CN103965056B - Integrated process for hexamethylenediamine production - Google Patents
Integrated process for hexamethylenediamine production Download PDFInfo
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- CN103965056B CN103965056B CN201310681844.2A CN201310681844A CN103965056B CN 103965056 B CN103965056 B CN 103965056B CN 201310681844 A CN201310681844 A CN 201310681844A CN 103965056 B CN103965056 B CN 103965056B
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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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
Cross-Reference to Related Applications
This application claims the priority of the U.S. Provisional Application 61/738734 of No. 18 submissions of in December, 2012, disclosed in it
Full content is merged into herein.
Technical field
The present invention relates to the method for producing hexamethylene diamine.Especially, the present invention by following steps come ameliorative way
Efficiency, i.e., produce stream by reclaiming hydrogen stream and hydrogen cyanide from thick hydrogen cyanide product, hydrogen cyanide is produced into stream for butadiene
Hydrogen stream is used for the hydrogenation of adiponitrile to form hexamethylene diamine by hydrocyanation to form adiponitrile.
Background technology
Hexamethylene diamine（“HMD”）As in the product in industry, textile, resin, carpet and coating industry
Mesosome and produce on an industrial scale.Additionally, HMD can be used for coating, curing agent, petroleum additive, adhesive, ink, scale inhibition delaying
In erosion agent and Water Treatment Chemicals.A kind of big commercial use of HMD is the intermediate as nylon, and the nylon includes Buddhist nun
Dragon -6,6, nylon-6,10 and nylon-6,12, it is nylon-6 also including molecular formula, other nylon of x, wherein x is in diacid
Carbon number.For example, HMD can by under pressure, high temperature by adiponitrile（“ADN”）Hydrogenation, by by ADN and excess of ammonia
Gas and hydrogen mix, and the mixture is commercialized into preparation by catalyst bed, the catalyst bed include with or without
There are copper, nickel or the cobalt of carrier.The scope of high temperature can be 85 to 150 DEG C and pressure limit can be 200 to 500 atmospheric pressure（For example
See United States Patent (USP) 3398195）.
ADN is also used as producing ACN（ACN）Intermediate.Can by ACN cyclisation using formed can as nylon-
The caprolactam of 6 intermediate.ADN can be prepared by a number of procedures, and be published within 1997 including Weissermel etc.
Integrated Organic Chemistry, the 245-250 page of method, the method is the chlorination fourth two in the presence of Cymag
Alkene, then hydrogenates, hydrogenates propylene dimer nitrile and hydrocyanation butadiene.Hydrocyanation butadiene includes two process.First, will
1,3- butadiene is in catalyst（Usually nickel（0）Catalyst）Upper hydrocyanation, to form 3 pentene nitrile.Then 3 pentene nitrile is existed
Nickel（0）Hydrocyanation is generally carried out in the presence of a lewis acid into ADN on catalyst.（For example see United States Patent (USP) 7528275）.
As described herein, preparing the method for HMD can need multiple reactions and feed stream, including hydrogen, butadiene, ADN and
Hydrogen cyanide.Generally, by Andrussow methods or BMA methods（For example see Ullman ' s Encyclopedia of
Industrial Chemicstry, the A8 volume, Weinheim etc. writes, page 1987,161-163）In commercial quantity to produce cyaniding
Hydrogen（“HCN”）.For example in Andrussow methods, ammonia can be in the reactor made in the presence of a suitable catalyst and contains methane
Gas and oxygen-containing gas react commercially to prepare HCN at high temperature（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 ammonolysis of methane.For example, see 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.Will by making reactor effluent stream contact with ammonium phosphate solution in ammonia absorber
Unreacted ammonia is separated with HCN.By detached ammonia purify and concentrate, for being recycled to the conversion of HCN in.Generally by by its
Absorb in water to reclaim HCN in the reactor effluent stream from after process.The HCN for being reclaimed can be by further refinement
Operation processing, to prepare the HCN of purifying.Document Clean Development Mechanism Project Design
Document Form (CDM PDD, Version 3), 2006 graphically explain Andrussow HCN autofrettages.Purifying
HCN can be used for hydrocyanation reaction, the such as hydrocyanation or 1,3-butadiene and the hydrocyanation of allyl acetonitrile of the group containing alkene, on
The hydrocyanation stated can be used to manufacture adiponitrile (" ADN ").In BMA methods, HCN exists substantially without oxygen and in platinum catalyst
Under conditions of by methane and ammonia synthesis, its result be generate HCN, hydrogen, nitrogen, residual ammonia and residual methane（As joined
See：Ullman ' s Encyclopedia of Industrial Chemistry, Volume A8, Weinheim 1987,
P161-163）.Business operator requires that process safety is managed, to control the dangerous property of hydrogen cyanide（Referring to Maxwell etc.
People, Assuring process safety in the transfer of hydrogen cyanide manufacturing
technology,JHazMat 142（2007）, 677-684）.In addition, the row from production equipment in HCN manufacturing process
Putting may observe regulation, and this may affect the economy of HCN productions.（Referring to Crump, Economic Impact
Analysis For The Proposed Cyanide Manufacturing NESHAP, EPA, May 2000）.
US2797148 discloses a kind of method that ammonia is reclaimed from the admixture of gas containing ammonia and hydrogen cyanide.Ammonia with it is hydrocarbonaceous
The reaction end gas that gas and oxygen-containing gas are reacted and prepared the technique of hydrogen cyanide include ammonia, hydrogen cyanide, hydrogen, nitrogen
Gas and water steam and carbon dioxide.The tail gas is cooled to 55 to 90 DEG C of temperature, then passes to adsorption tower, by ammonia from tail gas
Isolate.
US3647388 discloses a kind of gaseous hydrocarbon by being up to six carbon atom（Such as methane）Hydrogen cyanide is produced with ammonia
Technique.Selection process is carried out in the burner, and the burner has for the center conduit of oxygen-bearing fluid flowing and for hydrogen
One or more ring ducts adjacent with center conduit that gas, ammonia and gaseous hydrocarbon flow parallel, the conduit terminates in reaction
In room, wherein in the reative cell, the gaseous hydrocarbon and ammonia flame front of flame in hydrogen and oxygen combustion is reacted.
This technique eliminates the use of catalyst.
Recovery method although Andrussow methods and HCN be it is well known that prepare HCN technical process from catalysis
Middle separation tail gas was not almost disclosed in the method for reclaiming hydrogen stream.Additionally, still not by HCN production systems and HMD and/or
Any report of CAN production systems integration.
Accordingly, it would be desirable to such a technique, it can not only in the presence of a catalyst produce HCN, it is also possible to from reaction
Hydrogen is reclaimed in device tail gas, so as to can be all integrated with HMD production systems by both HCN and hydrogen.
Publication document mentioned above is incorporated herein in by way of reference.
The content of the invention
In one embodiment, the present invention relates to the method for producing hexamethylene diamine, including：（a）It is determined that containing methane
The methane content of gas, and when the content of methane is defined as less than 90 volume %, purify methane-containing gas；（b）To include
At least ternary gas mixture of the oxygen of 25 volumes % is reacted in the presence of a catalyst in the reactor includes cyanogen to be formed
Change the thick hydrogen cyanide product of hydrogen and waste gas, wherein ternary gas mixture includes methane-containing gas, containing ammonia gas and oxygen-containing
Gas gas；（c）Separate thick hydrogen cyanide product to form hydrogen cyanide product stream and including hydrogen gas and water, carbon monoxide and carbon dioxide
Tail gas stream；（d）Separate tail gas stream to form the hydrogen stream comprising hydrogen, and the row comprising carbon monoxide, carbon dioxide and water
Effluent stream；（e）At least a portion hydrogen cyanide product stream is used to hydrocyanation butadiene form adiponitrile；With（f）To at least one
Hydrogen partial stream is used to hydrogenation of adiponitrile form hexamethylene diamine.Hydrogenation of adiponitrile can also form ACN.One
In a little embodiments, ternary gas mixture can include the oxygen of 25 to 32 volumes %.Oxygenous gas may include more than 21 bodies
The oxygen of product %, for example, at least oxygen of 80 volumes %, the oxygen or pure oxygen of at least 95 volumes %.Tail gas stream can include 40 to 90 bodies
Accumulate the carbon dioxide of hydrogen, the water of 0.1 to 20 volumes %, the carbon monoxide of 0.1 to 20 volumes and 0.1 to 20 volumes % of %.Can
Tail gas stream is separated using pressure-variable adsorption, molecular sieve or film.Pressure-variable adsorption can be under the pressure from 1400kPa to 2400kPa simultaneously
Carry out at a temperature of 16 to 55 DEG C.Pressure swing adsorber may include at least two adsorbent beds.Each of at least two adsorbent beds
Comprising at least one adsorbent in the group selected from zeolite, activated carbon, silica gel, aluminum oxide and its combination composition.Hydrogen stream
Comprising at least hydrogen of 95 volumes % or at least hydrogen of 99 volumes %.Thick hydrogen cyanide product stream may include the hydrogen less than 10 volumes %
Gas, less than the hydrogen of 5 volumes %, or can substantially without hydrogen.Hydrogen from least 70 volumes % of ternary gas mixture can
In being recycled to hydrogen stream.Step（c）Can further include to separate thick hydrogen cyanide product to form ammonia stream.Can be by ammonia stream at least
A part is returned in reactor.
In another embodiment, the present invention relates to be used to prepare the method for hexamethylene diamine, it includes：（a）Really
Determine the methane content of methane-containing gas, and when the content of methane is defined as less than 90 volume %, purify methane-containing gas；
（b）By including at least oxygen of 25 volumes % ternary gas mixture reacted in the presence of a catalyst in the reactor with
Formation includes the thick hydrogen cyanide product of hydrogen cyanide and waste gas, and wherein ternary gas mixture includes methane-containing gas, gas containing ammonia
Body, and oxygenous gas；（c）Separate thick hydrogen cyanide product with formed hydrogen cyanide product stream, ammonia stream and including hydrogen gas and water, one
The tail gas stream of carbonoxide and carbon dioxide；（d）Separate tail gas stream to form the hydrogen stream comprising hydrogen, and comprising carbon monoxide,
The discharge stream of carbon dioxide and water；（e）At least a portion hydrogen cyanide product stream is used to hydrocyanation butadiene form adiponitrile；
With（f）At least a portion hydrogen stream is used to hydrogenation of adiponitrile form hexamethylene diamine or hexamethylene diamine and 6- amino
The conjugate of own nitrile.At least a portion ammonia stream can be returned to reactor.In some embodiments, ternary gas mixture can
Oxygen comprising 25 to 32 volumes %.Oxygenous gas may include the oxygen more than 21 volumes %, for example, at least oxygen of 80 volumes %
The oxygen or pure oxygen of gas, at least 95 volumes %.Tail gas stream can include the hydrogen of 40 to 90 volumes %, the water of 0.1 to 20 volumes %, 0.1
To the carbon monoxide and the carbon dioxide of 0.1 to 20 volumes % of 20 volumes.Can be separated using pressure-variable adsorption, molecular sieve or film
Tail gas stream.Pressure-variable adsorption can be carried out under the pressure from 1400kPa to 2400kPa and at a temperature of 16 to 55 DEG C.Transformation is inhaled
Adnexa may include at least two adsorbent beds.Each of at least two adsorbent beds is comprising selected from zeolite, activated carbon, silica gel, oxygen
Change at least one adsorbent in the group of aluminium and its combination composition.Hydrogen stream includes at least hydrogen of 95 volumes % or at least 99
The hydrogen of volume %.Thick hydrogen cyanide product stream may include the hydrogen less than 10 volumes %, less than the hydrogen of 5 volumes %, or can not have substantially
There is hydrogen.Hydrogen from least 70 volumes % of ternary gas mixture can be recycled in hydrogen stream.
In another embodiment, the present invention relates to be used to produce the method for hexamethylene diamine, it includes：（a）Really
Determine the methane content of methane-containing gas, and when the content of methane is defined as less than 90 volume %, purify methane-containing gas；
（b）By including at least oxygen of 25 volumes % ternary gas mixture reacted in the presence of a catalyst in the reactor with
Formation includes the thick hydrogen cyanide product of hydrogen cyanide and waste gas, and wherein ternary gas mixture includes methane-containing gas, gas containing ammonia
Body, and oxygenous gas；（c）Separate thick hydrogen cyanide product to form hydrogen cyanide product stream and including hydrogen gas and water, carbon monoxide
With the tail gas stream of carbon dioxide；（d）Separate tail gas stream in pressure swing adsorber to form the hydrogen comprising at least hydrogen of 95 volumes %
Air-flow, and the discharge logistics comprising carbon monoxide, carbon dioxide and water；（e）At least a portion hydrogen cyanide product stream is used for into hydrogen
Cyaniding butadiene is forming adiponitrile；With（f）At least a portion hydrogen stream is used to hydrogenation of adiponitrile form hexa-methylene two
The conjugate of amine or hexamethylene diamine and ACN.In some embodiments, ternary gas mixture can include 25
To the oxygen of 32 volumes %.Oxygenous gas may include the oxygen more than 21 volumes %, for example, at least the oxygen of 80 volumes %, at least
The oxygen or pure oxygen of 95 volumes %.Tail gas stream can include hydrogen, the water of 0.1 to 20 volumes %, 0.1 to 20 bodies of 40 to 90 volumes %
Long-pending carbon monoxide and the carbon dioxide of 0.1 to 20 volumes %.Pressure-variable adsorption can be under the pressure from 1400kPa to 2400kPa
And carry out at a temperature of 16 to 55 DEG C.Pressure swing adsorber may include at least two adsorbent beds.At least two adsorbent beds it is each
Individual protection is selected from least one adsorbent in the group of zeolite, activated carbon, silica gel, aluminum oxide and its combination composition.Hydrogen
Stream includes at least hydrogen of 95 volumes % or at least hydrogen of 99 volumes %.Thick hydrogen cyanide product stream may include less than 10 volumes %
Hydrogen, less than the hydrogen of 5 volumes %, or can substantially without hydrogen.From the hydrogen of at least 70 volumes % of ternary gas mixture
Can be recycled in hydrogen stream.Step（c）Can further include to separate thick hydrogen cyanide product to form ammonia stream.At least part of ammonia stream
May return to reactor.
Description of the drawings
Fig. 1 is the schematic diagram of the HMD production systems of integration.
Specific embodiment
Term used herein is not intended to limit the present invention merely for the purpose of description particular.Unless on
Other situation is hereinafter clearly shown, singulative " one " as used herein and " being somebody's turn to do " also include plural form.
It is also understood that illustrating to exist described feature, whole when the term " including " for using in this manual and/or " including "
Body, step, operation, part and/or component, but without prejudice to one or more other features, entirety, step, operation, parts group,
The presence or addition of component and/or component groups.
Such as " including ", "comprising", " having ", the term and its variant of " containing " or " being related to " should widely understand, and
And comprising listed main body and equivalent, also unlisted other main body.In addition, when by transitional phrases " bag
Containing ", " including " or " containing " draw when component, parts group, technique or method and step or any other statement, should manage
Solution it is contemplated herein that identical component, parts group, technique or method and step, or with the component, parts group, technique or
Transitional phrases "consisting essentially of ...", " Consists of " or " choosing before the record of method and step or any other statement
Any other statement of free ... the group of composition ".
If applicable, the corresponding structure, material, action and all functional devices or step in claim
Rapid equivalent includes any knot for carrying out perform function in combination with the miscellaneous part specifically stated in claim
Structure, material or action.The present invention specification for introduce and describe purpose and provide, but be not exhaustive or will this
Invention is restricted to disclosed form.On the premise of without departing from scope and spirit of the present invention, it is many change and variant for
It is obvious for one of ordinary skill in the art.Here select and describe some embodiments, it is therefore an objective to this
The principle and practical application of invention carries out optimal explanation, and causes others of ordinary skill in the art it will be appreciated that originally
The different embodiments of invention have various changes, as being suitable for the special-purpose.Correspondingly, although the present invention
It is described according to embodiment, but it would be recognized by those skilled in the art that the present invention can change ground and in institute
Implement within attached spirit and scope by the claims.
Now with detailed reference to specific disclosed theme.Although disclosed theme will be wanted with reference to cited right
Ask to describe, it being understood, however, that they are not restricted to disclosed theme in these claims.Conversely, disclosed
Theme cover all of replacement scheme, change and equivalent, these can be contained in institute defined by the claims
Within the scope of disclosed theme.
The invention provides HMD is produced into the method integrated with the method for production HCN.The production method of HCN includes
Reclaim hydrogen stream and reclaim HCN.Can be integrated with HMD production systems by hydrogen stream and HCN streams.Generally, existing skill
Hydrogen can be reclaimed from steam methane reforming or ethane cracking in art.The hydrogen for obtaining in this way has many impurity,
It can be introduced in the operation that each uses hydrogen.Reclaimed from HCN techniques using creative method as described herein
Hydrogen be high-purity and impurity will not be introduced in subsequent technique.Additionally, existing process may call for multiple feed streams and/or
Reaction system is producing HMD.The system that these reaction systems include production HCN, ADN and HMD.Therefore, by by these systems
Integration, can realize process efficiency and the cost savings for improving.
The formation of HMD can be expressed by following equation：
NC(CH2)4CN+4H2→H2N(CH2)6NH2
As described herein, HMD at high temperatures and pressures, is formed in the presence of a catalyst.By excess of ammonia and hydrogen
Gas mixes to hydrogenate ADN and formation HMD with ADN.Ammonia can be liquid phase, and hydrogen can have dividing for 1000kPa to 30000kPa
Pressure.ADN can be 1 than the mol ratio of ammonia:40 to 1:55 scope.Catalyst may include cobalt, nickel, iron and noble metal, your gold
Category includes rubidium, rhenium, platinum and palladium.In some embodiments, catalyst includes nickel or cobalt.Catalyst can be supported on carrier（Bag
Include alumina support）On.
The conversion ratio of ADN can be 80 to 100%, and with 40 to 80% HMD and/or ACN（ACN）Choosing
Selecting property.In some embodiments, the conversion ratio of ADN can be more than 98%.It is understood that the ratio of the HMD for being formed and ACN
Rate can be controlled by adjusting the time of staying and/or other process conditions.The conversion ratio of ADN is by being calculated as below：
The selectivity of HMD is by being calculated as below：
The selectivity of ACN is by being calculated as below：
ADN can be formed by following two step method：
As it appears from the above, butadiene by hydrocyanation into 3 pentene nitrile（“3PN”）With 2- methyl -3- butene nitriles（“2M3BN”）'s
Mixture.If necessary, also isomerization steps of 2M3BN to 3PN.Then by 3PN hydrocyanations forming adiponitrile.Often
One hydrocyanation step can be catalyzed by Raney nickel, the Raney nickel of preferred zeroth order.This is described in United States Patent (USP) 8088943
The example of catalyst is planted, entire contents are incorporated by reference in the present invention.The hydrocyanation of 3PN can be helped there is lewis acid
Carry out under catalyst, this is also described in United States Patent (USP) 8088943.Reaction can in the liquid phase, in 500-5000kPa,
For example in 1000-5000kPa, and at 0-200 DEG C, for example, carry out at 50-100 DEG C.Unless stated otherwise, all of pressure
It is absolute pressure.
For butadiene and the hydrogen cyanide of the hydrocyanation of 3PN, can obtain from Andrussow methods or BMA methods.For shape
Into in the Andrussow methods of HCN, by methane, ammonia and oxygen feed in the presence of the temperature and catalyst higher than 1000 DEG C
React to produce the thick hydrogen cyanide comprising HCN, hydrogen, carbon monoxide, carbon dioxide, nitrogen, residual ammonia, residual methane and water
Product.These compositions, i.e. raw material are provided as ternary gas mixture and arrives reactor, the ternary gas mixture includes containing
Oxygen gas, the ternary gas mixture containing ammonia gas and methane-containing gas.As it will be appreciated by those skilled in the art that
, may be different containing methane source, and can from renewable resource be, for example, refuse landfill, farm, from fermentation biogas and
Obtain, or obtained by fossil fuel such as natural gas, oil field gas, coal gas and gas hydrate, such as VN Parmon exist
In " Source of Methane for Sustainable Development " 273-284, and Derouane etc. exists
“Sustainable Strategies for the Upgrading of Natural Gas:Fundamentals,
Further described in Challenges, and Opportunities (2003) ".For the purposes of the present invention, containing methane source
Methane purity and constant composition are important.In some embodiments, the technique may include to determine that the methane containing methane source contains
Amount, and when the content of methane is defined as less than 90 volume %, purifying contains methane source.Can be using gas chromatographic measurement method, bag
Include Raman spectrum to determine methane content.Methane content is continuously determined in real time, or ought be introduced in process containing methane source
Methane content is determined as needed during new source.In addition, in order to realize higher purity, when methane is containing for more than 90 volumes %, such as
During 90-95 volumes %, can also purify this and contain methane source.Can be purified using known purification process containing methane source, with except deoiling,
Condensation product, water, C2+ hydrocarbon（Such as ethane, propane, butane, pentane, hexane and its isomers）, sulphur and carbon dioxide.
Natural gas typically serves as methane source, and air, oxygen-enriched air or oxygen can serve as source of oxygen.By ternary gas
Mixture is through catalyst forming thick hydrogen cyanide product.Then thick hydrocyanation product is separated to reclaim HCN.In the present invention
In, also thick hydrocyanation product is separated to reclaim hydrogen.
As used herein term " air " refers to composition and takes from air（Generally at ground）Gas primitive component
Roughly the same admixture of gas.In some instances, air takes from surrounding environment.Air has following composition, including about 78%
The carbon dioxide of the nitrogen of volume, the oxygen of about 21% volume, the argon gas of about 1% volume and about 0.04% volume, and a small amount of its
Its gas.
As used herein term " oxygen-enriched air " refers to gas of the composition comprising the more oxygen in the presence of than air
Mixture.Oxygen-enriched air has following composition, including the oxygen more than 21% volume, the nitrogen less than 78% volume, less than 1% body
Long-pending argon gas and the carbon dioxide less than 0.04% volume.In some embodiments, oxygen-enriched air includes at least 28% volume
The oxygen of oxygen, for example, at least oxygen of 80% volume, for example, at least 95% volume, or at least oxygen of 99% volume.
As used herein term " natural gas " refers to such mixture, i.e., comprising methane and optional ethane,
The mixture of propane, butane, carbon dioxide, oxygen, nitrogen and hydrogen sulfide.Natural gas can also include the rare gas of trace, bag
Include helium, neon, argon gas and xenon.In some embodiments, natural gas can include the methane less than 90 volumes %.
The formation of the HCN in Andrussow methods is typically expressed as following General reactions：
2CH4+2NH3+3O2→2HCN+6H2O
It will be understood that above-mentioned reaction represent be an increasingly complex dynamic process simplification, in institute
In stating dynamic process, a part of hydrocarbon is oxidized first, supports for remaining hydrocarbon and ammonia to carry out HCN to produce necessary heat energy
Heat absorption synthesis.
Three basic side reactions also can occur during the synthesis of HCN：
CH4+H2O→CO+3H2
2CH4+3O2→2CO+4H2O
4NH3+3O2→2N2+6H2O
Except the amount of the nitrogen of generation in side reaction, according to oxygen source, may there is extra nitrogen in the crude product.
Although suggestion can use oxygen-enriched air or purity oxygen as oxygen source in prior art, using the excellent of oxygen-enriched air or purity oxygen
Point is not fairly well-developed.When oxygen source is used air as, the aeriferous component of hydrogen cyanide crude product bag, such as from about 78 volumes %
Nitrogen, and in the side reaction of ammonia and oxygen produce 2 moles of nitrogen.
Substantial amounts of nitrogen in due to air, therefore oxygen-enriched air is favourable used in the synthesis of HCN, this is because
Air can cause the synthesis in substantial amounts of inert gas as oxygen source used in the production of HCN（Nitrogen）In carry out, this needs
The larger equipment used in synthesis step, and cause the low concentration of the HCN in product gas.Further, since inert nitrogen
Presence, in order to the temperature of ternary gas mixture component is improved to the temperature that HCN can be maintained to synthesize, need burning more
Methane.Thick hydrogen cyanide product includes HCN, and also includes byproduct hydrogen gas, methyl hydride combustion accessory substance（Carbon monoxide, carbon dioxide,
Water）, residual methane and residual ammonia.But, when using air（The such as from about oxygen of 21 volumes %）When, by HCN and callable ammonia
After separating from other gas components, the presence of inert nitrogen causes the fuel value that the gas stream for remaining is carried to be likely lower than reason
The value for energy regenerating thought.
Therefore, oxygen-enriched air or pure oxygen substitute air and provide some advantages used in HCN productions, including can reclaim
Hydrogen.Other advantages include, improve natural gas and reduce therewith to the conversion ratio and process equipment size of HCN.Therefore, make
Can reduce the size of reactor and dirty by being lowered into the inert compound of synthesis procedure with oxygen-enriched air or purity oxygen
The size of at least one part of gas processing device.Also can be reduced oxygenous feed gas using oxygen-enriched air or purity oxygen
The energy ezpenditure being heated to needed for reaction temperature.
When using the air comprising 21 volumes % or less oxygen, for the consideration of energy and economy, the amount of nitrogen
So that hydrogen is reclaimed without practical significance.Surprisingly, it was found that when using oxygen-enriched air or purity oxygen, Ke Yiyou
Effect and economic method reclaim hydrogen from thick hydrogen cyanide product, such as using pressure swing adsorber.The hydrogen for being reclaimed has height
Therefore purity simultaneously can be used in the HMD production methods of integration.
When thick hydrogen cyanide product is prepared using oxygen-enriched air or purity oxygen, need to process from thick hydrogen cyanide product
Waste gas is reclaiming hydrogen components rather than in the boiler burn it.Absorber can be used waste gas from thick hydrogen cyanide product
Separate.Using pressure-variable adsorption（PSA）, UF membrane or other known purifying/recovery methods by hydrogen from least partially
Reclaim out in waste gas.In some embodiments, PSA unit is used to reclaim hydrogen.In this case, first by gas pressure
130kPa to 2600kPa, such as 130kPa to 2275kPa, 130kPa to 1700kPa or 136kPa to 1687kPa are reduced to, then
In being sent to PSA unit.The high-purity hydrogen of recovery is bigger as the value that raw material is used for fuel, because it can be used as
The feed stream of his technique such as ADN to the hydrogenation of ACN and HMD.It should be noted that, the amount of the nitrogen in waste gas can shadow
Ring and reclaim the economic feasibility of hydrogen and do not affect to burn waste gas in the boiler from waste gas.Other compositions or composition also can affect
Reclaim the feasibility of hydrogen.For example, the HCN concentration in tail gas stream（As by measured by on-line sensor）More than expected maximum
In the case of, tail gas stream can be reintroduced back at steam generation boiler or torch and not carry out hydrogen recovery.
The embodiment that Fig. 1 shows the HMD production methods of integration.As shown in figure 1, ternary gas mixture 105 is wrapped
Containing methane-containing gas 102, containing ammonia gas 103 and oxygenous gas 104.As described herein, in order that the recovery of hydrogen is in Jing
Feasible with energy in Ji, the oxygen content in oxygenous gas 104 is more than 21 volumes %, such as oxygen-enriched air or purity oxygen.
In some embodiments, the oxygen content in oxygenous gas 104 is at least oxygen of 28 volumes %, the oxygen of at least 80 volumes %
Gas, at least oxygen of 95 volumes % or at least oxygen of 99 volumes %.
The amount of the oxygen in ternary gas mixture 105 is controlled by flammability limits.The spy of air, methane and ammonia
Fixed combination is flammable, and therefore will after firing develop into flame.If gas composition in upper flammable limit and lower limit it
Between, then the mixture of air, methane and ammonia will burn.The mixture of air, methane and ammonia beyond the scope is usual
It is non-flammable.The combustible concentration in ternary gas mixture is changed using oxygen-enriched air.Increase oxygenous gas to enter
Oxygen content can significantly widen flammable range in stream.For example, the mixing of the methane of air and 55 volumes % containing 45 volumes %
Thing is considered as very fuel enrichment and non-flammable, but the mixing of the methane of the oxygen containing 45 volumes % and 55 volumes %
Thing is flammable.
Another focus is explosion limit.For example, under atmospheric pressure and room temperature, the oxygen containing 60 volumes %, 20 bodies
The admixture of gas of the ammonia of the methane and 20 volumes % of product % can explode.
Therefore, although discovery oxygen-enriched air used in HCN productions is favourable, but the air of collecting oxygen will necessarily
The combustible concentration in ternary gas mixture is caused to change, and this change of combustible concentration improves feeding reaction
The upper flammable limit of the ternary gas mixture of device.Therefore, the detonation of ternary gas mixture and blast is sensitive to oxygen concentration
's.Term " detonation " used herein above " refers to that place is passed with subsonic speed before flame is in close proximity to relative to unburned gas
The combustion wave broadcast.On the other hand, " blast " refer to relative to unburned gas before flame is in close proximity to place with supersonic speed biography
The combustion wave broadcast.Deflagration typically results in appropriate pressure and rises, but blast can cause king-sized pressure to rise.
But once advised increasing the production capacity of HCN using oxygen-enriched air, this is typically avoided in flammable range
Operation.See United States Patent (USP) 5882618；6491876 and 6656442, its all the elements is incorporated by reference in the present invention.
In the present invention, oxygen-enriched air or purity oxygen charging are controlled to be formed and in flammable range but be not at three vigour of detonable range
Body mixture.Therefore, in some embodiments, ternary gas mixture 105 includes the oxygen more than 25 volumes %, for example greatly
In the oxygen of 28 volumes %.In some embodiments, oxygen of the ternary gas mixture comprising 25-30 volumes %, such as 26-30
The oxygen of volume %.Ternary gas mixture can have the ammonia of 1.2-1.6 than oxygen molar ratio, and the ammonia of such as 1.3-1.5-
Oxygen molar ratio, the ammonia of 1-1.5 is than methane mol ratio, such as ammonia-methane mol ratio of 1.1-1.45, and 1-1.25
Methane is than oxygen molar ratio, such as the methane-oxygen mol ratio of 1.05-1.15.For example, ternary gas mixture can have 1.3
Ammonia compare oxygen mole than oxygen molar ratio and 1.2 methane.In another exemplary embodiment, ternary gas
The ammonia that mixture can have 1.5 compares oxygen mole than oxygen molar ratio and 1.15 methane.In ternary gas mixture
Oxygen content can change according to these mol ratios.
Ternary gas mixture 105 is fed to into reactor 106, here by the ternary gas mixture through being catalyzed
Agent is forming thick hydrogen cyanide product 107.Catalyst is usually woven wire platinum/rhodium alloy or woven wire platinum/iridium alloy.Can make
Other catalytic components include but is not limited to platinum group metal, or platinum-group metal alloy, the platinum group metal of load or load
Platinum-group metal alloy.Also can be using other catalyst structures, including but not limited to loose structure, the loose structure includes knitting
Thing, non-woven and weaving structure, silk screen, lamellar body, spheroid, block, foam, dip coating or coating cleaning.Catalyst must be sufficient
Reach solid to bear the two-forty that can be used in combination with the ternary gas mixture comprising at least oxygen of 25 volumes %.Therefore,
85/15 platinum/rhodium alloy can be used in the catalyst load of plane.90/10 platinum/rhodium alloy can with urging with plane
Agent load is compared the corrugated load of the surface area of raising and is used.
Generally, thick hydrogen cyanide product 107 may include the hydrogen of 34 to 36 volumes %, such as 34 to 35% hydrogen, and
It is left before reactor with high temperature, by heat exchanger cool down, 400 DEG C are for example cool below from 1200 DEG C, less than 300 DEG C or
Temperature less than 250 DEG C.The composition of exemplary coarse hydrogen cyanide product displayed in Table 1.
Table 1：The composition of thick hydrogen cyanide product
| Nominal is constituted, volume % | Oxygen Andrussow methods | Air Andrussow methods |
| H2 | 34.5 | 13.3 |
| N2 | 2.4 | 49.2 |
| CO | 4.7 | 3.8 |
| Ar | 0.1 | |
| CH4 | 0.8 | 0.3 |
| CO2 | 0.4 | 0.4 |
| NH3 | 6.6 | 2.3 |
| HCN | 16.9 | 7.6 |
| Other nitriles | <0.1 | ** |
| H2O | 33.4 | 23.1 |
As shown in table 1, the hydrogen that HCN only produces 13.3 volumes % is prepared using air method, and oxygen method causes what is improved
The hydrogen of 34.5 volumes %.The amount of hydrogen may depend on the oxygen concentration and reactant ratio of feed gas and change, and can be
In the range of the hydrogen of 34 to 36 volumes %.Except table 1, the oxygen content of thick hydrogen cyanide product is very low, preferably less than 0.5 body
Product %, and the higher oxygen content of thick hydrogen cyanide product can trigger parking or necessary flushing.According to the ammonia for being used,
The mol ratio of oxygen and methane, the composition alterable of the thick hydrogen cyanide product prepared using Andrussow methods, as shown in table 2.
Table 2：The composition of the thick hydrogen cyanide product prepared using oxygen Andrussow methods
| Volume % | Volume % | |
| H2 | 20 to 50 | 30 to 40 |
| N2 | 1 to 5 | 1 to 4 |
| CO | 0.5 to 10 | 1 to 5 |
| Ar | 0.01 to 1 | 0.05 to 0.5 |
| CH4 | 0.05 to 1 | 0.1 to 1 |
| CO2 | 0.01 to 3 | 0.1 to 0.5 |
| NH3 | 5 to 15 | 5 to 10 |
| HCN | 12 to 20 | 14 to 18 |
| Other nitriles | <0.1 | ** |
| H2O | 25 to 50 | 30 to 40 |
Then thick hydrogen cyanide product 107 is separated, optionally using absorber 110 is carrying out pre-separation as is described herein
To remove ammonia, formation includes the tail gas stream 111 of hydrogen gas and water, carbon dioxide and carbon monoxide；With the hydrogen cyanide comprising hydrogen cyanide
Product stream 112.Hydrogen cyanide product stream includes the hydrogen less than 10 volumes %, such as hydrogen less than 5 volumes %, less than 1 volume %
Hydrogen, the hydrogen less than 100mpm are substantially free of hydrogen.Preferably, most hydrogen is concentrated in tail gas stream 111.
It is displayed in Table 3 for oxygen Andrussow methods and the air Andrussow methods of contrast in, from thick hydrogen cyanide product 107
The contrast of the composition of tail gas stream 111 after separation and in every kind of method the contrast of nitrogen amount,
The contrast of table 3HCN tail gas stream compositions
| Nominal component, volume % | Oxygen Andrussow methods | Air Andrussow |
| H2 | 80.1 | 16.61 |
| N2 | 5.6 | 76.32 |
| CO | 11.0 | 4.44 |
| AR | 0.2 | 0.48 |
| O2 | 0.2 | --- |
| CH4 | 1.6 | 0.83 |
| CO2 | 0.8 | 0.29 |
| NH3 | --- | --- |
| HCN | 0.1 | 0.11 |
| Other nitriles | Trace | 0.01 |
| H2O | 0.4 | 0.91 |
As shown in table 3, when using oxygen Andrussow methods, tail gas stream 111 includes the hydrogen more than 80 volumes %.One
In a little embodiments, hydrogen of the tail gas stream 111 comprising 40-90 volumes %, such as hydrogen of 45-85 volumes % or 50-80 volumes %
Hydrogen.Tail gas stream 111 can further include the water of 0.1-20 volumes %, such as water of the water of 1-15 volumes % or 1-10 volumes %.Tail
Air-flow 111 can also include the carbon monoxide of 0.1-20 volumes %, an oxygen of such as carbon monoxide of 1-15 volumes % or 1-10 volumes %
Change carbon.Tail gas stream 111 can also include the carbon dioxide of 0.1-20 volumes %, the carbon dioxide or 0.75- of such as 0.5-15 volumes %
The carbon dioxide of 10 volumes %.In one embodiment, hydrogen of the tail gas stream 111 comprising 78 volumes %, an oxidation of 12 volumes %
Carbon, the carbon dioxide of 6 volumes % and balance of water and hydrogen cyanide.Tail gas stream 111 can also include the nitrile and a small amount of its of trace
His composition, including methane, ammonia, nitrogen, argon gas and oxygen.These compositions of high level can trigger operation to be stopped, particularly
The oxygen of higher concentration.Preferably, these other compositions exist to be less than the total amount of 10 volumes %.The amount of nitrogen is less than 20 bodies
Product %, such as less than 15 volumes % or less than 10 volumes %.
As described herein, tail gas stream 111 can be separated with PSA unit 130.In United States Patent (USP) 3430418 and 3986849
In describe typical PSA techniques and equipment, its entire content is incorporated by reference in the present invention.PSA130 can be comprising at least
Two beds, for example, at least 3 beds or at least 4 beds, and run under the pressure of 1400kPa-2600kPa, for example exist
Run under the pressure of 1400kPa-2400kPa, 1600kPa-2300kPa or 1800kPa-2200kPa.PSA 130 is at 16-55 DEG C
At a temperature of run, such as at a temperature of 20-50 DEG C or 30-40 DEG C run.PSA can be the PSA of multiple-hearth.Each bed bag
Containing adsorbent.In some embodiments, each bed includes identical adsorbent.In other embodiments, each bed is included
Different adsorbents.Adsorbent can be the conventional adsorbent for being used in PSA unit, including zeolite, activated carbon, silica gel, oxidation
Aluminium and its combination.Particularly, the combination of zeolite and activated carbon can be used.Can be 150 to 210 by the circulation time of each
Second, the scope of such as 180 to 200 seconds, and total cycle time can be at 300 seconds to 1000 seconds, the model of such as 400 seconds to 900 seconds
Enclose, this depends on the quantity of used bed.
Separate tail gas stream 111 in PSA 130 to form hydrogen stream 132 and discharge stream 131.Hydrogen stream 132 can be considered as
It is high-purity hydrogen air-flow and the hydrogen comprising at least 95 volumes %, for example, at least hydrogen of 99 volumes %, the hydrogen of at least 99.5 volumes %
Gas or at least hydrogen of 99.9 volumes %.Discharge stream 131 and include carbon dioxide, carbon monoxide, water and hydrogen.Discharging stream 131 can make
It is burned off for fuel.Hydrogen stream 132 will be discussed further below.
Hydrogen is reclaimed by using PSA 130 to cause to have reclaimed in thick hydrogen cyanide product 107 at least 70% hydrogen, for example
At least 72.5%, at least 75% or at least 76% hydrogen.
Fig. 1 is returned to, before waste gas is separated from thick hydrogen cyanide product 107, optionally by thick hydrogen cyanide product
107 are further processed.When implementing under conditions of optimum, Andrussow methods are in diving that hydrogen cyanide product stream has
In callable residual ammonia.Because HCN rates of polymerization are raised as pH is raised, it is therefore necessary to remove residual ammonia to avoid HCN
Polymerization.HCN polymerizations not only show process efficiency problem, also show operation arduousness, and this is that the HCN due to being polymerized can cause
The blocking of process pipeline, so as to cause pressure to increase and related process control issues.Waste gas is being separated from hydrogen cyanide product
Before, residual ammonia can be removed from thick hydrogen cyanide product.Unit 108 can be removed using ammonia to complete to remove ammonia, the ammonia is removed
Unit 108 may include washer, desorption device and its combination.The thick hydrogen cyanide product 107 of at least a portion can be incorporated into 108 ammonia
In washer, desorption device and its combination, to remove residual ammonia.In this optional lock out operation, the composition and cyanogen of tail gas stream 111
Change hydrogen goes out product and keeps together and will not be removed with any callable residual ammonia.
After removing remaining ammonia, thick hydrogen cyanide product 109 includes the ammonia less than 1000mpm, such as less than 500mpm or
Ammonia less than 300mpm.Ammonia stream 113 can be recycled to the reactant that reactor 106, ternary gas mixture 105 are used as to recycle
Charging, or HMD production technologies are recycled to, will be discussed further below.By by hydrogen cyanide stream with excess acid（For example
H2SO4Or H3PO4）Suppressing HCN to be polymerized, so remaining free ammonia is captured as ammonium salt and by solution to immediate response by acid
PH keep acid.Formic acid and oxalic acid in recovery ammonia feed stream is captured to the water of ammonia recovery system with formates and oxalates
In solution.
As is described herein, subsequently thick hydrogen cyanide product 109 separated to remove waste gas, to form hydrogen cyanide product stream
112.The logistics 112 further can be processed to reclaim the final hydrogen cyanide stream 121 for hydrocyanation in HCN purification sections 120.
Term " hydrocyanation " used herein means to include the hydrocyanation of aliphatic unsaturated compound, the aliphatic
Unsaturated compound includes at least one carbon-carbon double bond or at least one triple carbon-carbon bonds or its combination, and the aliphatic is unsaturated
Compound can also include other functions group, including but not limited to nitrile, esters and aromatic hydrocarbons.Such aliphatic unsaturationization
The example of compound includes but is not limited to alkene（Such as alkene）, alkynes, 1,3- butadiene and allyl acetonitrile.Hydrocyanation is included 1,3-
Butadiene and allyl acetonitrile hydrocyanation production ADN.
The HCN reclaimed from final hydrogen cyanide stream 121 is the HCN of non-inhibity.Term " non-inhibited " is used for here table
Show that HCN does not stablize polymerization inhibitor substantially.As understood by those skilled in the art, generally the such stabilizer of addition with
The polymerization of HCN is minimized, and HCN is used for into hydrocyanation, such as before 1,3-butadiene and allyl acetonitrile are to produce ADN, it is desirable to extremely
It is few partially to remove stabilizer.The polymerization inhibitor of HCN includes but is not limited to inorganic acid, such as sulfuric acid and phosphoric acid；Organic acid,
Such as acetic acid；Sulfur dioxide and its combination.
Fig. 1 is returned, the final hydrogen cyanide stream 121 of at least a portion is passed through into ADN production reactors 140.Although only show
One reactor, it should be appreciated that this is that simplification shows and ADN productions are two step operations.ADN production technologies may include point
From equipment（Do not show）.
Adiponitrile 141 leaves ADN production reactors and is passed in HMD reactors 150 by the road.Ammonia stream 142 is also led to
In entering the reactor.Ammonia stream 142 can be fresh ammonia stream or the ammonia that can include an at least recovery from pipeline 113.Hydrogen
At least a portion of air-flow 132 is also introduced in HMD reactors 150, preferably up in the top half of the reactor, for example, is reacted
At the top 1/3rd of device, HMD crude product streams 151 are formed with hydrogenation of adiponitrile.HMD crude product streams 151 include HMD and
May include CAN.In some embodiments, mole calculating, forming HMDs more more than ACN.In one embodiment,
So that mole calculating, hydrogen stream 132 provides at least 20% of the hydrogen required for hydrogenation AND.If desired, can by from
The extra hydrogen in the source outside the technique is combined with hydrogen stream 132.Before hydrogen enters HMD reactors 150, can be by hydrogen
Air-flow 132 is compressed at least pressure of 2100kPa.
HMD crude product streams 151 leave reactor 150 and enter purification system 160, wherein separate HMD crude product streams
With formation HMD products 161 and comprising ACN, unreacted ADN and including tetrahydrochysene azepine（tetrahydroazepine）
（“THA”）Byproduct of reaction residue 162.The separation of HMD, entire contents are described in United States Patent (USP) 6887352
In being incorporated by reference into the present invention.HMD products 161 include the THA less than 1000mpm, such as less than 500mpm, be less than
150mpm, or it is substantially free of THA.If desired, recyclable ACN.
As will be appreciated by a person skilled in the art, aforementioned function and/or method may be embodied as system, method or calculating
Machine program product.For example, function and/or method may be embodied as the executable programmed instruction of computer, and the instruction record is in meter
In the readable memory device of calculation machine, when the instruction is retrieved and executed by computer processor, its control computer system with
Perform the function and/or method of the embodiment above.In one embodiment, computer system can include one or more
CPU, computer storage（Such as read-only storage, random access storage device）And data storage device（For example it is hard
Disk drive）.The executable instruction of computer can use any suitable computer programming language（Such as C++, JAVA etc.）
To encode.Therefore, some aspects of the invention can take the form of the generally embodiment of software（Including firmware, reside
Software, microcode etc.）, or the embodiment for combining software aspects and hardware aspect.
It will be apparent that the present invention can be well suited for realizing target and reach mentioned excellent here from described above
Gesture and disclosure institute inherent advantages.Although having been described with the preferred embodiment party of the present invention for the purpose of this disclosure
Case, it being understood, however, that can carry out obvious to those skilled in the art and can be in the present invention
Spirit under the change that completed.
The present invention can be further understood by reference to following examples.
Embodiment 1
Combine to form ternary gas mixture by purity oxygen, containing ammonia gas and methane-containing gas.It is mixed in ternary gas
In compound, ammonia is 1.3: 1 than oxygen molar ratio, and methane is 1.2: 1 than the mol ratio of oxygen.Comprising 27 to 29.5 bodies
The ternary gas mixture of the oxygen of product % is reacted to be formed comprising 34 to 36 volumes % in the presence of platinum/rhodium catalyst
The thick hydrogen cyanide product of hydrogen.Hydrogen is formed during reaction.Thick hydrogen cyanide product is removed from reactor and is sent to ammonia and is moved
Go out unit to separate the ammonia of remnants from thick hydrogen cyanide product.Then thick hydrogen cyanide product is sent to into absorber with formed waste gas and
Hydrogen cyanide product stream.Waste gas has such as table 3（Oxygen Andrussow methods）Shown composition, is then compressed to 2275kPa by waste gas
Pressure and be sent to PSA unit.PSA unit includes four beds, and each bed includes activated carbon and zeolite.Each bed adsorption waste gas
In non-hydrogen composition, such as nitrogen, carbon monoxide, carbon dioxide and water.PSA operates 800 seconds whole at a temperature of 40 DEG C
The body circulation time（About 190 seconds in each bed）.In thick hydrogen cyanide product 75 to 80% hydrogen is recovered to into hydrogen stream
In.Hydrogen stream has 99.5% or higher purity.
Embodiment 2
To be introduced in HMD production systems from the hydrogen stream of embodiment 1, the HMD production systems are included for producing hydrogen
Change the HMD reactors of AND.Before HMD production systems are entered into, hydrogen stream can be pressurized at least pressure of 2100kPa.
HMD production methods are described in United States Patent (USP) 3398195.In mol, hydrogen stream can be provided for hydrogenating ADN to be formed
At least 20% of hydrogen required for the combination of HMD or HMD and ACN.
Comparative example A
According to embodiment 1（Except replacing pure oxygen to form ternary gas mixture using air）, waste gas is carried out
Separate.Therefore ternary gas mixture has the oxygen and increased nitrogen gas concn less than 25 volumes %.Due to the phase of embodiment 1
Than increased nitrogen amount, the size of ammonia separation equipment is bigger than the equipment that embodiment 1 is used, and absorber is bigger than embodiment 1.Table
The composition of 3 waste gas for showing air Andrussow methods.Waste gas is compressed and is sent into for the PSA unit of embodiment 1.Compression
The quantity of machine is the octuple of the number of compressors in embodiment 1 required for compressed exhaust gas.Additionally, during compressing, due to compression
The nitrogen of large volume and the heat that produces, therefore used cooling step.After having adsorbed non-hydrogen components in first, PSA meetings
Can not rerun because the amount of hydrogen is not enough.Withdrawing hydrogen will be no longer economical or effective.It is thus impossible to produce into one with HMD
Step integration.
Claims (20)
1. a kind of method for producing hexamethylene diamine, including：
A () determines the methane content of methane-containing gas, and when the content of methane is defined as less than 90 volume %, purifying contains
Methane gas；
B () makes in the reactor the ternary gas mixture for including at least oxygen of 25 volumes % carry out in the presence of a catalyst instead
Should, to form the thick hydrogen cyanide product for including hydrogen cyanide and waste gas, wherein ternary gas mixture is including methane-containing gas, containing ammonia
Gas gas and oxygenous gas；
C () separates thick hydrogen cyanide product to form hydrogen cyanide product stream and including hydrogen gas and water, carbon monoxide and carbon dioxide
Tail gas stream；
D () separates tail gas stream to form the hydrogen stream comprising hydrogen and the discharge stream comprising carbon monoxide, carbon dioxide and water；
E at least a portion hydrogen cyanide product stream is used to hydrocyanation butadiene form adiponitrile by ()；With
F at least a portion hydrogen stream is used for hydrogenation of adiponitrile by (), to form hexamethylene diamine or hexamethylene diamine and 6-
The mixture of amino-capronitrile.
2. method according to claim 1, it is characterised in that the step (c) also includes separating thick hydrogen cyanide product
To form ammonia stream, and at least a portion ammonia stream is returned to into the reactor.
3. method according to claim 1, it is characterised in that in mol, the hexa-methylene two that the step (f) is formed
Amine is more than ACN.
4. method according to claim 1, it is characterised in that the ternary gas mixture is comprising 25 to 32 volumes %
Oxygen.
5. method according to claim 1, it is characterised in that the oxygenous gas includes the oxygen more than 80 volumes %
Gas.
6. method according to claim 5, it is characterised in that oxygen of the oxygen-containing gas comprising at least 95 volumes %.
7. method according to claim 1, it is characterised in that the oxygenous gas includes purity oxygen.
8. method according to claim 1, it is characterised in that the tail gas stream is included：The hydrogen of 40 to 90 volumes %,
The water of 0.1 to 20 volumes %, the carbon monoxide of 0.1 to 20 volumes %, the carbon dioxide of 0.1 to 20 volumes % and less than 20 bodies
The nitrogen of product %.
9. method according to claim 1, it is characterised in that separated using pressure swing adsorber, molecular sieve or film described
Tail gas stream is forming hydrogen stream.
10. method according to claim 9, it is characterised in that the pressure swing adsorber is 1400kPa's to 2600kPa
Run under pressure.
11. methods according to claim 9, it is characterised in that the pressure swing adsorber is transported at a temperature of 16 to 55 DEG C
OK.
12. methods according to claim 9, it is characterised in that the pressure swing adsorber includes at least two adsorbent beds.
13. methods according to claim 12, it is characterised in that the pressure swing adsorber includes four adsorbent beds.
14. methods according to claim 12, it is characterised in that at least two adsorbent bed include selected from zeolite,
At least one adsorbent of the group of activated carbon, silica gel, aluminum oxide or its combination composition.
15. methods according to claim 1, it is characterised in that hydrogen of the hydrogen stream comprising at least 95 volumes %.
16. methods according to claim 15, it is characterised in that hydrogen of the hydrogen stream comprising at least 99 volumes %.
17. methods according to claim 1, it is characterised in that the hydrogen cyanide product stream is comprising less than 10 volumes %
Hydrogen.
18. methods according to claim 17, it is characterised in that the hydrogen cyanide product stream is substantially free of hydrogen.
19. methods according to claim 1, it is characterised in that will in the thick hydrogen cyanide product at least 70 bodies
The hydrogen of product % is recovered in hydrogen stream.
20. methods according to claim 19, it is characterised in that will be at least 72.5% in the thick hydrogen cyanide product
Hydrogen be recovered in hydrogen stream.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200102A (en) * | 1995-09-01 | 1998-11-25 | 帝国化学工业公司 | Hydrogen cyanide process and apparatus therefor |
| CN1315934A (en) * | 1998-08-28 | 2001-10-03 | Basf公司 | Improved method for producing hexamethylene diamine |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1934838A (en) | 1930-04-14 | 1933-11-14 | Ig Farbenindustrie Ag | Production of hydrocyanic acid |
| US2797148A (en) | 1951-03-13 | 1957-06-25 | Du Pont | Recovery of nh3 from a gaseous mixture containing nh3 and hcn |
| 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 |
| US5882618A (en) | 1997-04-28 | 1999-03-16 | Air Liquide America Corporation | Process for cyanic acid production |
| 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 |
-
2013
- 2013-12-12 TW TW102145762A patent/TWI486324B/en not_active IP Right Cessation
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200102A (en) * | 1995-09-01 | 1998-11-25 | 帝国化学工业公司 | Hydrogen cyanide process and apparatus therefor |
| CN1315934A (en) * | 1998-08-28 | 2001-10-03 | Basf公司 | Improved method for producing hexamethylene diamine |
Non-Patent Citations (1)
| Title |
|---|
| 由丁二烯合成己二腈及己二胺的技术发展现状;刘启波等;《化工进展》;20091231;第28卷(第5期);第832-835,903页 * |
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| CN103965056A (en) | 2014-08-06 |
| HK1200808A1 (en) | 2015-08-14 |
| TW201425276A (en) | 2014-07-01 |
| TWI486324B (en) | 2015-06-01 |
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