CN103864112B - The device and method of the torch improved in andrussow process - Google Patents
The device and method of the torch improved in andrussow process Download PDFInfo
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- CN103864112B CN103864112B CN201310681867.3A CN201310681867A CN103864112B CN 103864112 B CN103864112 B CN 103864112B CN 201310681867 A CN201310681867 A CN 201310681867A CN 103864112 B CN103864112 B CN 103864112B
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/022—Apparatus therefor
- C01C3/0225—Apparatus therefor characterised by the synthesis reactor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
- F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/08—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases using flares, e.g. in stacks
-
- 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
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Describe a kind of system and method for preparing hydrogen cyanide via andrussow process.The system may include reactor zone, wherein oxygen, ammonia and methane is allowed to react in the presence of the catalyst comprising platinum at least to provide hydrogen cyanide (HCN), hydrogen and waste.The recovery area HCN can substantially remove hydrogen cyanide from hydrogen and waste.Torch area can be at least with hydrogen mode combustion combustible gas mixture at least to generate carbon dioxide and water, and the combustible gas mixture includes at least part of the hydrogen and at least part of the waste.
Description
Cross reference to related applications
The claim of this application on December 18th, 2012 submit it is entitled " device of the torch improved in andrussow process and
The beauty of method (APPARATUS AND METHOD OF AN IMPROVED FLARE IN AN ANDRUSSOW PROCESS) "
The priority of state's Provisional Application Serial number 61/738,817, it is open to be incorporated herein by reference in their entirety.
Technical field
This disclosure relates to the reactor scheme of the andrussow process for preparing hydrogen cyanide (HCN) by methane, ammonia and oxygen.
Background technique
Andrussow process can be used for hydrogen cyanide (HCN) and be prepared by the gas phase of methane, ammonia and oxygen on platinum catalyst.Incited somebody to action
Ammonia, natural gas and the air feed of filtration are heated to about 800 into reactor and in the presence of including at least the catalyst of platinum
DEG C to about 2,500 DEG C.Methane can further can be purified by naturally stripping confession.Hydrocarbon at least two carbon can be deposited
It is in natural gas.Air can be used as oxygen source.Reactor outlet gas containing HCN and unreacted ammonia can be in waste heat
About 100 DEG C to 400 DEG C are chilled in boiler.Chilling reactor outlet gas containing HCN can be conveyed and be absorbed by ammonia
Journey is to remove unreacted ammonia, such as by making reactor outlet gas and ammonium phosphate solution, phosphoric acid or sulfuric acid contact to remove ammonia.It can
Sending product exit gas from ammonia absorber to by HCN absorber, cold water can be added herein to take away HCN.HCN absorber
It can produce the substantially gaseous waste stream containing hydrogen and by-product.It is attributed to the composition of gaseous waste stream, disposition
(disposal) it can be environment-conscious, can cannot burn out or their combination.
The various aspects of HCN preparation: Eric.L.Crump, Environmental Protection Agency are described in following article
(U.S.Environmental Protection Agency), air quality plan and standard office room (Office of Air
Quality Planning and Standards), for the economic impact analysis NESHAP of the cyanide preparation proposed
(Economic Impact Analysis For the Proposed Cyanide Manufacturing NESHAP)(2000
May in year),Http:// nepis.epa.gov/Exe/ZyPDF.cgi? Dockey=P100AHG1.PDFIt can obtain, be related to online
The preparation of HCN, final use and economic impact；The higher homologue of N.V.Trusov, sulphur compound and methane is to by An Delu
Influence (the Effect of Sulfur Compounds and Higher Homologues of of the hydrogen cyanide preparation of shuttle method
Methane on Hydrogen Cyanide Production by the Andrussow Method), Rus.J.of
Applied Chemistry, volume 74, the 10th phase, the 1693-97 pages (2001) is related to the inevitable component of natural gas, such as
The influence that the higher homologue of sulphur and methane prepares the HCN by andrussow process；Clean Development Mechanism (CDM) executive director
Meeting (Clean Development Mechanism (CDM) Executive Board), United Nations Framework Convention on Climate Change
(United Nations Framework Convention on Climate Change) (UNFCCC), Clean Development Mechanism
Project design document table (Clean Development Mechanism Project Design Document Form)
(CDM PDD), the 3rd edition, (July 28,2006),Http:// cdm.unfccc.int/Reference/PDDs Forms/ PDDs/PDD form04_v03_2.pdfIt can obtain online, be related to preparation of the HCN by andrussow process；And Gary
R.Maxwell etc. ensures process safety (Assuring process safety in the transfer of hydrogen cyanide technology of preparing
The transfer of hydrogen cyanide manufacturing technology), J.of Hazardous
Materials, volume 142, the 677-84 pages (2007) is related to safely preparing for HCN.
Summary of the invention
This disclosure relates to a kind of solution party of the disposition of the gaseous waste stream of the HCN absorber in andrussow process
Case.The solution may include a kind of system and method for preparing hydrogen cyanide via andrussow process.The system can be with
Including reactor zone, wherein allowing oxygen, ammonia and methane to react in the presence of the catalyst comprising platinum, at least to provide hydrogen cyanide
(HCN), hydrogen and waste.The recovery area HCN can substantially remove hydrogen cyanide from hydrogen and waste.Torch area can mix fuel gas
Object is closed with hydrogen mode combustion, at least to generate carbon dioxide and water, the combustible gas mixture includes at least part of hydrogen
With at least part of off-gas.Combustible gas mixture may include natural gas.
Hydrocarbon mixture can methane in offer system.Hydrocarbon mixture may include natural gas, biogas, substantially pure
Or mixtures thereof methane,.The system may include hydrogen retrieval system, can follow in the downstream that hydrogen retrieval system recycles or upstream
Ring, storage utilize hydrogen.The system may include that ammonia extracts area, wherein ammonia is substantially removed from HCN, hydrogen and waste.
Hydrogen cyanide recovery area can provide the hydrogen cyanide product stream that may include at least about purity of 98.5% hydrogen cyanide, or
Off-gas stream is provided and is less than about 1.5%HCN so that existing.The combustible gaseous mixture of waste for being fed into torch may include
At least about 8 volume % hydrogen.Torch muzzle velocity can be less than about 37.2 meter per seconds, such as less than about Vmax, wherein VmaxIs defined as:
Vmax=(XH2-K1)*K2, wherein
Vmax=maximum allowable torch muzzle velocity, meter per second
K1=constant, 6.0 volume % hydrogen
K2=constant, 3.9 meter per seconds/volume % hydrogen
XH2=volume % hydrogen, based on wet basis, such as by using American Society for Testing Materials (the American Society
For Testing and Materials) (ASTM) method D1946-77 calculating.
Torch area is configurable to operate in greater than about 1350 DEG C of temperature.Torch can be by one's own efforts or it is stable.Fire
Torch area may include at least 3.0 inch diameter torch points.
Torch area is also configured as torch burning with the non-hydrogen combustible gas mixture of non-hydrogen mode combustion, such as at least about
The non-hydrogen combustible gas mixture of the thermal content of 200BTU/scf.The system may include the liquid point of at least one torch upstream
From device, to remove at least part of liquid present in combustible gas mixture or non-hydrogen combustible gas mixture.
According to the disclosure, it is a kind of for burn by andrussow process generate waste method may include: allow oxygen, ammonia
It is reacted in the presence of the catalyst comprising platinum with methane, to provide the product stream for including at least hydrogen cyanide, hydrogen and waste.It can be with
Hydrogen cyanide is extracted from product stream to prepare HCN product stream and at least part of gaseous waste stream comprising hydrogen and waste, and
And gaseous waste stream can be fed into hydrogen mode torch.
This method may include: to extract ammonia from product stream, such as before extracting hydrogen cyanide.It can be by least one of liquid
Divide before gaseous waste stream is fed into hydrogen mode torch from gaseous waste flow separation.Hydrogen can be flowed back to from gaseous waste
It receives.This gaseous waste stream with reduced hydrogen content can still using method described herein and device, effectively torch fires
It burns.This method may include the component with hydrogen or hydrocarbon such as methane supplement torch burning.
This method may include that will extract stream to be less than about 37.2 meter per seconds such as VmaxTorch muzzle velocity torch burning.Fire
Torch area can be operated in greater than about 1650 DEG C of temperature.This method may include auxiliary or stable torch.
These and other examples and feature of system and method for the invention will parts in the following detailed description
It provides.Summary of the invention is intended to provide the general introduction of subject of the present invention, and is not meant to provide exclusive or detailed explanation.Including
Following specific embodiment is to provide the further information about system and method for the invention.
Detailed description of the invention
Fig. 1 is the schematic block flow chart prepared according to the HCN via andrussow process of the disclosure.
Specific embodiment
Hydrogen cyanide is by the synthesis of andrussow process (see, e.g., Ullmann ' s Encyclopedia of
Industrial Chemistry, volume 8, VCH Verlagsgesellschaft, Weinheim, 1987, the 161-162 pages)
It can be carried out on the catalyst comprising platinum or platinum alloy or other metals in the gas phase.As U.S. Patent number 1,934,
It finds and is described suitable for the catalyst for carrying out andrussow process in original peace moral Rousseau patent etc. disclosed in 838.Pacifying
In the original work of moral Rousseau, he discloses catalyst can not melt the oxidation of (solid) selected from the operating temperature at about 1000 DEG C
Catalyst；He by platinum, iridium, rhodium, palladium, osmium, gold or silver include as or pure form or alloy form catalytically-active metals.
He, which is also noted that, also can be used certain base metals (base metals) such as rare earth metal, thorium, uranium, if do not melted oxide
Or phosphatic form, and by catalyst or net (sieve) can be formed as, or be deposited on heat resistance solid carrier such as dioxy
In SiClx or aluminium oxide.
Subsequent development in, the catalyst of platiniferous has been selected, even the effect of this is attributed to them and metal
The heat resistance of silk screen or web form.It is, for example, possible to use platinum-rhodium alloys as catalyst, can be wire mesh or sieve such as
The form of weaving or braiding silk netting, can also be deposited on carrier structure body.In an example, weave or weave silk netting
Sieve shape structure, the size with 20-80 mesh, for example, the opening of the size with about 0.18mm to about 0.85mm can be formed.
Catalyst may include about 85 weight % to about 95 weight %Pt and about 5 weight % to about 15 weight %Rh, such as 85/5Pt/Rh,
90/10 or 95/5Pt/Rh.Platinum-rhodium catalyst can also include a small amount of metal impurities, as iron (Fe), palladium (Pd), iridium (Ir),
Ruthenium (Ru) and other metals.Foreign metal can be existed below with trace, such as from about 10ppm.
The possible embodiment of the wide scope of andrussow process describes in Deutsche Bundespatent 549,055.In an example,
At about 800 to 2,500 DEG C, 1,000 to 1,500 DEG C, or about 980 to 1050 DEG C of temperature uses multiple tools comprising being arranged in series
There is the catalyst of the gauze wire of the Pt of 10% rhodium.For example, catalyst can be commercially available catalyst, it is such as available from Britain's human relations
The Pt-Rh catalyst silk screen of honest Johnson Matthey Plc, or it is available from the Heraeus Precious of Hanau, Germany
The Pt-Rh catalyst silk screen of Metals GmbH&Co..
The composition of gaseous waste stream from andrussow process can make the disposition of the stream difficult.For example, gaseous waste
Stream can make torch burning insufficient, to environment nocuousness, except the parameter area of place or federal regulations or their group
It closes.This disclosure relates to a kind of device and method for via andrussow process synthesis HCN, wherein improved torch can examined
Gaseous waste stream is disposed in the case where considering environmental concerns, efficiency misgivings or government regulation.
Fig. 1 is the schematic block flow chart for preparing the instance system 10 of hydrogen cyanide (HCN) via andrussow process.
In instance system 10, ammonia (NH is provided to HCN reaction zone 123) stream 2, methane (CH4) stream 4 and gaseous oxygen feeding flow 6 (it includes
Oxygen (O2)).Air may include air and other oxygen-containing gas mixtures, including having the oxygen concentration of greater than about 21 volume %
Enriched in oxygen air.When andrussow process is suitable for using the gaseous oxygen feeding flow 6 containing the horizontal oxygen more slightly higher than air
When, the example of this paper can be particularly useful.For example, this gaseous oxygen feeding flow 6 can contain at least about 25 volume % oxygen,
At least about 30 volume % oxygen, at least about 40 volume % oxygen, at least about 50 volume % oxygen, at least about 60 volume % oxygen, at least about 70
Volume % oxygen, at least about 80 volume % oxygen, at least about 90 volume % oxygen, at least about 95 volume % oxygen, at least about 98 volume % oxygen.
Andrussow process may include air andrussow process, for example, the gaseous oxygen feeding flow 6 comprising about 21 volume % oxygen；Air-richness
Jian De Lusuo method, for example, comprising being greater than about 21 volume % oxygen but less than about the gaseous oxygen feeding flow 6 of 100 volume % oxygen；Or
Oxygen andrussow process, for example, the gaseous oxygen feeding flow 6 comprising about 100% oxygen.
Three kinds of feeding flows 2,4,6 are mixed and are reacted in one or more reactors, with root in the presence of a catalyst
Hydrogen cyanide and water are converted into according to reaction equation 1:
2NH3+2CH4+3O2→2HCN+6H2O [1]
One or more reactors may include HCN catalyst, such as platinum (Pt) or platinum alloy, such as contain at least about 85 weights
Measure the platinum of % platinum and the alloy of rhodium (Rd) or palladium (Pd).The alloy used in andrussow process may include, but be not limited to,
10 weight %Rh-90 weight %Pt, 8 weight %Rh-92 weight %Pt, 5 weight %Pd-5 weight %Rh-90 weight %Pt or 5
Weight %Rh-95 weight %Pt.It can be used containing the alloy for being up to about 5 weight % iridium (Ir).In an example, it can incite somebody to action
HCN Catalyst Design is to reduce by-product, such as N2O by-product, and therefore can have increased rhodium (Rh) and contain
Amount or other substances, such as cobalt (Co).HCN catalyst can be contained in packed bed, such as in packed bed reactor or conduct
Silk screen is formed, such as by weaving or being woven to wire mesh structure for wire.The catalyst being thusly-formed is wide in the art
General approval, and catalysis material described herein can be contained.
HCN catalyst can be commercially available catalyst, as being available from London Johnson Matthey Plc
Pt-Rh catalyst silk screen, or it is available from the Pt-Rh catalyst of Hanau, Germany Heraeus Precious Metals GmbH&Co.
Silk screen.
Obtained product stream 14 from HCN reaction zone 12 can be fed into and be configured to recycle unreacted NH3's
Ammonia recovery system 16.Ammonia can by via to product stream 14 provide it is one or more can with from product stream 14 absorb NH3's
Phosphoric acid (H3PO4), sulfuric acid (H2SO4) or ammonium phosphate solution NH3It absorbs and recycles.In the example depicted in fig. 1, recovery ammonia system
NH can be absorbed in phosphoric acid stream 18 in system 163.It can be by ammonia from H3PO4/NH3Solution using one or more strippers remove with
From H3PO4Separate NH3.It can be by NH3Via NH3Recirculation flow 20 is recycled back to HCN reaction zone 12.It can be by H3PO4And its
He discharges waste as waste water stream 22, while can be by NH3Stripped HCN stream 24 is fed into HCN recovery system 26.
HCN recovery system 26 may be configured to one or more units behaviour that 24 separation and purification HCN are flowed from HCN
Make.As HCN recovery system 26 as a result, the HCN product stream 28 of preparation purification.HCN recovery system 26 can also generate gaseous state
Waste streams 30 or waste water stream 32.Waste water stream 22,32 can be fed into wastewater treatment 36 to be used to be further processed, such as ammonia or cyaniding
The recycling of hydrogen.It can be by the final further processing of waste water stream 40, storage or the disposition from wastewater treatment 36.
As shown in fig. 1, HCN recovery system 26 may include gaseous waste stream 30.Gaseous waste stream 30 can wrap it is hydrogeneous,
Or mixtures thereof carbon monoxide, nitrogen, carbon dioxide, hydrogen cyanide,.In an example, gaseous waste stream 30, which may include, does not show
The other waste streams of example.For example, can future autoreactor 12 or waste streams of other operations combined with gaseous waste stream 30.
The composition of gaseous waste stream 30 can change according to many factors, the composition including feeding flow 2,4,6, the effect of HCN reaction zone 12
Rate, the efficiency of ammonia recovery system 16, the efficiency of HCN recovery system 26, operating condition or their combination.
In an example, gaseous waste stream 30 can be fed into hydrogen retrieval system 42.In general, gaseous waste stream 30 can
With the HCN containing residual, and significant hydrogen or including unreacted methane, carbon dioxide, carbon monoxide, water, nitrogen and
The multiple gases of a variety of organic nitriles.The removal of HCN can be substantially completely, not only make valuable HCN do not lose to
Waste streams, and for health and environmental concerns, and because the HCN of significant quantity can be such that the processing of waste streams complicates.Example
Such as, some potential device absorbents that can be used for hydrogen retrieval can have less than about 2.0%HCN, or be less than about 1.5%HCN
Operation limitation.Therefore, gaseous waste stream can have less than about 2.0%HCN, or be less than about 1.5%HCN, or be less than about 1%
HCN, or it is less than about 0.5%HCN, or be less than about 0.2%HCN, or be less than about 0.1%HCN.In some cases, gaseous waste
The HCN content of stream 30 can change, for example, changing between about 0.5% to about 1.0%.For example, gaseous waste stream 30 can wrap
The %H of volume containing 40-752, 15-35 volume %CO, 5-15 volume %N2, 1-2 volume %CO2, 1-2 volume %CH4Or 0-1 body
Product %HCN.
The hydrogen stream 50 of recycling can be stored and be used for following processing or sale, sent to other hydrogen processing unit, then follow
Ring is to upstream or point downstream, for supplementing torch 48 (as discussed further below) or their combination.Hydrogen retrieval system 42
The level of the adjustable hydrogen recycled by gaseous waste stream 30.For example, if gaseous waste stream 30 is hydrogen-rich, such as larger than about 40
Volume %, hydrogen retrieval system 42 can recycle greater percentage of hydrogen.Although it is pure that the hydrogen stream 50 recycled needs not be 100%
, but at least most of carbon dioxide, carbon monoxide or nitrile can be from the removal of hydrogen it is desired, with when use recycled
Hydrogen, for example, be used for hydrogenation when, avoid by-product and pollutant.For example, the hydrogen recycled can be at least about 90%
It is pure, or at least about 91% is pure, or at least about 92% pure, or at least about 93% pure, or at least about 94% pure, or extremely
Few about 95% is pure, or at least about 96% pure, or at least about 97% pure, or at least about 98% pure, or at least about 99%
Pure hydrogen.In addition, if the processing unit in downstream such as torch 48 is designed as operating in a certain range of hydrogen concentration, can optimize
Processed gaseous waste stream 52 to be supplied to the processing unit in downstream by hydrogen retrieval system 42.In an example, hydrogen retrieval
System 42 can produce the processed gaseous waste stream comprising at least about 8 volume % hydrogen.Processed gaseous waste stream 52 can
Comprising being less than about 1.5%HCN.Valve can be located at 42 downstream of hydrogen retrieval system, but on processed gaseous waste stream 52
Trip, so that gaseous waste stream 30 directly feeds and is only fed into hydrogen retrieval system 42.
In an example, instance system 10 may include torch 48, to burn gaseous waste stream 30.Torch 48 can be with
It is designed as thoroughly destroying off-gas.If off-gas be it is dilute, gaseous waste stream 30 can be made to be enriched with hydrocarbon fuel 56 such as
Natural gas, to increase obtained heat value of mixture, to ensure thoroughly to destroy waste.Hydrogen has lower than many hydrocarbon fuels
Net heating value.For example, the net heating value of methane is about 913BTU/scf.On the other hand, the net heating value of hydrogen is only about 275BTU/scf.
In view of this unbalanced, people's gaseous mixture that expectability does not contain relatively low intensity of hydrogen will be enough thoroughly to destroy will be with
Its dilute off-gas mixed.Unexpectedly, however, the inventors found that in the gaseous mixture of institute's torch burning
Minimum is about at least 5 volume %, about at least 7 volume %, about at least 8 volume %, and the hydrogen of about at least 10 volume % is enough to ensure that
The destruction of off-gas.
In an example, detector can quantify the component in combustible gas mixture.Valve can be operatively connected
To detector, the non-of the lower threshold corresponding to thermal content is detected in combustible gas mixture wherein valve is configured to work as
When the setting value of combustible component, allow with such as hydrogen of the enriched fuel containing hydrogen or methane supplement gaseous waste stream 30.Pass through burning
The amount of hydrogeneous enriched fuel needed for thoroughly destroying dilute off-gas material also relies on, partly, dilute gaseous state of torch burning
The calorific value of waste materials.Rich stream can hydrogen or hydrocarbon containing sufficient amount so that when being mixed with gaseous waste stream 30, gained
To mixture thinking with enough calorific values thoroughly to destroy dilute off-gas material by the burning in torch 48.
In an example, valve can be operably connected to detector, and wherein valve is configured to when in gaseous waste stream
When detecting the hydrogen concentration lower than threshold value in 30, allow to supplement the oxygen for being allowed to reaction.The increase of the amount of gaseous oxygen feeding flow 6 can
To lead to the increase of hydrogen concentration in gaseous waste stream 30.In an example, can connect by 12 upstream of HCN reactor or with it
Gaseous oxygen feeding flow 6 or oxygen the supplement stream connect provides oxygen.Unexpectedly, bigger oxygen concentration is provided to HCN reactor 12, and
And therefore lower inert gas concentration (for example, N2), it can be provided in the gaseous waste stream 30 that can be used in torch 48
Benefit.Typically, inert gas is used to provide heat transmitting benefit during the reaction.For example, the presence of nitrogen can in reactor
To help to reduce temperature spikes.The present inventor has invented a kind of HCN method, and the method can be by using torch
Such as torch 48, controlled with increasing the temperature of system, to handle oxygen concentration bigger in feeding flow.In addition, bigger in feeding flow
Oxygen concentration can provide reduce fuel quantity benefit, as be used for HCN reactor 12 needed for methane 4.
In an example, torch 48 can be designed as meeting the local environment of torch or federal environmental rate request.
For example, torch muzzle velocity can be for less than about 37.2 meter per seconds.Torch muzzle velocity is the fire at the tip of torch device 48
The speed of torch.It in another example, can be less than V by torch speed designsmax, wherein VmaxIt is defined as
Vmax=(XH2-K1)*K2, wherein
Vmax=maximum allowable torch muzzle velocity, meter per second
K1=constant, 6.0 volume % hydrogen
K2=constant, 3.9 meter per seconds/volume % hydrogen
XH2=volume % hydrogen, based on wet basis, such as by using American Society for Testing Materials (the American Society
For Testing and Materials) (ASTM) method D1946-77 calculating.
Increasing allows the amount of the oxygen reacted that can provide in HCN reactor 12 increases the concentration of hydrogen in gaseous waste stream 30
Benefit, therefore increase torch speed as described above.
In an example, torch 48 can be designed as in greater than about 1000 DEG C, greater than about 1200 DEG C, greater than about 1350
DEG C, greater than about 1500 DEG C, greater than about 1600 DEG C, or greater than about 1800 DEG C of temperature combustion combustible gaseous mixture.Torch burning
Temperature may include the temperature of the ignition temperature of one or more components greater than combustible gaseous mixture.In an example,
Combustible gaseous mixture may include the hydrocarbon of supplement, such as natural gas or hydrogen, to increase the combustibility of combustible gaseous mixture.
Torch 48 may include any torch for being suitable for destroying combustible gaseous mixture.For example, torch 48 may include
Torch or the torch of auxiliary by one's own efforts, stable or non-stable torch.The torch of auxiliary includes that other stream such as water vapour assists
Or air auxiliary, to provide increased torch muzzle velocity, increased flammable composition, more consistent flammable composition, or
Their combination.Stable torch may include other stream as hydrocarbon is stable or air-stable, to increase torch consistency,
Such as rate of departure or temperature.The torch nozzle of torch 48 is adapted to the regulation of any design, such as torch point or jet size.
In an example, torch area may include at least 3.0 inch diameter torch points.
In an example, torch area is also configured as grasping to the non-hydrogen combustible gas mixture of non-hydrogen mode combustion
Make.Non-hydrogen combustible gas mixture may include at least about calorific value of 200BTU/scf.Torch 48 can such as burn in hydrogen mode
The hydrogen or non-hydrogen mode of minimum percentage, as switched between zero volume % hydrogen or their combination.Torch 48 can provide increasing
The benefit of the operating flexibility added.
In an example, instance system 10 may include the washer of 42 downstream of hydrogen retrieval system or upstream to remove gas
At least part of liquid, such as water present in state waste streams 30.The liquid that removal is supplied to torch 48 can provide stable
Torch is supplied to the more predictable thermal capacity of the charging of torch 48.Gaseous waste stream 30 can be fed into instance system 10
Other technique 54, can such as be used in downstream to recycle the boiler of thermal energy.
According to the disclosure, the method for being used to prepare hydrogen cyanide may include allowing oxygen, ammonia and methane in the catalysis comprising platinum
It is reacted in the presence of agent, to provide the product stream for including at least hydrogen cyanide, hydrogen and waste.This method can be with further include: from product
Stream extracts hydrogen cyanide, to generate HCN product stream (Fig. 1, element 28) and give up comprising at least part of gaseous state in hydrogen and waste
Abandoned stream (Fig. 1, element 30), and gaseous waste stream is fed into hydrogen mode torch (Fig. 1, element 48).Gaseous waste stream can be with
Comprising the more than one gaseous waste stream combined with gaseous waste stream, so that by least part of the waste from system,
Such as the torch burning in torch 48.
In an example, this method may include separating at least part of liquid in gaseous waste stream, such as pass through gas-
Liquid/gas separator, flash drum, knock-out drum, knockout drum, compressor suction drum, suction port of compressor drum, demister or their combination.
In an example, this method includes extracting ammonia from product stream, such as passes through ammonia scrubber.This method can also wrap
It includes: flowing back to receipts hydrogen from gaseous waste stream or combined gaseous waste.For example, the hydrogen composition of gaseous waste stream can be more than hydrogen mode
Burning is horizontal.In such a case, it is possible to recycle excessive hydrogen and the use elsewhere in factory, storage makes for following
With or sale or their combination.
This method may include adjusting torch, so that torch muzzle velocity is less than about 37.2 meter per seconds.Adjust torch outlet
Speed can provide the benefit of stable torch, to increase the destruction of burnt element or compound.In addition, method can wrap
Include the temperature torch burning by gaseous waste stream at greater than about 1650 DEG C.
Embodiment
Embodiment 1: compare air, air enrichment and oxygen andrussow process waste gas composite
Peace moral Rousseau side of the embodiment example using the andrussow process in the enrichment source of oxygen than using air as oxygen source
Method generally produces the waste streams with higher hydrogen content.
This method may include adjusting torch, so that torch muzzle velocity is less than about 37.2 meter per seconds.Adjust torch outlet
Speed can provide the benefit of stable torch, to increase the destruction of burnt element or compound component.In addition, the party
Method may include the temperature combustion by gaseous waste stream at greater than about 1650 DEG C.
Pilot scale is used for using the internal 4 inch inner diameter stainless steel reactors with ceramic insulation lining.Load 40
90 weight %Pt/10 weight %Rh, 40 mesh silk screen derived from Johnson Matthey (U.S.) is as catalyst bed.Using wearing
The alumina wafer in hole is used for catalyst plate carrier.Overall flow rate is set in 2532SCFH (standard cubic foot/hour).Hydrogen cyanide
It is prepared via a variety of andrussow process.A kind of technique, air andrussow process, using the oxygen-containing gas comprising 21 volume % oxygen
(air).Second of technique, air-enrichment andrussow process are greater than about 21 volume % oxygen and less than about 100 bodies using having
The oxygen-containing gas of product % oxygen.The third technique, oxygen andrussow process, using the oxygen-containing gas of about 100 volume % oxygen.
By ammonia, each from product stream removes in the method for including absorption into ammonium phosphate stream respectively.Later by cyanogen
Change hydrogen and removed in the method for including acidifying water from the product stream that ammonia exhausts, so that respectively each technique generates hydrogen cyanide production
Object and gaseous state waste streams.
The composition of waste gas stream from air, air enrichment and oxygen method is shown in table 1 as follows.
Table 1
As exemplary, oxygen reaction is used air as the andrussow process ratio in the source of oxygen reactant using enriched in oxygen stream
The andrussow process in the source of object generates more hydrogen significantly.
Embodiment 2: compare the BTU value of air, air enrichment and oxygen andrussow process waste gas composite
The embodiment example is usually produced using the andrussow process in the enrichment source of oxygen than the method for using air as oxygen source
The raw waste streams with higher calorific value.
HCN is prepared using the three kinds of methods provided in such as embodiment 1.Gaseous state from air, air enrichment and oxygen method
The calorific value of waste streams is given in Table 2 as follows.
Table 2
As exemplary, oxygen reaction is used air as the andrussow process ratio in the source of oxygen reactant using enriched in oxygen stream
The andrussow process in the source of object generates the waste streams with higher calorific value significantly.
Specific embodiment above is intended that schematically, and unrestricted.For example, examples detailed above (or one
A or multiple elements) it can be in combination with one another.After reading above instructions, other examples can be used, such as by this field
Technical staff uses.Equally, different characteristic or element can gather together so that the disclosure simplify and more efficiently.This is not
It should be interpreted that being intended that the open feature being not claimed is important any claim.But the theme invented
It can be in whole features less than specifically disclosed example.Therefore, therefore by following following claims it is bound to specific implementation
In mode, wherein each claim is own as separable example.The scope of the present invention should refer to appended right
It is required that and being determined together with the full breadth of the equivalencing of these claim prescriptions.
In the case where having inconsistent usage between any document being incorporated by reference herein and so, with herein
Usage subject to.
Herein, such as common in the patent literature using term "one" or "an", including one or it is more than one
It is a, and it is unrelated with other any examples or use of "at least one" or " one or more ".Herein, unless in addition referring to
Out, refer to non-exclusive using term "or" or, so that " A or B " includes " A but be not B, " " B but be not A ", and " A
And B ".Herein, use term " includes " and " wherein " as the colloquial language etc. of corresponding term "comprising" and " wherein "
Valence.Equally, in following following claims, in other words it, includes except in claim that term " includes " and "comprising", which are open,
In those of listed after these terms except system, device, article, composition, formula or the method for element appoint and recognized
To be fallen within the scope of the claims.In addition, in following following claims, term " first ", " second " and " third "
It is used as to mark Deng only and use, and be not intended to assign numerical requirements to their object.
Method described herein example can be machinery or computer implemented, at least partly.Some examples can wrap
The computer-readable medium or machine-readable medium with instruction encoding are included, described instruction operability is to configure electronic device to carry out
Method or method and step as described in above example.The realization of this method or method and step may include code, such as micro- generation
Code, assembler language code, higher-level language code etc..This code may include the computer-readable finger for carrying out distinct methods
It enables.Code can form a part of computer program product.In addition, in an example, code can be visibly stored in
In one or more volatibility, non-transitory or non-volatile visible computer readable medium, such as in the process of implementation or at it
His time.The example of these tangible computer scale media may include, but be not limited to, hard disk, interchangeability disk, interchangeable CD
(for example, compress disk (CD) and digital video disks (DVD)), cassette, storage card or stick, random access memory (RAM),
Read-only memory (ROM) etc..
Abstract is provided to meet 37C.F.R. § 1.72 (b), to allow reader soon to determine property disclosed in technology.It answers
It is submitted in the case where understanding that it will not be used to interpret or limit the scope of the claims or meaning.
Although describing the present invention by reference to exemplary embodiment, those skilled in the art will appreciate that can be in form
It is changed without departing from the spirit and scope of the present invention in details.
Broadly and the present invention has been generally described herein.Fall into the relatively narrow species and subgroup in general disclosure
Each also form a part of the invention.This includes that there is condition or negative limitation to remove any object from general type
General remark of the invention, and whether specifically stated herein with the object of exclusion unrelated.In addition, in feature of the invention or
In the case that aspect is described with marlcush group, it will be appreciated by one of skill in the art that the present invention is also to the list of any marlcush group
The subgroup of only member or member describes.
Following statement describes some elements or feature of the invention.Because the application is provisional application, these statements can
It can change during the preparation of non-provisional application and submission.If this change occurs, this change is not intended to influence basis
The range of the equivalents of the claim provided by non-provisional application.According to 35U.S.C. § 111 (b), claim is for interim
Application is not required.Therefore, statement of the invention can not be interpreted the claim according to 35U.S.C. § 112.
Statement of the invention:
1. a kind of system for preparing hydrogen cyanide via andrussow process, the system comprises:
It is at least wrapped wherein oxygen, ammonia and methane is allowed to react in the presence of the catalyst comprising platinum with providing reactor zone
Product stream containing hydrogen cyanide (HCN), hydrogen and waste；
The recovery area HCN, wherein the hydrogen cyanide is substantially removed from the product stream, to generate hydrogen cyanide product and packet
Combustible gas mixture containing the hydrogen and the waste；And
Torch area, wherein at least by combustible gas mixture with hydrogen mode combustion, at least to generate carbon dioxide and water.
2. system described in statement 1, wherein hydrocarbon mixture includes the methane.
3. system described in statement 2, wherein the hydrocarbon mixture includes natural gas, biogas, substantially pure methane, or
Its mixture.
4. state system described in any one of 1-3, the system also includes hydrogen retrieval system, the hydrogen retrieval system from
At least one of the product stream and the combustible gas mixture recycle at least some hydrogen.
5. state system described in any one of 1-4, the system also includes ammonia recovery system, the ammonia recovery system from
The product stream substantially removes ammonia.
6. system described in any one of 1-5 is stated, wherein the hydrogen cyanide product is that at least about 98.5 volume % are pure
Hydrogen cyanide.
7. system described in any one of 1-6 is stated, wherein the combustible gas mixture includes at least about 8 volume %
Hydrogen.
8. system described in any one of 1-7 is stated, wherein there is the torch torch less than about 37.2 meter per seconds to export
Speed.
9. system described in any one of 1-8 is stated, wherein the torch, which has, is less than about VmaxTorch muzzle velocity,
Wherein VmaxIs defined as:
Vmax=(XH2-K1)*K2, wherein
Vmax=maximum allowable torch muzzle velocity, meter per second
K1=constant, 6.0 volume % hydrogen
K2=constant, 3.9 meter per seconds/volume % hydrogen
XH2=volume % hydrogen, based on wet basis, such as by using American Society for Testing Materials (the American Society
For Testing and Materials) (ASTM) method D1946-77 calculating.
10. system described in any one of 1-9 is stated, wherein the torch area includes greater than about 1000 DEG C, greater than about
1200 DEG C, greater than about 1350 DEG C, greater than about 1500 DEG C, greater than about 1600 DEG C, or greater than about 1800 DEG C of temperature.
11. system described in any one of 1-10 is stated, wherein the torch area includes torch by one's own efforts.
12. system described in any one of 1-11 is stated, wherein the torch area includes at least 3.0 inch diameter torches
Point.
13. stating system described in any one of 1-12, the system also includes torch stabilizer.
14. system described in any one of 1-13 is stated, wherein the torch area also includes natural gas.
15. state system described in any one of 1-14, the system also includes: hydrogen is added to the fuel gas and is mixed
Close the hydrogen source of object.
16. stating system described in any one of 1-15, the system also includes quantify in the combustible gas mixture
Component detector.
17. system described in statement 16, the system also includes the valve for being operably connected to the detector, wherein institute
Valve is stated to be configured to when the non-flammable component for detecting the lower threshold corresponding to thermal content in the combustible gas mixture
Setting value when, allow to supplement the combustible gas mixture with hydrogen or methane.
18. system described in statement 16, the system also includes the valve for being operably connected to the detector, wherein institute
It states valve to be configured to when detecting the hydrogen concentration lower than threshold value in the combustible gas mixture, allows supplement to be allowed to anti-
The oxygen answered.
19. system described in statement 18, wherein thermal content value of the threshold value based on the combustible gas mixture.
20. system described in statement 18 or 19, wherein the valve operation is connected to air feed stream.
21. system described in statement 18 or 19, wherein the valve operation is connected to oxygen feeding flow.
22. system described in statement 18 or 19, wherein the valve operation is connected to the air feed stream of enriched in oxygen.
23. system described in any one of 1-22 is stated, wherein the torch area further includes with the non-of non-hydrogen mode combustion
Hydrogen combustible gas mixture.
24. system described in statement 23, wherein the non-hydrogen combustible gas mixture includes at least about 200BTU/scf's
Calorific value.
25. system described in any one of 1-24 is stated, wherein the waste includes to be less than about 1.5 volume %HCN.
26. stating system described in any one of 1-25, the system also includes at least one liquid of the torch upstream
Body separator, to remove at least one of liquid present in the combustible gas mixture or non-hydrogen combustible gas mixture
Point.
27. a kind of method for the waste generated by andrussow process that burns, which comprises
Allow oxygen, ammonia and methane to react in the presence of the catalyst comprising platinum, with provide include at least hydrogen cyanide, hydrogen and
The product stream of waste；
Extract the hydrogen cyanide from the product stream, with generate hydrogen cyanide stream and comprising the hydrogen and the waste at least
The gaseous waste stream of a part；And
The gaseous waste stream is fed into hydrogen mode torch.
28. method described in statement 27, the method also includes: ammonia is extracted from the product stream.
29. method described in statement 27 or 23, the method also includes: the extraction stream is being fed into the hydrogen mode
Before torch, by least part of liquid from the gaseous waste flow separation.
30. stating method described in any one of 27-29, the method also includes flowing back to receipts hydrogen from the gaseous waste.
31. state method described in any one of 27-30, the method also includes: in the premise for extracting the hydrogen cyanide
Take ammonia.
32. state method described in any one of 27-31, the method also includes: the torch to be less than about 37.2 meter per seconds
Gaseous waste stream described in muzzle velocity torch burning.
33. state method described in any one of 27-32, the method also includes: to be less than about VmaxTorch export speed
Gaseous waste stream described in torch burning is spent, wherein VmaxIs defined as:
Vmax=(XH2-K1)*K2, wherein
Vmax=maximum allowable torch muzzle velocity, meter per second
K1=constant, 6.0 volume % hydrogen
K2=constant, 3.9 meter per seconds/volume % hydrogen
XH2=volume % hydrogen, based on wet basis, such as by using American Society for Testing Materials (the American Society
For Testing and Materials) (ASTM) method D1946-77 calculating.
34. state method described in any one of 27-33, the method also includes: the gaseous waste stream is being greater than
About 1650 DEG C of temperature combustion.
35. state method described in any one of 27-34, the method also includes: the stabilizer that applies a torch stablizes the hydrogen
Mode torch.
36. state method described in any one of 27-35, the method also includes: increase the hydrogen of the gaseous waste stream
Concentration is to increase the calorific value of the gaseous waste stream.
37. state method described in any one of 27-36, the method also includes: stream, which is supplemented, with hydrogen supplements the gaseous state
Waste streams.
38. method described in statement 36, the method also includes: increase the amount of the oxygen for allowing to react.
39. state method described in any one of 27-37, the method also includes: detect the hydrogen of the gaseous waste stream
Concentration；And increase the amount for allowing the oxygen reacted when detecting the hydrogen concentration lower than threshold value.
40. method described in statement 39, the method also includes: increase the oxygen concentration of air feed stream.
41. system described in statement any one of 1-40 or any combination or method be optionally configured so that can be used or
Select all elements or operation described.
Claims (13)
1. a kind of method for the waste generated by andrussow process that burns, which comprises
Allow oxygen, ammonia and methane to react in the presence of the catalyst comprising platinum, includes at least hydrogen cyanide, hydrogen and waste to provide
Product stream；
The hydrogen cyanide is extracted from the product stream, it is described with the gaseous waste stream for generating hydrogen cyanide stream He extracting hydrogen cyanide
The gaseous waste stream for extracting hydrogen cyanide includes 42.6-74.4 volume %H2, 15-35 volume %CO, 5-15 volume %N2, 1-2 body
Product %CO2, 1-2 volume %CH4With 0-1 volume %HCN；
Receipts hydrogen is flowed back to from the gaseous waste for extracting hydrogen cyanide, to generate containing at least recycling of 5 volume % hydrogen hydrogen
Gaseous waste stream；And
The gaseous waste stream for recycling hydrogen is fed into hydrogen mode torch,
Wherein the oxygen is provided as the oxygen-containing gas containing 45-90 volume % oxygen.
2. method described in claim 1, the method also includes: ammonia is extracted from the product stream.
3. method of any of claims 1 or 2, the method also includes: the gaseous waste for recycling hydrogen is being flowed into material
Before to the hydrogen mode torch, at least part of liquid from the gaseous waste stream for extracting hydrogen cyanide or was recycled
The gaseous waste flow separation of hydrogen.
4. method of any of claims 1 or 2, wherein the gaseous waste stream for recycling hydrogen contains the hydrogen of at least 8 volume %.
5. method of any of claims 1 or 2, the method also includes: before extracting the hydrogen cyanide extract ammonia.
6. method of any of claims 1 or 2, the method also includes: with the torch muzzle velocity torch less than 37.2 meter per seconds
Burn the gaseous waste stream for recycling hydrogen.
7. method of any of claims 1 or 2, the method also includes to be less than VmaxTorch muzzle velocity torch burning institute
The gaseous waste stream for recycling hydrogen is stated, wherein VmaxIs defined as:
Vmax=(XH2-K1)*K2, wherein
Vmax=maximum allowable torch muzzle velocity, meter per second
K1=constant, 6.0 volume % hydrogen
K2=constant, 3.9 meter per seconds/volume % hydrogen
XH2=volume % hydrogen is calculated based on wet basis by using American Society for Testing Materials (ASTM) method D1946-77.
8. method of any of claims 1 or 2, the method also includes: the gaseous waste stream for recycling hydrogen is being greater than
1650 DEG C of temperature torch burning.
9. method of any of claims 1 or 2, the method also includes: the stabilizer that applies a torch stablizes the hydrogen mode torch.
10. method of any of claims 1 or 2, the method also includes: increase the hydrogen concentration of the gaseous waste stream to increase
The calorific value of the gaseous waste stream.
11. method of any of claims 1 or 2, the method also includes: stream, which is supplemented, with hydrogen supplements the gaseous waste stream.
12. method described in any one of claim 10, the method also includes: increase the amount of the oxygen for allowing to react.
13. method of any of claims 1 or 2, the method also includes:
Detect the hydrogen concentration of the gaseous waste stream；And
When detecting the hydrogen concentration lower than threshold value, increase the amount for allowing the oxygen reacted.
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| US201261738817P | 2012-12-18 | 2012-12-18 | |
| US61/738,817 | 2012-12-18 |
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| CN103864112A CN103864112A (en) | 2014-06-18 |
| CN103864112B true CN103864112B (en) | 2019-01-04 |
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| Country | Link |
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| CN (1) | CN103864112B (en) |
| HK (1) | HK1198994A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687658A (en) * | 2007-05-14 | 2010-03-31 | 因温斯特技术公司 | High efficiency reactor and process |
| CN204057984U (en) * | 2012-12-18 | 2014-12-31 | 因温斯特技术公司 | The system of the torch improved in Andrussow process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1934838A (en) | 1930-04-14 | 1933-11-14 | Ig Farbenindustrie Ag | Production of hydrocyanic acid |
| DE549055C (en) | 1930-04-15 | 1932-04-22 | I G Farbenindustrie Akt Ges | Process for the production of hydrogen cyanide |
| US20020071798A1 (en) * | 2000-07-12 | 2002-06-13 | Decourcy Michael Stanley | Laboratory Scale reaction systems |
| DE102007014586A1 (en) * | 2007-03-23 | 2008-09-25 | Evonik Röhm Gmbh | Process for the production of hydrogen cyanide (HCN) |
-
2013
- 2013-12-12 TW TW102145959A patent/TW201441156A/en unknown
- 2013-12-12 CN CN201310681867.3A patent/CN103864112B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687658A (en) * | 2007-05-14 | 2010-03-31 | 因温斯特技术公司 | High efficiency reactor and process |
| CN204057984U (en) * | 2012-12-18 | 2014-12-31 | 因温斯特技术公司 | The system of the torch improved in Andrussow process |
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| Publication number | Publication date |
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| CN103864112A (en) | 2014-06-18 |
| TW201441156A (en) | 2014-11-01 |
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| HK1198994A1 (en) | 2015-06-19 |
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