CN103965056A - Integrated process for hexamethylenediamine production - Google Patents
Integrated process for hexamethylenediamine production Download PDFInfo
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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
- C01C3/04—Separation from gases
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
Described is a process for the integrated production of hexamethylenediamine. The process includes integrating an HCN production process, an adiponitrile production process, and an HMD production process. The HCN.production process provides HCN for hydrocyanating butadiene to form adiponitrile and a hydrogen stream for hydrogenating adiponitrile to form HMD. The HCN production process includes forming a crude hydrogen cyanide product and separating the crude hydrogen cyanide product to form an off-gas stream and a hydrogen cyanide product stream. The off-gas stream is further separated to recover hydrogen. The hydrogen cyanide product stream is further processed to recover hydrogen cyanide.
Description
the cross reference of related application
The application requires the right of priority of the U.S. Provisional Application 61/738734 of submitting on December 18th, 2012, and its disclosed full content merges to herein.
Technical field
The present invention relates to produce the method for hexamethylene-diamine.Especially, the present invention improves the efficiency of method by following steps, by the stream of recover hydrogen from thick prussic acid product and prussic acid runoff yield, prussic acid runoff yield is used for to the hydrocyanation of divinyl to form adiponitrile, and the hydrogenation that hydrogen stream is used for to adiponitrile is to form hexamethylene-diamine.
Background technology
Hexamethylene-diamine (" HMD ") is as the intermediate of product in industry, textiles, resin, carpet and coating industry and with industrial-scale production.In addition, HMD can be used in coating, solidifying agent, petroleum additive, tackiness agent, ink, anti-incrustation corrosion inhibitor and Water Treatment Chemicals.A kind of large commercial use of HMD is the intermediate as nylon, and described nylon comprises nylon-6,6, nylon-6,10 and nylon-6,12, also comprise that molecular formula is nylon-6, and other nylon of x, wherein x is the carbonatoms in diacid.For example, HMD can pass through under pressure, high temperature adiponitrile (" ADN ") hydrogenation, by ADN is mixed with excess of ammonia gas and hydrogen, and this mixture is carried out to commercialization preparation by catalyst bed, described catalyst bed comprises copper, nickel or the cobalt of with or without carrier.The scope of high temperature can be 85 to 150 DEG C and pressure range and can be 200 to 500 normal atmosphere (for example seeing United States Patent (USP) 3398195).
ADN also can be as the intermediate of producing ACN (ACN).Can be by ACN cyclisation to form the hexanolactam of the intermediate that can be used as nylon-6.ADN can be prepared by a number of procedures, comprise that Weissermel etc. is published in Integrated Organic Chemistry for 1997, the method of 245-250 page, the method is chlorination divinyl under sodium cyanide exists, then hydrogenation, hydrogenation propylene dimer nitrile and hydrocyanation divinyl.Hydrocyanation divinyl comprises two process.First, by 1,3-butadiene hydrocyanation on catalyzer (being generally nickel (0) catalyzer), to form 3 pentene nitrile.Then 3 pentene nitrile hydrocyanation on nickel (0) catalyzer is become to ADN, conventionally under Lewis acid exists, carry out.(for example seeing United States Patent (USP) 7528275).
As described herein, the method for preparing HMD can need multiple reactions and incoming flow, comprises hydrogen, divinyl, ADN and prussic acid.Conventionally, for example, in commercial quantity produce prussic acid (" HCN ") by Andrussow method or BMA method (seeing Ullman ' sEncyclopedia of Industrial Chemicstry, A8 volume, the work such as Weinheim, 1987,161-163 page).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 SulfurCompounds and Higher Homologues of Methane on Hyfrogen Cyanide Production bythe 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 DevelopmentMechanism Project Design Document Form (CDM PDD, Version 3), 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, Weinheim 1987, 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 cyanidemanufacturing technology, JHazMat 142(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 ManufacturingNESHAP, EPA, May 2000).
US2797148 discloses a kind of method that reclaims ammonia from the gaseous mixture containing ammonia and prussic acid.Ammonia reacts with gas containing hydrocarbon and oxygen-containing gas and the reaction end gas of preparing the technique of prussic acid comprises ammonia, prussic acid, hydrogen, nitrogen, water vapour and carbonic acid gas.This tail gas is cooled to the temperature of 55 to 90 DEG C, then passes into adsorption tower, and ammonia is isolated from tail gas.
US3647388 discloses a kind of technique of producing prussic acid by the hydrocarbon gas (as methane) up to six carbon atom and ammonia.Selection process carries out in burner, this burner is useful on the mobile center conduit of oxygen-bearing fluid and for the parallel one or more annular pipes adjacent with center conduit that flow of hydrogen, ammonia and hydrocarbon gas, described conduit terminates in reaction chamber, wherein, in described reaction chamber, the flame front of hydrocarbon gas and ammonia flame in the time of hydrogen and oxygen combustion reacts.This technique has been got rid of the use of catalyzer.
Although the recovery method of Andrussow method and HCN is well-known, prepares and HCN technological process, separate tail gas and be not almost disclosed with the method for recover hydrogen stream from catalysis.In addition, still not by HCN production system and HMD and/or the integrated any report of CAN production system.
Therefore, need so a kind of technique, it not only can produce HCN under the existence of catalyzer, also can be from reactor tail gas recover hydrogen, thereby can be by all integrated with HMD production system to HCN and hydrogen.
The above-mentioned publication document of mentioning mode is by reference attached to herein.
Summary of the invention
In one embodiment, the present invention relates to produce the method for hexamethylene-diamine, comprising: (a) determine the methane content of methane-containing gas, and in the time that the content of methane is defined as being less than 90 volume %, purifying methane-containing gas; (b) ternary gas mixture of the oxygen that comprises at least 25 volume % under existing, catalyzer is reacted to form the thick prussic acid product that comprises prussic acid and waste gas in reactor, wherein ternary gas mixture comprises methane-containing gas, containing ammonia gas, and oxygenous gas; (c) separate thick prussic acid product to form prussic acid product stream and the tail gas stream that comprises hydrogen, water, carbon monoxide and carbonic acid gas; (d) separate tail gas stream to form the hydrogen stream that comprises hydrogen, and the discharge logistics that comprises carbon monoxide, carbonic acid gas and water; (e) at least a portion prussic acid product stream is used for to hydrocyanation divinyl to form adiponitrile; (f) at least a portion hydrogen stream is used for to hydrogenation of adiponitrile to form hexamethylene-diamine.Hydrogenation of adiponitrile also can form ACN.In some embodiments, ternary gas mixture can comprise the oxygen of 25 to 32 volume %.Oxygenous gas can comprise the oxygen that is greater than 21 volume %, for example oxygen of at least 80 volume %, the oxygen of at least 95 volume % or pure oxygen.Tail gas stream can comprise the hydrogen of 40 to 90 volume %, water, the carbon monoxide of 0.1 to 20 volume and the carbonic acid gas of 0.1 to 20 volume % of 0.1 to 20 volume %.Useful pressure-variable adsorption, molecular sieve or film separate tail gas stream.Pressure-variable adsorption can carry out under the pressure from 1400kPa to 2400kPa and at the temperature of 16 to 55 DEG C.Pressure-variable adsorption device can comprise at least two adsorption beds.Each of at least two adsorption beds comprise select free zeolite, gac, silica gel, aluminum oxide with and in conjunction with at least one sorbent material in the group of composition.The hydrogen of the hydrogen that hydrogen stream comprises at least 95 volume % or at least 99 volume %.Thick prussic acid product stream can comprise the hydrogen that is less than 10 volume %, is less than the hydrogen of 5 volume %, or can substantially there is no hydrogen.Hydrogen from least 70 volume % of ternary gas mixture can be recycled in hydrogen stream.Step (c) can further comprise that separating thick prussic acid product flows to form ammonia.At least a portion of ammonia stream can be turned back in reactor.
In another embodiment, the present invention relates to the method for the preparation of hexamethylene-diamine, it comprises: (a) determine the methane content of methane-containing gas, and in the time that the content of methane is defined as being less than 90 volume %, purifying methane-containing gas; (b) ternary gas mixture of the oxygen that comprises at least 25 volume % under existing, catalyzer is reacted to form the thick prussic acid product that comprises prussic acid and waste gas in reactor, wherein ternary gas mixture comprises methane-containing gas, containing ammonia gas, and oxygenous gas; (c) separate thick prussic acid product to form prussic acid product stream, ammonia stream and to comprise the tail gas stream of hydrogen, water, carbon monoxide and carbonic acid gas; (d) separate tail gas stream to form the hydrogen stream that comprises hydrogen, and the discharging current that comprises carbon monoxide, carbonic acid gas and water; (e) at least a portion prussic acid product stream is used for to hydrocyanation divinyl to form adiponitrile; (f) at least a portion hydrogen stream is used for to hydrogenation of adiponitrile to form the binding substances of hexamethylene-diamine or hexamethylene-diamine and ACN.At least a portion ammonia stream can be turned back to reactor.In some embodiments, ternary gas mixture can comprise the oxygen of 25 to 32 volume %.Oxygenous gas can comprise the oxygen that is greater than 21 volume %, for example oxygen of at least 80 volume %, the oxygen of at least 95 volume % or pure oxygen.Tail gas stream can comprise the hydrogen of 40 to 90 volume %, water, the carbon monoxide of 0.1 to 20 volume and the carbonic acid gas of 0.1 to 20 volume % of 0.1 to 20 volume %.Useful pressure-variable adsorption, molecular sieve or film separate tail gas stream.Pressure-variable adsorption can carry out under the pressure from 1400kPa to 2400kPa and at the temperature of 16 to 55 DEG C.Pressure-variable adsorption device can comprise at least two adsorption beds.Each of at least two adsorption beds comprise select free zeolite, gac, silica gel, aluminum oxide with and in conjunction with at least one sorbent material in the group of composition.The hydrogen of the hydrogen that hydrogen stream comprises at least 95 volume % or at least 99 volume %.Thick prussic acid product stream can comprise the hydrogen that is less than 10 volume %, is less than the hydrogen of 5 volume %, or can substantially there is no hydrogen.Hydrogen from least 70 volume % of ternary gas mixture can be recycled in hydrogen stream.
In another embodiment, the present invention relates to the method for the production of hexamethylene-diamine, it comprises: (a) determine the methane content of methane-containing gas, and in the time that the content of methane is defined as being less than 90 volume %, purifying methane-containing gas; (b) ternary gas mixture of the oxygen that comprises at least 25 volume % under existing, catalyzer is reacted to form the thick prussic acid product that comprises prussic acid and waste gas in reactor, wherein ternary gas mixture comprises methane-containing gas, containing ammonia gas, and oxygenous gas; (c) separate thick prussic acid product to form prussic acid product stream and the tail gas stream that comprises hydrogen, water, carbon monoxide and carbonic acid gas; (d) in pressure-variable adsorption device, separate tail gas stream to form the hydrogen stream of the hydrogen that comprises at least 95 volume %, and the discharge logistics that comprises carbon monoxide, carbonic acid gas and water; (e) at least a portion prussic acid product stream is used for to hydrocyanation divinyl to form adiponitrile; (f) at least a portion hydrogen stream is used for to hydrogenation of adiponitrile to form the binding substances of hexamethylene-diamine or hexamethylene-diamine and ACN.In some embodiments, ternary gas mixture can comprise the oxygen of 25 to 32 volume %.Oxygenous gas can comprise the oxygen that is greater than 21 volume %, for example oxygen of at least 80 volume %, the oxygen of at least 95 volume % or pure oxygen.Tail gas stream can comprise the hydrogen of 40 to 90 volume %, water, the carbon monoxide of 0.1 to 20 volume and the carbonic acid gas of 0.1 to 20 volume % of 0.1 to 20 volume %.Pressure-variable adsorption can carry out under the pressure from 1400kPa to 2400kPa and at the temperature of 16 to 55 DEG C.Pressure-variable adsorption device can comprise at least two adsorption beds.Each protection of at least two adsorption beds select free zeolite, gac, silica gel, aluminum oxide with and in conjunction with at least one sorbent material in the group of composition.The hydrogen of the hydrogen that hydrogen stream comprises at least 95 volume % or at least 99 volume %.Thick prussic acid product stream can comprise the hydrogen that is less than 10 volume %, is less than the hydrogen of 5 volume %, or can substantially there is no hydrogen.Hydrogen from least 70 volume % of ternary gas mixture can be recycled in hydrogen stream.Step (c) can further comprise that separating thick prussic acid product flows to form ammonia.Ammonia stream can be back to reactor at least partly.
Brief description of the drawings
Fig. 1 is the schematic diagram of integrated HMD production system.
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.
The invention provides the production of HMD and the integrated method of method of producing HCN.The production method of HCN comprises recover hydrogen stream and reclaims HCN.Can in hydrogen stream and HCN stream is integrated with HMD production system.Conventionally, in prior art, hydrogen can reclaim from steam methane reforming or ethane cracking.The hydrogen obtaining in this way has a lot of impurity, and it can be introduced in the operation of each use hydrogen.The hydrogen that uses creationary method as described herein to reclaim from HCN technique is high-purity and can in subsequent technique, introduce impurity.In addition, existing technique can require multiple incoming flows and/or reactive system to produce HMD.These reactive systems comprise the system of producing HCN, ADN and HMD.Therefore,, by by these system integrations, can realize process efficiency and the cost savings improved.
The formation of HMD can be expressed by following equation:
NC(CH
2)
4CN+4H
2→H
2N(CH
2)
6NH
2
As described herein, HMD, under high moderate pressure, forms under the existence of catalyzer.Excess of ammonia and hydrogen are mixed with ADN to ADN hydrogenation is formed to HMD.Ammonia can be liquid phase, and hydrogen can have the dividing potential drop of 1000kPa to 30000kPa.ADN can be in the scope of 1:40 to 1:55 than the mol ratio of ammonia.Catalyzer can comprise cobalt, nickel, iron and precious metal, and described precious metal comprises rubidium, rhenium, platinum and palladium.In some embodiments, catalyzer comprises nickel or cobalt.Catalyzer can load on carrier (comprising alumina supporter).
The transformation efficiency of ADN can be 80 to 100%, and has 40 to 80% HMD and/or the selectivity of ACN (ACN).In some embodiments, the transformation efficiency of ADN can exceed 98%.Be understandable that, the HMD forming and the ratio of ACN can be by regulating the residence time and/or other processing condition to control.The transformation efficiency of ADN calculates by following:
The selectivity of HMD is calculated by following:
The selectivity of ACN is calculated by following:
ADN can form by following two step method:
As implied above, divinyl is become the mixture of 3 pentene nitrile (" 3PN ") and 2-methyl-3-crotononitrile (" 2M3BN ") by hydrocyanation.If necessary, also has the isomerization steps of 2M3BN to 3PN.Then by 3PN hydrocyanation with form adiponitrile.Each hydrocyanation step can be carried out catalysis by nickel catalyzator, preferably the nickel catalyzator of zeroth order.The example of having described this catalyzer in United States Patent (USP) 8088943, its full content is incorporated in the present invention by reference.The hydrocyanation of 3PN can carry out existing under Lewis acid promotor, and this is also described in United States Patent (USP) 8088943.Reaction can, in liquid phase, at 500-5000kPa, for example, at 1000-5000kPa, and at 0-200 DEG C, for example, be carried out at 50-100 DEG C.Unless stated otherwise, all pressure is all absolute pressures.
The prussic acid that is used for the hydrocyanation of divinyl and 3PN can obtain from Andrussow method or BMA method.In the Andrussow method that is used to form HCN, methane, ammonia and oxygen feed are reacted under the existence of the temperature higher than 1000 DEG C and catalyzer to the thick prussic acid product that comprises HCN, hydrogen, carbon monoxide, carbonic acid gas, nitrogen, residual ammonia, remaining methane and water to produce.By these compositions, raw material is provided to reactor as ternary gas mixture, and described ternary gas mixture comprises oxygenous gas, contains the ternary gas mixture of ammonia gas and methane-containing gas.Just as understood by the skilled person in the art, may be different containing methane source, and can be for example refuse landfill from renewable resources, farm, obtain from the biogas fermenting, or by such as Sweet natural gas of fossil oil, oil field gas, coal gas and gas hydrate and obtain, if VN Parmon is in " Source of Methane for Sustainable Development " 273-284, with Derouane etc. at " Sustainable Strategies for the Upgrading of Natural Gas:Fundamentals, Challenges, and Opportunities (2003) " in institute further describe.For the purposes of the present invention, be important containing methane purity and the constant composition in methane source.In some embodiments, this technique can comprise the methane content of determining containing methane source, and in the time that the content of methane is defined as being less than 90 volume %, purifying is containing methane source.Useful gas chromatographic measurement method, comprise that Raman spectrum determines methane content.Determine in real time continuously methane content, or when introduce the new source that contains methane source in technique time, determine as required methane content.In addition, in order to realize higher purity, when methane is containing being 90 volume % when above, during as 90-95 volume %, also can should contain methane source by purifying.Can carry out purifying containing methane source with known purification process, with except deoiling, condensation product, water, C2+ hydrocarbon (as ethane, propane, butane, pentane, hexane and isomer thereof), sulphur and carbonic acid gas.
Sweet natural gas is typically as methane source, and air, oxygen-rich air or oxygen can be used as source of oxygen.Ternary gas mixture is passed through to catalyzer to form thick prussic acid product.Then by thick hydrocyanation product separation with reclaim HCN.In the present invention, also thick hydrocyanation product separation is carried out to recover hydrogen.
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.
Term " Sweet natural gas " refers to such mixture as used herein, comprises the mixture of methane and optional ethane, propane, butane, carbonic acid gas, oxygen, nitrogen and hydrogen sulfide.Sweet natural gas also can comprise the rare gas of trace, comprises helium, neon, argon gas and xenon.In some embodiments, Sweet natural gas can comprise the methane that is less than 90 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 crude 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 aeriferous component of prussic acid crude product bag, the nitrogen of 78 volume % according to appointment, and 2 moles of nitrogen that produce in the side reaction of ammonia and oxygen.
Due to airborne a large amount of nitrogen, therefore in HCN synthetic, use oxygen-rich air 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, more methane need to burn.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 HCN produces, use oxygen-rich air or pure oxygen replaces air that some advantages are provided, comprising can recover hydrogen.Other advantage comprises, has improved Sweet natural gas and has reduced to transformation efficiency and the processing unit size of HCN thereupon.Therefore the inert compound that, uses oxygen-rich air or purity oxygen to enter synthesis procedure by reduction reduces the size of the size of reactor and at least one parts of dirty gas processing device.Use oxygen-rich air or purity oxygen also can reduce oxygenous feed gas is heated to the required energy expenditure of temperature of reaction.
In the time of air that use comprises 21 volume % or oxygen still less, for the consideration of energy and economy, the amount of nitrogen makes hydrogen recovery there is no practical significance.Unexpectedly, find, in the time using oxygen-rich air or purity oxygen, method that can be effective and economic is recover hydrogen from thick prussic acid product, for example, use pressure-variable adsorption device.The hydrogen reclaiming has high purity and therefore can be used in integrated HMD production method.
In the time preparing thick prussic acid product with oxygen-rich air or purity oxygen, need to process from the waste gas of thick prussic acid product with recover hydrogen composition instead of it is burnt in boiler.Can use adsorber that waste gas is separated from thick prussic acid product.Use pressure-variable adsorption (PSA), membrane sepn or other known purifying/recovery methods that hydrogen is reclaimed out from least a portion waste gas.In some embodiments, PSA unit is for recover hydrogen.In this case, first by gas compression to 130kPa to 2600kPa, for example 130kPa to 2275kPa, 130kPa to 1700kPa or 136kPa to 1687kPa, then sent in PSA unit.Reclaim high-purity hydrogen larger as the value of fuel as raw material ratio because can used as other techniques for example ADN to the incoming flow of the hydrogenation of ACN and HMD.It should be noted that, the amount of the nitrogen in waste gas can affect the economic feasibility of recover hydrogen from waste gas and not affect burns waste gas in boiler.Other compositions or composition also can affect the feasibility of recover hydrogen.For example, the HCN concentration (as measured by on-line sensor) in tail gas stream exceedes in the peaked situation of expection, tail gas stream can be reintroduced back to steam generation boiler or torch place and not carry out hydrogen recovery.
Fig. 1 has shown the embodiment of integrated HMD production method.As shown in Figure 1, ternary gas mixture 105 comprises methane-containing gas 102, contains ammonia gas 103 and oxygenous gas 104.As described here, for make hydrogen be recovered in economically with energy on feasible, the oxygen content in oxygenous gas 104 is greater than 21 volume %, for example oxygen-rich air or purity oxygen.In some embodiments, the oxygen content in oxygenous gas 104 is the oxygen of at least 28 volume %, oxygen, the oxygen of at least 95 volume % or the oxygen of at least 99 volume % of at least 80 volume %.
Control the amount of the oxygen in ternary gas mixture 105 by limits of inflammability.The particular combinations of air, methane and ammonia is flammable, and will therefore after igniting, develop into flame.If gas composition is between upper flammable limit and lower limit, the mixture of air, methane and ammonia will burn.The mixture of air, methane and ammonia beyond this scope is normally non-flammable.Use oxygen-rich air to change the combustible concentration in ternary gas mixture.Increase oxygen content in oxygenous gas feed stream and can significantly widen flammable range.For example, the mixture of the methane of the air that contains 45 volume % and 55 volume % is to be considered to very fuel enrichment and non-flammable, but the mixture of the methane of the oxygen that contains 45 volume % and 55 volume % is flammable.
Another one focus is limits of explosion.For example, under normal atmosphere and room temperature, the gaseous mixture of the ammonia of the oxygen that contains 60 volume %, the methane of 20 volume % and 20 volume % can explode.
Therefore, although find that it is favourable using oxygen-rich air in HCN produces, but the air of collecting oxygen will inevitably cause the combustible concentration in ternary gas mixture to change, and this change of combustiblematerials concentration has improved the upper flammable limit of the ternary gas mixture of sending into reactor.Therefore, the detonation of ternary gas mixture and blast are responsive to oxygen concentration.Here the term " detonation " that used " refers to respect to unburned gas and before being in close proximity to flame, sentences the combustion wave that subsonic speed is propagated.On the other hand, " blast " refer to respect to unburned gas before being in close proximity to flame, sentence supersonic speed propagate combustion wave.Deflagration typically causes appropriate pressure rise, but blast can cause king-sized pressure rise.
But once advised increasing with oxygen-rich air the throughput of HCN, this has typically avoided the operation in flammable range.See United States Patent (USP) 5882618; 6491876 and 6656442, its all the elements are incorporated in the present invention by reference.In the present invention, control oxygen-rich air or purity oxygen charging to form in flammable range but the ternary gas mixture in detonable range not.Therefore, in some embodiments, ternary gas mixture 105 comprises the oxygen that is greater than 25 volume %, for example, be greater than the oxygen of 28 volume %.In some embodiments, the oxygen that ternary gas mixture comprises 25-30 volume %, for example oxygen of 26-30 volume %.Ternary gas mixture can have the ammonia of 1.2-1.6 than oxygen mol ratio, ammonia-oxygen mol ratio of for example 1.3-1.5, the ammonia of 1-1.5 is than methane mol ratio, ammonia-methane mol ratio of for example 1.1-1.45, and the methane of 1-1.25 is than oxygen mol ratio, methane-oxygen mol ratio of for example 1.05-1.15.For example, ternary gas mixture can have 1.3 ammonia than the methane of oxygen mol ratio and 1.2 than oxygen mole.In another exemplary embodiment, ternary gas mixture can have 1.5 ammonia than the methane of oxygen mol ratio and 1.15 than oxygen mole.Oxygen content in ternary gas mixture can change according to these mol ratios.
Ternary gas mixture 105 is fed to reactor 106, described ternary gas mixture is passed through to catalyzer to form thick prussic acid product 107 here.Catalyzer is generally wire cloth platinum/rhodium alloy or wire cloth platinum/iridium alloy.Spendable other catalyst components include but not limited to platinum metals, or platinum-group metal alloy, the platinum metals of load or the platinum-group metal alloy of load.The catalyst structure that also can use other, includes but not limited to vesicular structure, and described vesicular structure comprises fabric, non-woven and weaving structure, silk screen, lamellar body, spheroid, block, foam, Dipping or coating cleaning.Catalyzer must be enough solid to bear the two-forty that can be combined with the ternary gas mixture of the oxygen that comprises at least 25 volume %.Therefore, platinum/rhodium alloy of 85/15 can be used on the catalyst cupport of plane.Platinum/rhodium alloy of 90/10 can with there is the corrugated load of the surface-area of raising compared with the catalyst cupport of plane and use.
Conventionally, thick prussic acid product 107 can comprise the hydrogen of 34 to 36 volume %, for example 34 to 35% hydrogen, and before it leaves reactor with high temperature, cooling by interchanger, for example from 1200 DEG C be cooled to lower than 400 DEG C, lower than 300 DEG C or lower than the temperature of 250 DEG C.Be displayed in Table 1 the composition of exemplary coarse prussic acid product.
Table 1: the composition of thick prussic acid product
| Nominal composition, volume % | Oxygen Andrussow method | Air Andrussow method |
| H 2 | 34.5 | 13.3 |
| N 2 | 2.4 | 49.2 |
| CO | 4.7 | 3.8 |
| Ar | 0.1 | |
| CH 4 | 0.8 | 0.3 |
| CO 2 | 0.4 | 0.4 |
| NH 3 | 6.6 | 2.3 |
| HCN | 16.9 | 7.6 |
| Other nitriles | <0.1 | ** |
| H 2O | 33.4 | 23.1 |
As shown in table 1, use air legal system only produces the hydrogen of 13.3 volume % for HCN, and oxygen method causes the hydrogen of the 34.5 volume % that improve.The amount of hydrogen can be depending on the oxygen concentration of feed gas and reactant ratio and changes, and can be in the scope of the hydrogen of 34 to 36 volume %.Except table 1, the oxygen content of thick prussic acid product is very low, be preferably and be less than 0.5 volume %, and the higher oxygen content of thick prussic acid product can trigger parking or necessary flushing.According to the mol ratio of used ammonia, oxygen and methane, use the composition of the standby thick prussic acid product of Andrussow legal system to change, as shown in table 2.
Table 2: the composition that uses the standby thick prussic acid product of oxygen Andrussow legal system
| Volume % | Volume % | |
| H 2 | 20 to 50 | 30 to 40 |
| N 2 | 1 to 5 | 1 to 4 |
| CO | 0.5 to 10 | 1 to 5 |
| Ar | 0.01 to 1 | 0.05 to 0.5 |
| CH 4 | 0.05 to 1 | 0.1 to 1 |
| CO 2 | 0.01 to 3 | 0.1 to 0.5 |
| NH 3 | 5 to 15 | 5 to 10 |
| HCN | 12 to 20 | 14 to 18 |
| Other nitriles | <0.1 | ** |
| H 2O | 25 to 50 | 30 to 40 |
Then thick prussic acid product 107 is separated, optionally, using adsorber 110 to carry out pre-separation to remove ammonia as described, form the tail gas stream 111 that comprises hydrogen, water, carbonic acid gas and carbon monoxide here; With the prussic acid product stream 112 that comprises prussic acid.Prussic acid product stream comprises the hydrogen that is less than 10 volume %, be for example less than 5 volume % hydrogen, be less than 1 volume % hydrogen, be less than the hydrogen of 100mpm or hydrogen not substantially.Preferably, most hydrogen is concentrated in tail gas stream 111.Be displayed in Table 3 in the air Andrussow method for oxygen Andrussow method and contrast, from the contrast of tail gas stream 111 compositions of thick prussic acid product 107 after separatings and every kind of method nitrogen amount contrast,
The contrast of table 3HCN tail gas stream composition
| Nominal component, volume % | Oxygen Andrussow method | Air Andrussow |
| H 2 | 80.1 | 16.61 |
| N 2 | 5.6 | 76.32 |
| CO | 11.0 | 4.44 |
| AR | 0.2 | 0.48 |
| O 2 | 0.2 | --- |
| CH 4 | 1.6 | 0.83 |
| CO 2 | 0.8 | 0.29 |
| NH 3 | --- | --- |
| HCN | 0.1 | 0.11 |
| Other nitriles | Trace | 0.01 |
| H 2O | 0.4 | 0.91 |
As shown in table 3, in the time using oxygen Andrussow method, tail gas stream 111 comprises the hydrogen that is greater than 80 volume %.In some embodiments, the hydrogen that tail gas stream 111 comprises 40-90 volume %, the hydrogen of for example hydrogen of 45-85 volume % or 50-80 volume %.Tail gas stream 111 can further comprise the water of 0.1-20 volume %, the water of for example water of 1-15 volume % or 1-10 volume %.Tail gas stream 111 also can comprise the carbon monoxide of 0.1-20 volume %, the carbon monoxide of for example carbon monoxide of 1-15 volume % or 1-10 volume %.Tail gas stream 111 also can comprise the carbonic acid gas of 0.1-20 volume %, the carbonic acid gas of for example carbonic acid gas of 0.5-15 volume % or 0.75-10 volume %.In one embodiment, the hydrogen that tail gas stream 111 comprises 78 volume %, the carbon monoxide of 12 volume %, the carbonic acid gas of 6 volume % and surplus are water and prussic acid.Tail gas stream 111 also can comprise the nitrile of trace and other a small amount of compositions, comprises methane, ammonia, nitrogen, argon gas and oxygen.These compositions of high level can stop by trigger action, particularly the oxygen of higher concentration.Preferably, these other compositions exist to be less than the total amount of 10 volume %.The amount of nitrogen is less than 20 volume %, for example, be less than 15 volume % or be less than 10 volume %.
As described herein, can separate tail gas stream 111 with PSA unit 130.In United States Patent (USP) 3430418 and 3986849, described typical PSA technology and equipment, its whole content is incorporated in the present invention by reference.PSA130 can comprise at least two beds, for example at least 3 beds or at least 4 beds, and move under the pressure of 1400kPa-2600kPa, for example under the pressure of 1400kPa-2400kPa, 1600kPa-2300kPa or 1800kPa-2200kPa, move.PSA 130 moves at the temperature of 16-55 DEG C, for example, at the temperature of 20-50 DEG C or 30-40 DEG C, move.PSA can be the PSA of multiple-hearth.Each bed comprises sorbent material.In some embodiments, each bed comprises identical sorbent material.In other embodiments, each bed comprises different sorbent materials.Sorbent material can be the traditional sorbent material that is used in PSA unit, comprise zeolite, gac, silica gel, aluminum oxide with and combination.Particularly, can use the combination of zeolite and gac.By the cycling time of each can be at 150 to 210 seconds, for example scope of 180 to 200 seconds, and total cycle time can be at 300 seconds to 1000 seconds, for example scope of 400 seconds to 900 seconds, this depends on the quantity of used bed.
In PSA 130, separate tail gas stream 111 to form hydrogen stream 132 and discharging current 131.The hydrogen that hydrogen stream 132 can be considered to high-purity hydrogen air-flow and comprise at least 95 volume %, for example hydrogen of the hydrogen of at least 99 volume %, at least 99.5 volume % or the hydrogen of at least 99.9 volume %.Discharging current 131 comprises carbonic acid gas, carbon monoxide, water and hydrogen.Discharging current 131 can be used as fuel and burned fall.Hydrogen stream 132 will be further discussed hereinafter.
For example, by using PSA 130 recover hydrogen to make to reclaim in thick prussic acid product 107 at least 70% hydrogen, at least 72.5%, at least 75% or at least 76% hydrogen.
Turn back to Fig. 1, before waste gas is separated from thick prussic acid product 107, optionally thick prussic acid product 107 is further processed.In the time implementing under optimum condition, the potential callable residual ammonia that Andrussow method has at prussic acid product stream.Because HCN rate of polymerization, along with pH raises and raises, therefore must be removed residual ammonia to avoid HCN polymerization.HCN polymerization has not only shown process efficiency problem, has also shown that operation is arduous, and this is to cause the obstruction of process pipeline due to the HCN of polymerization, thereby causes pressure to increase and relevant technology controlling and process problem.Separate waste gas from prussic acid product before, can from thick prussic acid product, remove residual ammonia.Useful ammonia removes unit 108 and completes and remove ammonia, and described ammonia removes unit 108 can comprise washer, desorption device and its combination.Thick at least a portion prussic acid product 107 can be incorporated into 108 ammonia scrubber, desorption device and its in conjunction with in, to remove residual ammonia.In the operation of this optionally separating, the composition of tail gas stream 111 and prussic acid go out that product keeps together and can not be removed along with any callable residual ammonia.
After removing remaining ammonia, thick prussic acid product 109 comprises the ammonia that is less than 1000mpm, for example, be less than 500mpm or be less than the ammonia of 300mpm.Ammonia can be flowed to 113 and be circulated to reactor 106, ternary gas mixture 105 as the reaction-ure feeding recycling, or be circulated to HMD production technique, will further discuss hereinafter.For example, by prussic acid is flowed and excessive acid (H
2sO
4or H
3pO
4) immediate response suppresses HCN polymerization, remaining free ammonia is caught and is become ammonium salt and the pH of solution is kept to acid by acid like this.Formic acid and oxalic acid that ammonia reclaims in incoming flow are captured in the aqueous solution of ammonia recovery system with formate and oxalate.
As described, subsequently thick prussic acid product 109 is separated to remove waste gas, to form prussic acid product stream 112 here.This logistics 112 further can be processed in HCN purification section 120 to reclaim the final prussic acid stream 121 for hydrocyanation.
Term used herein " hydrocyanation " means the hydrocyanation that comprises aliphatics unsaturated compound, described aliphatics unsaturated compound comprises at least one carbon-carbon double bond or at least one carbon carbon triple bond or its combination, described aliphatics unsaturated compound also can comprise other functional groups, includes but not limited to nitrile, ester class and aromatic hydrocarbons.The example of such aliphatics unsaturated compound includes but not limited to alkene (for example alkene), alkynes, 1,3-butadiene and pentenenitrile.Hydrocyanation comprises produces ADN by 1,3-butadiene and pentenenitrile hydrocyanation.
The HCN reclaiming from final prussic acid stream 121 is the HCN of non-inhibity.Term " non-inhibition " is used for representing that HCN does not have stable polymerization inhibitor substantially here.As understood by those skilled in the art, conventionally add such stablizer to minimize the polymerization of HCN, and HCN is used for to hydrocyanation, for example 1,3-butadiene and pentenenitrile, with before producing ADN, require to remove at least in part stablizer.The polymerization retarder of HCN includes but not limited to mineral acid, for example sulfuric acid and phosphoric acid; Organic acid, for example acetic acid; Sulfurous gas with and combination.
Return to Fig. 1, final at least a portion prussic acid stream 121 is passed into ADN and produce reactor 140.Although only shown a reactor, should be appreciated that this is that simplification shows and ADN production is two step operations.ADN production technique can comprise separating device (not shown).
Adiponitrile 141 leaves ADN production reactor and is passed in HMD reactor 150 by the road.Ammonia stream 142 is also passed in this reactor.Ammonia stream 142 can be that fresh ammonia stream maybe can comprise the ammonia of at least one portion from the recovery of pipeline 113.At least a portion of hydrogen stream 132 is also introduced in HMD reactor 150, and preferably, in upper part of this reactor, 1/3rd places, top of for example reactor, form HMD crude product stream 151 with hydrogenation of adiponitrile.HMD crude product stream 151 comprises HMD and also can comprise CAN.In some embodiments, mole to calculate, form than the more HMD of ACN.In one embodiment, mole to calculate, hydrogen stream 132 provides at least 20% of the needed hydrogen of hydrogenation AND.If necessary, can be by the extra hydrogen in the source from outside this technique and hydrogen stream 132 combinations.Before hydrogen enters HMD reactor 150, hydrogen stream 132 can be compressed to at least pressure of 2100kPa.
HMD crude product stream 151 is left reactor 150 and is entered purification system 160, HMD crude product stream is separated to form therein HMD product 161 and comprises ACN, unreacted ADN and comprise the residuum 162 of the byproduct of reaction of tetrahydrochysene azepine (tetrahydroazepine) (" THA ").In United States Patent (USP) 6887352, described the separation of HMD, its full content is incorporated in the present invention by reference.HMD product 161 comprises the THA that is less than 1000mpm, for example, be less than 500mpm, be less than 150mpm, or substantially do not contain THA.If necessary, recyclable ACN.
As understood by one of ordinary skill in the art, aforementioned function and/or method may be embodied as system, method or computer program product.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.
Can further understand the present invention by reference to following examples.
embodiment 1
By purity oxygen, containing ammonia gas and the methane-containing gas formation ternary gas mixture that combines.In ternary gas mixture, ammonia is 1.3: 1 than oxygen mol ratio, and methane is 1.2: 1 than the mol ratio of oxygen.The ternary gas mixture of the oxygen that comprises 27 to 29.5 volume % reacts to form the thick prussic acid product of the hydrogen that comprises 34 to 36 volume % under the existence of platinum/rhodium catalyst.Hydrogen during reaction forms.Thick prussic acid product is shifted out and deliver to ammonia from reactor and shift out unit to separate remaining ammonia from thick prussic acid product.Then thick prussic acid product is delivered to adsorber to form waste gas and prussic acid product stream.Waste gas has the method as table 3(oxygen Andrussow) as shown in composition, then waste gas is compressed to the pressure of 2275kPa and delivers to PSA unit.PSA unit comprises four beds, and each bed comprises gac and zeolite.Non-hydrogen composition in each bed absorption waste gas, for example nitrogen, carbon monoxide, carbonic acid gas and water.PSA operates the overall cycling time (in each bed about 190 seconds) of 800 seconds at the temperature of 40 DEG C.By from 75 to 80% hydrogen recovery in thick prussic acid product in hydrogen stream.Hydrogen stream has 99.5% or higher purity.
embodiment 2
Hydrogen stream from embodiment 1 is introduced in HMD production system, and described HMD production system comprises the HMD reactor for the production of hydrogenation AND.Before entering into HMD production system, hydrogen stream can be pressurized to at least pressure of 2100kPa.HMD production method has been described in United States Patent (USP) 3398195.In mole, hydrogen stream can be provided for hydrogenation ADN with form HMD or HMD and ACN the needed hydrogen of combination at least 20%.
comparative example A
According to (except using air to replace pure oxygen to form ternary gas mixture) described in embodiment 1, waste gas is separated.Therefore ternary gas mixture has and is less than 25 oxygen of volume % and the nitrogen gas concn of increase.Due to the nitrogen amount of increase compared with embodiment 1, the equipment that the size of ammonia separating device is used than embodiment 1 is large, and adsorber is larger than embodiment 1.Table 3 has shown the composition of the waste gas of air Andrussow method.Waste gas is compressed and send into the PSA unit for embodiment 1.The quantity of compressor is the octuple of the needed number of compressors of compressed exhaust gas in embodiment 1.In addition,, between compression period, due to the heat that the nitrogen of compression large volume produces, therefore used cooling step.In first, adsorbed after non-hydrogen component, PSA can not rerun due to the quantity not sufficient of hydrogen.Regaining hydrogen will be no longer economical or effective.Therefore, can not produce further integrated with HMD.
Claims (15)
1. a method of producing hexamethylene-diamine, comprising:
(a) determine the methane content of methane-containing gas, and in the time that the content of methane is defined as being less than 90 volume %, purifying methane-containing gas;
(b) in reactor, make the ternary gas mixture of the oxygen that comprises at least 25 volume % react under catalyzer exists, to form the thick prussic acid product that comprises prussic acid and waste gas, wherein ternary gas mixture comprises methane-containing gas, contains ammonia gas and oxygenous gas;
(c) separate thick prussic acid product to form prussic acid product stream and to comprise the tail gas stream of hydrogen, water, carbon monoxide and carbonic acid gas;
(d) separate tail gas stream to form the hydrogen stream that comprises hydrogen and the discharging current that comprises carbon monoxide, carbonic acid gas and water;
(e) at least a portion prussic acid product stream is used for to hydrocyanation divinyl to form adiponitrile; With
(f) at least a portion hydrogen stream is used for to hydrogenation of adiponitrile, to form the mixture of hexamethylene-diamine or hexamethylene-diamine and ACN.
2. method according to claim 1, is characterized in that, described step (c) also comprises thick prussic acid product separation to form ammonia stream, and at least a portion ammonia stream is turned back to described reactor.
3. method according to claim 1, is characterized in that, in mole, described step (f) form hexamethylene-diamine more than ACN.
4. method according to claim 1, is characterized in that, the oxygen that described ternary gas mixture comprises 25 to 32 volume %.
5. method according to claim 1, is characterized in that, described oxygenous gas comprises the oxygen that is greater than 80 volume %, preferably the oxygen of at least 95 volume %.
6. method according to claim 1, is characterized in that, described oxygenous gas comprises purity oxygen.
7. method according to claim 1, is characterized in that, described tail gas stream comprises: the carbon monoxide of the hydrogen of 40 to 90 volume %, the water of 0.1 to 20 volume %, 0.1 to 20 volume %, the carbonic acid gas of 0.1 to 20 volume % and be less than the nitrogen of 20 volume %.
8. method according to claim 1, is characterized in that, with pressure-variable adsorption device, molecular sieve or film separate described tail gas stream with form hydrogen stream.
9. method according to claim 8, is characterized in that, described pressure-variable adsorption device moves under the pressure of 1400kPa to 2600kPa.
10. method according to claim 8, is characterized in that, described pressure-variable adsorption device moves at the temperature of 16 to 55 DEG C.
11. methods according to claim 8, is characterized in that, described pressure-variable adsorption device comprises at least two adsorption beds, preferably four adsorption beds.
12. methods according to claim 11, is characterized in that, described at least two adsorption beds comprise and select free zeolite, gac, silica gel, aluminum oxide or its at least one sorbent material in conjunction with the group of composition.
13. methods according to claim 1, is characterized in that, the hydrogen that described hydrogen stream comprises at least 95 volume % is preferably the hydrogen of at least 99 volume %.
14. methods according to claim 1, is characterized in that, described prussic acid product stream comprises the hydrogen that is less than 10 volume %, are preferably and substantially do not contain hydrogen.
15. methods according to claim 1, is characterized in that, by the hydrogen from least 70 volume % in described thick prussic acid product, preferably at least 72.5% hydrogen recovery in hydrogen stream.
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| US201261738734P | 2012-12-18 | 2012-12-18 | |
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| CN107207406A (en) * | 2014-06-27 | 2017-09-26 | 因温斯特技术公司 | The integration method of nitrile is manufactured with enhanced liquid-liquid extraction |
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| GB1118911A (en) | 1965-01-11 | 1968-07-03 | Ici Ltd | Process for the manufacture of hexamethylene diamine |
| US3430418A (en) | 1967-08-09 | 1969-03-04 | Union Carbide Corp | Selective adsorption process |
| US3647388A (en) | 1970-05-04 | 1972-03-07 | Du Pont | Process for the manufacture of hydrogen cyanide |
| US3986849A (en) | 1975-11-07 | 1976-10-19 | Union Carbide Corporation | Selective adsorption process |
| CN1095806C (en) | 1995-09-01 | 2002-12-11 | 因奥斯－艾瑞利克斯英国有限公司 | Hydrogen cyanide process and apparatus therefor |
| US5882618A (en) | 1997-04-28 | 1999-03-16 | Air Liquide America Corporation | Process for cyanic acid production |
| DE19839346A1 (en) * | 1998-08-28 | 2000-03-02 | Basf Ag | Improved process for the production of hexamethylenediamine |
| DE10034193A1 (en) | 2000-07-13 | 2002-03-28 | Roehm Gmbh | Process for the production of hydrogen cyanide |
| US6887352B2 (en) | 2003-03-07 | 2005-05-03 | Invista North America S.A.R.L. | Distillative method for separating hexamethylenediamine from a mixture comprising hexamethylenediamine, 6-aminocapronitrile and tetrahydroazepine |
| DE102004004682A1 (en) | 2004-01-29 | 2005-08-18 | Basf Ag | Process for the preparation of adiponitrile by hydrocyanation of 1,3-butadiene |
| EP2229353B1 (en) | 2008-01-15 | 2018-01-03 | INVISTA Textiles (U.K.) Limited | Hydrocyanation of pentenenitriles |
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| 刘启波等: "由丁二烯合成己二腈及己二胺的技术发展现状", 《化工进展》 * |
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| CN107207406A (en) * | 2014-06-27 | 2017-09-26 | 因温斯特技术公司 | The integration method of nitrile is manufactured with enhanced liquid-liquid extraction |
| CN107207406B (en) * | 2014-06-27 | 2019-12-03 | 英威达纺织（英国）有限公司 | The integration method of nitrile is manufactured with the liquid-liquid extraction of enhancing |
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