen cyanide product comprising from 0.05 to 1 vol.% methane.
Description
the cross reference of related application
The application requires to enjoy in the right of priority of U. S. application 61/738,623 of submitting on December 18th, 2012, the full content of this application and disclose incorporated herein.
Technical field
The present invention relates to a kind of method for the production of prussic acid.More specifically, the present invention relates to a kind of by control the amount of methane in thick prussic acid product by a kind of controlled feed composition, and the method for producing prussic acid with productive rate and the output of booster stage.
Background technology
Traditionally, prussic acid (HCN) by Andrussow method or BMA method carry out plant-scale production (for example, referring to Ullman ' s Encyclopedia of Indusrial Chemistry, Volume A8, Weinheim1987, P.161-163).For example, in Andrussow method, can under applicable catalyzer exists, in reactor, make ammonia and contain the gas of methane and oxygen-containing gas and at high temperature react commercialization and prepare HCN(United States Patent (USP) 1,934,838 and 6,596,251).The higher homologue of sulphur compound and methane may affect the parameter of the oxidation ammonia solution of methane.For example, referring to Trusov, Effect of Sulfur Compounds and Higher Homologues of Methane on Hyfrogen Cyanide Production by the Andrussow Method, Russian J.Applied Chemistry, 74:10 (2001), pp.1693-1697.By making reactor effluent stream contact unreacted ammonia is separated with HCN with ammonium phosphate solution in ammonia absorber.By the ammonia purifying separating and concentrated, for being recycled to the conversion of HCN.Conventionally from reactor effluent stream after treatment, reclaimed HCN by absorbing in water.The HCN reclaiming can process by further refinement operation, to prepare the HCN of purifying.Document Clean Development Mechanism Project Design Document Form (CDM PDD, Version3), has explained to 2006 n-lustrative Andrussow HCN manufacturing process.The HCN of purifying can be used for hydrocyanation reaction, as the hydrocyanation of the hydrocyanation of the group that contains alkene or 1,3-butadiene and pentenenitrile, and above-mentioned hydrocyanation can be used for manufacturing adiponitrile (" ADN ").In BMA method, HCN substantially there is no oxygen and under the condition of platinum catalyst by methane and ammonia synthesis, HCN, hydrogen, nitrogen, residual ammonia and residual methane are consequently produced (as referring to Ullman ' s Encyclopedia of Industrial Chemistry, Volume A8, Weinheim1987, P161-163).Business operator requires process safety management, to control the dangerous character of prussic acid (referring to people such as Maxwell, Assuring process safety in the transfer of hydrogen cyanide manufacturing technology, JHazMat142(2007), 677-684).In addition, the abidance by rule possibly of the discharge from production unit in HCN manufacturing process, this may affect the economy that HCN produces.(referring to Crump, Economic Impact Analysis For The Proposed Cyanide Manufacturing NESHAP, EPA, in May, 2000).
Existing HCN production technique exists variety of issue, comprises the efficiency deficiency in production loss and the recovery of residual ammonia and the circulation of producing in HCN.
Summary of the invention
In one embodiment, the present invention relates to a kind of method for the production of prussic acid, comprising: form the ternary gas gaseous mixture that comprises methane-containing gas, contains ammonia gas and oxygen-containing gas; In reactor, described ternary gas mixture is contacted with catalyst bed and form thick prussic acid product, wherein said catalyst bed is supported by ring support, the district that passes through that this ring support provides area to be at least cross-sectional reactor area 90%, and described ring support has prevented the catalyst bed by-pass flow of ternary gas mixture or its component substantially; And control methane-containing gas, containing at least one flow velocity in ammonia gas and oxygen-containing gas so that the methane concentration in thick prussic acid product is remained on to 0.05-1 volume %.Described methane-containing gas, containing ammonia gas and the oxygen-containing gas formation ternary gas mixture that can combine in the mixing vessel of the upstream of described reactor.Described oxygen-containing gas can comprise the oxygen that is greater than 21 volume %, as the oxygen of at least 80 volume %.The oxygen that described ternary gas mixture contains at least 25 volume %.In described ternary gas mixture, ammonia can be 1.2-1.6 than the mol ratio of oxygen.In described ternary gas mixture, methane can be 1-1.25 than the mol ratio of oxygen.Described method can further comprise the described thick prussic acid product of separation, and wherein said separation comprises: from thick prussic acid product, remove residual ammonia so that prussic acid product to be provided; Separate described prussic acid product to form exhaust gas stream and prussic acid logistics; And described in purifying prussic acid logistics to form final prussic acid product.Described prussic acid logistics can comprise the acetonitrile that is less than the acetonitrile of 0.25 volume % or is less than 0.15 volume %.
In second embodiment, the present invention relates at a kind of thick prussic acid product for the preparation of the production in prussic acid method, the methane that wherein said thick prussic acid product comprises prussic acid and 0.05-1 volume %, as the methane of 0.05-0.55 volume % or 0.2-0.3 volume %.
In the 3rd embodiment, the present invention relates to the reaction unit for prepare prussic acid at reaction unit, described reaction unit comprises: at least one import of ternary gas mixture; The catalyzer supporting component that provides area to be at least the ring support that passes through district of cross-sectional reactor area 90% is provided; The catalyst bed being supported by described catalyzer supporting component, wherein said ring support has prevented the catalyst bed by-pass flow of ternary gas mixture or its component substantially; And for slightly at least one outlet of prussic acid product; Wherein, described ternary gas mixture comprises methane-containing gas, contains ammonia gas and oxygen-containing gas; Wherein said ternary gas mixture passes at least one described import, and by described catalyst bed; And wherein control methane-containing gas, containing at least one flow velocity in ammonia gas and oxygen-containing gas so that the methane concentration in thick prussic acid product is remained on to 0.05-1 volume %, for example 0.05-0.55 volume % or 0.2-0.3 volume % methane.Described catalyzer supporting component can comprise that tool orifice plate is to allow gas to pass through.Described catalyzer supporting component can be arranged to substantially be adjacent to the lower surface of described catalyst bed.Described catalyzer supporting component can further comprise the support that is arranged essentially parallel to catalyst bed and extends beyond described catalyst bed size.Described support can contain stupalith.
In the 4th embodiment, the present invention relates to the method for controlling thick prussic acid methane content, comprising: by comprising methane-containing gas, be provided at least one import of reactor containing the ternary gas mixture of ammonia gas and oxygen-containing gas; In reactor, described ternary gas mixture is contacted with catalyzer and form thick prussic acid product; Wherein catalyzer is supported by ring support, the district that passes through that described ring support provides area to be at least cross-sectional reactor area 90%, and described ring support has prevented the catalyst bed by-pass flow of ternary gas mixture or its component substantially; Measure the methane content in described thick prussic acid product; And adjust ammonia than the mol ratio of oxygen, ammonia than the mol ratio of methane or methane than at least one mol ratio in the mol ratio of oxygen, so that the thick prussic acid product that comprises 0.05-0.1 volume % or 0.05-0.55 volume % or 0.2-0.3 volume % methane to be provided.
In the 5th embodiment, the present invention relates to at least one import of ternary gas mixture, catalyst bed, for the catalyzer supporting component of support catalyst bed and at least one outlet of thick prussic acid product, wherein said catalyzer supporting component comprises tool orifice plate and is arranged essentially parallel to catalyst bed and extends beyond the support of described catalyst bed size, and wherein said support comprises stupalith; Wherein reactor assembly moves under the condition that is conducive to the thick prussic acid product of producing the methane that contains 0.05-1 volume % methane or 0.05-0.55 volume %.Ternary gas mixture can comprise methane-containing gas, contain ammonia gas and oxygen-containing gas.Described support can contact with the reactor wall of reactor assembly.Described catalyst bed can be vesicular structure, silk screen, spheroid, lamellar body, block, foam, Dipping or coating cleaning.Described catalyst bed can be wire cloth platinum/rhodium alloy or platinum/iridium alloy.Described support can be airtight.Described support can be parallel with tool orifice plate.Reactor assembly can further comprise the spark arrester in catalyst bed upstream, and wherein said spark arrester is refractory ceramic material.
In the 6th embodiment, the present invention relates to a reaction unit for the preparation of prussic acid, described reaction unit comprises: at least one import of ternary gas mixture, catalyzer supporting component, the catalyst bed being supported by catalyzer supporting component and at least one outlet of thick prussic acid product, wherein said ternary gas mixture comprises methane-containing gas, containing ammonia gas and oxygen-containing gas, wherein said ternary gas mixture is introduced into described at least one import, and pass through catalyst bed, and wherein said reactor moves under the condition that is conducive to the thick prussic acid product of producing the methane that contains 0.05-1 volume % methane or 0.05-0.55 volume %.
Described catalyzer supporting component can contain tool orifice plate.Described catalyzer supporting component can be arranged to substantially be adjacent to the lower surface of described catalyst bed.Described catalyzer supporting component can further comprise the support that is arranged essentially parallel to catalyst bed and extends beyond described catalyst bed size.Described support can comprise stupalith.Described catalyst bed can be vesicular structure, silk screen, lamellar body, spheroid, block, foam, Dipping or coating cleaning.Described catalyst bed can be wire cloth platinum/rhodium alloy or platinum/iridium alloy.Described support can be airtight.Described support and tool orifice plate can be in the same plane.Reactor assembly can further comprise the spark arrester in catalyst bed upstream, and wherein said spark arrester is refractory ceramic material.
Brief description of the drawings
Fig. 1 is the concise and to the point block diagram of the HCN synthesis system of an embodiment of the invention.
Fig. 2 A and 2B are the cross-sectional view of the catalyst bed on the catalyzer supporting component in comprising support of an embodiment of the invention.
Fig. 3 is the chart having represented as the nitrile formation of the function of methane content in thick prussic acid product.
Embodiment
Term used herein only, for the object of describing particular, is not intended to limit the present invention.Unless clearly shown other situation in context, singulative " " and " being somebody's turn to do " also comprise plural form as used herein.It should also be understood that, the term using in this manual " comprises " and/or has illustrated when " including " and have described feature, entirety, step, operation, parts and/or member, but do not hinder existence or the interpolation of one or more other features, entirety, step, operation, parts group, member and/or member group.
For example " comprise ", term and the variant thereof of " comprising ", " having ", " containing " or " relating to " should understand widely, and comprises listed main body and equivalent, also has unlisted other main body.In addition, when " being comprised " by transitional term, " comprising " or " containing " while drawing component, parts group, technique or method steps or any other statement, be to be understood that and also considered identical component, parts group, technique or method steps herein, or there is any other statement of transitional term before the record of this component, parts group, technique or method steps or any other statement " substantially by ... composition ", " by ... composition " or " choosing freely ... the group of formation ".
If applicable words, the device of corresponding structure, material, action and all functions in claim or the equivalent of step comprise that the miscellaneous part for specifically stating with claim carries out any structure, material or the action of function in combination.Specification sheets of the present invention provides for the object of introducing and describe, but be not exhaustive or limit the invention to disclosed form.Do not departing under the prerequisite of scope and spirit of the present invention, many changes and variant are apparent for the person of ordinary skill of the art.Here select and described some embodiments, object is that principle of the present invention and practical application are carried out to best explanation, and other those of ordinary skill that make this area can be understood different embodiments of the present invention and have multiple variation, as being suitable for this specific end use.Correspondingly, although the present invention is described according to embodiment, but those skilled in the art will recognize that, the present invention can change to some extent ground and implement within the spirit and scope of claims.
Now with detailed reference to specific disclosed theme.Although disclosed theme is described in connection with cited claim, however be appreciated that they not by disclosed subject matter restricted in these claims.On the contrary, disclosed theme has covered all replacement schemes, change and equivalent, within these can be contained in the scope of disclosed theme defined by the claims.
In the Andrussow method that is used to form HCN, under the existence of catalyzer, at methane, ammonia and the oxygen raw material temperature more than approximately 1000 DEG C, reaction generates the thick prussic acid product that contains HCN, hydrogen, carbon monoxide, carbonic acid gas, nitrogen, residual ammonia, residual methane and water.By these components, if raw material is as comprising oxygen-containing gas, providing to reactor containing the ternary gas mixture of ammonia gas and methane-containing gas.Catalyzer is generally silk screen platinum/rhodium alloy or silk screen platinum/iridium alloy.Described catalyst bed can be made by braiding or layout.Other catalyst component be can use, platinum metals, platinum-group metal alloy, loading type platinum family metal or loading type platinum family metal alloy included but not limited to.The catalyst configuration that also can use other, includes but not limited to vesicular structure, silk screen, lamellar body, spheroid, block, foam, Dipping and coating cleaning.Conventionally use the raw material of Sweet natural gas as methane, use air, oxygen-rich air or pure oxygen as oxygen source.Ternary gas mixture by catalyzer to form thick prussic acid product.Then separate described thick prussic acid product to reclaim HCN.
As described here, comprise HCN, residual ammonia and residual oxygen from the thick prussic acid product of Andrussow method or BMA method.In Andrussow method, control residual methane content by some variablees, comprise the mol ratio of reactants, methane, ammonia and oxygen, transformation efficiency and the reaction efficiency of reactant.Advantageously, can improve the method by the amount of controlling the methane in thick prussic acid product.If the methane existing in thick prussic acid product very little, residual ammonia possibility cracking is to form nitrogen and hydrogen.If there is too many methane in thick prussic acid product, at purification of crude prussic acid when reclaiming HCN, may in thick prussic acid product, can form not conceivable impurity, comprise nitrile, as acetonitrile.Further polymerization hinder separating technology of nitrile, thus production efficiency deficiency caused.Described nitrile will have to from separating technology, discharge to avoid obstruction.Based on object of the present invention, the methane content in controlled thick prussic acid product is between 0.05 and 1 volume %, as 0.05-0.55 volume % or 0.2-0.3 volume %.In the time that the methane content in thick prussic acid product is between 0.6 and 1 volume %, the quantity not sufficient of the nitrile of formation is removed in sepn process with needs, and therefore this methane content is acceptable in thick prussic acid product.But along with the growth of time, these nitrile polymerizables also block separating device.Therefore, when separating device continuously or when semi-continuous running at least 6 months, optimization methane content is 0.05-0.55 volume % or 0.2-0.3 volume %.
Therefore, in one embodiment, the present invention relates to a kind of thick prussic acid product of producing in the method for the preparation of prussic acid, the methane that wherein said thick prussic acid product comprises prussic acid and 0.05-1 volume %, as the methane of 0.05-0.55 volume % or 0.2-0.3 volume %.This thick prussic acid product composition may be irrelevant with its preparation method, as long as contain methane in reactant.
As described here, there are several variablees of the amount of controlling this methane.According to Andrussow method, be used to form the reactant that HCN uses and comprise ammonia, methane and oxygen, wherein every kind is all to provide with gas form.For example also mixed in the combination in mixing vessel of the upstream of reactor before entering reactor by import containing ammonia gas, methane-containing gas and oxygen-containing gas.A variable controlling the amount of methane in thick prussic acid product is that ammonia in ternary gas mixture is than the mol ratio of oxygen.In some embodiments, the ammonia in ternary gas mixture is 1.2-1.6 than the mol ratio of oxygen.Methane can be 1-1.25 than the mol ratio of oxygen.If need to adjust methane than the mol ratio of oxygen, preferably adjust the flow velocity of methane and keep the flow velocity of oxygen.
Therefore, the present invention also relates to control ammonia than oxygen and methane than the method for the mol ratio of oxygen.In the time that adjustment comprises the mol ratio of oxygen, there are several Considerations.This is due to the combustibility of ternary gas mixture and limits of explosion, if particularly using oxygen-rich air as oxygen-containing gas, as contained the air that is greater than 21 volume % oxygen, as the air that contains at least 80 volume % oxygen is as oxygen-containing gas.
For accurately adjust ammonia than oxygen and methane than the mol ratio of oxygen, need to reduce or eliminate the leakage of ternary gas mixture and component thereof, for example, the leakage of the gas containing methane around catalyst bed.Above-mentioned leakage, can be by comprising that a ring catalyst support described herein reduces described leakage also referred to as by-pass flow.Reduce or eliminate the by-pass flow of catalyst bed methane-containing gas around by reducing for example essence, if compare methane-containing gas by-pass flow catalyst bed, it can more predictably control the flow velocity of methane in thick prussic acid product.In other words,, in the time that methane can by-pass flow catalyst bed, the control that methane is leaked is impossible.Advantage of the present invention is by utilizing a kind of air-locked ring support to eliminate the catalyst bed by-pass flow of methane around, so can control methane by the flow velocity that regulates methane.
strengthen oxygen content
As described here, can use ammonia than the mol ratio of oxygen and methane than the amount of mole recently controlling methane in thick prussic acid product of oxygen.The method that regulates these ratios at least in part based on oxygen-containing gas, be therefore also the oxygen level of ternary gas mixture.
Term " air " refers to the gaseous mixture that composition is roughly the same with the original composition of gas of taking from atmosphere (conventionally at ground place) as used herein.In some instances, air is taken from surrounding environment.Air has following composition, comprises oxygen, the argon gas of approximately 1% volume and the carbonic acid gas of approximately 0.04% volume of the nitrogen of approximately 78% volume, approximately 21% volume, and other a small amount of gas.
Term " oxygen-rich air " refers to that composition comprises than the gaseous mixture of existing more oxygen in air as used herein.Oxygen-rich air has following composition, comprise be greater than 21% volume oxygen, be less than 78% volume nitrogen, be less than the argon gas of 1% volume and be less than the carbonic acid gas of 0.04% volume.In some embodiments, oxygen-rich air comprises the oxygen of at least 28% volume, for example oxygen of at least 80% volume, for example oxygen of at least 95% volume, or the oxygen of at least 99% volume.
The formation of HCN in Andrussow method is typically expressed as following general reaction:
2CH
4+2NH
3+3O
2→2HCN+6H
2O
But, it will be appreciated that, what above-mentioned reaction represented is the simplification of a more complicated dynamic process, and in described dynamic process, a part of hydrocarbon is first oxidized, and to produce necessary heat energy, to support remaining hydrocarbon and the ammonia to carry out the heat absorption of HCN synthetic.
Between the synthesis phase of HCN, also can there are three basic side reactions:
CH
4+H
2O→CO+3H
2
2CH
4+3O
2→2CO+4H
2O
4NH
3+3O
2→2N
2+6H
2O
Except the amount of the nitrogen that produces, according to oxygen source, in thick product, may there is extra nitrogen in side reaction.Although suggestion can be used oxygen-rich air or purity oxygen as oxygen source in prior art, use the advantage of oxygen-rich air or purity oxygen not developed completely.In the time using air as oxygen source, the thick aeriferous component of prussic acid product bag, the nitrogen of 78 volume % according to appointment, and produced nitrogen in the side reaction of ammonia and oxygen.
Due to airborne a large amount of nitrogen, therefore in HCN synthetic, use and oxygen-rich air that nitrogen that air ratio contains is few is favourable, this is because use air can cause described synthesizing in a large amount of rare gas element (nitrogen) to be carried out as oxygen source in the production of HCN, this need to use larger equipment in synthesis step, and causes the lower concentration of HCN in product gas.In addition, due to the existence of inert nitrogen, for the temperature of ternary gas mixture component is increased to and can maintains the synthetic temperature of HCN, the more methane that need to burn (in the time using air, comparing with oxygen-rich air).Thick prussic acid product comprises HCN, and also comprises by product hydrogen, methyl hydride combustion by product (carbon monoxide, carbonic acid gas, water), residual methane and residual ammonia.But, when using air when (oxygen of 21 volume % according to appointment), at the after separating from other gaseous fractions by HCN and callable ammonia, the existence of inert nitrogen make residual gas stream with fuel value may be lower than the desirable value for energy recovery.
Therefore, in the production of HCN, use oxygen-rich air or pure oxygen to replace air that several benefits can be provided, comprise the raising of Sweet natural gas to the transformation efficiency of HCN, and be attended by reducing of processing unit size.Therefore, the inert compound that uses oxygen-rich air or pure oxygen to enter synthesis technique by minimizing has reduced the size of reactor, and has reduced at least one parts of gas downstream treatment facility.The use of oxygen-rich air or pure oxygen has also reduced heating and has contained oxygen feed gas to the desired energy expenditure of temperature of reaction.
Have been found that partly oxygen-containing gas by enough oxygen enrichments are provided and by adjust ammonia than the mol ratio of methane to sufficiently high level, can make the throughput of HCN and production efficiency all improve significantly, keep stable operation simultaneously.In one embodiment, described oxygen-containing gas contains the oxygen that is greater than 21 volume %, as the oxygen of the oxygen of the oxygen of at least 80 volume %, at least 95 volume % or at least 99 volume %, ammonia in ternary gas mixture than the mol ratio of oxygen in the scope of 1.3-1.5, as in the scope of 1.3-1.4, and ammonia in ternary gas mixture than the mol ratio of methane in the scope of 1.1-1.45.In another embodiment, the oxygen that ternary gas mixture contains at least 25 volume %, ammonia is 1.2-1.6 than the mol ratio of oxygen, and ammonia is 1-1.5 than the mol ratio of methane, and as 1.1-1.45, and methane is 1-1.25 than the mol ratio of oxygen, as 1.05-1.15.For example, ternary gas mixture can have 1.3 ammonia than the methane of the mol ratio of oxygen and 1.2 than the mol ratio of oxygen.In another exemplary, ternary gas mixture can have 1.5 ammonia than the methane of the mol ratio of oxygen and 1.15 than the mol ratio of oxygen.Wherein oxygen concn may be according to the difference of these mol ratios and difference.
The amount of the oxygen that utilizes flammable limit to control to exist in ternary gas mixture.The combination of some air, methane and ammonia is flammable, and therefore will be after lighting propagating flame.If between the upper and lower bound of the gas composition of the mixture of a kind of air, methane and ammonia in flammable limit, this mixture will burn.The mixture of air, methane and ammonia outside this scope is generally non-combustible.The use of oxygen rich gas can change the concentration of the inflammable substance in ternary gas mixture.The oxygen level that improves oxygen-containing gas feed stream can significantly expand flammable range.For example, the mixture of the methane of the air that contains 45 volume % and 55 volume % is considered to fuel enrichment and nonflammable, and the methane of the oxygen that contains 45 volume % and 55 volume % is flammable.
Another problem is limits of explosion.For example, under normal atmosphere and room temperature, the methane that contains 60 volume % oxygen, 20 volume % and the gaseous mixture of 20 volume % ammonias can explode.
Therefore, although find that the use of oxygen-rich air is favourable in the production of HCN, but the air that is rich in oxygen must cause the change of the concentration of the inflammable substance in ternary gas mixture, and the change of this inflammable substance concentration can improve the upper limit of flammability of the ternary gas mixture that enters reactor.Therefore, the detonation of ternary gas mixture and blast are very sensitive to the concentration of oxygen.Term " deflagration " used herein refers to the combustion wave of propagating with subsonic velocity before being in close proximity to flame with respect to unburned gas." blast " refers to sentence before being in close proximity to flame with respect to unburned gas the combustion wave of Supersonic transport.Deflagration causes appropriate increased pressure conventionally, and blast may cause excessive increased pressure.
Other suggestions are used oxygen rich gas for increasing HCN production capacity, and they generally avoid operating in zone of flammability.Referring to U.S. Patent number 5,882,618,6,491,876 and 6,656,442, its whole content is contained in herein by reference.In the present invention, the charging of controlling oxygen-rich air or purity oxygen is the ternary gas mixture in blast area not to form in zone of flammability.Therefore, in some embodiments, the oxygen that ternary gas mixture contains at least 25 volume %, as the oxygen of at least 28 volume %.In certain embodiments, the oxygen that ternary gas mixture contains 25-32 volume %, as the oxygen of 26-30 volume %.
the preparation of methane-containing gas
As one of ordinary skill in the art can understand, the source of methane may be different, and may be from as garbage loading embeading district, farm, in renewable raw materials from the biogas fermenting, obtain, or from as Sweet natural gas, oil field gas, in the fossil oil of coal gas and gas hydrate, obtain, as VN Parmon, " Source of Methane for Sustainable Development ", P.273-284 with Derouane chief editor's Sustainable Strategies for the Upgranding of Natural Gas:Fundamentals, Challenges, and Opportunities(2003) in further describe.For the purposes of the present invention, the consistent composition in the purity of methane and the source of containing methane is very important.
As the one source of the methane for methane-containing gas, Sweet natural gas is a kind of not pure state of methane.That is to say, Sweet natural gas be a kind of can be to be in fact used to HCN for producing to provide the methane-containing gas of carbon atom in technique of the present invention.But, except methane, in Sweet natural gas, may contain impurity, as hydrogen sulfide, carbonic acid gas, nitrogen, water, and the hydrocarbon of high molecular, as ethane, propane, butane, pentane and more senior hydrocarbon.Here, the hydrocarbon of these high components is called as " C2+ hydrocarbon ".Can make in all sorts of ways and from Sweet natural gas, remove C2+ hydrocarbon, comprise hydrocarbon partition method.Hydrocarbon partition method can be implemented by absorption method or low-temperature expansion method.Absorption process can be mainly used in removing C3+ hydrocarbon, and low-temperature expansion method can be mainly used in removing ethane, also can remove C3+ hydrocarbon simultaneously.
The gas composition of different sources has significant difference.The composition of the Sweet natural gas providing by pipeline also can be in time passing or even under very short time span, alter a great deal because source is by pipeline opening and closing.The amount of this difference of composition, the particularly existence of C2+ hydrocarbon and C2+ hydrocarbon, has caused being difficult to maintaining best and stable processing performance.The existence of the C2+ hydrocarbon in gas composition is because following reason is particularly troublesome: 1) its calorific value higher than methane; 2) its inactivating effect to HCN catalyst reactor, particularly C3+ hydrocarbon; 3) may form senior nitrile as the side reaction of acetonitrile, vinyl cyanide and propionitrile.Owing to making inertia load reduction by the oxygen coalescence of oxygen-containing gas, therefore the susceptibility of the variation of HCN building-up process to a large amount of C2+ hydrocarbon aggravates thereupon.
Therefore, methane-containing gas can be processed into and comprise the C2+ hydrocarbon that is less than 1 volume %, as is less than 5000mpm, is less than 1000mpm, is less than 150mpm or there is no in fact C2+ hydrocarbon." there is no in fact C2+ hydrocarbon " and comprises the C2+ hydrocarbon of 0-100mpm.Should also can be described as " Sweet natural gas of purifying " containing the logistics of methane.In some embodiments, there is no impurity containing on the logistics essence of methane.In addition, the logistics that contains methane can be essentially anhydrous.
Produce HCN and can improve the life-span of catalyzer and the output of HCN to obtain methane-containing gas with the Sweet natural gas of purifying.Particularly, utilize the natural gas stream of purifying to make remaining set compound be stabilized in same level, so that optimization downstream HCN's is synthetic, and by reduce large temperature departure in the synthesis step of HCN, to can use oxygen or the pure oxygen material of high enrichment, wherein said temperature departure is conventionally relevant with the variation of the content of higher hydrocarbon, and is (for example loss of catalyst breakage, interlocking and working hour) being harmful to for best output and operability.Use the Sweet natural gas of purifying also the formation of senior nitrile can be minimized, and the associated loss of yield of the HCN in the time removing nitrile is minimized.In addition, use the Sweet natural gas of purifying as the raw material of methane-containing gas, content by Stable Carbon and hydrogen and calorific value and the variability of charging is minimized, and thus by whole HCN synthesis system stabilization, thereby allow determine and control best methane than oxygen with ammonia than the mol ratio of oxygen, for stable operation and more effective HCN output.In addition, use the Sweet natural gas of purifying relevant temperature peak value and the catalyst impairment causing can be minimized.
containing the preparation of ammonia gas
Before mixing with oxygen-containing gas and methane-containing gas, can accept processing containing ammonia body source.This operation can comprise from removing impurity, Ru Shui, oil and iron (Fe) containing ammonia body source.Catalyst life be can reduce containing the impurity in ammonia gas, low reaction yield and replacing more early caused.This operation can comprise use treatment facility, as vaporizer and strainer, so that the treated ammonia gas that contains to be provided.
For example, can in vaporizer, process the available liquefied ammonia of business, with the first liquid logistics that partially purified ammonia steam stream is provided and contains water, iron, iron granules and other non-volatile impurities.Useful ammonia separator, the impurity and all liquid that exist in partially purified ammonia steam stream as described in separating as ammonia mist eliminator, treated containing ammonia gas (pure in fact ammonia steam stream) with contain the second liquid logistics of carrying impurity and all liquid secretly being present in described partially purified ammonia steam stream to make.
In one embodiment, the first liquid logistics that contains water, iron, iron granules and other non-volatile impurities is passed into after-fractionating device, a part of liquid stream evaporation therein, generate the ammonia steam stream of second section purifying and the more concentrated second liquid logistics that contains water, iron, iron granules and other non-volatile impurities, it can be used as discharge opeing or waste stream is further processed.The ammonia steam stream of second section purifying can be passed into ammonia separator.In another embodiment, the more concentrated second liquid logistics that contains water, iron, iron granules and other non-volatile impurities is passed into the 3rd distiller, so that this logistics was being reduced further to its ammonia content before discharge opeing or waste stream processing.
Rising in distiller steeped oneself-meeting and limited the distillation rate of ammonia, and reduces the purity of the ammonia steam of producing.Conventionally, by directly in distiller or introduce defoamer stop foaming in distiller feed stream.Defoamer belongs to a large class of polymeric material and solution, and it can eliminate or significantly reduce the ability of liquid and/or the foaming of liquids and gases mixture.By reducing the surface tension of solution, the formation of foam in the liquid that defoamer has suppressed to stir.The example of defoamer comprises organosilicon, organophosphate and alcohols.In one embodiment, the defoamer of q.s is added containing in ammonia gas 132, be about 2-20mpm to maintain containing the concentration of defoamer in ammonia gas 132.A non-limitative example of defoamer is Unichem of Hobbs, NM(New Mexico) UNICHEM7923 of manufacturing.Also can comprise filter system containing the processing of ammonia body source 130, it is for removing particulate, to prevent the poisoning of catalyzer in reactor 152.Filter system can be single strainer or multiple strainer.
hCN reactor
The invention still further relates to reactor assembly 106, described reactor assembly 106 is for the production of thick prussic acid product 107, the methane that described thick prussic acid product 107 comprises 0.05-1 volume %, as the methane that comprises 0.05-0.55 or 0.2-0.3 volume %.Reactor assembly 106 contains a hydrid component 155, its for introduce and hybrid reaction gas with form introduce reaction part 157 completely mix ternary gas mixture 105.Reaction part 157 comprises at least one import 160 of ternary gas mixture 105, catalyzer supporting component 161, the catalyst bed 162 that supported by catalyzer supporting component, and at least one outlet 163 of thick prussic acid product 107.As described here, controlling reactor efficiency is a variable controlling methane content in thick prussic acid product.
As described here, a method of control reactor efficiency is to provide catalyzer supporting component.As shown in Figure 2 A, catalyzer supporting component can be arranged to essence and be adjacent to the lower surface 164 of catalyst bed 162, and is arranged to this catalyst bed 162 and relies on catalyzer supporting component and by catalyzer supporting component and support.Catalyzer supporting component comprise tool orifice plate (as, bulk or foamed ceramics) 170 and support 171, as ring support.Ring support 171 can stretch out with uniform distance from the inwall of reaction part 157 165.Ring support 171 is along the circumference of reaction part 157.Tool orifice plate 170 can be with ring support 171 in same plane.Tool orifice plate 170 allows gas to pass through.Ring support 171 is solid and gas can not see through.Ring support 171 is parallel to catalyst bed 162 for essence, and contacts with reactor wall 165.In some embodiments, ring support 171 is made up of pottery, and is the part of the whole of reactor.In some embodiments, ring support 171 is made up of the material identical with reactor.Ring support 171 can be arranged to allow to exist by district, thereby contacts with catalyst bed and form thick prussic acid product with the thick prussic acid product that allows to be formed by ternary gas mixture.Described thick prussic acid product can contain the component of ternary gas mixture, such as methane, oxygen and/or ammonia.Describedly ventilative pass through district and can at least account for 85% of reactor cross-section area, as at least 90%, this depends on the catalyzer shrinkage of expectation and the HCN output of expectation.Scope by district can be 85-95%, as by 90% to 95%.For example, if the internal diameter of reactor is 137.16cm, and suppose that the diameter of passing catalyzer is in time contracted between 0.64cm-1.26cm, ring support 171 can extend 2.54cm to 3.18cm from reactor wall.Can make to be reduced by least in 85% by district to larger extension in reactor, and reduce productive rate.If catalyzer shrink exceed the estimates or move in reactor, be greater than 95% be faced with equally some problems by the little annular wall in district greatly.As a rule, contraction of catalyst can occur at least partly in the time starting, and state then remains retracted in reactor operation always.In addition, make support from reactor wall further extension can reduce reactor and close to change the frequency of catalyst bed, but also can increase reactor pressure decrease, cause reducing HCN output.
As shown in Figure 2 B, in the form of a simplification, because catalyzer has experienced contraction, the extensible catalyst bed 162 that exceedes of ring support 171.Along with the prolongation of catalyst life, catalyzer may shrink as shown in Figure 2 B, causes catalyst bed 162 no longer to contact with reactor wall 165.Contraction of catalyst can allow component (the comprising methane) by-pass flow of ternary gas mixture to cross described catalyzer, causes the methane content in thick prussic acid product to increase.By comprising ring support 171, the by-pass flow can reduce, essence reducing and/or eliminate this ternary gas mixture.
Spark arrester is spatially arranged on catalyst bed, so that space to be provided there.Spark arrester can extinguish the indoor upstream burning causing owing to refluxing of any internal-response.Ceramic foam along define internal-response chamber and catalyzer housing inwall at least a portion arrange.In the time that reactor is closed, ceramic foam minimizes the by-pass flow of shrinking caused unstripped gas due to catalyzer.Be arranged in the formation that ceramic foam on catalyst bed minimized, reduced pressure drop for the operating process at reactor by the volume of ternary gas and suppresses free radical.In each outlet of housing, be furnished with lasso, it provides the fluid between catalyst bed and the upper section of waste heat boiler to be communicated with.
In catalyst bed, be prepared the reaction of HCN.The suitable catalyzer using in the catalyst bed of Andrussow technique contains VIII family metal.VIII family metal comprises platinum, rhodium, iridium, palladium, osmium or ruthenium, and described catalyzer can be the plural alloy in mixture or these metals of these metals, these metals.Producing in a lot of examples of HCN, use the catalyzer that contains the platinum based on catalyzer total mass 50-100 quality %.Described catalyzer is essential enough strong, the speed that may increase while using oxygen-rich air or pure oxygen preparation to contain the three-element mixed gas that is greater than 25 volume % oxygen bearing.Therefore, can in plane support of the catalyst, use 85/15 platinum/rhodium alloy.Also can in the corrugated load than plane support of the catalyst with larger surface-area, use 90/10 platinum/rhodium alloy.
the production of thick prussic acid product
As shown in Figure 1, in prussic acid production system 100, ternary gas mixture 105 comprises methane-containing gas 102, contains ammonia gas 103 and oxygen-containing gas 104.Described ternary gas mixture 105 passes in reactor assembly 106 to produce thick prussic acid product 107, the methane that described thick prussic acid product 107 comprises 0.05-1 volume %, as the methane that contains 0.05-0.55 volume % or 0.2-0.3 volume %.Thick prussic acid product 107 passes in ammonia absorber 110, the HCN logistics and the residual ammonia logistics 112 that flow out to form tower top.
Conventionally,, before further carrying out HCN purifying, preferably unreacted ammonia (also referred to as residual ammonia) is removed from thick prussic acid product.Ammonia absorber 110 possesses the absorber portion of sufficient amount, to obtain the separation of level of expectation.The industrial practice of standard can be determined the quantity of necessary section.Thick prussic acid product 107 is introduced to ammonia absorber 110, and from thick prussic acid product 107 absorbing ammonia, described ammonia enters poor phosphoric acid salt feed stream (not shown).
In one embodiment, described poor phosphoric acid salt feed stream has NH for comprising
4 +/ PO
4 3+than the phosphoric acid hydrogen one ammonium (NH in the scope of 1.2-1.4
4h
2pO
4) and Secondary ammonium phosphate ((NH
4)
2hPO
4) " poor ammonia " aqueous solution, and the pH value of described " poor ammonia " aqueous solution is 5-6.1, as 5.3-6.0.NH
4 +/ PO
4 3+the value of ratio comprises the ammonia only having with phosphoric acid salt binding, and does not consider with other compounds as the ammonia of formate or oxalate binding.Before solution passes into ammonia absorber top as poor phosphoric acid salt feed stream, can in poor ammonia phosphate solution, add supplementary phosphoric acid logistics.Control at least in part the operation of ammonia absorber 110 by monitoring and adjust temperature, pH and solution density.By the temperature of poor phosphoric acid salt feed stream be controlled at 90 DEG C and higher than the freezing point of described poor phosphoric acid salt feed stream (sometimes also referred to as frost point, it is defined as saturation point herein, during lower than described temperature, solid just starts sedimentation) between, absorb with the ammonia of realizing expectation.Thick prussic acid product 107, upwards by ammonia absorber 110, contacts with the poor phosphoric acid salt feed stream of the ammonia absorber 110 of flowing through downwards in the mode of adverse current.In thick prussic acid, the 107 unreacted ammonia that exist are absorbed by " poor ammonia " phosphate solution, and the extra Secondary ammonium phosphate of reaction formation, and " rich ammonia " phosphate solution that flow to ammonia absorber bottom is provided thus.To there is NH
4 +/ PO
4 3+from ammonia absorber 110, discharge as residual ammonia logistics 112 to the rich ammonia phosphate solution being less than in 7.0 scope 6.2 than (in another embodiment in the scope of 1.7-1.9) and pH value within the scope of 1.5-2.0.
In another embodiment, in ammonia absorber charging stock tank, store poor ammonium phosphate solution, before poor ammonia phosphate solution passes into ammonia absorber top as poor phosphoric acid salt feed stream, can in poor ammonium phosphate solution, add supplementary phosphoric acid logistics here.Can be by ammonia absorber charging stock tank heating or cooling, to keep the temperature of poor ammonia phosphate solution to be in the desired temperature of absorbing ammonia in ammonia absorber 110.
In another embodiment, poor phosphoric acid salt feed stream comprises and has NH
4 +/ PO
4 3+than the phosphoric acid hydrogen one ammonium (NH within the scope of 1.2-1.4
4h
2pO
4) and Secondary ammonium phosphate ((NH
4)
2hPO
4) poor aqueous phosphatic, and the pH value of poor aqueous phosphatic is 5-6.1, such as, 5.3-6.0.By described poor phosphoric acid salt feed stream with two different logistics in different positions with two kinds of different NH
4 +/ PO
4 3+than introducing in ammonia absorber 110, as set forth more fully like that in the US Patent No. 3,718,731 of Carlson etc., this patent is incorporated herein by reference herein.Ammonia absorber 110 can utilize filler and/or column plate.In one embodiment, the absorber portion in ammonia absorber 110 is valve column plate.Valve column plate is well known in the art, and can select the design of column plate to realize good circulation, to prevent retention areas, and prevents polymerization and corrosion.For fear of polymerization, equipment can be designed so that roughly to exist the retention areas of HCN to minimize, as the retention areas in the region that is being further purified HCN in ammonia absorber 110 and described here.Ammonia absorber 110 also can be combined with entrainment trap on top tray, so that entrainment is minimized.Entrainment trap generally comprise use as underspeed, the technology of centrifugation, mist eliminator, sieve or filler or their combination.
In another embodiment, provide ammonia absorber 110, wherein ammonia absorber top provides filler and multiple valve column plates are arranged at ammonia absorber bottom.Filler is used for reducing/preventing ammonia and phosphoric acid salt is overflowed from ammonia absorber 110 via top HCN logistics 111, and enters afterwards the region that is further purified HCN.Filler provides additional surface-area for ammonia absorbs, and has reduced the entrainment in top HCN logistics 111 simultaneously, has caused the entirety of ammonia receptivity to improve.Can be the structured packing of any low pressure drop that can carry out above-mentioned functions at ammonia absorber top use filler, as Wichita, the 250Y that the Koch-Glisch of KS sells
filler.
In another embodiment, at least in part by withdrawing from liquid from ammonia absorber bottom, it is circulated by water cooler and after return and enter the temperature that keeps ammonia absorber 110 ammonia absorber 110 from recalling the point of a top.
Residual desorption device logistics 142 can be circulated to HCN resorber 130.The residual logistics 142 of desorption device does not have in fact HCN.Before entering HCN resorber, by the temperature of residual desorption device logistics 142 from the cooling 30-65 DEG C that is down to up to 120 DEG C.Desorption device overhead stream 141 contains a large amount of HCN and a small amount of water and nitrile.
Desorption device overhead stream 141 can be introduced to HCN enricher 150 subsequently, separated to form HCN product 151 and the residual logistics 152 of enricher there.HCN enricher 150 comprises column plate, as frozen valve tray or sieve plate.Valve column plate and sieve plate are the well-known of this area.Select tray designs to realize good vapour-liquid mass and retention areas is minimized, with reduce polymerization, dirty and corrosion possibility.Include but not limited to 316 stainless steels for the suitable material of building HCN enricher 150 column plates.
The residual logistics 152 of enricher contains HCN, water and comprises other organic constituents of mid-boiling point impurity.Make the residual logistics 152 of enricher and residual logistics 142 combinations of desorption device, be then circulated to HCN resorber 130, so remove mid-boiling point impurity, as acetonitrile, propionitrile and vinyl cyanide, otherwise it can accumulate in HCN desorption device and enricher tower.
Nitrile is as acetonitrile, propionitrile and vinyl cyanide and at HCN/H
2other mid-boiling point impurity in O system can be assembled in the bottom of HCN enricher 150.Can utilize nitrile discharge opeing to remove the mid-boiling point impurity from HCN enricher 150.The gathering of nitrile can cause the temperature rise in HCN enricher 150, and it can hinder use temperature to infer acceptable HCN purity, and finally causes polluting and unacceptable HCN purity.Described nitrile discharge opeing sustainability ground or intermittently carry out.By the logistics that contains nitrile discharge opeing is circulated to HCN resorber 130, described nitrile can be removed to waste gas 131 and remove.
As described here, do not retrained by theory, can think by the amount of the methane in thick prussic acid product is controlled to 0.05-1 volume %, as 0.05-0.55 volume % or 0.2-0.3 volume %, can reduce the formation of nitrile.By reducing the formation of nitrile, nitrile bleed stream can reduce, thereby allows to improve the recovery of HCN.
In HCN product 151, contain the water of the pure HCN of essence and trace, as be less than 100mpm or be less than the water of 10mpm.HCN product 151 can be used in further technique, as the hydrocyanation for containing olefin group, or as can be used for manufacturing the 1,3-butadiene of ADN and the hydrocyanation of pentenenitrile.
Get back to residual ammonia logistics 112, this logistics can directly pass into ammonia recovery zone 101, and it can comprise further ammonia purifying, the ammonia that obtains subsequently capable of circulation and with containing ammonia gas 103 combinations.Ammonia recovery zone 101 can comprise one or more desorption devices, to remove HCN with acid and ammonia is separated from other impurity.Ammonia recovery zone 101 also can comprise ammonia enricher, to be further purified ammonia.By controlling the amount of the methane in thick prussic acid product, the recovery that can improve ammonia.Do not retrained by theory, can think that residual ammonia can be cracked into nitrogen, has therefore reduced the content of ammonia in the time that existence in thick prussic acid product 107 is less than the methane of 0.05 volume %.Also think, if there is the methane more than 1 volume % in thick prussic acid product 107, can there is the formation of less desirable acetonitrile in the downstream in technique.
Can control reactant gas flow by various Controlling System.For example, can use flow velocity, the temperature and pressure of measuring reactant gas feed stream, and the under meter that allows Controlling System to provide " in real time " of the flow velocity of pressure compensation and temperature compensation to feed back for operator and/or operating device.
As understood by one of ordinary skill in the art, aforementioned function and/or method may be embodied as system, method or computer program.For example, function and/or method may be embodied as the executable programmed instruction of computer, this instruction is recorded in computer-readable memory device, and in the time retrieving and carry out this instruction by computer processor, it controls computer system to carry out function and/or the method for above-mentioned embodiment.In one embodiment, computer system can comprise one or more central processing unit, computer memory (for example read-only storage, random access storage device) and data storage device (for example hard disk drive).The executable instruction of computer can be used any applicable computer programming language (such as C++, JAVA etc.) to encode.Therefore, the form (comprise firmware, resident software, microcode etc.) of entirety for the embodiment of software can be taked in aspects more of the present invention, or combines the embodiment of software aspect and hardware aspect.
Can be clear from above-mentioned explanation, the present invention can be well suited for realize target and reach mentioned advantage and disclosure institute inherent advantages here.Although described for the purpose of this disclosure preferred embodiment of the present invention, but be understandable that, can carry out the apparent and change that can complete to those skilled in the art under spirit of the present invention.
In order more effectively to understand invention disclosed herein, following examples are provided.It should be understood that the only object for illustrating of this embodiment, and should not be interpreted as by any way limiting the present invention.
Embodiment 1
According to Andrussow method, form three-element mixed gas body with air as oxygen-containing gas and produce thick prussic acid product.By three-element mixed gas body by catalyst bed to form thick prussic acid product.In the time that described thick prussic acid product is discharged to reactor assembly, measure its methane content.As shown in Figure 3, along with the increase of methane concentration in thick cyaniding cyanogen product, the concentration of acetonitrile also can increase.In the time using pure oxygen to replace air as air inlet, the trend that the nitrile of this increase forms also can be expected.
According to Andrussow method, utilize purity oxygen to form three-element mixed gas body as oxygen-containing gas and produce thick prussic acid product.Be that 1.3:1 and methane are that 1.2:1 forms described three-element mixed gas body than the mol ratio of oxygen with ammonia than the mol ratio of oxygen.The oxygen that this three-element mixed gas body comprises 28.5 volume %.Reactor has 142.2cm internal diameter, and platinum/rhodium catalyst bed is placed on a casting ring support that extends into 2.86cm in reactor, make described catalyst bed formed thick prussic acid product 90% pass through district.In 150 days of operate continuously, the diameter of described catalyst bed has shunk 0.64 to 1.26cm, there is no methane by-pass flow catalyst bed, and this is because described ring support has supported the catalyst bed shrinking.The methane that comprises 0.2-0.3 volume % in described thick cyaniding cyanogen product.
Comparative example A
Except ring support, to extend into reactor more, and are decreased to outside 85% by district, identical with embodiment 2 of technique and reactor.Compared with embodiment 2, in reactor, pressure drop has raise 20%, so that the yield reducation of HCN.
Claims (15)
1. for the production of a method for prussic acid, comprising:
Formation comprises methane-containing gas, contains the ternary gas mixture of ammonia gas and oxygen-containing gas; And
In reactor, described ternary gas mixture is contacted with catalyst bed and form thick prussic acid product, wherein catalyst bed is supported by ring support, described ring support provide area be at least cross-sectional reactor area 90% pass through district, and described ring support has substantially prevented the catalyst bed by-pass flow of ternary gas mixture or its component and has entered thick cyaniding cyanogen product; And
Control methane-containing gas, containing at least one the flow velocity in ammonia gas and oxygen-containing gas, so that the methane concentration in thick prussic acid product is remained on to 0.05-1 volume %.
2. method according to claim 1, wherein, described method comprises the flow velocity of controlling methane-containing gas.
3. method according to claim 1, wherein, described ternary gas mixture can not see through described ring support.
4. method according to claim 1, wherein, the methane that described thick prussic acid product comprises 0.05-0.55 volume %.
5. according to the method described in any one in claim 1-4, wherein, the methane that described thick cyaniding cyanogen product comprises 0.2-0.3 volume %.
6. method according to claim 1, wherein, described methane-containing gas, combines in the mixing vessel of the upstream of described reactor containing ammonia gas and oxygen-containing gas, to form ternary gas mixture.
7. method according to claim 1, wherein, described oxygen-containing gas comprises the oxygen that is greater than 21 volume %, is preferably the oxygen of at least 80 volume %.
8. method according to claim 1, wherein, described oxygen-containing gas comprises purity oxygen.
9. method according to claim 1, wherein, the oxygen that described ternary gas mixture comprises at least 25 volume %.
10. method according to claim 1, wherein, the oxygen that described ternary gas mixture comprises 25-32 volume %.
11. methods according to claim 1, wherein, the ammonia in described ternary gas mixture than the mol ratio of oxygen between 1.2-1.6.
12. methods according to claim 1, wherein, the methane in described ternary gas mixture than the mol ratio of oxygen between 1-1.25.
13. methods according to claim 1, wherein, separate thick prussic acid product, and wherein said separation comprises:
From described thick prussic acid, remove residual ammonia so that prussic acid product to be provided;
Separate described prussic acid product to form exhaust gas stream and prussic acid logistics; And
Described in purifying, prussic acid logistics is to form final prussic acid product.
14. methods according to claim 13, wherein, described prussic acid logistics comprises the acetonitrile that is less than 0.25 volume %.
15. methods according to claim 13, wherein, described prussic acid logistics comprises the acetonitrile that is less than 0.15 volume %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| US201261738623P | 2012-12-18 | 2012-12-18 | |
| US61/738,623 | 2012-12-18 |
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| CN (1) | CN103864105B (en) |
| HK (1) | HK1199001A1 (en) |
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| TW202335966A (en) | 2021-10-29 | 2023-09-16 | 德商羅伊姆公司 | Optimized process for production and isolation of hydrogen cyanide and process for conversion thereof into methacrylic acid (mas) and/or alkyl methacrylate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2832675A (en) * | 1951-12-06 | 1958-04-29 | Goodrich Co B F | Catalyst holder and support unit |
| US3104945A (en) * | 1961-07-19 | 1963-09-24 | Du Pont | Method of producing hydrogen cyanide |
| CN101269824A (en) * | 2007-03-23 | 2008-09-24 | 赢创罗姆有限责任公司 | Method for producing hydrocyanic acid (HCN) |
| CN102530868A (en) * | 2010-12-28 | 2012-07-04 | 李宽义 | Environmental-protection process method for removing ammonia from ammoxidation synthesis gas |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262145A (en) * | 1990-10-09 | 1993-11-16 | E. I. Du Pont De Nemours And Company | Catalyst for ammonia conversion to HCN |
| US5882618A (en) * | 1997-04-28 | 1999-03-16 | Air Liquide America Corporation | Process for cyanic acid production |
| US20050047988A1 (en) * | 2003-09-03 | 2005-03-03 | Kim Tae Hoon | Method of making hydrocyanic acid using a mass spectrometer control system |
| DE102007034715A1 (en) * | 2007-07-23 | 2009-01-29 | Evonik Röhm Gmbh | Reactor for the production of hydrogen cyanide by the Andrussow method |
-
2013
- 2013-12-12 TW TW102145773A patent/TWI519477B/en not_active IP Right Cessation
- 2013-12-12 CN CN201310680715.1A patent/CN103864105B/en active Active
- 2013-12-12 WO PCT/US2013/074538 patent/WO2014099568A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2832675A (en) * | 1951-12-06 | 1958-04-29 | Goodrich Co B F | Catalyst holder and support unit |
| US3104945A (en) * | 1961-07-19 | 1963-09-24 | Du Pont | Method of producing hydrogen cyanide |
| CN101269824A (en) * | 2007-03-23 | 2008-09-24 | 赢创罗姆有限责任公司 | Method for producing hydrocyanic acid (HCN) |
| CN102530868A (en) * | 2010-12-28 | 2012-07-04 | 李宽义 | Environmental-protection process method for removing ammonia from ammoxidation synthesis gas |
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| CN103864105B (en) | 2018-04-17 |
| TWI519477B (en) | 2016-02-01 |
| HK1199001A1 (en) | 2015-06-19 |
| WO2014099568A1 (en) | 2014-06-26 |
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