CN204057984U - The system of the torch improved in Andrussow process - Google Patents

The system of the torch improved in Andrussow process Download PDF

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CN204057984U
CN204057984U CN201320822923.6U CN201320822923U CN204057984U CN 204057984 U CN204057984 U CN 204057984U CN 201320822923 U CN201320822923 U CN 201320822923U CN 204057984 U CN204057984 U CN 204057984U
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torch
hydrogen
oxygen
hcn
gas mixture
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斯图尔特·福赛思
刘爱国
马丁·J·伦纳
布伦特·J·斯塔尔曼
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Invista North America LLC
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Invista Technologies SARL Switzerland
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Abstract

The utility model describes a kind of system and method for preparing prussic acid via Andrussow process.Described system can comprise reactor zone, wherein allows oxygen, ammonia and methane to react at least to provide prussic acid (HCN), hydrogen and refuse under the existence of catalyzer comprising platinum.HCN recovery zone can remove prussic acid substantially from hydrogen and refuse.Torch district can at least with hydrogen mode combustion combustible gas mixture at least to produce carbonic acid gas and water, described combustible gas mixture comprise described hydrogen at least partially with described refuse at least partially.

Description

The system of the torch improved in Andrussow process
The cross reference of related application
The U.S. Provisional Patent Application series number 61/738 being entitled as " apparatus and method (APPARATUS AND METHOD OF AN IMPROVED FLARE IN AN ANDRUSSOW PROCESS) of the torch improved in Andrussow process " of the application's claim 2012 submission in 18, on December, the right of priority of 828, it is openly combined in this with its full content by reference.
Technical field
The disclosure relates to the reactor scheme of the Andrussow process for being prepared prussic acid (HCN) by methane, ammonia and oxygen.
Background technology
Andrussow process may be used for prussic acid (HCN) to be prepared by methane, ammonia and the oxygen gas phase on platinum catalyst.About 800 DEG C will be heated to about 2 under the existence of catalyzer at least comprising platinum, 500 DEG C in filtered ammonia, Sweet natural gas and air feed to reactor.Methane can by natural stripping confession, and it can be purified further.The hydrocarbon with at least two carbon may reside in Sweet natural gas.Air can be used as oxygen source.Reactor outlet gas containing HCN and unreacted ammonia can be chilled to about 100 DEG C to 400 DEG C in waste heat boiler.Quench reactor containing HCN can be worked off one's feeling vent one's spleen and be conducted through ammonia absorption process to remove unreacted ammonia, as by making reactor outlet gas and ammonium phosphate solution, phosphoric acid or sulfuric acid contact to remove ammonia.Can product exit gas be delivered to by HCN resorber from ammonia absorber, cold water can be added to take away HCN at this.HCN resorber can produce the gaseous waste stream substantially containing hydrogen and by product.Owing to the composition of gaseous waste stream, disposing (disposal) can be environment-conscious, can not burnout, or their combination.
All respects prepared by HCN are described: Eric.L.Crump in following article; Environmental Protection Agency (U.S.Environmental Protection Agency); Air quality plan and standard office room (Office of Air Quality Planning and Standards); for economic impact analysis NESHAP (Economic Impact Analysis For the Proposed Cyanide Manufacturing NESHAP) (in May, 2000) prepared by proposed prussiate, http:// nepis.epa.gov/Exe/ZyPDF.cgi Dockey=P100AHG1.PDFcan obtain online, relate to the preparation of HCN, final utilization and economic impact; N.V.Trusov, the impact (Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method) that the higher homologue of sulphur compound and methane is prepared the prussic acid by Andrussow process, Rus.J.of Applied Chemistry, 74th volume, 10th phase, 1693-97 page (2001) relates to the inevitable component of Sweet natural gas, the impact that the higher homologue as sulphur and methane is prepared the HCN by Andrussow process; Clean Development Mechanism (CDM) Executive Council (Clean Development Mechanism (CDM) Executive Board), UNFCCC (United Nations Framework Convention on Climate Change) (United Nations Framework Convention on Climate Change) (UNFCCC), Clean Development Mechanism PDD form (Clean Development Mechanism Project Design Document Form) (CDM PDD), 3rd edition, (July 28,2006), exist http:// cdm.unfccc.int/Reference/PDDs_Forms/PDDs/PDD_form04_v03_ 2.pdfcan obtain online, relate to the preparation of HCN by Andrussow process; And Gary R.Maxwell etc., process safety (Assuring process safety in the transfer of hydrogen cyanide manufacturing technology) is guaranteed in the transfer of prussic acid technology of preparing, J.of Hazardous Materials, 142nd volume, 677-84 page (2007) relates to the safety preparation of HCN.
Utility model content
The disclosure relates to a kind of solution of disposal of the gaseous waste stream from the HCN resorber in Andrussow process.This solution can comprise a kind of system and method for preparing prussic acid via Andrussow process.This system can comprise reactor zone, wherein allows oxygen, ammonia and methane to react under the existence of catalyzer comprising platinum, at least to provide prussic acid (HCN), hydrogen and refuse.HCN recovery zone can remove prussic acid substantially from hydrogen and refuse.Torch district can by combustible gas mixture with hydrogen mode combustion, at least to produce carbonic acid gas and water, described combustible gas mixture comprise hydrogen at least partially with off-gas at least partially.Combustible gas mixture can comprise Sweet natural gas.
Hydrocarbon mixture can provide the methane in system.Hydrocarbon mixture can comprise Sweet natural gas, biogas, substantially pure methane, or its mixture.This system can comprise hydrogen retrieval system, its can at the downstream of hydrogen retrieval system recoveries or recirculated upstream, store or utilize hydrogen.This system can comprise ammonia and extract district, is wherein substantially removed from HCN, hydrogen and refuse by ammonia.
Prussic acid recovery zone can provide the prussic acid product stream of the purity that can comprise at least about 98.5% prussic acid, or provides off-gas stream to be less than about 1.5%HCN to make existence.The combustible gaseous mixture of waste being fed to torch can comprise at least about 8 volume % hydrogen.Torch velocity of discharge can be less than about 37.2 meter per seconds, as being less than about V max, wherein V maxbe defined as:
V max=(X h2-K 1) * K 2, wherein
V max=maximum permission torch velocity of discharge, meter per second
K 1=constant, 6.0 volume % hydrogen
K 2=constant, 3.9 meter per seconds/volume % hydrogen
X h2=volume % hydrogen, by wet basis, as calculated by use American Society for testing and materials (the American Society for Testing and Materials) (ASTM) method D1946-77.
Torch district can be configured at the temperature operation being greater than about 1350 DEG C.Torch can be by one's own efforts or stable.Torch district can comprise at least 3.0 inch diameter torch points.
Torch district can also be configured to torch burning with the non-hydrogen combustible gas mixture of non-hydrogen mode combustion, as the non-hydrogen combustible gas mixture of the thermal content at least about 200BTU/scf.This system can comprise the liquid trap of at least one torch upstream, to remove the liquid that exists in combustible gas mixture or non-hydrogen combustible gas mixture at least partially.
According to the disclosure, a kind of method for the refuse produced by Andrussow process that burns can comprise: allow oxygen, ammonia and methane to react under the existence of catalyzer comprising platinum, to provide the product stream at least comprising prussic acid, hydrogen and refuse.Prussic acid can be extracted to prepare HCN product stream from product stream and comprise the gaseous waste stream at least partially of hydrogen and refuse, and gaseous waste stream can be fed to hydrogen pattern torch.
The method can comprise: extract ammonia from product stream, as before extraction prussic acid.Can by liquid at least partially before gaseous waste stream is fed to hydrogen pattern torch from gaseous waste flow point from.Hydrogen can be flowed back to receipts from gaseous waste.This gaseous waste stream with the hydrogen richness of minimizing still can use method and apparatus described herein torch burning effectively.The method can comprise supplements the component of torch burning with hydrogen or hydrocarbon such as methane.
The method can comprise extraction stream to be less than about 37.2 meter per seconds as V maxtorch velocity of discharge torch burning.Torch district can at the temperature operation being greater than about 1650 DEG C.The method can comprise auxiliary or stable torch.
Part in following embodiment provides by these and other examples of system and method for the present disclosure and feature.Utility model content is intended to the general introduction providing theme of the present disclosure, and is not meant to and provides exclusive or detailed explanation.Comprise embodiment below to provide the further information about system and method for the present disclosure.
Accompanying drawing explanation
Fig. 1 is according to the schematic block schema prepared via the HCN of Andrussow process of the present disclosure.
Embodiment
Prussic acid by the synthesis of Andrussow process (see, such as, Ullmann's Encyclopedia of Industrial Chemistry, 8th volume, VCH Verlagsgesellschaft, Weinheim, 1987,161-162 page) platinum or platinum alloy can comprised in the gas phase, or the catalyzer of other metals carries out.As U.S. Patent number 1,934, finds and describes the catalyzer being suitable for carrying out Andrussow process in original peace moral Rousseau patent etc. disclosed in 838.In the original work of peace moral Rousseau, he discloses catalyzer can be selected from oxide catalyst the working temperature molten (solid) of about 1000 DEG C; He platinum, iridium, rhodium, palladium, osmium, gold or silver are comprised as or the catalytically-active metals of pure form or alloy form.He is also noted that and some base metal (base metals) also can be used as rare earth metal, thorium, uranium etc., as not molten oxide compound or phosphatic form, and by catalyzer or net (sieve) can be formed as, or be deposited on thermotolerance solid carrier as on silicon-dioxide or aluminum oxide.
Development subsequently in, have selected the catalyzer of platiniferous, even the thermotolerance of this effect owing to them and metal silk screen or net form formula.Such as, platinum-rhodium alloy can be used as catalyzer, it can be the form of wire cloth or sieve as weaving or braided wires mesh sheet, also can be deposited on carrier structure body.In an example, weaving or braided wires mesh sheet can form sieve shape structure, and it has 20-80 object size, such as, have the opening of the size of about 0.18mm to about 0.85mm.Catalyzer can comprise about 85 % by weight to about 95 % by weight Pt and about 5 % by weight to about 15 % by weight Rh, as 85/5Pt/Rh, and 90/10, or 95/5Pt/Rh.Platinum-rhodium catalyst can also comprise metallic impurity in a small amount, as iron (Fe), palladium (Pd), iridium (Ir), ruthenium (Ru) and other metals.Foreign metal can with trace, and below 10ppm exists according to appointment.
The possible embodiment of the wide region of Andrussow process is described in German Patent 549, in 055.In an example, about 800 to 2,500 DEG C, 1,000 to 1,500 DEG C, or the temperature use of about 980 to 1050 DEG C comprises the multiple catalyzer with the gauze wire of the Pt of 10% rhodium be arranged in series.Such as, catalyzer can be commercially available catalyzer, as the Pt-Rh catalyzer silk screen of the Johnson Matthey Plc of London can be derived from, the Pt-Rh catalyzer silk screen of the Heraeus Precious Metals GmbH & Co. of Hanau, Germany maybe can be derived from.
Composition from the gaseous waste stream of Andrussow process can make the disposal difficulty of this stream.Such as, gaseous waste stream can make torch burning insufficient, to bad environmental, outside the parameter area of local or federal regulations, or their combination.The disclosure relates to a kind of for the apparatus and method via Andrussow process synthesis HCN, and the torch wherein improved can dispose gaseous waste stream when considering environmental concerns, efficiency misgivings or government regulations.
Fig. 1 is the schematic block schema of the case method 10 for preparing prussic acid (HCN) via Andrussow process.In case method 10, provide ammonia (NH to HCN reaction zone 12 3) stream 2, methane (CH 4) stream 4 and airflow 6 (it comprises oxygen (O 2)).Air can comprise air and other oxygen-containing gas mixtures, comprises the air of the enriched in oxygen of the oxygen concn had higher than about 21 volume %.When Andrussow process is suitable for the gaseous oxygen incoming flow 6 of the oxygen adopted containing the level slightly higher than air, example herein can be useful especially.Such as, this gaseous oxygen incoming 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.Method 10 can comprise air Andrussow process, such as, comprises the airflow 6 of about 21 volume % oxygen; Air-enrichment peace moral Rousseau method, such as, comprises and is greater than about 21 volume % oxygen but the airflow 6 being less than about 100 volume % oxygen; Or oxygen Andrussow process, such as, comprise the airflow 6 of about 100% oxygen.
Mixed for three kinds of incoming flows 2,4,6 being incorporated in one or more reactor is reacted, to be converted into prussic acid and water according to reaction formula 1 in the presence of a catalyst:
2NH 3+2CH 4+3O 2→2HCN+6H 2O [1]
One or more reactor can comprise HCN catalyzer, as platinum (Pt) or platinum alloy, as contained at least about the platinum of 85 % by weight platinum and the alloy of rhodium (Rd) or palladium (Pd).The alloy used in Andrussow process can comprise, but is not limited to, 10 % by weight Rh-90 % by weight Pt, 8 % by weight Rh-92 % by weight Pt, 5 % by weight Pd-5 % by weight Rh-90 % by weight Pt, or 5 % by weight Rh-95 % by weight Pt.Can use containing the alloy up to about 5 % by weight iridium (Ir).In an example, by HCN Catalyst Design for reducing by product, as N2O by-product, and rhodium (Rh) content of increase therefore can be had, or other materials, as cobalt (Co).HCN catalyzer can be contained in packed bed, as in packed bed reactor, or is formed as silk screen, as passed through wire weaving or being woven to wire mesh structure.The catalyzer of formation like this is extensively accreditation in the art, and can contain catalytic material described herein.
HCN catalyzer can be commercially available catalyzer, as the Pt-Rh catalyzer silk screen of London Johnson Matthey Plc can be derived from, the Pt-Rh catalyzer silk screen of Hanau, Germany Heraeus Precious Metals GmbH & Co. maybe can be derived from.
The product stream 14 obtained from HCN reaction zone 12 can be fed to and be configured to reclaim unreacted NH 3ammonia recovery system 16.Ammonia can by via providing one or more can to absorb NH from product stream 14 to product stream 14 3phosphoric acid (H 3pO 4), sulfuric acid (H 2sO 4) or the NH of ammonium phosphate solution 3absorb and reclaim.In the example depicted in fig. 1, the phosphoric acid stream 18 in ammonia recovery system 16 can absorb NH 3.Can by ammonia from H 3pO 4/ NH 3solution uses one or more stripper to remove with from H 3pO 4be separated NH 3.Can by NH 3via NH 3recirculation flow 20 recirculation is back to HCN reaction zone 12.Can by H 3pO 4discharge as wastewater streams 22 with other refuses, simultaneously can by NH 3stripped HCN stream 24 is fed to HCN recovery system 26.
HCN recovery system 26 can comprise the one or more unit operations being configured to flow 24 isolation andpurification HCN from HCN.As the result of HCN recovery system 26, the HCN product stream 28 that preparation is purified.HCN recovery system 26 can also produce waste gas 30 or wastewater streams 32.Wastewater streams 22,32 can be fed to wastewater treatment 36 and be used for further processing, as the recovery of ammonia or prussic acid.Final wastewater streams 40 from wastewater treatment 36 can be processed further, stores or is disposed.
As shown in fig. 1, HCN recovery system 26 can comprise gaseous waste stream 30.Gaseous waste stream 30 can comprise hydrogen, carbon monoxide, nitrogen, carbonic acid gas, prussic acid, or its mixture.In an example, gaseous waste stream 30 can comprise not illustrated other waste streams.Such as, can autoreactor 12 or other waste streams operated combine with stream 30 in the future.The composition of gaseous exhaust stream 30 can change according to many factors, comprises the composition of incoming flow 2,4,6, the efficiency of HCN reaction zone 12, the efficiency of ammonia recovery system 16, the efficiency of HCN recovery system 26, operational condition, or their combination.
In an example, gaseous waste stream 30 can be fed to hydrogen retrieval system 42.Usually, gaseous waste stream 30 can containing the HCN of residual, and significant hydrogen or comprise the multiple gases of unreacted methane, carbonic acid gas, carbon monoxide, water, nitrogen and multiple organic nitrile.Removing of HCN can be substantially completely, not only makes valuable HCN not lose to waste streams, and for healthy and environmental concerns, and because the HCN of significant quantity can make the process of waste streams complicated.Such as, some the potential device absorption agents that may be used for hydrogen retrieval can have and are less than about 2.0%HCN, or are less than the performance constraint of about 1.5%HCN.Therefore, gaseous waste stream can have and is less than about 2.0%HCN, or is less than about 1.5%HCN, or is less than about 1%HCN, or is less than about 0.5%HCN, or is less than about 0.2%HCN, or is less than about 0.1%HCN.In some cases, the HCN content of gaseous waste stream 30 can change, such as, about 0.5% to about changing between 1.0%.Such as, gaseous waste stream 30 can comprise 40-75 volume %H 2, 15-35 volume %CO, 5-15 volume %N 2, 1-2 volume %CO 2, 1-2 volume %CH 4or 0-1 volume %HCN.
The hydrogen stream 50 of recovery can be stored and be used for following process or sale, deliver to other hydrogen processing unit, be recycled to upstream or point downstream, for supplementary torch 48 (as discussed further below), or their combination.Hydrogen retrieval system 42 can regulate the level of the hydrogen reclaimed by combination gaseous waste stream 20.Such as, if combination gaseous stream 30 is Fu Qing, as being greater than about 40 volume %, hydrogen retrieval system 42 can reclaim the hydrogen of larger percentage ratio.Although the hydrogen stream 50 reclaimed needs not be 100% pure, at least most carbonic acid gas, carbon monoxide or nitrile can be wish from removing of hydrogen, with when using the hydrogen reclaimed, such as, during for hydrogenation, avoid by product and pollutent.Such as, the hydrogen reclaimed can be pure at least about 90%, pure at least about 91%, or pure at least about 92%, or pure at least about 93%, or it is pure at least about 94%, pure at least about 95%, or pure at least about 96%, or pure at least about 97%, or pure at least about 98%, or at least about 99% pure hydrogen.In addition, if be designed to operate in the hydrogen concentration of certain limit as torch 48 by the processing unit in downstream, hydrogen retrieval system 42 can be optimized the gaseous waste processed stream 52 to be supplied to the processing unit in downstream.In an example, hydrogen retrieval system 42 can produce the gaseous waste stream of the process comprised at least about 8 volume % hydrogen.Gaseous waste stream 52 can comprise and be less than about 1.5%HCN.Valve can be positioned at hydrogen retrieval system 42 downstream, but gaseous waste stream 52 upstream processed, to make the direct charging of gaseous waste stream 30 and to be only fed to hydrogen retrieval system 42.
In an example, system 10 can comprise torch 48, to burn gaseous waste stream 30.Torch 48 can be designed as and thoroughly destroys off-gas.If off-gas is rare, stream 30 can be made to be enriched with hydrocarbon fuel 56 as Sweet natural gas, to increase obtained heat value of mixture, to guarantee refuse thoroughly to destroy.Hydrogen has the net thermal value lower than a lot of hydrocarbon fuel.Such as, the net thermal value of methane is about 913BTU/scf.On the other hand, the net thermal value of hydrogen is only about 275BTU/scf.Consider this unbalanced, people's gaseous mixture that expectability does not contain the hydrogen of relative lower concentration thoroughly destroys being enough to the rare off-gas will mixed with it.But unexpectedly, contriver of the present disclosure finds that in the gaseous mixture of institute's torch burning, minimum is about at least 5 volume %, about at least 7 volume %, and about at least 8 volume %, the hydrogen of about at least 10 volume % is enough to the destruction of guaranteeing off-gas.
In an example, detector can quantize the component in combustible gas mixture.Valve operability can be connected to detector, when by valve configurations being wherein the set(ting)value when the non-combustibleconstituents lower threshold corresponding to thermal content being detected in combustible gas mixture, allow to supplement combustible gas mixture 30 with enriched fuel such as hydrogen or the methane containing hydrogen.Also depended on by the amount of the hydrogeneous enriched fuel thoroughly destroyed needed for rare off-gas material of burning, partly, the calorific value of rare off-gas material of torch burning.Rich stream can contain hydrogen or the hydrocarbon of q.s, and to make when mixing with gaseous waste stream 30, the mixture thinking obtained is to have enough calorific values thoroughly to destroy rare off-gas material by the burning in torch 48.
In an example, valve operability can be connected to detector, and wherein valve configurations is when the hydrogen concentration lower than threshold value being detected in combustible gas mixture 30, allows to supplement the oxygen being allowed to react.The increase of the amount of oxygen 6 can cause the increase of hydrogen concentration in combustible gas mixture 30.In an example, stream can be supplemented by HCN reactor 12 upstream or connected airflow 6 or oxygen and oxygen is provided.Unexpectedly, provide larger oxygen concn to HCN reactor 12, and therefore lower inert gas concentration (such as, N 2), can be provided in the benefit of the more inflammable gas refuse 30 that can adopt in torch 48.Typically, adopt rare gas element to provide heat trnasfer benefit in reaction process.Such as, in reactor, the existence of nitrogen can contribute to reducing temperature spikes.Contriver of the present disclosure has invented a kind of HCN method, and described method by making to apply a torch as torch 48, can control with the temperature increasing system, thus oxygen concn larger in process incoming flow.In addition, oxygen concn larger in incoming flow can provide and reduce the benefit of fuel quantity, as the methane 4 needed for HCN reactor 12.
In an example, torch 48 can be designed to the local environment or the federal environmental rate request that meet torch.Such as, torch velocity of discharge can for being less than about 37.2 meter per seconds.Torch velocity of discharge is the speed of the torch at tip place at torch device 48.In another example, can by torch speed designs for being less than V max, wherein V maxbe defined as
V max=(X h2-K 1) * K 2, wherein
V max=maximum permission torch velocity of discharge, meter per second
K 1=constant, 6.0 volume % hydrogen
K 2=constant, 3.9 meter per seconds/volume % hydrogen
X h2=volume % hydrogen, by wet basis, as calculated by use American Society for testing and materials (the American Society for Testing and Materials) (ASTM) method D1946-77.
Increase in HCN reactor 12 and allow the amount of the oxygen reacted can provide the benefit of the concentration increasing hydrogen in waste streams 30, therefore increase torch speed as above.
In an example, torch 48 can be designed as and is being greater than about 1000 DEG C, is greater than about 1200 DEG C, is greater than about 1350 DEG C, be greater than about 1500 DEG C, be greater than about 1600 DEG C, or is greater than the temperature combustion combustible gaseous mixture of about 1800 DEG C.Torch burning temperature can comprise the temperature of the temperature of combustion of one or more components being greater than combustible gaseous mixture.In an example, combustible gaseous mixture can comprise supplementary hydrocarbon, as Sweet natural gas, or hydrogen, to increase the combustibility of combustible gaseous mixture.
Torch 48 can comprise any torch being suitable for destroying combustible gaseous mixture.Such as, torch 48 can comprise torch or auxiliary torch by one's own efforts, stable or non-stable torch.Auxiliary torch comprises other stream and to assist as water vapor or air is assisted, to provide the torch velocity of discharge of increase, and the flammable composition of increase, more consistent flammable composition, or their combination.It is as stable in hydrocarbon or air-stable that stable torch can comprise other stream, to increase torch consistence, as rate of opening or temperature.The torch nozzle of torch 48 can be adapted to the regulation of any design, as torch point or jet size.In an example, torch district can comprise at least 3.0 inch diameter torch points.
In an example, torch district can also be configured to operate in order to the non-hydrogen combustible gas mixture of non-hydrogen mode combustion.Non-hydrogen combustible gas mixture can comprise the calorific value at least about 200BTU/scf.Torch 48 can in hydrogen pattern, as the hydrogen of minimum percentage of burning, or non-hydrogen pattern, as zero volume % hydrogen, or switch between their combination.Torch 48 can provide the benefit of the flexibility of operation of increase.
In an example, system 10 can comprise the washer of hydrogen retrieval system 42 downstream or upstream to remove the liquid at least partially existed in gaseous waste stream 30, as water.Remove the liquid being supplied to torch 48 and stable torch can be provided, be supplied to the more predictable thermal capacity of the charging of torch 48.Combustible gaseous refuse 30 can be fed to the other technique 54 of system 10, as adopted in downstream with the boiler reclaiming heat energy.
According to the disclosure, the method for the preparation of prussic acid can comprise permission oxygen, ammonia and methane and react under the existence of catalyzer comprising platinum, to provide the product stream at least comprising prussic acid, hydrogen and refuse.The method can also comprise: extract prussic acid from product stream, to produce HCN product stream (Fig. 1, key element 28) and gaseous waste stream (Fig. 1 at least partially of comprising in hydrogen and refuse, key element 30), and gaseous waste stream is fed to hydrogen pattern torch (Fig. 1, key element 48).Gaseous waste stream can comprise combine with gaseous waste stream more than a kind of gaseous waste stream, to make by the refuse from system at least partially, such as torch burning in torch 48.
In an example, the method can to comprise in separating gaseous waste streams liquid at least partially, as by gas-liquid separator, flash drum, knockout drum, separating tank, compressor suction drum, suction port of compressor drum, mist eliminator, or their combination.
In an example, the method comprises from product stream extraction ammonia, as passed through ammonia scrubber.The method can also comprise: flow back to receipts hydrogen from the gaseous waste of gaseous waste stream or merging.Such as, the hydrogen composition of gaseous waste stream can exceed hydrogen mode combustion level.In this case, excessive hydrogen can be reclaimed and use at the elsewhere of factory, storing and be used for following use or sale, or their combination.
The method can comprise adjustment torch, is less than about 37.2 meter per seconds to make torch velocity of discharge.Regulate torch velocity of discharge can provide the benefit of stable torch, thus increase the destruction of element or the compound burnt.In addition, method can comprise gaseous waste stream at the temperature torch burning being greater than about 1650 DEG C.
Embodiment
Embodiment 1: compare air, air enrichment and oxygen Andrussow process waste gas composite
This embodiment example uses the Andrussow process in the enrichment source of oxygen usually to produce the waste streams with higher hydrogen richness than the peace moral Rousseau method adopting air as oxygen source.
The method can comprise adjustment torch, is less than about 37.2 meter per seconds to make torch velocity of discharge.Regulate torch velocity of discharge can provide the benefit of stable torch, thus increase the destruction of element or the compound component of burning.In addition, the method can comprise gaseous waste stream at the temperature combustion being greater than about 1650 DEG C.
Inside is used to have 4 inches of internal diameter stainless steel reactors of ceramic insulation lining for pilot scale.Load the 90 % by weight Pt/10 % by weight Rh40 order silk screens deriving from Johnson Matthey (U.S.) of 40 as catalyst bed.The alumina wafer of perforation is used to be used for catalyst plate carrier.Overall flow rate is set in 2532SCFH (standard cubic foot/hour).Prussic acid is prepared via multiple Andrussow process.A kind of technique, air Andrussow process, adopts the oxygen-containing gas (air) comprising 21 volume % oxygen.The second technique, air-enrichment Andrussow process, adopts and has and be greater than about 21 volume % oxygen and the oxygen-containing gas being less than about 100 volume % oxygen.The third technique, oxygen Andrussow process, adopts the oxygen-containing gas of about 100 volume % oxygen.
Ammonia is removed from each of product stream comprising respectively to the method for the absorption ammonium phosphate stream.Afterwards the product stream that prussic acid exhausts from ammonia is removed the method comprising acidified water, thus each technique produces prussic acid product and gaseous state waste streams respectively.
The composed as follows of exhaust flow from air, air enrichment and oxygen method illustrates in Table 1.
Table 1
As example, enriched in oxygen stream is adopted to produce more hydrogen significantly as the Andrussow process in the source of oxygen reactant than the Andrussow process adopting air as the source of oxygen reactant.
Embodiment 2: the BTU value comparing air, air enrichment and oxygen Andrussow process waste gas composite
This embodiment example uses the Andrussow process in the enrichment source of oxygen usually to produce the waste streams with higher calorific value than the method adopting air as oxygen source.
Three kinds of methods as provided in embodiment 1 are used to prepare HCN.Calorific value from the gaseous waste stream of air, air enrichment and oxygen method provides as follows in table 2.
Table 2
As example, enriched in oxygen stream is adopted to produce the waste streams with calorific value higher significantly as the Andrussow process in the source of oxygen reactant than the Andrussow process adopting air as the source of oxygen reactant.
Embodiment is above intended that schematically, and nonrestrictive.Such as, above-mentioned example (or one or more key element) can combination with one another use.After the above specification sheets of reading, other examples can be used, as used by those skilled in the art.Equally, different characteristics or key element can gather together, also more efficient to make the disclosure simplify.This open feature that should not be interpreted as being intended that failed call protection is important to any claim.But institute's subject matter of an invention can be to be less than in whole features of concrete disclosed example.Therefore, be therefore bonded in embodiment by following claim, wherein each claim is using himself as separable example.The scope of the present disclosure with reference to claims, and should be determined together with the full breadth of the equivalencing of these claim prescriptions.
When having inconsistent usage between this paper with any document be so combined by reference, be as the criterion with usage in this article.
In this article, use term " " or " one ", as common in the patent literature, comprise one or more than one, and have nothing to do with other examples any of " at least one " or " one or more " or use.In this article, unless otherwise noted, use term "or" refer to non-exclusive or, to make " A or B " comprise " A but be not B, " " B but be not A ", and " A and B ".In this article, use term " comprise " and " wherein " " comprise " as corresponding term and " wherein " colloquial language equivalence.Equally, in following claim, term " comprises " and " comprising " is open, in other words, comprise except in the claims list after these terms those except the system of key element, device, article, composition, formula or method appoint be considered to fall into this claim scope within.In addition, in following claim, term " first ", " second " and " the 3rd " etc. only use as mark, and are not intended to give numerical requirements to their object.
Method example described herein can be machinery or computer implemented, at least in part.Some examples can comprise by the computer-readable medium of instruction encoding or machine-readable medium, and described command operating is to configure electron device to carry out method as described in above example or method steps.The realization of this method or method steps can comprise code, as microcode, assembler language code, higher-level language code etc.This code can comprise the computer-readable instruction for carrying out different methods.Code can form a part for computer program.In addition, in an example, code can visibly be stored on one or more volatibility, non-transitory or non-volatile tangible computer computer-readable recording medium, as in the process of implementation or at other times.The example of these tangible computer scale media can comprise, but be not limited to, hard disk, interchangeability disk, interchangeable CD (such as, Zip disk (CD) and digital video disks (DVD)), tape cassete, storage card or rod, random access memory (RAM), read-only storage (ROM) etc.
There is provided summary to meet 37C.F.R. § 1.72 (b), determine character disclosed in technology soon to allow reader.Submit to when being understood that it is explained being not used in or limits scope or the implication of claim.
Although reference example embodiment describes the disclosure, those skilled in the art will recognize that and can carry out in form and details changing and not departing from spirit and scope of the present disclosure.
Herein broadly and generally describe the disclosure.Fall into each disclosing interior narrower species and subgroup general and also form a part of this disclosure.Whether this comprises and has any object is removed in the restriction of conditioned disjunction negative general remark of the present disclosure from general type, and state irrelevant particularly herein with the object got rid of.In addition, when feature of the present disclosure or in describe by Ma Kushi group, it will be appreciated by one of skill in the art that the disclosure is also thus describe with the subgroup of the independent member of any Ma Kushi group or member.
Below statement describes key elements more of the present disclosure or feature.Because the application is provisional application, these statements may change in the preparation of non-provisional application and submission process.If this change occurs, the scope of the equivalents affected according to the claim provided by non-provisional application is not wished in this change.According to 35U.S.C. § 111 (b), claim is optional for provisional application.Therefore, statement of the present disclosure can not be interpreted as the claim according to 35U.S.C. § 112.
Statement of the present disclosure:
1., for preparing a system for prussic acid via Andrussow process, described system comprises:
Reactor zone, wherein allows oxygen, ammonia and methane to react under the existence of catalyzer comprising platinum, to provide the product stream at least comprising prussic acid (HCN), hydrogen and refuse;
HCN recovery zone, wherein removes from described product stream substantially by described prussic acid, to produce prussic acid product and the combustible gas mixture comprising described hydrogen and described refuse; And
Torch district, wherein to major general's combustible gas mixture with hydrogen mode combustion, at least to produce carbonic acid gas and water.
2. the system of statement described in 1, wherein hydrocarbon mixture comprises described methane.
3. the system of statement described in 2, wherein said hydrocarbon mixture comprises Sweet natural gas, biogas, substantially pure methane, or its mixture.
4. the system of statement according to any one of 1-3, described system also comprises hydrogen retrieval system, and described hydrogen retrieval system reclaims at least some hydrogen from least one of described product stream and described combustible gas mixture.
5. the system of statement according to any one of 1-4, described system also comprises ammonia recovery system, and described ammonia recovery system removes ammonia substantially from described product stream.
6. the system of statement according to any one of 1-5, wherein said prussic acid product is at least about the pure prussic acid of 98.5 volume %.
7. the system of statement according to any one of 1-6, wherein said combustible gas mixture comprises at least about 8 volume % hydrogen.
8. the system of statement according to any one of 1-7, wherein said torch has the torch velocity of discharge being less than about 37.2 meter per seconds.
9. the system of statement according to any one of 1-8, wherein said torch has and is less than about V maxtorch velocity of discharge, wherein V maxbe defined as:
V max=(X h2-K 1) * K 2, wherein
V max=maximum permission torch velocity of discharge, meter per second
K 1=constant, 6.0 volume % hydrogen
K 2=constant, 3.9 meter per seconds/volume % hydrogen
X h2=volume % hydrogen, by wet basis, as calculated by use American Society for testing and materials (the American Society for Testing and Materials) (ASTM) method D1946-77.
10. the system of statement according to any one of 1-9, wherein said torch district comprises and is greater than about 1000 DEG C, is greater than about 1200 DEG C, is greater than about 1350 DEG C, is greater than about 1500 DEG C, is greater than about 1600 DEG C, or is greater than the temperature of about 1800 DEG C.
The system of 11. statements according to any one of 1-10, wherein said torch district comprises torch by one's own efforts.
The system of 12. statements according to any one of 1-11, wherein said torch district comprises at least 3.0 inch diameter torch points.
The system of 13. statements according to any one of 1-12, described system also comprises torch stabilizer.
The system of 14. statements according to any one of 1-13, wherein said torch district also comprises Sweet natural gas.
The system of 15. statements according to any one of 1-14, described system also comprises: hydrogen source hydrogen being added to described combustible gas mixture.
The system of 16. statements according to any one of 1-15, described system also comprises the detector of the component quantized in described combustible gas mixture.
The system of 17. statements described in 16, described system also comprises the valve that operability is connected to described detector, when wherein said valve configurations is the set(ting)value when the non-combustibleconstituents lower threshold corresponding to thermal content being detected in described combustible gas mixture, permission hydrogen or methane supplement described combustible gas mixture.
The system of 18. statements described in 16, described system also comprises the valve that operability is connected to described detector, and wherein said valve configurations is when the hydrogen concentration lower than threshold value being detected in described combustible gas mixture, allows to supplement the oxygen being allowed to react.
The system of 19. statements described in 18, wherein said threshold value is based on the thermal content value of described combustible gas mixture.
The system of 20. statements described in 18 or 19, wherein said valve operation is connected to air feed stream.
The system of 21. statements described in 18 or 19, wherein said valve operation is connected to oxygen incoming flow.
The system of 22. statements described in 18 or 19, wherein said valve operation is connected to the air feed stream of enriched in oxygen.
The system of 23. statements according to any one of 1-22, wherein said torch district also comprises the non-hydrogen combustible gas mixture with non-hydrogen mode combustion.
The system of 24. statements described in 23, wherein said non-hydrogen combustible gas mixture comprises the calorific value at least about 200BTU/scf.
The system of 25. statements according to any one of 1-24, wherein said refuse comprises and is less than about 1.5 volume %HCN.
The system of 26. statements according to any one of 1-25, described system also comprises at least one liquid trap of described torch upstream, to remove the liquid that exists in described combustible gas mixture or non-hydrogen combustible gas mixture at least partially.
27. 1 kinds of methods for the refuse produced by Andrussow process that burns, described method comprises:
Oxygen, ammonia and methane is allowed to react under the existence of catalyzer comprising platinum, to provide the product stream at least comprising prussic acid, hydrogen and refuse;
Described prussic acid is extracted, to produce prussic acid stream and the gaseous waste stream at least partially comprising described hydrogen and described refuse from described product stream; And
Described gaseous waste stream is fed to hydrogen pattern torch.
The method of 28. statements described in 27, described method also comprises: extract ammonia from described product stream.
The method of 29. statements described in 27 or 23, described method also comprises: before described extraction stream is fed to described hydrogen pattern torch, by liquid at least partially from described gaseous waste flow point from.
The method of 30. statements according to any one of 27-29, described method also comprises and flows back to receipts hydrogen from described gaseous waste.
The method of 31. statements according to any one of 27-30, described method also comprises: before the described prussic acid of extraction, extract ammonia.
The method of 32. statements according to any one of 27-31, described method also comprises: with gaseous waste stream described in the torch velocity of discharge torch burning being less than about 37.2 meter per seconds.
The method of 33. statements according to any one of 27-32, described method also comprises: to be less than about V maxtorch velocity of discharge torch burning described in gaseous waste stream, wherein V maxbe defined as:
V max=(X h2-K 1) * K 2, wherein
V max=maximum permission torch velocity of discharge, meter per second
K 1=constant, 6.0 volume % hydrogen
K 2=constant, 3.9 meter per seconds/volume % hydrogen
X h2=volume % hydrogen, by wet basis, as calculated by use American Society for testing and materials (the American Society for Testing and Materials) (ASTM) method D1946-77.
The method of 34. statements according to any one of 27-33, described method also comprises: by described gaseous waste stream at the temperature combustion being greater than about 1650 DEG C.
The method of 35. statements according to any one of 27-34, described method also comprises: the stabilizer that applies a torch stablizes described hydrogen pattern torch.
The method of 36. statements according to any one of 27-35, described method also comprises: increase the hydrogen concentration of described gaseous waste stream to increase the calorific value of described gaseous waste stream.
The method of 37. statements according to any one of 27-36, described method also comprises: supplement stream with hydrogen and supplement described gaseous waste stream.
The method of 38. statements described in 36, described method also comprises: increase the described amount allowing the oxygen of reaction.
The method of 39. statements according to any one of 27-37, described method also comprises: the hydrogen concentration detecting described gaseous waste stream; And when detecting that described hydrogen concentration is lower than the amount increasing the oxygen allowing reaction during threshold value.
The method of 40. statements described in 39, described method also comprises: the oxygen concn increasing air feed stream.
System any one of 41. statement 1-40 or described in arbitrary combination or method are optionally configured to make to use or to select described all key elements or operation.
Concrete statement of the present utility model:
1., for preparing a system for prussic acid via Andrussow process, described system comprises:
Reactor zone, wherein allows oxygen, ammonia and methane to react under the existence of catalyzer comprising platinum, to provide the product stream at least comprising prussic acid (HCN), hydrogen and refuse;
HCN recovery zone, wherein removes from described product stream substantially by described prussic acid, to produce prussic acid product and the combustible gas mixture comprising described hydrogen and described refuse; And
Torch district, wherein to combustible gas mixture described in major general with hydrogen mode combustion, at least to produce carbonic acid gas and water.
2. the system of statement described in 1, wherein hydrocarbon mixture comprises described methane.
3. the system of statement described in 2, wherein said hydrocarbon mixture comprises Sweet natural gas, biogas, substantially pure methane, or its mixture.
4. the system of statement described in 1, described system also comprises the hydrogen retrieval system being connected to described reactor zone, and described hydrogen retrieval system reclaims at least some hydrogen from least one of described product stream and described combustible gas mixture.
5. the system of statement described in 1, described system also comprises ammonia recovery system, and described ammonia recovery system removes ammonia substantially from described product stream.
6. the system of statement described in 1, wherein said prussic acid product is the prussic acid that at least 98.5 volume % are pure.
7. the system of statement described in 1, wherein said combustible gas mixture comprises at least 8 volume % hydrogen.
8. the system of statement described in 1, wherein said torch has the torch velocity of discharge being less than 37.2 meter per seconds.
9. the system of statement described in 1, wherein said torch has and is less than V maxtorch velocity of discharge, wherein V maxbe defined as:
V max=(X h2-K 1) * K 2, wherein
V max=maximum permission torch velocity of discharge, meter per second
K 1=constant, 6.0 volume % hydrogen
K 2=constant, 3.9 meter per seconds/volume % hydrogen
X h2=volume % hydrogen, by wet basis, as calculated by use American Society for testing and materials (ASTM) method D1946-77.
10. the system of statement described in 1, wherein said torch district comprises the temperature being greater than 1350 DEG C.
The system of 11. statements described in 1, wherein said torch district comprises torch by one's own efforts.
The system of 12. statements described in 1, wherein said torch district comprises at least 3.0 inch diameter torch points.
The system of 13. statements described in 1, described system also comprises torch stabilizer.
The system of 14. statements described in 1, wherein said torch district also comprises Sweet natural gas.
The system of 15. statements described in 1, described system also comprises: hydrogen source hydrogen being added to described combustible gas mixture.
The system of 16. statements described in 1, described system also comprises the detector of the component quantized in described combustible gas mixture.
The system of 17. statements described in 16, described system also comprises the valve that operability is connected to described detector, when wherein said valve configurations is the set(ting)value when the non-combustibleconstituents lower threshold corresponding to thermal content being detected in described combustible gas mixture, permission hydrogen or methane supplement described combustible gas mixture.
The system of 18. statements described in 16, described system also comprises the valve that operability is connected to described detector, and wherein said valve configurations is when the hydrogen concentration lower than threshold value being detected in described combustible gas mixture, allows to supplement the oxygen being allowed to react.
The system of 19. statements described in 18, wherein said threshold value is based on the thermal content value of described combustible gas mixture.
The system of 20. statements described in 18 or 19, wherein said valve operation is connected to air feed stream.
The system of 21. statements described in 18 or 19, wherein said valve operation is connected to oxygen incoming flow.
The system of 22. statements described in 18 or 19, wherein said valve operation is connected to the air feed stream of enriched in oxygen.
The system of 23. statements described in 1, wherein said torch district also comprises the non-hydrogen combustible gas mixture with non-hydrogen mode combustion.
The system of 24. statements described in 23, wherein said non-hydrogen combustible gas mixture comprises the calorific value of at least 200BTU/scf.
The system of 25. statements described in 1, wherein said refuse comprises and is less than 1.5 volume %HCN.
The system of 26. statements described in 1, described system also comprises at least one liquid trap of described torch upstream, to remove the liquid that exists in described combustible gas mixture or non-hydrogen combustible gas mixture at least partially.

Claims (13)

1. the system of torch for improving in Andrussow process, described system comprises:
Allow the reactor zone of oxygen, ammonia and methane reaction;
Described prussic acid is removed from described product stream the HCN recovery zone producing prussic acid product and combustible gas mixture substantially; And
To combustible gas mixture described in major general with the torch district of hydrogen mode combustion.
2. system according to claim 1, described system also comprises the hydrogen retrieval system being connected to described reactor zone.
3. system according to claim 1, described system also comprises ammonia recovery system.
4. system according to claim 1, wherein said torch district comprises torch by one's own efforts.
5. system according to claim 1, wherein said torch district comprises at least 3.0 inch diameter torch points.
6. system according to claim 1, described system also comprises torch stabilizer.
7. system according to claim 1, described system also comprises: hydrogen source hydrogen being added to described combustible gas mixture.
8. system according to claim 1, described system also comprises the detector of the component quantized in described combustible gas mixture.
9. system according to claim 8, described system also comprises the valve that operability is connected to described detector.
10. system according to claim 9, wherein said valve operation is connected to air feed stream.
11. systems according to claim 9, wherein said valve operation is connected to oxygen incoming flow.
12. systems according to claim 9, wherein said valve operation is connected to the air feed stream of enriched in oxygen.
13. systems according to claim 1, described system also comprises at least one liquid trap of described torch upstream.
CN201320822923.6U 2012-12-18 2013-12-12 The system of the torch improved in Andrussow process Expired - Lifetime CN204057984U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864112A (en) * 2012-12-18 2014-06-18 因温斯特技术公司 Apparatus and method of improved flare in Andrussow process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864112A (en) * 2012-12-18 2014-06-18 因温斯特技术公司 Apparatus and method of improved flare in Andrussow process
CN103864112B (en) * 2012-12-18 2019-01-04 英威达纺织（英国）有限公司 The device and method of the torch improved in andrussow process

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