CN204251332U

CN204251332U - For the system of hydrogen retrieval in Andrussow process

Info

Publication number: CN204251332U
Application number: CN201320821951.6U
Authority: CN
Inventors: 斯图尔特·福赛思; 马丁·J·伦纳; 刘爱国; 布伦特·J·斯塔尔曼
Original assignee: Invista Technologies SARL Switzerland
Current assignee: Invista North America LLC
Priority date: 2012-12-18
Filing date: 2013-12-12
Publication date: 2015-04-08
Anticipated expiration: 2023-12-12
Also published as: TWM490479U

Abstract

The method and system being used for reclaiming hydrogen from the method for the preparation of prussic acid is described herein.

Description

For the system of hydrogen retrieval 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 FOR HYDROGENRECOVERY IN AN ANDRUSSOW PROCESS) for hydrogen retrieval in Andrussow process " of the application's claim 2012 submission in 18, on December, the right of priority of 860, it is openly combined in this with its full content by reference.

Technical field

The disclosure relates to the hydrogen retrieval of the Andrussow process for being prepared prussic acid (HCN) by methane, ammonia and oxygen.

Background technology

Peace moral Rousseau reaction is at suitable catalyzer, as carried out under the existence of the catalyzer containing Pt, as follows:

2NH ₃+2CH ₄+3O ₂→2HCN+6H ₂O

Comprise gaseous ammonia incoming flow, the reactant gas incoming flow of gaseous methane incoming flow and gaseous oxygen incoming flow reacts to form the prussic acid (HCN) in product stream and water under the existence of catalyst made from platonic.But reaction is not carried out with 100% efficiency, and product stream is except containing except prussic acid, also containing other compounds multiple, as unreacted ammonia, unreacted methane, carbonic acid gas, carbon monoxide, water, nitrogen, hydrogen and multiple organic nitrile.

When using pure oxygen substantially, instead of air as oxygen source for Andrussow process time, waste streams can hydrogen containing significant proportion.This waste streams is waste by the disposal of torch burning.

Many aspects 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 ProposedCyanide Manufacturmg NESHAP) (in May, 2000) prepared by proposed prussiate, http:// nepis.epa.gov/Exe/ZvPDF.cgi? Dockey=P100AHG1.PDFcan obtain online, relate to the preparation of HCN, final utilization and economic impact; N.V.Trusov, the impact (Effect of SulfurCompounds and Higher Homologues of Methane onHydrogen CyanideProduction 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) ExecutiveBoard), UNFCCC (United Nations Framework Convention on Climate Change) (United Nations Framework Conventionon Climate Change) (UNFCCC), Clean Development Mechanism PDD form (CleanDevelopment 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 thetransfer of hydrogen cyanide manufacturing technology) is guaranteed in the transfer of prussic acid technology of preparing, J.of HazardousMaterials, 142nd volume, 677-84 page (2007) relates to the safety preparation of HCN.

Utility model content

The problem of wasting hydrogen in Andrussow process is by from waste gas recovery hydrogen instead of such as solved by its torch burning or improve.Hydrogen retrieval from the waste streams of Andrussow process is passable, such as, provides whole hydrogen needs of hexamethylene-diamine production unit substantially.Therefore, hydrogen retrieval can eliminate the needs for steam reformer, described steam reformer otherwise may need for being prepared by the hydrogen of the hydrocarbon fuel bought (such as, Sweet natural gas, propane, coal gas, wet goods).Therefore hydrogen retrieval from Andrussow process can be reduced to the carbon emission in air and provide substantial cost savings to HCN manufacturers.

But not every peace moral Rousseau equipment maybe can should be suitable for hydrogen retrieval.For making hydrogen retrieval attractive economically, Andrussow process can not be carried out with air as its gaseous oxygen incoming flow.On the contrary, only when adopt enriched in oxygen or oxygen peace moral Rousseau's method time, hydrogen retrieval is just attractive economically.Although when use enriched in oxygen or oxygen incoming flow as oxygen source for Andrussow process time, waste streams can hydrogen containing significant quantity, and the use of this enrichment oxygen source can provide various problems.

Use enriched in oxygen or some problem easy understand of oxygen incoming flow.Such as, enriched in oxygen and the incoming flow of pure oxygen substantially more expensive than air.Concentrated oxygen source and the waste streams containing high-caliber hydrogen are easily lighted, especially at the high temperature (about 850 DEG C to about 2,500 DEG C, or about 1000 DEG C to about 1,500 DEG C) for Andrussow process.Enriched in oxygen or oxygen Andrussow process can need than adopting air as the additional security prevention and corntrol of the Andrussow process of its gaseous oxygen incoming flow.Hydrogen is highly combustible and by the concentration in atmosphere at wide region, such as, burns under 4% to 75 volume %.Can adopt usually not use in air Andrussow process or need equipment de-sign, maintenance of the equipment and operational condition, with solve when hydrogen retrieval is entered with enriched in oxygen or oxygen Andrussow process combines time produced problem.

Exist little enriched in oxygen or oxygen peace moral Rousseau Preparation equipment.Except more easily manifest to enriched in oxygen or oxygen pacify the relevant misgivings of moral Rousseau Preparation equipment as described above except those, there is the other problem being much not easy or extensively knowing.

Such as, enriched in oxygen or oxygen Andrussow process more responsive to the change in the concentration of reactant than adopting the Andrussow process of air.Enriched in oxygen or change larger in method efficiency that change in oxygen Andrussow process on the concentration of reactant or flow velocity can cause than observing in air Andrussow process.Enriched in oxygen or oxygen Andrussow process more responsive to the change on the calorific value of feed gas; Change little on the composition of incoming flow can cause temperature fluctuation larger in the reactor observed for incoming flow composition similar in air Andrussow process.Localized variation in the concentration of the reactant of contact catalyst can cause the temperature variation in catalyst bed, and as focus, it compares the life-span that can reduce catalyzer with air Andrussow process.Enriched in oxygen or oxygen Andrussow process can also need other security controlling feature, such as, to avoid the problem of lighting or exploding.In air about 78% nitrogen existence under for the gaseous mixture in diluent air Andrussow process, it not only reduces the danger of lighting but also reduces the generation of by product and the needs for the reaction controlling improved.

From enriched in oxygen or the heat trnasfer of effluent of oxygen Andrussow process cause the more problem being compared to air Andrussow process and observing.From enriched in oxygen or the effluent of oxygen Andrussow process denseer than air Andrussow process.Although this dense effluent cooling preferably promptly carried out forming by product with stopped reaction thing, effluent should be cooled to the condensation point of HCN, because HCN has larger polymerization tendency upon condensation.HCN polymerization can cause blast, and especially enriched in oxygen or in oxygen Andrussow process use insurance with control and avoid this problem.

Enriched in oxygen or oxygen Andrussow process tend to carry out in more concentrated mode than air Andrussow process.So, enriched in oxygen or oxygen Andrussow process tend to produce whole products of greater concn, comprise by product.Therefore, for enriched in oxygen or the reactor of oxygen Andrussow process and relevant device impurity is more easily accumulated in systems in which, can more easily blow out in the equipment that described impurity adopts in air Andrussow process.Larger byproducts build-up speed may cause frequently closedown and the maintenance of multiple parts of erosion rate increase and technique.The equipment that may be affected significantly by byproducts build-up, corrosion and associated problem comprises, such as, and one or more reactor, one or more ammonia recovery system and one or more HCN recovery system.

Although the equipment needed for the preparation of the HCN of equivalent for enriched in oxygen or oxygen Andrussow process be compared to air Andrussow process can compacter (less), a lot of manufacturers is by selection operation air Andrussow process, wherein hydrogen retrieval is unworthy economically, with avoid to enriched in oxygen or problem that oxygen Andrussow process is relevant.By hydrogen retrieval and enriched in oxygen or oxygen Andrussow process combine relevant problem and be not described in well in existing document, and difficulty is enough large to make most of manufacturers can not attempt this combination.

But benefit can be huge unexpectedly.Such as, adopt from enriched in oxygen or the available hydrogen of oxygen Andrussow process reclaims, cost prepared by adiponitrile can reduce 10%, or 20%, or 30%, or 40%, or more.

The benefit solved these and other problems is realized by method and system described herein.

This document describes that a kind of gaseous waste from Andrussow process flows back to the method receiving hydrogen, described method comprises:

(a) adjustment kit containing the reaction mixture of methane, ammonia and oxygen to provide sufficient oxygen to reaction mixture, to produce the gaseous waste stream with at least 40% hydrogen after the recovery removing with prussic acid of ammonia; And

B () is drifted except component is to produce the hydrogen reclaimed from gaseous waste.

System described herein comprises:

(a) reactor, described reactor configurations is used under the existence of platinum catalyst, preparing prussic acid by the reaction mixture comprising methane, ammonia and oxygen, and wherein reactor produces the gaseous product stream comprising prussic acid; With

B () hydrogen retrieval system, described hydrogen retrieval system configuration is from ammonia and prussic acid are being flowed back to receipts hydrogen from the gaseous waste produced after gaseous product stream removes substantially.

The reactor of system can also be configured to reaction mixture provide sufficient oxygen with produce ammonia remove and prussic acid recovery after there is the gaseous waste stream of at least 40% hydrogen.

Accompanying drawing explanation

Fig. 1 example comprises the exemplary peace moral Rousseau system of hydrogen retrieval unit.

Fig. 2 example operability can be connected to the exemplary hydrogen retrieval system of pacifying moral Rousseau preparation system.

Embodiment

The disclosure by use hydrogen retrieval method and system described herein solve safely from enriched in oxygen or oxygen Andrussow process product stream hydrogen waste loss problem.By prussic acid from enriched in oxygen or oxygen peace moral Rousseau reacting product stream be separated after can there is a large amount of hydrogen remaining gaseous waste stream.

Andrussow process

In the process of Andrussow process, comprise gaseous ammonia incoming flow, gaseous methane incoming flow and gaseous oxygen incoming flow reactant gas incoming flow reaction to form the product stream containing prussic acid and water.This reaction is described in by pacifying moral Rousseau the United States Patent (USP) 1,934 published on November 14th, 1933, in 838, and is described in United States Patent (USP) 3 by Jenks, 164, in 945.

Andrussow process can use the multiple source for gaseous oxygen incoming flow to carry out.Such as, gaseous oxygen incoming flow can be the mixture of pure oxygen, oxygen and rare gas element, and the mixture of air and oxygen.Usually, the oxygen of larger in gaseous oxygen incoming flow per-cent will provide the hydrogen of per-cent larger in gaseous waste stream.Such as, the Andrussow process as the gaseous oxygen incoming flow of pure oxygen is substantially adopted can to produce the gaseous waste stream with as many as 70-80% hydrogen.But, adopt air in its waste streams, to have significantly less hydrogen as the Andrussow process of its gaseous oxygen incoming flow, such as, few to 15-18%.Therefore, from use enriched in oxygen or substantially pure oxygen gas can be more be added with economic attractiveness than from this recovery using air as the Andrussow process of its gaseous oxygen incoming flow as the hydrogen retrieval of Andrussow process containing oxygen incoming flow.Such as, hydrogen retrieval cannot carry out valuably together with air Andrussow process.

As used herein, air Andrussow process uses air as containing oxygen incoming flow, and it has about 20.95 % by mole of oxygen.The Andrussow process of enriched in oxygen uses has about 21 % by mole of oxygen to about 26%, 27%, 28%, 29%, or to about 30 % by mole of oxygen, according to appointment 22 % by mole of oxygen, 23%, 24%, or about 25 % by mole of oxygen containing oxygen incoming flow.

Oxygen Andrussow process uses has about 26 % by mole of oxygen, 27%, 28%, 29%, or about 30 % by mole of oxygen to about 100 % by mole of oxygen containing oxygen incoming flow.Oxygen Andrussow process can also use has about 35 % by mole of oxygen, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99%, 99.9%, 99.99% or about 100 % by mole of oxygen containing oxygen incoming flow.

Some organic substances can be had containing oxygen charging, but be only in a small amount.Such as, oxygen charging can have and is less than 2.0% organic substance, or is less than 1.0% organic substance, or is less than 0.5% organic substance, or is less than 0.1% organic substance.This organic substance can produce carbonic acid gas, carbon monoxide, alkane (except methane), and higher hydrocarbon.The by product reduced in the Rousseau's reaction of peace moral and product handling facilities containing the organic substance reduced in oxygen incoming flow is formed and carbon accumulation.

In different examples, in the Andrussow process of enriched in oxygen or adopt have be less than 100 % by mole of oxygen containing in the oxygen Andrussow process of oxygen incoming flow can by air be mixed with oxygen containing oxygen incoming flow, by by the gas of oxygen and any appropriate or the combined hybrid of gas, or by producing from oxygen-containing gas composition as air removes one or more gas.

Methane feed stream can comprise some impurity, such as, and the alkane with 1-4 carbon atom of low per-cent, carbonic acid gas, nitrogen, oxygen, and their combination.Such as, Sweet natural gas can be methane source, but in Sweet natural gas, the type of impurity can change with amount.But the use with the methane feed stream of the impurity of remarkable per-cent can cause the carbon accumulation on platinum catalyst.The higher hydrocarbon of even low per-cent, such as, with about 96% volume/volume methane blended, can cause some carbon accumulations, and it reduces HCN yield, and if continue, causes the physical decomposition of catalyst structure.Although there is little carbon accumulation with pure methane incoming flow, this carbon accumulation is relatively slow, and yield and transformation efficiency only leniently reduce, and catalyzer can continue several moon.Such as, methane feed stream containing being greater than about 2% alkane, and/or should not be not more than about 2% carbonic acid gas, and/or is not more than the hydrogen sulfide of 2%, and/or is not more than about 3% nitrogen, and/or is not more than about 2% carbonic acid gas.Impurity can be removed from methane feed by available program.In methane, the minimizing of impurity can reduce hydrogen retrieval can be made to become complicated by product and the formation of impurity.

Substantially pure methane is usually available, and can enriched in oxygen or use in oxygen Andrussow process.This substantially pure methane can be 95% methane, or 98% methane, or 99% methane.Substantially pure methane can have and is less than 100ppm impurity, or is less than 10ppm impurity, or the impurity of even below 1ppm.

Ammonia charging can containing some moisture and/or trace air or oxygen.This trace comprise total gas composition up to but be not more than 2 volume %.But the oxygen of remarkable per-cent and/or water can cause problem can the aqua ammonia of parts of etching reactor or moisture trap as formed.Therefore, if there is high-caliber oxygen in charging, ammonia charging can be processed so that the total content of oxygen is reduced to 1 below volume %.In the case of water, ammonia incoming flow can containing mix with ammonia up to 5 volume % water vapors, or up to 2 volume % water vapors.Ammonia incoming flow can also be 90% ammonia, or 95% ammonia, 99% ammonia or 100% ammonia.

Prussic acid by the synthesis of Andrussow process (see, such as, Ullmann ' s Encyclopedia ofIndustrial Chemistry, 8th volume, VCH Verlagsgesellschaft, Weinheim, 1987,161-162 page) can carry out on the catalyzer comprising platinum or platinum alloy or other metals in the gas phase.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.Such as, pacify moral Rousseau describe can comprise platinum, iridium, rhodium, palladium, osmium, gold or silver-colored as or the catalyzer of 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.

In development subsequently, 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 85/15Pt/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.

German Patent 549 is described in, in 055 to the further information of Andrussow process.In an example, at about 800 to about 2,500 DEG C, 1,000 to 1,500 DEG C, or the temperature use of about 980 to 1,050 DEG C comprises 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.

From pacifying moral Rousseau reactor product stream out except containing except prussic acid, also containing multiple compounds, as unreacted ammonia, unreacted methane, carbonic acid gas, carbon monoxide, water, nitrogen, hydrogen and multiple organic nitrile.

For purifying prussic acid, typically first removing the ammonia in product stream, is that prussic acid is separated afterwards.Remaining gaseous waste stream contains the hydrogen that methods, devices and systems described herein can be used to be separated.

Ammonia removes/recirculation

Exit gas from peace moral Rousseau reactor is called product stream herein.This product stream contains HCN and ammonia, and other compounds and gas are as hydrogen, unreacted methane, carbonic acid gas, carbon monoxide, water, nitrogen, multiple organic nitrile and other compounds.For removing the ammonia that its recirculation can be returned in peace moral Rousseau reaction, product stream can be fed to ammonia absorber unit.This ammonia absorber unit can contain the solution of absorbing ammonia, such as, and ammonium phosphate solution, phosphoric acid solution or sulphuric acid soln.

An example of operable ammonium phosphate solution comprises the compound with following formula:

(NH ₄) _nH _3-nPO ₄

N is the number of about 0-3 simultaneously.NH ₃with H ₃pO ₄mol ratio, with temperature, and in product stream other components (such as, water) concentration together, the solution that can affect is for the capacity of absorbing ammonia.Usually, wherein n lower than 1.5 solution there is the ammonia of minimizing and the solution that can be greater than 1.5 than the wherein n of the ammonia with higher amount absorbs more ammonia.The gaseous stream leaving ammonia absorber is called half purified product stream and can is hydrogen source.

After the absorption of ammonia, form rich ammonia ammonium phosphate solution.This rich ammonia ammonium phosphate solution can have, such as, and the ammonium ion higher than 1.5 and phosphate anion ratio.Rich ammonia ammonium phosphate solution can be fed in ammonia stripper unit.Ammonia stripper unit can be the distillation tower with multiple column plate.Heat can be provided to force ammonia from the desorb of rich ammonium phosphate solution by the reboiler section of distillation tower.Rich ammonium phosphate solution can be transformed back poor ammonium phosphate solution by the method.

The stream of ammonia and water vapour can leave the top of ammonia stripper unit.Can by ammonia recirculation or re-use in peace moral Rousseau reaction.The stream of poor ammonium phosphate solution can flow out ammonia stripper unit, or is pumped in cooling unit to produce the stream of the poor ammonium phosphate solution of cooling.

After the removing, only the ammonia of a small amount of typically remains in the half purified product stream containing HCN.Such as, be less than about 5% volume/volume, or be less than about 4% volume/volume, or be less than about 3% volume/volume, or be less than about 2% volume/volume, or be less than about 1% volume/volume, or be less than about 0.5% volume/volume, or the residual ammonia being less than about 0.1% volume/volume typically remains in the half purified product stream containing HCN.In some cases, the ammonia in half purified product cannot by typical program as detected to hydrochloric acid or sulfuric acid by using Nessler's solution (when ammonia exists for yellow) or absorbing.

HCN reclaims

HCN can be reclaimed from half purified product stream (such as, after ammonia removes) by multiple programs.Such as, after the removing of ammonia, can half purified product stream be delivered to by HCN absorber unit, add cold water to take away HCN at this.HCN-water mixture can be delivered to prussiate stripper afterwards, can by refuse from liquid removal at this.In addition, HCN-water mixture can also be delivered to by fractionator with concentrated HCN, afterwards by product storage in groove or be directly used in the synthesis of other compounds.

Hydrogen is flowed back to receipts from the gaseous waste stayed after HCN removes.Removing of HCN is typically substantially complete, not only makes valuable HCN not lose to waste streams, and for healthy and environmental concerns.

Hydrogen retrieval

At ammonia and prussic acid from after the removing of peace moral Rousseau product stream, leave the off-gas stream containing multiple gases, described gas comprises the HCN of hydrogen, unreacted methane, carbonic acid gas, carbon monoxide, water, nitrogen, multiple organic nitrile and trace.In off-gas stream, the amount of these gases can depend on peace moral Rousseau's reaction conditions and change.The variable that can affect the composition of off-gas stream comprises the ratio of the amount of oxygen in peace moral Rousseau reaction, methane and ammonia, the temperature of reactor, catalyst efficiency, enters and pass through to pacify the flow etc. of moral Rousseau reactor.

Such as, when using pure oxygen as the reactant in Andrussow process and reaction conditions is usually optimized, can exist up to about 75% (volume/volume) hydrogen in waste streams, but when adopt air as pacify moral Rousseau reaction oxygen source time, only can there is about 1.5% (volume/volume) hydrogen in waste streams.Therefore, the gaseous state to peace moral Rousseau reactor contains oxygen incoming flow can contain wide per-cent oxygen relative to other gases, and still provides significant hydrogen in gaseous waste stream.

Hydrogen can thus obtain gainfully, not only from use 100% oxygen as containing the Andrussow process of oxygen incoming flow, and be less than 100% oxygen from employing and react as the peace moral Rousseau containing oxygen incoming flow.Such as, hydrogen can derive from and adopt the peace moral Rousseau of the mixture of oxygen and other gas (such as, nitrogen or argon) to react, or derives from the peace moral Rousseau reaction of the air adopting enriched in oxygen.When by oxygen and other gas and vapor permeation, those other gases usually only comprise low-level carbon compound (except methane).If to measure existence significantly, carbon compound such as alkane and hydrocarbon can cause pacifying the carbon accumulation in moral Rousseau's reactor apparatus and catalyzer.Therefore, carbon compound is being avoided containing in oxygen incoming flow.

When Andrussow process be suitable for adopting the oxygen containing the level slightly higher than air containing oxygen incoming flow time, methods, devices and systems described herein can be particularly useful.Such as, this can containing at least about 25% oxygen containing oxygen incoming flow, at least about 30% oxygen, at least about 40% oxygen, at least about 50% oxygen, at least about 60% oxygen, at least about 70% oxygen, at least about 80% oxygen, at least about 90% oxygen, at least about 95% oxygen, at least about 98% oxygen, at least 99% oxygen, at least 99.9% oxygen, or at least 99.99% oxygen.Can also adopt substantially pure oxygen as containing oxygen incoming flow.

The efficiency of Andrussow process can depend on factor and change, described factor as the balance of the optimum of ammonia and the purity of methane feed stream, the effect of catalyst bed and/or age, the temperature of peace moral Rousseau reaction, the shape of reactor and mixed nature, adjustment and maintenance reactant feed flow the measure of caution that adopts, and their combination.Therefore, can adopt method for assessment of the oxygen containing what ratio in oxygen incoming flow be enough to make hydrogen retrieval attractive economically.The method can comprise: at a series of Andrussow process separated (such as, in parallel or series operation) change to about 100% by containing the volume percent of oxygen in oxygen incoming flow by about 35% in process, and determine hydrogen per-cent in the gaseous waste stream from each Andrussow process; And identify the volume percent (X per-cent oxysome amasss) of the oxygen producing about 40% hydrogen in exhaust flow.It is be enough to make the hydrogen retrieval attractive ratio containing oxygen in oxygen incoming flow economically that this X per-cent oxysome amasss.

The gaseous waste stream stayed after ammonia and HCN remove can containing multiple compounds as unreacted ammonia, unreacted methane, carbonic acid gas, water, carbon monoxide, water, nitrogen, hydrogen and organic nitrile.Gaseous waste stream can valuably containing the nitrogen than the lower amount existed in air.Such as, gaseous waste stream containing being less than about 60% nitrogen, can being less than about 50% nitrogen, being less than about 40% nitrogen, being less than about 30% nitrogen, being less than about 20%, or be less than about 10%.

Gaseous waste stream remaining after removing at ammonia and HCN can be processed to produce in many ways the hydrogen of the recovery with required purity.Such as, component can be flowed through from gaseous waste and comprise pressure-variable adsorption (absorption), selective membrane, amine washing (absorption), deep cooling purifying, water gas shift reaction, or the method for their combination removes.Water-content in gaseous waste stream can by gaseous waste flow through by Dehumidifying element as condenser by reduce.Removing of water or can occur in other purification step processes afterwards.But, can more effectively be flow through by the absorption of some types, absorption at gaseous waste and remove water containing before the passing through of film unit.

Pressure-variable adsorption (PSA) comprises the mixture of selected species of gases from gas under stress according to the molecular characterization of species and being separated of the affinity for sorbent material.Pressure-variable adsorption can operate close to envrionment temperature and therefore be different from the deep cooling distillation technique of gas delivery.Sorbing material (such as, zeolite) can use as molecular sieve in pressure-swing adsorption process, and depends on sorbing material, and impurity or object gas species typically absorb at high pressure.Can change after the method to low with from sorbent material desorption of impurities or object gas species.Therefore, pressure-variable adsorption can be adopted so that the feed gas comprising stronger adsorbable component and not stronger adsorbable component is separated into the non-adsorbed stream of enrichment and the absorption stream of enrichment on stronger adsorbable component on not stronger adsorbable component.

PSA sorbing material can be the base film of film, particle, crystallization, pellet, bead, nanotube, fiber, sieve, dish, matrix, mixing, and the form of their combination.This material can be placed in one or more towers, bed, pipe or other containers in psa unit.

PSA sorbing material can comprise gac, graphite, silicon-dioxide, aluminum oxide, zeolite, metal (such as, platinum or palladium), and their combination.Wetting ability and polar compound (as oxygenatedchemicals) passable, such as, be adsorbed to silica gel and zeolite.Hydrophobic compound (as alkane and other carbon-rich compounds) is passable, such as, is adsorbed to gac and graphite.Compound based on polymkeric substance is passable, and such as, adsorbed by the porous polymer matrix with polarity or non-polar functional group, described porous polymer matrix is suitable for adsorbing the polymkeric substance that can be connected to this functional group.

Silicon-dioxide may be used for heavy nonpolar hydrocarbon from the drying (water removes) of gaseous waste stream and absorption.Silicon-dioxide is the SiO of unreactiveness, nontoxic, polarity and dimensional stabilizing (< 400 DEG C or 750 °F) amorphous form ₂.It can be prepared in the following manner: the reaction between water glass and acetic acid, is that a series of post-treating method is as aging, pickling, washing and drying afterwards.Silicon-dioxide as sorbing material can have different pore size distributions, and aperture can be suitable for contributing to getting rid of or comprise the molecule selecting size.

Zeolite also may be used for gaseous waste stream drying (water removes) and for removing carbonic acid gas and carbon monoxide.Zeolite by water glass, alumina trihydrate and sodium hydroxide being mixed, and can allow mixture gelation and/or crystalline.After wash crystallization, they can experience cationic exchange with by other positively charged ions of sodium as calcium, potassium or some metal ions replace.The composition of this synthetic zeolite can be controlled, to make it possible to select cationic type.This zeolite can have the aluminium than silicon-dioxide less amount, and there is no iron.Zeolite can also not have cadmium.Nonpolar (siliceous) zeolite can synthesize by without aluminium silica source or by containing the dealuminated of aluminium zeolite.The dealuminated temperature can passing through to be raised by zeolite water vapor, is typically greater than 500 DEG C (930 °F) process and carries out.This high-temperature thermal treatment can make aluminium-oxygen bond rupture, to make aluminium atom pull out from zeolite framework.The pore size distribution that zeolite is all right different, and aperture can be suitable for helping to get rid of or comprise the molecule selecting size.

Activated carbon may be used for the absorption of organism and nonpolar adsorbate.Gac is one of the most widely used sorbent material, because can regulate its major part chemistry (such as surface group) and physical properties (such as pore size distribution and surface-area) according to required.Its validity is also from its large micropore (and sometimes mesopore) volume and the high surface area that obtains.

In an example of pressure swing absorption process, hydrogen minimum whole other impurity to be removed from hydrogen by absorbed component.Polarity or poiarizable compounds as carbonic acid gas and water normally than a nonpolar class as methane with nitrogen is easy removes.But if psa unit does not optimally operate, carbon monoxide and oxide gas typically are the first impurity seen in the hydrogen stream of purifying, because carbon monoxide and nitrogen typically have only secondary minimum adsorption rate.

Such as, after the removing of component of water and other easily condensations, can by hydrogen from gaseous waste flow through via one or more psa unit by reclaiming to remove unwanted component.Undesirable component can at least about 12 bar (definitely) pressure, or at least about 13 bar pressures, or at least about 14 bar pressures, or adsorb at least about under the pressure in the scope of 15 bar pressures.Such as, unwanted component can with about 12 bar to about 40 bar, or about 15 bar extremely about 20 bar absolute pressures be adsorbed in pressure-variable adsorption material.By after one or more psa unit, hydrogen can be at least 90% pure, or at least 95%, or at least 99%, or at least 99.9% is pure.By unwanted component from one or more psa unit desorb, can be able to re-use to make these unit.The desorb of unwanted component can realize to about 10 bar absolute pressures by pressure being reduced to about 1 bar absolute pressure.

The sorbing material that can be used for hydrogen retrieval comprises the zeolite containing calcium oxide (CaO), alkaline hydrated aluminium silicate, with and composition thereof.Aluminium content can be less than dioxide-containing silica.Although zeolite can have some metals as platinum and/or palladium, zeolite typically only has iron in a small amount or does not substantially have iron or cadmium.Such as, zeolite containing being less than 1.0 % by weight iron, or can be less than the iron of 0.7 % by weight, or is less than 0.5% iron, or is less than the iron of 0.3 % by weight, or is less than 0.1% iron.This zeolite can comprise multiple aperture, as there are about 3 dusts to about 7 dusts, or the hole of the diameter of about 4 dust to 5 dusts.These zeolites can remove water from gas stream, carbonic acid gas, sulfurous pollutants and other components.

The example that can be suitable for the pressure-variable adsorption agent system of method and system described herein comprises those that provided by UOP (Honeywell).Such as, pressure-variable adsorption agent can comprise zeolitic material as derived from those of UOP.Such as, at least two kinds of different materials can be adopted to remove components different in gaseous waste stream.The sorbent material of at least one type can be adopted to remove organic constituent as the HCN of remnants, methane and organic nitrile.The sorbent material of at least one other types can be used to remove other components as nitrogen, carbon monoxide, carbonic acid gas etc.This material can use (website see uop.com/processing-solutions/refining/hydrogen-managemen t/ place) in PolybedPSA System.UOP Polybed PSA System be wherein by the impurity in the stream (steam) containing hydrogen at High Pressure Absorption and subsequently in the circulation means that low pressure is discharged.

Gaseous mixture can also by the selectivity separation by diffusion via film.By gas concentration, can place under stress, or experience pressure gradient.Separation can occur with the difference in thermodynamics distribution or equilibrium property via transporting of component of mixture in mould material.Such as, the distribution of film mesoporous can be suitable for the consideration for the diameter of component molecular in gaseous waste stream, is realized by molecular repulsion or molecular screening to make to be separated.In much bigger aperture, when its mesoporous reaches the mean free path of component molecular in gaseous waste stream, exert gloomy (Knudsen) diffusion and can occur and be separated can being realized by the collision of molecule and hole wall.See, such as, Knudsen, Ann Phys28:75 (1908); Gilron & Soffer, J.Membr Sci209 (2): 339-352 (2002); Zalc etc., Chem EngSci59 (14): 2947-60 (2004).

When the molecular diameter of the crucial component of mixture that being greater than at least partially in porous material will be separated, but enough not large to make significant Knudsen diffusion occur time, close mutually diffusion can occur.When pressure, temperature and gas composition make specific components in mixture can owing to Kelvin or capillary condensation in hole during condensation, therefore these components as liquid condensation diffuse through hole under capillary pressure gradient, can realize the separation of gaseous mixture.In some porous semi-permeable membraness, porous adsorbing material optionally adsorbs at least one of the main ingredient in gaseous waste stream of signal portion, the component adsorbed is spread by the surface flow of passing hole in Adsorption Phase owing to the adsorbed phase concentration gradient set up by the pressure gradient of crossing over film, and at least one of diffusing products therefore enrichment main ingredient.The existence of adsorbing main ingredient in hole hinders the diffusion of accessory constituent compared with low strength absorption or non-adsorbed, to make not spread or non-absorptive portion enrichment accessory constituent.The main mechanism of this separation is the mechanism of Adsorption Phase surface flow.This film can operate under certain temperature or pressure, higher than this temperature or lower than this pressure, can occur Kelvin or capillary condensation for interested gaseous mixture.Therefore this film is suitable for the separation of non-condensable gas mixture.

Table 1 lists the molecular diameter of the different kinds of molecules that can exist in off-gas stream.This molecular diameter is defined as kinetic diameter σ herein, it is by D.W.Breck, ZEOLITE MOLECULARSIEVES, 633-645 page, and the table 8.14 at the 636th page of place, Kruger Publishing Co. (1984) describes in more detail, and its content is combined in this with its full content by reference.

Table 1

Component	Molecular diameter σ, dust
		Helium	2.6
Hydrogen	2.89
		Carbonic acid gas	3.3
Oxygen	3.46
		Nitrogen	3.64
Carbon monoxide	3.76
		Methane	3.8
Ethene	3.9
		Propane	4.3
Normal butane	4.3

Film may be used for receiving from the elimination of gaseous waste stream, absorption or removing the component of different size.Such as, the molecular sieve that may be used for the type absorbing water vapour is 4A molecular sieve, and it has the aperture of 4 dusts.Usually can not adsorb the molecule being greater than arbitrarily 4 dusts.By the absorption of 4A molecular sieve generally than the molecular sieve of some other types or sorbent material better and more conventional, because 4A molecular sieve uses less energy and do not have significant deleterious effects to gaseous feed.4A molecular sieve can derive from multiple supplier, as Delta Adsorbents (such as, see, the website at deltaadsorbents.com place) or Texas Technologies Inc. (see, such as, the website at texastechnologies.com place).

Can be amine washing from drift another method of removing of gaseous waste by unwanted component.Amine washing comprises gaseous waste and flows through passing through by the aqueous solution of multiple alkylamine, to remove hydrogen sulfide (H ₂and carbonic acid gas (CO S) ₂).Operable alkylamine comprises monoethanolamine, diethanolamine, methyldiethanolamine, Diisopropylamine, aminoethoxyethanol (amunoethoxythanol), with and composition thereof.The concentration of alkylamine can be changed to about 75% from about 5%.But the different alkylamine of different concentration can be effective to remove different waste components.Although peace moral Rousseau reaction can produce carbonic acid gas and the carbon monoxide of significant quantity, hydrogen sulfide can not exist with any significant amount.Therefore, for removing of carbonic acid gas and carbon monoxide, can with about 25% to about 45%, or about 30% to about 35%, or adopt monoethanolamine in the concentration of about 32%.When using diethanolamine, about 10% to about 30%, or the concentration of about 20% to about 25% may be used for removing carbonic acid gas and carbon monoxide.When adopting methyldiethanolamine, about 25% to about 60%, or the concentration of about 30 to about 55% may be used for removing carbonic acid gas and carbon monoxide.When using diglycolamine, about 40% to about 60% can be adopted, or about 45% to about 55%, or the concentration of about 50% is used for removing carbonic acid gas and carbon monoxide.

Tower or groove by the tower containing amine washings or groove, wherein can be heated to about 30 DEG C to about 60 DEG C by gaseous waste stream, or the temperature of about 35 DEG C to about 50 DEG C.

For hydrogen retrieval, deep cooling purifying typically comprises by applying pressure and cool gaseous state waste streams to make unwanted gaseous component condensation or absorption leave hydrogen.Sorbent material can be used if gac is to promote removing of refuse.A series of tower or absorbing unit can be used to obtain the hydrogen product with lower level pollutent.

For drifting except carbon monoxide from gaseous waste, water gas shift reaction can be adopted.When heating together with catalyzer, water and carbon monoxide in water-gas reacting condition process chemical combination to produce carbonic acid gas and hydrogen.

CO+H ₂O→CO ₂+H ₂

This reaction is that some is temperature sensitive and can comprise two steps: high-temperature step and lesser temps step.Comparatively high temps step can at about 325 DEG C to about 375 DEG C (such as, about 350 DEG C) use to comprise and carry out with the catalyzer of the ferric oxide of chromic oxide co catalysis, and lesser temps step can at about 180 DEG C to about 22 DEG C, or about 190 DEG C of catalyzer to about 210 DEG C of copper be used on the mixed carrier comprising zinc oxide and aluminum oxide carry out.

The combination of step can be adopted to promote hydrogen retrieval.Such as, first gaseous waste stream can be compressed, by any liquid removal of condensation in side cooler, the gaseous waste of compression can be flow through filter, and afterwards can by the gas feed of remainder to one or more psa unit.Water gas shift reaction can be adopted to increase the yield of hydrogen.Except adopting pressure change, can by psa unit cooling to promote the absorption in high pressure phase process and more optimally unwanted component chelating to be left the hydrogen do not adsorbed.Can adopt and there is or do not have cooling module to cool a series of psa units of sorbing material.

Although the hydrogen reclaimed needs not be 100% pure, at least most carbonic acid gas, carbon monoxide and nitrile are suitable from removing of hydrogen, to avoid when using the hydrogen that reclaims such as, for by product during hydrogenation and pollutent.Such as, method and apparatus described herein can reclaim hydrogen product from the preparation of gaseous waste stream, and wherein reclaimed hydrogen can be at least about 80% hydrogen, or at least about 85% hydrogen, or at least about 90% hydrogen, or pure at least about 91%, or it is pure at least about 92%, pure at least about 93%, or pure at least about 94%, or pure at least about 95%, or it is pure at least about 96%, pure at least about 97%, or pure at least about 98%, or at least about 99% pure hydrogen.The methane of some traces or nitrogen can be acceptable in hydrogen product.

The hydrogen reclaimed can use in hydrogenation (such as, with hydrogenation saturation of olefins, alkynes or the hydrocarbon with saturated bond).Alternatively, the hydrogen reclaimed may be used for heat or energy generation.Such as, reclaimed hydrogen can be burnt to produce in the boiler the water vapor that can be used as heat and use.The hydrogen reclaimed can also be used for generating, such as, produces in the common power generation system of water vapor and electricity.

Hydrogen retrieval system

Carry out in the hydrogen retrieval system that method described herein can be connected to the Rousseau's reaction of peace moral and HCN exhausting line in operability.Peace moral Rousseau reaction can be carried out, to produce product stream 15 containing HCN with ammonia together with refuse, describing in more detail as shown in fig. 1 and above in peace moral Rousseau reactor 10.Ammonia in product stream 15 can be removed in ammonia stripper unit 20 the half purified product stream 25 produced containing HCN and refuse.HCN can be reclaimed to produce HCN product and gaseous state waste streams 35 from half purified product stream 25 by process HCN absorber unit 30.Hydrogen can be reclaimed from gaseous waste stream 35 in hydrogen retrieval system 40.Gaseous waste stream 35 can be advanced through moisture and remove unit as condenser (not shown) before entering in gaseous waste stream 35.

Hydrogen retrieval system 40 can comprise any component described herein and material.Such as, as shown in Figure 2, gaseous waste stream 35 can enter hydrogen retrieval system 40, it can comprise one or more first module 50, one or more second unit 60, one or more 3rd unit 70, and/or one or more 4th unit 80, wherein variable n, x, y and z is the integer respectively separately with the value of 0 to 8.Therefore, 0 to 8 first module 50 can be had, 0 to 8 second unit, 60,0 to 8 the 3rd unit 70, and/or 0 to 8 the 4th unit 80.

50,60,70 can carry out similar function with Unit 80 and can have similar material in them.Such as, each of Unit 50,60,70 and 80 can have the part that comprises carbon adsorbing material and comprise and can absorb gaseous component as oxygen (O ₂), nitrogen (N ₂) and/or the separate section of zeolite of argon.Such as, the part comprising carbon adsorbing material can in the bottom of Unit 50,60,70 and 80, and the part comprising zeolite can at the top of Unit 50,60,70 and 80.

As Fig. 2 also example, hydrogen retrieval system can comprise one or more valve and one or more analyzer.Such as, hydrogen retrieval system can comprise and can control to make exhaust flow enter to the valve 57,67,77 and 87 of one or more Unit 50,60,70 and 80.Exhaust flow can be left by one or more analyzers 55,65,75 and 85 of the composition that can detect effluent from corresponding Unit 50,60,70 and 80 by one or more Unit 50,60,70 and 80.50, Unit 60,70 and 80 can in parallel or series connection use.Such as, valve 57 can allow gaseous waste stream to flow in first module 50, is removed by impurity at this from waste streams.Valve 57 can have the analyzer that operability is connected to it, and described valve only allows gaseous waste stream to flow in first module 50 when gaseous waste stream has enough hydrogen to make the recovery of hydrogen economically worthy.When gaseous waste stream flows in first module 50, refuse is by the materials adsorption in first module 50, and hydrogen passes through analyzer 55 from the top of first module 50.Analyzer 55 analyzes the composition from first module 50 hydrogen out.When the composition from first module 50 hydrogen is out greater than or equal to set(ting)value, or from the composition of first module 50 hydrogen out containing when being less than the impurity of set(ting)value, gaseous waste stream can continue flow through first module 50.But, when falling under set(ting)value from the purity of first module 50 hydrogen out, or when from the composition of first module 50 hydrogen out containing when being greater than the impurity of set(ting)value, analyzer 55 pairs of valves (value) 57 provide signal to stop to the flowing in first module 50.Analyzer 55 can also provide signal to allow waste streams to the flowing in second unit 60 to valve (value) 67, gives the unit splitter that signal at stop is connected with analyzer 55 operability simultaneously.

The closedown of the unit splitter be connected with analyzer 55 operability makes gaseous waste stream walk around first module 50 and flows through valve 67 and enter in second unit 60.When waste streams is by second unit 60, refuse is removed from waste streams.Hydrogen from the top of second unit 60 by and analyzer 65 by having the function similar to analyzer 55.As above for described in analyzer 55, analyzer 65 continues to allow exhaust-gas flow in second unit 60, and condition is that to flow through the hydrogen of analyzer 65 at least equally pure with set(ting)value, or the level of impurity is not more than set(ting)value.When the hydrogen flowing through analyzer 65 is no longer equally pure with set(ting)value, or the level of impurity is identical with set(ting)value or more, and analyzer 65 provides signal at stop valve 67 and walks around second unit 60 to make waste streams.Analyzer 65 can also provide signal to allow waste gas to the flowing in the 3rd unit 70 to valve 77, closes the unit splitter be connected with analyzer 65 operability simultaneously.Analyzer 75 and 85 has the function identical with 65 with analyzer 55.Similarly, valve 77 and 87 has the function identical with 67 with valve 57.

First therefore gaseous waste stream can flow through one or more first module 50, to make hydrogen first reclaim from these first modules 50.The second, gaseous waste stream can flow through one or more second unit 60, to make hydrogen second reclaim from these second units 60 and collect.When hydrogen is reclaimed from these second units 60 and/or collected, first module 50 can be made to purge out the refuse adsorbed, and sorbent material regeneration is used in the further use removed in refuse from the waste gas containing hydrogen.Such as, first module 50 can be heated and purge to make adsorbed refuse remove as tail gas 100 from first module with hydrogen.Gaseous waste stream can flow through one or more second unit 60, collects hydrogen to make second from these second units 60.When the sorbent material in second unit 60 needs regeneration, gaseous waste stream can flow through one or more 3rd unit 70, and then by one or more 4th unit 80.Tail gas 100 can be processed on demand or deliver to torch.

One or more analyzer 95 can monitor the oxygen concn of final hydrogen product.This oxygen concn analyzer can in conjunction with or operability be connected to effluent splitter, if with the oxygen level of gas containing hydrogen higher than the first oxygen level setting point, the gas containing hydrogen is guided to torch.Such as, the first oxygen level setting point can be about 3 volume/volume %, or about 2 volume/volume %, or about 1% volume/volume, or about 0.5% volume/volume oxygen.

Analyzer 95 can comprise or operability is connected to starter for interlocking, and described starter starts when the second oxygen setting point being detected.This interlocking can close to the flow valve of operating torch.This interlocking can also close one or more first module 50, one or more second unit 60, and one or more 3rd unit 70 with by the gas distribution containing hydrogen to container.Such as, the second oxygen level setting point can be about 5 volume/volume %, or about 3% volume/volume, or about 2% volume/volume oxygen.For guaranteeing that starter suitably starts, can only when two or three analyzers 95 detect that hydrogen-containing gas activates starter when having the oxygen concn of at least the second oxygen level setting point.

Herein in the material and the function that such as further describe this unit with lower part.

Following non-limiting embodiments example is used for always flowing back to from the gaseous waste for the preparation of the Andrussow process of prussic acid some programs receiving hydrogen.

Embodiment 1: contrast air and oxygen Andrussow process waste gas composition

This embodiment example uses the Andrussow process in the highly enriched source of oxygen usually to produce the waste streams than the method adopting air as oxygen source with higher hydrogen richness.

Inner side is used to have 4 inches of internal diameter stainless steel reactors of ceramic insulation lining for pilot scale.Load from the 90 % by weight Pt/10 % by weight Rh40 order silk screens of 40 of Johnson Matthey (U.S.) 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).Via two kinds independently Andrussow process prepare prussic acid.A kind of method adopts the oxygen Andrussow process comprising 35 volume % methane, 38 volume % ammonia and the 27 volume % gaseous reaction mixture of pure oxygen substantially.Second method is the air Andrussow process adopting about 17 volume % methane, 19 volume % ammonia and 64 volume % air.All catalyst made from platonic is used for two kinds of methods.

By ammonia from often kind of product stream comprise absorb remove respectively to the process of ammonium phosphate stream.Afterwards prussic acid is removed from poor ammonia product stream in the process of water comprising acidifying, thus prussic acid product and gaseous state waste streams are produced respectively for each method.

After ammonia and HCN remove from the gaseous waste stream of oxygen and air method composed as follows in table 2 shown in.

Table 2: gaseous waste stream forms

Analog result	O ₂	Air
			Component	％(v／v)	％(v／v)
H ₂	78.78	16.74
			N ₂	5.43	76.33
CO	11.18	4.43
			Ar	0.17	0.48
O ₂	0.09	0.00
			CH ₄	1.03	0.83
CO ₂	0.99	0.29
			NH ₃	0.00	0.00
HCN	0.13	0.05
			Vinyl cyanide	0.00	0.00
Acetonitrile	0.05	0.01
			Propionitrile	0.00	0.00
H ₂O	2.14	0.91
			H ₂SO ₄	0.00	0.00
H ₂PO ₄	0.00	0.00
			Always	100	100

As shown, highly enriched oxygen is adopted to produce significantly more hydrogen as the Andrussow process in the source containing oxygen incoming flow than the Andrussow process adopting air as the source containing oxygen incoming flow.

Embodiment 2: the hydrogen richness in gaseous waste stream

How the hydrogen richness of this embodiment example gaseous waste stream changes in the Andrussow process using the reactant containing oxygen incoming flow with the amount of different oxygen.

Via a series of independently as prepared prussic acid for the Andrussow process carried out described by embodiment 1.But often kind of method uses different reactants to carry out containing oxygen incoming flow, and wherein in incoming flow, the content of oxygen changes between about 20.9% volume/volume to about 100% volume/volume oxygen, as shown in table 3.

By ammonia from often kind of product stream comprise absorb remove respectively to the process of ammonium phosphate stream.Afterwards prussic acid is removed from poor ammonia product stream in the process comprising acidified water, thus prussic acid product and gaseous state waste streams are produced respectively for each method.

From with have different oxygen levels containing oxygen incoming flow run peace moral Rousseau method gaseous waste stream composed as follows in table 3 shown in.

Table 3:

Along with the exhaust flow BTU value that oxygen per-cent increases

¹exhaust flow refers to the % hydrogen in the waste streams after ammonia and HCN remove.

²" valuable " refers to whether exhaust flow can be used as fuel gas (such as, burning) when not adding Sweet natural gas.

Embodiment 3: hydrogen is by the recovery of pressure-variable adsorption

How hydrogen can example can use pressure swing absorption unit to reclaim from peace moral Rousseau product stream by this embodiment.

Prussic acid uses via Andrussow process and comprises 35 volume % methane, 38 volume % ammonia, and the gaseous reaction mixture of 27 volume % pure oxygen is substantially prepared under the existence of platinum catalyst.Inner side is used to have 4 inches of internal diameter stainless steel reactors of ceramic insulation lining for pilot scale.Load from the 90 % by weight Pt/10 % by weight Rh40 order silk screens of 40 of Johnson Matthey (U.S.) 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).The gaseous product stream carrying out autoreactor contains 16.6 volume % prussic acid, the unreacted ammonia of 6.1 volume %, 34.5 volume % hydrogen, 6.0 volume %CO and 33.6 volume %H ₂o.

By ammonia from often kind of product stream comprise absorb remove respectively to the process of ammonium phosphate stream.Afterwards prussic acid is removed from poor ammonia product stream in the process comprising acidified water, thus produce prussic acid product and gaseous state waste streams.

Gaseous waste is flowed through dehumidification by condensation to reduce moisture content.Can also by other impurity as the acid of trace be removed by the waste gas of condensation from dehumidifying.Afterwards the waste streams of dehumidifying is compressed in the pressure swing absorption unit containing zeolite or adsorbent of molecular sieve.Room in device is forced into about 20 bar, thus allows the selective adsorption of impurity.

The hydrogen removed from this room produced has and is less than about 5 volume % impurity, mainly nitrogen (N ₂) and methane (CH ₄).

This room is reduced pressure to remove adsorbed impurity after hydrogen retrieval.

The whole patent quoted herein or mention and be openly the instruction of level of disclosure those skilled in the art, and each this patent of quoting or open with such as it is combined in this by reference particularly individually through quoting to combine with its full content or provide identical degree with its full content herein.Applicant retain by from the patent quoted so arbitrarily or disclosed arbitrarily and all material and information physical be bonded to right in this specification sheets.

Specific method described herein, device and composition are the representative of preferred embodiment and are exemplary and are not intended to limit the scope of the present disclosure.Other targets, aspect and embodiment will be that those skilled in the art can know after considering this specification sheets, and are included in the scope of the present disclosure by the scope definition of claim.Those skilled in the art easily will understand and can make change substitutions and modifications to the disclosure disclosed herein and not depart from the scope of the present disclosure and spirit.

The disclosure of description exemplified here can aptly do not exist not as main points in disclosed any one or more key element particularly herein, or to implement when one or more restriction.The Method and process schematically described herein can be implemented with the step of different order, and the method and technique do not need the order being limited to the step pointed out in this paper or claim.

As herein and claims use, unless the upper limit is for additionally clearly to point out, singulative " ", " one " and " described " comprise plural reference.Therefore, such as, mention that " reactor " or " moisture trap " or " incoming flow " comprise multiple this reactor, moisture trap or incoming flow (such as, series reaction device, moisture trap or incoming flow), etc.In this article, unless otherwise mentioned, use term "or" to refer to nonrestrictive, comprise " A but be not B ", " B but be not A " and " A and B " to make " A or B ".

Under any circumstance the disclosure should not be interpreted as being defined in concrete disclosed specific examples or embodiment or method herein.Any statement that under any circumstance disclosure all cannot be interpreted as being made by any other official of any auditor or patent and trademark office or employee limits, and to be set out in the answer of being write by applicant particularly and not to have conditioned disjunction preserve to adopt clearly unless this.

The term adopted and expression use as descriptive and non-limiting term, and without any intention with shown in getting rid of and any equivalent form of value of the feature described or its part in the use of this term and expression, but will be appreciated that multiple change is possible in required the scope of the present disclosure.Therefore, although will understand is that the disclosure is disclosed particularly by preferred embodiment and optional characteristic, those skilled in the art can take the modifications and changes of concept disclosed herein, and if this modifications and changes be considered to appended claim and statement of the present disclosure definition the scope of the present disclosure in.

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 with 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: in following statement, per-cent is % volume/volume unless otherwise mentioned.

1. reclaim a method for hydrogen from prussic acid product stream, described method comprises:

A () removes ammonia to produce half purified product stream from described product stream;

B () is drifted except prussic acid is to produce prussic acid product and the gaseous state waste streams of purifying from described half purified product; With

C () is drifted except component is to produce the hydrogen reclaimed from described gaseous waste;

Wherein said gaseous waste stream contains at least about 40% hydrogen.

2. flow back to the method receiving hydrogen from the gaseous waste of Andrussow process, described method comprises:

(a) adjustment kit containing the reaction mixture of methane, ammonia and oxygen to provide sufficient oxygen to described reaction mixture, to produce the gaseous waste stream with at least 40% hydrogen after the recovery removing with prussic acid of ammonia; And

B () is drifted except component is to produce the hydrogen reclaimed from described gaseous waste.

3. the method for statement described in 1 or 2, wherein said product stream comprises the species being selected from the group be made up of the following: HCN, ammonia, H ₂, CO, N ₂, H ₂o, CO ₂, CH ₄, one or more organic nitriles and their combination.

4. the method for statement according to any one of 1-3, wherein said gaseous waste stream comprises and is not more than about 1.5%HCN.

5. the method for statement described in 1, wherein said gaseous waste stream comprises at least 20% hydrogen, or at least 30% hydrogen, or at least 40% hydrogen, or at least 50% hydrogen, or at least 60% hydrogen, or at least 65% hydrogen, or at least 70% hydrogen.

6. the method for statement according to any one of 1-5, wherein said gaseous waste stream comprises about 70% to about 80% hydrogen.

7. the method for statement according to any one of 1-6, wherein said gaseous waste stream comprises about 73% to about 78% hydrogen.

8. the method for statement according to any one of 1-7, wherein said gaseous waste stream comprises at least 5% carbon monoxide, or at least 10% carbon monoxide.

9. the method for statement according to any one of 1-8, wherein said gaseous waste stream comprises about 10% to about 15% carbon monoxide.

10. the method for statement according to any one of 1-9, wherein said gaseous waste stream comprises at least 2% nitrogen, or at least 3% nitrogen.

The method of 11. statements according to any one of 1-10, wherein said gaseous waste stream comprises about 2% to about 6% nitrogen.

12. statements 1, method according to any one of 3-10 or 11, wherein said gaseous waste stream comprises about 80% to about 93% nitrogen.

The method of 13. statements according to any one of 1-12, wherein said gaseous waste stream comprises at least 0.2% methane, or at least 0.3% methane.

The method of 14. statements according to any one of 1-13, wherein said gaseous waste stream comprises about 0.2% methane to about 2.0% methane.

The method of 15. statements according to any one of 1-14, wherein said gaseous waste stream comprises about 0.4% methane to about 1.8% methane.

The method of 16. statements according to any one of 1-15, wherein said gaseous waste stream comprises about 0.2% carbonic acid gas to about 2.0% carbonic acid gas.

The method of 17. statements according to any one of 1-16, wherein said gaseous waste stream comprises about 0.3% carbonic acid gas to about 1.8% carbonic acid gas.

The method of 18. statements according to any one of 1-17, wherein said gaseous waste stream comprises about 0.001% organic nitrile to about 0.05% organic nitrile.

The method of 19. statements according to any one of 1-18, wherein said gaseous waste stream comprises one or more organic nitriles being selected from the group be made up of the following: acetonitrile, vinyl cyanide, propionitrile and their combination.

The method of 20. statements according to any one of 1-19, wherein said gaseous waste stream comprises about 72% hydrogen to about 78% hydrogen, about 12% carbon monoxide is to about 15% carbon monoxide, about 0.7% carbonic acid gas is to about 1.5% carbonic acid gas, and about 3% nitrogen is to about 5% nitrogen, and about 1% methane is to about 2.0% methane, about 0.01% organic nitrile is to about 0.1% organic nitrile, about 0.01%HCN to about 0.05%HCN, about 3% water is to about 5% water, and their combination.

The method of 21. statements according to any one of 1-20, wherein said gaseous waste stream comprises about 1% hydrogen to about 2% hydrogen, about 3% carbon monoxide is to about 8% carbon monoxide, about 0.2% carbonic acid gas is to about 0.8% carbonic acid gas, and about 80% nitrogen is to about 95% nitrogen, and about 0.1% methane is to about 1.0% methane, about 0.01% organic nitrile is to about 0.5% organic nitrile, about 0.05%HCN to about 0.5%HCN, about 0.2% water is to about 1.5% water, and their combination.

The method of 22. statements according to any one of 1-21, wherein drifts except component comprises from described gaseous waste: remove carbon monoxide, nitrogen, water, carbonic acid gas, methane, one or more organic nitriles, or their combination.

The method of 23. statements according to any one of 1-22, wherein drifts except component comprises from described gaseous waste: condensation, amine washing, pressure-variable adsorption, deep cooling purifying, or their combination.

The method of 24. statements according to any one of 1-23, wherein drift except component comprises from described gaseous waste: make described gaseous waste flow through hydrogen permeable film, palladium film, hydrocarbon absorbing medium, gas expansion unit, water-gas shift chemical converter unit, or their combination.

The method of 25. statements according to any one of 1-24, wherein drifts except component comprises from described gaseous waste: make described gaseous waste flow through sorbent material, to drift except unwanted component from described gaseous waste.

The method of 26. statements according to any one of 1-25, wherein drifts except component comprises from described gaseous waste: make described gaseous waste flow through sorbent material, and wherein said sorbent material comprises silica gel, gac, zeolite, molecular sieve, or their combination.

The method of 27. statements according to any one of 1-26, wherein drifts except component comprises from described gaseous waste: make described gaseous waste flow through water-gas shift conversion unit, so that carbon monoxide and water are converted into carbonic acid gas and hydrogen.

The method of 28. statements described in 27, if wherein said water-gas shift conversion rate produces more up to about 20% hydrogen by what produce than not making described gaseous waste flow through described water-gas shift conversion unit, or up to about 15% hydrogen, or up to about 13% hydrogen.

The method of 29. statements according to any one of 1-28, wherein drifts except component comprises from described gaseous waste: make described gaseous waste flow through one or more condensing unit.

The method of 30. statements described in 29, wherein said one or more condensing unit drifts except condensable components is as water vapour from described gaseous waste, and/or can the water-soluble matter of condensation together with water.

The method of 31. statements according to any one of 1-30, wherein drifts except component comprises from described gaseous waste: make described gaseous waste flow through one or more unit, and each unit comprises the part containing carbon adsorbing material and the part containing zeolite.

The system of 32. statements according to any one of 1-31, wherein drifts except component comprises from described gaseous waste: make described gaseous waste flow through 0 to 8 first module, 0 to 8 second unit, 0-8 Unit the 3rd, 0-8 Unit the 4th, and their combination; Each unit that wherein said hydrogen retrieval system comprises comprises the part containing carbon adsorbing material and the part containing zeolite.

The method of 33. statements described in 32, wherein said carbon adsorbing material removes carbonaceous component.

The method of 34. statements described in 33, wherein said carbonaceous component comprises carbonic acid gas, carbon monoxide, prussic acid, or their combination.

The method of 35. statements according to any one of 31-34, wherein said zeolite removes oxygen (O ₂), nitrogen (N ₂), argon and their combination.

The method of 36. statements according to any one of 1-35, the hydrogen of wherein said recovery is at least about 90% pure, 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.

Method according to any one of 37. claim 1-36, wherein said prussic acid produces in the reaction of methane, ammonia and oxygen.

38. methods according to claim 37, wherein said methane provides as Sweet natural gas.

39. methods according to claim 37, wherein said methane provides as substantially pure methane.

Method according to any one of 40. claim 1-39, wherein said prussic acid produces in the reaction of methane, ammonia and oxygen, and wherein said oxygen provides as the mixture of air, molecular oxygen, air and oxygen or the mixture of oxygen and nitrogen.

Method according to any one of 41. claim 1-40, wherein adopts the hydrogen reclaimed for hydrogenation.

Method according to any one of 42. claim 1-41, wherein adopts the hydrogen that reclaims for the hydrogenation of adiponitrile.

Method according to any one of 43. claim 1-42, wherein adopts the hydrogen that reclaims for the hydrogenation of adiponitrile to produce hexamethylene-diamine.

Method according to any one of 44. claim 1-40, wherein adopts the hydrogen reclaimed to generate for heat or energy.

Method according to any one of 45. claim 1-44, wherein said method reclaim in described gaseous waste stream at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% hydrogen.

46. 1 kinds of systems, described system comprises:

(a) reactor, described reactor configurations is used under the existence of platinum catalyst, preparing prussic acid from the reaction mixture comprising methane, ammonia and oxygen, and wherein said reactor produces the gaseous product stream comprising described prussic acid; With

B () hydrogen retrieval system, described hydrogen retrieval system configuration is from ammonia and described prussic acid are being flowed back to receipts hydrogen from the gaseous waste produced after described gaseous product stream removes substantially.

The system of 47. statements described in 46, described system also comprises ammonia stripper unit, to remove ammonia from described gaseous product stream thus to produce the half purified product stream containing HCN and refuse.

The system of 48. statements described in 46 or 47, described system also comprises HCN absorber unit to produce HCN product and described gaseous waste stream.

The system of 49. statements according to any one of 46-48, wherein said hydrogen retrieval system comprises one or more first module, one or more second unit, one or more Unit the 3rd, or one or more Unit the 4th.

The system of 50. statements according to any one of 46-49, wherein said hydrogen retrieval system comprises 0 to 8 first module, 0 to 8 second unit, 0-8 Unit the 3rd, 0-8 Unit the 4th, and their combination.

The system of 51. statements according to any one of 46-50, wherein said hydrogen retrieval system comprises one or more first module, one or more second unit, one or more Unit the 3rd, or one or more Unit the 4th, and each in wherein said first module, described second unit, described Unit the 3rd and described Unit the 4th comprises the material being selected from the group be made up of carbon adsorbing material, zeolite and their combination.

The system of 52. statements described in 51, each in wherein said first module, described second unit, described Unit the 3rd and described Unit the 4th comprises the part containing carbon adsorbing material and the part containing zeolite.

The system of 53. statements described in 51 or 52, wherein said carbon adsorbing material is from described gaseous waste stream absorption carbonaceous component.

The system of 54. statements according to any one of 51-53, wherein said carbon adsorbing material absorbing carbon dioxide, carbon monoxide, methane, remaining prussic acid, and their combination.

The system of 55. statements according to any one of 52-54, wherein said zeolite can adsorb oxygen (O ₂), nitrogen (N ₂), argon and their combination.

The system of 56. statements according to any one of 46-55, wherein said system comprises one or more condensing unit, and described condensing unit is configured to drift except moisture from described gaseous waste.

The system of 57. statements described in 56, wherein said one or more condensing unit can drift except condensable components is as water vapour from described gaseous waste, and optionally, can the water-soluble matter (if existence) of condensation together with water.

The system of 58. statements according to any one of 46-57, described system also comprises, and described effluent analyzer is for detecting the composition from described hydrogen retrieval system effluent out.

The system of 59. statements according to any one of 46-58, wherein said hydrogen retrieval system also comprises one or more air intake valve, described air intake valve operability is connected to one or more first module, one or more second unit, one or more Unit the 3rd, or one or more Unit the 4th, wherein said off-gas can flow in unit when the described air intake valve be connected with its operability is opened.

The system of 60. statements according to any one of 46-59, wherein said hydrogen retrieval system also comprises one or more element analysis device, described element analysis device operability is connected to one or more first module, one or more second unit, one or more Unit the 3rd, or one or more Unit the 4th, for detecting or quantizing from described one or more unit hydrogen out or the level of waste component.

The system of 61. statements described in 60, element analysis device described in wherein one or more also comprises one or more unit splitter, one or more first module is connected to close one or more operability, one or more second unit, one or more Unit the 3rd, or the outlet valve of one or more Unit the 4th.

The system of 62. statements described in 60 or 61, wherein one or more unit splitters are optionally connected to one or more element analysis device.

The system of 63. statements according to any one of 49-62, wherein when described first module, second unit, in Unit the 3rd or Unit the 4th one or more from described gaseous waste flow back to receive hydrogen time, by described first module, second unit, the one or more regeneration in Unit the 3rd or Unit the 4th.

The system of 64. statements according to any one of 46-63, described system also comprises hydrogen detector, described hydrogen detector operability is connected to, described waste streams splitter is used for when the hydrogen level that described hydrogen detector detects in described gaseous product stream is unacceptably low for hydrogen retrieval, and described gaseous product diverting flow is left described hydrogen retrieval unit.

The system of 65. statements described in 64, the described hydrogen level in wherein said gaseous product stream is worked as described hydrogen level and is less than 20%, or is less than 25%, or is less than 30%, or is less than 40%, or when being less than 50%, unacceptably low for hydrogen retrieval.

The system of 66. statements according to any one of 46-65, described system also comprises one or more oxygen detector, for monitoring from the oxygen concn in the effluent of described hydrogen retrieval system.

The system of 67. statements described in 66, wherein when the oxygen concn in described effluent is equal to or greater than the first oxygen level setting point, described one or more described oxygen detector starts the shunting of described effluent via one or more effluent splitter.

The system of 68. statements described in 67, wherein when at least two described oxygen detectors detect the described oxygen level of described effluent higher than described first oxygen level setting point, starts the shunting of described effluent.

The system of 69. statements described in 67 or 68, wherein when the oxygen concn in described effluent is equal to or greater than the first oxygen level setting point, described one or more oxygen detector starts the shunting of described effluent to torch.

The system of 70. statements described in 66-68, wherein when the oxygen concn in described effluent is equal to or greater than the first oxygen level setting point, described one or more oxygen detector starts described effluent via one or more effluent splitter to one or more described first module, one or more described second unit, one or more described Unit the 3rd, or the shunting in one or more described Unit the 4th.

The system of 71. statements according to any one of 67-70, wherein said first oxygen level setting point is about 1.5 volume/volume %, or about 1% volume/volume, or about 0.5% volume/volume oxygen.

The system of 72. statements according to any one of 46-71, described system also comprises when being activated by when monitoring and the second oxygen setting point detected from one or more oxygen detectors of the oxygen concn in the effluent of described hydrogen retrieval system.

The system of 73. statements according to any one of 46-72, described system also comprises interlocking, and when the second oxygen setting point being detected by monitoring from least two oxygen detectors of the oxygen concn in the effluent of described hydrogen retrieval system, described interlocking can be activated.

The system of 74. statements described in 72 or 73, wherein said interlocking can close the one or more described first module in described hydrogen retrieval system, one or more described second unit, one or more described Unit the 3rd, one or more described Unit the 4th, or their combination.

The system of 75. statements according to any one of 72-74, wherein said interlocking can close each of described first module, described second unit, described Unit the 3rd and described Unit the 4th.

The system of 76. statements according to any one of 46-75, described system also comprises interlocking, and described interlocking can close to the flow valve that operability is connected to the power generating unit of described hydrogen retrieval unit.

The system of 77. statements according to any one of 46-76, described system also comprises interlocking, and described interlocking can branch to from the effluent containing hydrogen described in described hydrogen retrieval system in one or more container.

The system of 78. statements according to any one of 46-77, described system also comprises interlocking, and described interlocking can branch to torch by from the effluent containing hydrogen described in described hydrogen retrieval system.

The system of 79. statements according to any one of 72-78, wherein said second oxygen level setting point is about 4 volume/volume %, or about 3% volume/volume, or about 2% volume/volume oxygen.

The system of 80. statements according to any one of 46-79, described system configuration be reclaim in described gaseous waste stream at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% hydrogen.

The system of 81. statements according to any one of 46-80, described system configuration states any one in the method according to any one of 1-45 for carrying out.

Concrete statement of the present utility model:

1. a system, described system comprises:

(a) reactor, described reactor configurations is used under the existence of platinum catalyst, preparing prussic acid from the reaction mixture comprising methane, ammonia and oxygen, wherein said reactor is also configured to provide sufficient oxygen to described reaction mixture, to produce the gaseous waste stream with at least 40% hydrogen after the recovery removing with prussic acid of ammonia; With

B () hydrogen retrieval system, described hydrogen retrieval system configuration is for flow back to receipts hydrogen from described gaseous waste.

2. the system of statement described in 1, wherein said sufficient oxygen provides as the oxygen incoming flow that contains comprising at least 40% oxygen or at least 45% oxygen.

3. the system of statement described in 1 or 2, described system also comprises: ammonia stripper unit, to remove ammonia from gaseous product stream thus to produce the half purified product stream containing HCN and refuse; And HCN absorber unit, to produce HCN product and described gaseous waste stream.

4. the system of statement described in 1, wherein said hydrogen retrieval system comprises: one or more unit, the flowing that described cell location is used for condensation, amine washing, pressure-variable adsorption, deep cooling purifying, the flowing that described gaseous waste flows through the flowing of hydrogen permeable film, described gaseous waste flows through palladium film, the flowing that described gaseous waste flows through the flowing of hydrocarbon absorbing medium, described gaseous waste flows through gas expansion unit, described gaseous waste flow through water-gas shift chemical converter unit, or their combination.

5. the system of statement described in 1, wherein said system comprises one or more condensing unit, and described condensing unit is configured to drift except moisture from described gaseous waste.

6. the system of statement described in 1, wherein said hydrogen retrieval system comprises one or more unit, and described unit contains and is selected from by carbon adsorbing material, zeolite, and the material of the group of their combination composition.

7. the system of statement described in 1, wherein said hydrogen retrieval system comprises one or more unit, and described unit operation connects to make described gaseous waste stream can flow to another from a unit.

8. the system of statement described in 1, wherein said hydrogen retrieval system comprises one or more unit, described unit operation connects to make described gaseous waste stream to enter first module until the material in described first module does not produce the hydrogen with at least 60% pure hydrogen, and by described gaseous waste diverting flow in second unit, can discharge by the material regeneration in described first module and/or by refuse afterwards simultaneously.

9. the system of statement described in 1, wherein said hydrogen retrieval system comprises one or more air intake valve, described air intake valve separately operability is connected at least one unit of described hydrogen retrieval system, can flow in one or more unit to make described off-gas via one or more air intake valve.

10. the system of statement described in 1, described system also comprises hydrogen detector, described hydrogen detector operability is connected to gaseous product stream splitter, described gaseous product stream splitter is used for when the hydrogen level that described hydrogen detector detects in described gaseous product stream is unacceptably low for hydrogen retrieval, and described gaseous product diverting flow is left described hydrogen retrieval unit.

The system of 11. statements described in 1, wherein said hydrogen retrieval system comprises one or more analyzer, and described analyzer is for detecting or quantizing the level from described one or more unit effluent component out.

The system of 12. statements described in 11, analyzer operability described in wherein one or more is connected to unit output steering device, to close the outlet valve of one or more described unit.

The system of 13. statements described in 1, described system also comprises one or more oxygen detector and/or one or more hydrogen detector, for monitoring from the oxygen in the effluent of described hydrogen retrieval system and/or hydrogen concentration.

The system of 14. statements described in 13, wherein when the oxygen concn in described effluent is equal to or greater than the first oxygen level setting point; Or when the described hydrogen concentration in described effluent is less than or equal to the first hydrogen richness setting point, described one or more described oxygen detector or one or more described hydrogen detector start the shunting of described effluent via one or more recovery system effluent splitter.

The system of 15. statements described in 14, wherein said one or more recovery system effluent splitter starts the shunting in the one or more described unit in described effluent to described hydrogen retrieval system.

The system of 16. statements described in 14 or 15, wherein when at least one or at least two described oxygen detectors detect the described oxygen level of described effluent higher than described first oxygen level setting point time, at least one recovery system effluent splitter is started, to shunt described effluent.

The system of 17. statements described in 1, described system also comprises interlocking, and when the second oxygen setting point being detected by monitoring from one or more oxygen detectors of the oxygen concn in the effluent of described hydrogen retrieval system, described interlocking can be activated.

The system of 18. statements described in 17, wherein said interlocking can close the one or more described unit of described hydrogen retrieval system.

The system of 19. statements described in 17 or 18, wherein said interlocking can open or close flow valve, goes to allow described effluent the torch just run.

The system of 20. statements described in 1, the described effluent containing hydrogen can branch to one or more container from described hydrogen retrieval system by wherein said interlocking.

Claims

1., for a system for the hydrogen retrieval in Andrussow process, described system comprises:

A () produces the Andrussow process reactor of gaseous waste stream; With

B () flows back to the hydrogen retrieval system receiving hydrogen from described gaseous waste.

2. system according to claim 1, described system also comprises: ammonia stripper unit; And HCN absorber unit.

3. system according to claim 1, wherein said hydrogen retrieval system comprises: one or more unit, the flowing that described cell location is used for condensation, amine washing, pressure-variable adsorption, deep cooling purifying, the flowing that described gaseous waste flows through the flowing of hydrogen permeable film, described gaseous waste flows through palladium film, the flowing that described gaseous waste flows through the flowing of hydrocarbon absorbing medium, described gaseous waste flows through gas expansion unit, described gaseous waste flow through water-gas shift chemical converter unit, or their combination.

4. system according to claim 1, wherein said system comprises one or more condensing unit.

5. system according to claim 1, wherein said hydrogen retrieval system comprises the unit that one or more operability connects.

6. system according to claim 1, wherein said hydrogen retrieval system comprises one or more air intake valve, and described air intake valve separately operability is connected at least one unit of described hydrogen retrieval system.

7. system according to claim 1, described system also comprises hydrogen detector, and described hydrogen detector operability is connected to gaseous product stream splitter.

8. system according to claim 1, wherein said hydrogen retrieval system comprises one or more analyzer, and described analyzer is for detecting or quantizing the level from described one or more unit effluent component out.

9. system according to claim 8, analyzer operability described in wherein one or more is connected to unit output steering device, to close the outlet valve of one or more described unit.

10. system according to claim 1, described system also comprises one or more oxygen detector and/or one or more hydrogen detector, for monitoring from the oxygen in the effluent of described hydrogen retrieval system and/or hydrogen concentration.

11. systems according to claim 1, described system also comprises interlocking.

12. systems according to claim 11, wherein said interlocking can close the one or more described unit of described hydrogen retrieval system.

System described in 13. claims 11 or 12, wherein said interlocking formation can open or close flow valve for making it.

14. systems according to claim 11, wherein said interlocking formation is that the described effluent containing hydrogen can be branched to one or more container from described hydrogen retrieval system by it.