CN85109166A - Improve the recovery of hydrogen by exhaust jet stream - Google Patents
Improve the recovery of hydrogen by exhaust jet stream Download PDFInfo
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- CN85109166A CN85109166A CN 85109166 CN85109166A CN85109166A CN 85109166 A CN85109166 A CN 85109166A CN 85109166 CN85109166 CN 85109166 CN 85109166 A CN85109166 A CN 85109166A CN 85109166 A CN85109166 A CN 85109166A
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Abstract
With steam reformation, the evacuation circuit that partial oxidation or gasification of coal are produced at conversion system, is handled in washing device and the pressure variation absorption system effectively, a kind ofly contains the hydrogen production air-flow through what purify to reclaim.The waste gas that a part is removed from the pressure variation absorption system is delivered to conversion system and/or the recirculation of exhaust generating unit, needn't application of cold temperature transform, before delivering to said pressure variation absorption system, needn't thoroughly remove carbonic acid gas contained in the gas, just can improve product and reclaim.
Description
The present invention addresses the purification of hydrogen-containing gas streams.Especially address and adopt the hydrogen product of a kind of pressure variation absorption system with reclaiming clean.
Present used hydrogen, having more than 90% is to carry out steam reformation or partial oxidation and get from various hydro carbons.The ejecta that obtains from these production methods or from other method such as hydrogeneous evacuation circuit that gasification of coal produced, the general water gas shift reaction of being familiar with by people changes wherein carbon monoxide into carbonic acid gas and " adding " hydrogen.After the pyrolytic conversion, the change table composition of this evacuation circuit is calculated as follows by the siccative molar percentage:
Project hydrogen, CO
2CO, CH
4And other
The ejecta 68-75 17-25 2-15 of steam reformation
Partial oxidation or coal gas 60-65 30-35 3-8
The ejecta of changing
This conversion air-flow also can further be handled with additive method, obtains needed hydrogen product.For this reason, this air-flow can be by a kind of washing device with CO
2Reduce to 0.1%, this evacuation circuit also can further be handled and remove residual CO
2Thereby, remaining CO
2Reduce to 1ppm(1,000,000/).Then CO
2Just remove and to send to the liquid nitrogen gas washing, or carry out the cryogenic purification method and produce and hydrogeneously reach 97% finished gas-flow or a kind of pure ammonia synthesis gas air-flow and pay the product combustion gas.
Another kind method is that in order further CO to be transformed, low temperature conversion is delivered in the exhaust after the pyrolytic conversion, passes through washing device then, CO
2Be scavenged into 0.1%.Can send to the methanation processing and make the purity of hydrogen reach 97% from the exhaust here.Any method that don't work all will all be removed the carbonic acid gas in the evacuation circuit, concerning a kind of method in back, must adopt high pyrolytic conversion and adopt very responsive low temperature conversion.
The final purification process can be finished with a kind of pressure variation absorption system ((Pressure Swing Adsorption System) is called for short PSA system or method) that is called, and realizes giving the hydrogen cleaning of thinking.PSA method, its advantage are simple, operate easily, and the purity of hydrogen is brought up to more than 99.99%.Than above-mentioned any method is good.Present technique field strong request PSA method can continue to improve, to improve the feasibility that it is applied to actual industrial production.Especially require the recovery aspect of the hydrogen product purified to be improved, thus can the optimal selection steam reformation, partial oxidation, or the scale of other various hydrogeneous evacuation circuit generating units.
The objective of the invention is to be to provide a kind of improved technology and system, produce the hydrogen-containing gas product.
Another object of the present invention is for a kind of method and apparatus being provided, strengthening reclaiming clean hydrogen production from evacuation circuit.
Further purpose of the present invention is, for handling a kind of evacuation circuit, provides a kind of improved already integrated approach and system, and the pressure variation absorption process is adopted in the wherein final purification of hydrogen-containing gas streams, can accomplish that high purity is high to reclaim.
These and other target has been arranged, will be described in detail the present invention below, some new feature also can put forward in claims especially.
A kind of hydrogenous evacuation circuit carries out water-gas at least and transforms under high-temperature situation, washing to be removing its contained most of carbonic acid gas, and delivers to the PSA system, therefrom the reclaiming clean hydrogen product.Get back to the conversion system from the waste gas that the PSA system is produced, or get back to the recirculation of evacuation circuit producer.Nitrogen in the system, argon, or the gathering of methane etc., the waste gas of some can bleed off them, or before this waste gas of discharging they is delivered to another additional pressure variation absorption system and absorb back and forth and add hydrogen.Nitrogen in the air-flow or argon if allow, for fear of gathering, can flow directly into the Purge gas product by the pressure variation absorption system.The countercurrent depressurization process and/or the clearing process of PSA operation can realize like this, promptly only allows hydrogeneous maximum generation effluent part recirculation and nitrogenous and the maximum partial discharge of argon are gone out;
The present invention is described in detail in detail below, and encloses the process flow sheet of the most preferred embodiment (using additional pressure change absorption system) of anticipatory remark invention.
Pay storage and carry out the present invention, the target that proposes above all can reach, and promptly advantageously obtains high purity high-recovery and contains hydrogen production.
The present invention adopts simple work program and equipment, gives prerequisite to water-gas conversion and carbonic acid gas washing, and this is favourable to Technological Economy of the present invention aspect.And use special processing conditions, and can avoid methane, nitrogen and/or argon harmful gathering the in system, also improved recovery finished product gas simultaneously.
As mentioned above, once and secondary reformed, partial oxidation and gasification of coal all are the examples for the known process operation of the used manufacturing evacuation circuit of the present invention.This air-flow contains the hydrogen as a kind of gas products neccessary composition, and with carbonic acid gas, carbon monoxide and other are formed as methane, nitrogen and argon, water vapor etc.According to the present invention, this evacuation circuit is to make it to transform through high-temperature water gas, and carbon monoxide is converted into hydrogen and carbonic acid gas.After the conversion, remove most carbonic acid gas in the evacuation circuit.This evacuation circuit remove behind the carbonic acid gas that removes is delivered to a kind of PSA system, be discharged as being difficult for absorbed composition in the evacuation circuit with a kind of hydrogen-containing gas of purification.Evacuation circuit after the processing, the absorbed component that is easy to that it is contained comprises carbonic acid gas and other impurity.This sorbent bed desorption process that carries out that easily is absorbed component in this system excludes the PSA system as waste gas.This waste gas has at least 40% to deliver to conversion procedure and/or deliver to the recirculation of original evacuation circuit generation operation through overdraft, and details are as follows.
The representative temperature of the evacuation circuit that obtains from producer gas generator be 800 ℃ or more than.This air-flow is cooled to about 350 ℃～400 ℃ earlier, carry out the water-gas catalyzed conversion then, every people who is familiar with this technology, the conversion under this temperature is understood in the capital, the pyrolytic conversion in the presence of commercial chromium based water gas conversion catalyst, carried out exactly reaction, the water gas shift reaction in the present technique field also has and carries out at low temperatures, for example about 250 ℃, it carries out in the presence of the known commercial copper-based catalysts.As one of above-mentioned ordinary method, after pyrolytic conversion is finished, then carry out low temperature conversion, this also is to list within the scope of the present invention.Should be understood that general of the present invention needs pyrolytic conversion reaction.Low temperature conversion uses copper-based catalysts to use the practical significance of chromium-based catalysts to be that it is more expensive than pyrolytic conversion, and is more accurate, or more responsive.
In a word, within the scope of the invention, adopt step of converting, promptly at least a high-temperature water gas catalytic conversion step can be the most of carbon monoxide in the evacuation circuit, and is about more than 80%, typical about 85% to 98%, all transformed.
Through the evacuation circuit after the conversion processing, by a kind of carbonic acid gas washing section, requirement there is so not strict compared with above-mentioned ordinary method.In this washing section, most of at least carbonic acid gas of removing in the evacuation circuit, but needn't be as traditional method, must be residual CO
2Reduce to 0.1% or about 1ppm.In general, the 70%(volume is arranged in evacuation circuit) carbonic acid gas, it is just enough preferably to be about 85-99.9%.Usually be about 25%, when washing step, be eliminated.Remove CO
2After the residual CO of evacuation circuit
2Content typically can drop to about 2%-7%, and is proper, the 3%-5% that can drop to.Those skilled in the art that recognize that evacuation circuit, needn't be removed carbonic acid gas wherein not by before the PSA system fully as yet.Form the hydrogen aspect from evacuation circuit, this also is the present invention's point more more superior than ordinary method.
According to the present invention, the evacuation circuit of having removed carbonic acid gas already can give off as the hydrogeneous product gas of a kind of purification that is difficult to be absorbed component in the evacuation circuit by the PSA system.In this evacuation circuit wherein the component of easy absorption comprise residual carbon dioxide and other impurity.Should recognize, the easiest said absorbent components be in each bed of PSA system fabrication cycles when carrying out countercurrent depressurization and/or remove step and exclude this system.The circulation of being done in an orderly way in each is sorbent bed of PSA system comprises: high pressure absorbs and emits from the product end of bed and to be difficult for absorbent components; Following current is reduced pressure and is emitted void space gas from the product end of bed; Countercurrent depressurization takes off with minimizing and inhales pressure and/or removing and emit impure waste gas from the feeding end of bed; Again pressurize to improve absorption pressure.Skilled practitioner all can be recognized in the present technique field, and PSA method and system can do various innovations and suitably improve in the horizontal given range of prior art, and do not depart from scope of the present invention.For example, generally there are four layers or above absorber layer in the PSA system, and the present invention can carry out work with this multilayer system immediately.Every professional who is familiar with the present technique field all can understand, in this multilayer system, following current when decompression, the hollow space gas that is discharged from the product end of a bed, can waltz through another bed in this system, to reach pressure equilibrium and/or the removing purpose is provided.
When carrying out countercurrent depressurization and/or clearing process, the waste gas that the PSA system is discharged has about 40% recirculation in conversion of the present invention and/or exhaust stage of growth at least through overdraft in this compressed exhaust gas.Referring to the accompanying drawing of realizing employed general flow chart of purpose of the present invention and various device, 1 a kind of conduit of expression or a kind of processing circuit, be used for to steam reformer, the partial oxidation device, coal gasification device or other hydrocarbon conversion device 2 are supplied with hydrocarbonaceous gas stream, and conversion system 2 is used for making hydrogeneous evacuation circuit.For the operation of steam catalytic reforming, steam is dosed convertor 2 by conduit 3.Pass through conduit means 4 from the evacuation circuit of steam reformer or 2 productions of other conversion systems, feed cooling and catalytic water-gas conversion system 5, be used for the carbon monoxide in this evacuation circuit is converted into hydrogen and carbonic acid gas.The evacuation circuit of having handled already leaves convertor under about 430 ℃ of temperature, through conduit 6, cool off a little and import liquid washer 7, and this washer can be removed away most carbonic acid gas at least from said evacuation circuit.The evacuation circuit of having removed carbonic acid gas already by conduit 8, enters PSA system 9 from said washer 7, and carbonated absorbent liquid or solvent, from washer 7,, enter flash tank 11 by conduit 10, flashed vapour is from jar 11, by circuit 12, enter into recycle compressor 13 easily so that get back to water-gas convertor 5 and/or, if needed, can get back to hydrocarbon conversion device 2.In specific embodiment, absorbent liquid by conduit 14, flows into separating tank 15 from flash tank 11, here by conduit 16, CO 2 waste gas is excluded in the production system.Can replace single stage flash jar 15 with multistage flash evaporation jar or stripping jar (adopting steam, nitrogen or other stripping gases).Absorbent liquid after the regeneration from jar 15, through conduit 17, flows to solvent pump 18, returns washer 7.Hydrogeneous finished product gas through purifying from PSA system 9, discharges by conduit 19, and this gas is as being difficult for adsorbed components in the evacuation circuit in the PSA system handles process.Once mentioned above, this product gas is high hydrogen production, according to the PSA technology, purity can reach 99.99% or more than.Each of PSA system is sorbent bed, in countercurrent depressurization and/or scavenging process, from the material feeding end of this bed, discharges impure waste gas, and this waste gas is from PSA system 9, by conduit 20, in 13 li pressurizations again of recycle compressor.According to actual job of the present invention, the waste gas that this is compressed at least about 40%, by recycling pipe 21, via conduit 22, flows to conversion system 5 recirculation and/or via conduit 23, flows to 2 recirculation of hydrocarbon conversion device.
Waste gas when said treated mistake contains methane, and tells a part of waste gas from this system, changes and does other purposes, and this also belongs within the scope of the present invention.People know that the waste gas that contains methane is fit to do fuel gas, for this reason, establish conduit 24, do this respect purposes.Contain nitrogen and/or argon in evacuation circuit, at least a part is contained the waste gas of nitrogen and/or argon, this can pass through conduit 24 too easily, and it is gone out from PSA system branch.Methane, nitrogen and/or argon are so shunted away, are to assemble too many this component for fear of the recirculation loop and the equipment thereof of method of the present invention.
Excessively assemble in said recirculation loop for fear of methane, and load onto other effective devices, this also belongs within the scope of the present invention.For this reason, have at least a part to contain the exhaust of methane in the PSA system, can for example, be recycled to convertor 2 in the recirculation in this exhaust generation operation down of boosting by conduit 23.Be made up of steam reformer or partial oxidation device when convertor 2, methane is transformed, and increases to give in addition and decides amounts of hydrogen.Equally, when convertor 2 is made up of the gasification of coal device, which part EGR gas also can recirculation in gasifier.
People can recognize, the part recirculated exhaust flow flows to convertor 2 or convertor 5, depend on fully the situation of given hydrogen manufacturing operation, for example, the comparatively ideal specific embodiment according to the present invention.The evacuation circuit that adopts the hydro carbons primary steam to reform and do not have secondary reformed to generate, then this evacuation circuit contains the volume at least about 3%() methane, in the EGR gas from the PSA system,, deliver to recirculation in this reformer at least about 20%.In a more special specific embodiment, about 20 to 60% in the EGR gas, about preferably 30 to 40%, recirculation in this reformer.In addition, the evacuation circuit as if from convertor 2 contains few methane, and then the most of waste gas in the PSA system will pass through conduit 22, flows directly into convertor 5 recirculation.For example, in a plurality of application, wherein have a kind of, the evacuation circuit that primary steam is reformed, handle through secondary reformed, the evacuation circuit of this secondary reformed device, its methane content are less than about 1%(volume), then from the EGR gas of PSA system, at least about 20%, normally most of, until about 90%, convertor 5 recirculation effectively.Other application method, for example in this EGR gas, contain methane content and belong to other content ranges, can determine the part EGR gas is delivered to reformer 2 and delivered to convertor 5 recirculation according to the special operation situation in this application, so that recover hydrogen and keep good Global Operation performance best.In each example, usually evacuation circuit is cooled to about 350 ℃, delivers to conversion procedure then.
In the more satisfactory specific embodiments of another one, the waste gas part from the PSA system contains methane under the rising absorption pressure, flows directly into additional PSA system.In the drawings, this specific embodiments is with dashed lines 25 expressions, and a part contains methane waste product can flow directly into additional PSA system 26.The product gas of the difficult absorption that therefrom ejects has comprised extra increase, and the hydrogen production that contains through purifying can pass through conduit 27, and extraction is gone.And the easy absorption waste gas of separating from said product gas in the PSA system 26 can pass through conduit 28, and it is removed.This contains methane gas stream, if necessary, is fit to do fuel gas.Should be understood that the above-mentioned methane accumulative poly-unit of avoiding, can list in the practical application of the present invention.Like this, the recirculated compressed gas that contains methane of some can feed reformer 2, be methane conversion the extra hydrogen that increases here, and a part of PSA waste gas can not be compressed, but can pass through conduit 24, sends to and makes fuel.In another embodiment, some PSA compressed exhaust gas can be shunted in conduit 21, by conduit 25, flow into additional PSA system 26, and some waste gas needn't compress in the PSA system, shunts away from this system, by conduit 24, take away and make fuel or make other purposes.
As mentioned above, excessively accumulate in the recirculation loop of the present invention, can utilize conduit 24, a PSA waste gas shunting part that is present in conduit 20 in this method and system for fear of nitrogen and/or argon.In addition, PSA system 9 can carry out the high pressure absorption process, goes so that nitrogen and/or argon are flowed directly in the hydrogeneous product gas that had purified already that each sorbent bed product end is discharged in this system.Certainly, method selected should meet the product specification that is suitable for mutually with any given range of application.Method selected also can take the working method different with other to unite use for obtaining optimal performance in special applications.
In the very favourable and unique specific embodiments of the present invention, can adopt the recycling pipe 21 among process recycling such as the figure, avoid nitrogen and/or argon unnecessarily to accumulate in the recirculation loop of the present invention, have only nitrogenous maximum waste gas part in the PSA system, reclaim it.Carry out countercurrent depressurization steps when being in initial high pressure in said PSA system 9, discharge this hydrogen-rich gas.In specific embodiments of the present invention, further countercurrent depressurization reduces the gas that desorption pressures discharged, and, if necessary, adopt clearing process, then reduce the additional gas that desorption pressures discharged,, it is shunted away from this production system by conduit 24 with this operation.Having been found that now nonnitrogenous and hydrogen-rich gas argon to be released when being in initial high pressure in the countercurrent depressurization process, typically account in all gas up to 40%, is to discharge in said countercurrent depressurization process.The gas that countercurrent depressurization discharged, if be used initial 20%, perhaps bring up to 40%, it is sent into recirculation in water-gas conversion procedure and/or the exhaust generation operation (not considering to utilize other relevant different courses of processing with methane), as a kind of device, avoid nitrogen and/or argon excessively to accumulate in the recirculation loop of the present invention, this is special needs.Again it, in a specific embodiments that needs more, after the countercurrent depressurization process of the absorption agent bed of said PSA system 9, then establish a clearing process, in the end in the scavenging process, from the additional gas that each bed discharged, from the gas that each bed discharged, send to recirculation when being in initial high pressure with the countercurrent depressurization process.Have now found that, the gas that last scavenging process is discharged, can reach at last 50% or below, its nonnitrogenous and/or argon.Will be appreciated that, in scavenging process, under the condition of boosting gradually, the hydrogen-containing gas of the nonnitrogenous and/or argon of obtaining especially, for purposes of the invention, preferably recirculation, and the starting stage of the latter stage of countercurrent depressurization operation and clearing process can shunt away the gas that discharges at an easy rate from method and system of the present invention.People can understand that very soon height ideal processing characteristics can strengthen reclaiming product hydrogen according to the simple of this comprehensive invention.
The those of skill in the art in present technique field can understand, the details of this processing method and equipment thereof can be done multiple change and improvement and do not leave in the scope of claim of the present invention.Should recognize, the PSA method and system that is adopted here, if promptly main PSA system and the additional PSA 26(of system are when using), in order to reclaim product hydrogen, can select for use the sorbent bed and any known process of any number of plies to circulate.In the practical application of the present invention, can adopt the raw sorbent of share of any concrete ideal selectivity.The absorption agent that is fit to comprises: various zeolite-type molecular sieves, gac, silica gel, activated alumina etc.Aspect the hydrogen in separation and purifying exhaust gas stream, in general, more satisfactory is the zeolite molecular sieve absorption agent.About the data of zeolite molecular sieve aspect, can be with reference to United States Patent (USP) 3,176,444(Kiyonaga) and the specific embodiments in other relevant patents of PSA method and system.Equally, the carbonic acid gas washing procedure can adopt any known, industrial available washing technology and liquid washing material.Benfield alkaline water washing method, Shell Sulfinol and Allied Chemical Selexol solvent extration are to be applicable to the example of removing the factory technique of carbonic acid gas from air-flow of the present invention.In a plurality of specific embodiments that belong to category of the present invention, it should be noted that method of the present invention also can be applicable to separate the mixture with purified hydrogen and nitrogen, is used for the gas mixture of synthetic ammonia.This application as the known method of this technology field, can be adopted the external source nitrogen operation of removing and/or pressurize, product air-flow through purifying, the content of hydrogen and nitrogen is greater than the 99%(mole usually), and argon, the content of methane or other gases is less than the 1%(mole).
In the application example of the present invention, equipment used from the exhaust of partial oxidation device, contains 0.5% methane as shown in drawings, by pyrolytic conversion, removes CO with washing method
2, feed the PSA system then, Hydrogen Separation and purification.The waste gas of 80% PSA system is delivered to convertor recirculation, and 15% delivers to the recirculation of partial oxidation device, and 5% gas that acts as a fuel emits from production system.Deliver to the feed gas of this PSA system, contain the 2.5%(mole) methane, be converted into finished hydrogen and pay a product carbonic acid gas from the most carbon monoxide in the evacuation circuit of partial oxidation device, being present in 99% of whole hydrogen in the said evacuation circuit can be recovered.Reach good like this effect, do not need to adopt low temperature conversion or before delivering to the PSA system, also do not need to remove fully the carbonic acid gas in the evacuation circuit.
In a similar application example, from the evacuation circuit of Sweet natural gas steam reformation, press siccative and calculate, contain the 2.5%(mole) methane.By above-mentioned working conditions, in this convertor and washing section, handle, deliver to the feeding gas of PSA system, contain 6.7% methane.2/3rds PSA waste gas are delivered to convertor recirculation, and 1/3rd deliver to steam reformer recirculation.According to practical application of the present invention, this hydrogen production process can all transform contained CO basically in process of production, also basically hydrogen is all reclaimed.
In an example that can further specify whole advantages of the present invention, the evacuation circuit of being released from the petroleum naphtha steam reformation, pressing siccative calculates, contain the 5%(mole) methane, the cooling back transforms, the evacuation circuit of treated mistake is delivered to the absorption washing tower, and its concentration of carbon dioxide is reduced to the 3.5%(mole).Then, said gas further at the PSA system purification, obtain 99.99% flow of pure hydrogen, and the PSA exhaust flow is contained: hydrogen 51.4%(mole); CO
2The 13.1%(mole); The CO12.1%(mole); Methane 23.4%(mole).20% of said PSA waste gas is discharged into fuel gas system; 50% takes away recompresses and delivers to steam reformer recirculation; Wherein 30% deliver to conversion system recirculation.Whole carbon monoxide according in the handled evacuation circuit of the present invention can be transformed basically, generate hydrogen and carbonic acid gas, are deposited in this technological process, and can therefrom all reclaim hydrogen basically.
It should be noted,, when carrying out coal or heavy oil gasification, except containing carbonic acid gas, also contain hydrogen sulfide in the evacuation circuit when adopting partial oxidation process or other conversion methods.According to method of the present invention, the major part of these components can be removed it in washing section at least, reasonable employing selective solvent, just carbonic acid gas is gone up substantially and is not contained H
2S, and rich H
2The S air-flow can extract respectively.In this specific embodiments of the present invention, there is no need in washing section, to accomplish basically to remove fully H
2S is because can finish final purification in the PSA system.
The conventional machining process is not taked cryogenic purification, and in order to reduce on request the methane content in the gained finished product gas, reformation operation or partial oxidation should strictly remain on high level. The steam reformation dress The conversion ratio of putting is generally between 85% to 93%. Because in the methanation operation that does not have under the cryogenic purification, there is the feeding gas of 2-3% to be converted and again becomes methane, so should be appreciated that, 83 to about 90% the feeding gas of only having an appointment transforms at last finished hydrogen and pays a product carbon dioxide. On the other hand, in practical application of the present invention, steam reformer can be worked under not too violent condition, and for example outlet maintains low temperature level and/or adopts if necessary low steam to carbon ratio example, reduces cost of investment and/or reduces the steam requirement to reach. In addition, in practical application of the present invention, the hydrocarbon feed that feeds reformer can reduce 8～17%. When adopting feed naphtha, this point particular importance. Many advantages of the present invention make it add less steam about 10 to about 30% to feeding gas, reduce the fuel requirement of this technical process for this reason and maybe can export steam from this technical process and device.
As mentioned above, the present invention in actual applications, can not take the low temperature conversion operation, in addition, owing to can adopt cheap carbon dioxide absorption operation, remove the carbon dioxide in the exhaust stream of already having processed, can remove at least major part wherein, consequently in the carbon dioxide removal operation, allow minimizing equipment expense. Carried above, unlike common process, in the practical application of the present invention, do not need methanation or cryogenic purification operation.
Adopt the PSA method to carry out the hydrogen final purification, compare with conventional method, can the higher hydrogen production of production purity. Should see that this can reduce the hydrogen requirement of downstream hydrogenation processing operation greatly, thereby greatly is conducive to the present invention. In a word, method and apparatus of the present invention provides incomparable efficient. Steam reformer, it is two kinds of products that all raw materials of partial oxidation device or other hydrogeneous exhaust stream generating means are converted to basically, be carbon dioxide and finished hydrogen, said finished hydrogen can be according to PSA of the present invention system, and high-recovery ground, high-purity ground is reclaimed. Because above-mentioned advantage according to method of the present invention, is produced the capital cost of hydrogen, compares with the capital cost of conventional factory, estimates few 2-12%. The more important thing is that adopt the present invention, fuel saving takes and raw material cost significantly, this saving is considerably beyond the expenditure on power of the recycle compressor of the present invention's employing. Great superiority and benefit that the method and apparatus of narrating in the specification and claims has estimate that for a factory that per hour produces 6 tons of hydrogen every year can Save manufacturing cost more than 1,000,000 dollars. For partial oxidation or Coal Gasification operation, the needed raw material of PSA method of the present invention and oxygen lack than conventional method. Above-mentioned various reasons, it should be understood that, the method that this paper and claims are narrated and equipment thereof, aspect the process for making hydrogen of exhaust stream, namely by steam reformation, the process for making hydrogen aspect of the hydrogeneous exhaust stream that partial oxidation, Coal Gasification etc. take place, made far reaching, development with having an economic benefit.
Claims (42)
1, a kind ofly produce improving one's methods of hydrogenous gas products, it is characterized in that it includes:
(a) produce a kind of evacuation circuit that contains hydrogen, carbonic acid gas, carbon monoxide and water vapor;
(b) said evacuation circuit carries out the conversion of high-temperature catalytic water-gas at least, therefrom most carbon monoxide is transformed into additional hydrogen and carbonic acid gas;
(c) from the said evacuation circuit of having handled, remove most carbonic acid gas at least;
(d) this evacuation circuit of having removed carbonic acid gas is delivered to the pressure variation absorption system, (being called for short the PSA system), what a kind of purification that is difficult for being absorbed component as this evacuation circuit can be discharged in the there contains hydrogen production gas, and the said the easiest absorption component in the said evacuation circuit contains remaining carbonic acid gas and other impurity, be when carrying out countercurrent depressurization and/or removing step in the fabrication cycles process of each bed of PSA system and exclude this system, said circulation comprises: high pressure absorbs and emits from the product end of bed and to be difficult for absorbent components; Following current is reduced pressure and is emitted void space gas from the product end of bed; Bed carry out countercurrent depressurization with minimizing take off inhale pressure and/or and emit impure waste gas from the feeding end of bed; Again pressurize to improve absorption pressure;
(e), discharge the waste gas compression and from the pressure variation absorption system at countercurrent depressurization process and/or clearing process;
(f) at least 40% compressed exhaust gas is got back to said conversion system and/or evacuation circuit generation operation; Whereby can be effectively said evacuation circuit be converted into give think contain hydrogen production air-flow and CO 2 waste gas, high-recovery ground reclaims and contains hydrogen production.
2, the process of claim 1 wherein said evacuation circuit, be to reform, and do not have secondary reformed from the hydro carbons primary steam.
3, the method for claim 2 comprises that the said evacuation circuit of once reforming is sent to carry out secondary reformed.
4, the process of claim 1 wherein that said evacuation circuit is from the hydro carbons partial oxidation.
5, the process of claim 1 wherein that said evacuation circuit is from gasification of coal.
6, the method for claim 2 is wherein through containing the 3%(volume at least in the evacuation circuit of reforming) methane, in the EGR gas from the PSA system,, deliver to said reformer recirculation at least about 20%, carry out said primary steam reforming process.
7, the method for claim 3, wherein the evacuation circuit of secondary reformed contains methane and is less than the 1%(volume), in the EGR gas from the PSA system, get back to recirculation in the conversion process at least about 20%.
8, the method for claim 1 is included in and carries out before the said step of converting, and said evacuation circuit is cooled to about 350 ℃.
9, the process of claim 1 wherein that said evacuation circuit also contains methane.
10, the method for claim 9 wherein has at least part to be back to recirculation in the evacuation circuit generation operation from the waste gas that contains methane of PSA system under boosting.
11, the method for claim 9 wherein from the part that contains methane waste product of PSA system, when improving absorption pressure in additional PSA system, transforms it; The difficult absorption product gas bag of therefrom being emitted is drawn together the additional hydrogen production that contains through purifying; The easiest absorption waste gas of therefrom removing comprises and is fit to be used for the methane gas stream that contains that fuel gas uses.
12, the method for claim 9 is wherein shunted away the waste gas that the part from the PSA system contains methane from this production system, the waste gas after the said shunting can be used as fuel gas.
13, the method for claim 10 is wherein delivered to the recirculation of said evacuation circuit generation operation from a part of waste gas of PSA system, and some waste gas is shunted away from this production system.
14, the method for claim 11 wherein is diverted to additional PSA system to a part of waste gas from the PSA system, and some waste gas is shunted away from whole production system.
15, the process of claim 1 wherein that said evacuation circuit also contains nitrogen and/or argon.
16, the method for claim 15, wherein said PSA system carries out the high pressure absorption process, goes so that nitrogen and/or argon are flowed directly in the hydrogeneous product gas that had purified already that the sorbent bed product end in this system discharged.
17, the method for claim 15, wherein have at least a part from the nitrogenous of PSA system and/or argon waste gas by shunting away in the production system.
18, the method for claim 15, wherein the EGR gas from the PSA system comprises: the countercurrent depressurization process is in unique hydrogen-rich gas that the initial high pressure stage is discharged; Further countercurrent depressurization lowers the gas that desorption pressures discharged and lowers any additional gas that desorption pressures discharged, the i.e. gas of shunting out from whole production system.
19, the method for claim 15, wherein the EGR gas from the PSA system comprises: the countercurrent depressurization process is in the hydrogen-rich gas that initial high pressure discharges during the stage and removes the gas that the step final stage is discharged, and when said countercurrent depressurization process is in the starting stage of final stage and said removing step pressurize, nitrogen and/or argon are disposed from said bed basically.
20, the method for claim 13, wherein said evacuation circuit are that the primary steam that results from hydro carbons is reformed, and do not have secondary reformed, and it is the 3%(volume at least that the evacuation circuit of this reformation contains) methane.From in the waste gas of pressure variation absorption system at least about having 20% to get back to a reformer recirculation.
21, the method for claim 20, wherein said evacuation circuit also contains nitrogen and/or argon, wherein said PSA system carries out the high pressure absorption process, so that go in the hydrogeneous product gas that had purified already that the product end that makes nitrogen and/or argon flow directly to the absorber layer in this system is discharged.
22, the method for claim 20, wherein said evacuation circuit also contains nitrogen and/or argon, wherein is in initial high pressure during the stage in the countercurrent depressurization process, only contains hydrogen-rich gas from the EGR gas of PSA system, does not comparatively contain the nitrogen and the argon that discharge.
23, the method for claim 20, wherein said exhaust system also contains nitrogen and/or argon, wherein the EGR gas from the PSA system comprises following gas, be that the countercurrent depressurization process is in the hydrogen-rich gas that initial high pressure was discharged during the stage, and remove the gas that the step final stage is discharged, the comparatively nonnitrogenous and/or argon of these EGR gases.
24, the method for claim 13, wherein said evacuation circuit is that the effluent from a reformer carries out secondary reformed or from the hydro carbons partial oxidation, contain in the said evacuation circuit and be less than the 1%(volume) methane, have 20% at least in the waste gas from the PSA system, send back to conversion process recirculation.
25, the method for claim 24, wherein said evacuation circuit, also contain nitrogen and/or argon, wherein said PSA system carries out the high pressure absorption process, contains hydrogen production gas so that said nitrogen and/or argon are flowed directly to from having purified already of being discharged of the product end of absorber layer.
26, the method for claim 24, wherein said evacuation circuit also contains nitrogen and/or argon, wherein from the EGR gas of PSA system, only contains in the countercurrent depressurization process and is in hydrogen-rich gas that the initial high pressure stage discharges and comparatively nonnitrogenous and argon.
27, the method for claim 24, wherein said evacuation circuit also contains nitrogen and/or argon, wherein the EGR gas from the PSA system contains following gas, and promptly the countercurrent depressurization process is in hydrogen-rich gas that the initial high pressure stage discharged and the gas that final stage discharged of removing step; The comparatively nonnitrogenous and/or argon of this recycle gas.
28, the method for claim 20 also contains nitrogen and/or argon in the wherein said evacuation circuit, wherein at least a part of waste gas from the PSA system is shunted away from production system.
29, the method for claim 24, wherein said evacuation circuit also contains nitrogen and/or argon, wherein at least a part of waste gas from the PSA system is shunted away from production system.
30, the process of claim 1 wherein that the said hydrogen production gas bag that contains contains a kind of as the hydrogen of synthetic ammonia and the mixed gas of nitrogen.
31, a kind of production contains the improved already equipment that hydrogen production gas is used, and it is characterized in that it comprises:
(a) produce a kind of hydrogen that contains, the generating unit that the evacuation circuit of carbon monoxide and carbonic acid gas is used;
(b) carbon monoxide in the said evacuation circuit is converted into used refrigerating unit of hydrogen and carbonic acid gas and high-temperature catalytic water-gas conversion system;
(c) can major part remove at least from the used washing device of carbonic acid gas in the evacuation circuit after this water-gas conversion;
(d) a kind of hydrogen-containing gas streams that purified be can give off, the residual carbon dioxide and the used a kind of pressure variation absorption system of other impurity that are present in the said evacuation circuit comprised;
(e) the used gas booster compressor of the said exhaust flow of compression;
(f) send back to said conversion system and/or the used conduit means of said evacuation circuit generating unit recirculation to about 40% of the said compressed exhaust gas of major general,
Can effectively said evacuation circuit be converted into by means of this and give fixed hydrogen production air-flow and the CO 2 waste gas of containing, high-recovery ground reclaims and contains hydrogen production.
32, the equipment of claim 31 comprises a kind of primary steam device with said evacuation circuit generating unit wherein.
33, the equipment of claim 32 comprises a kind of secondary reformed device.
34, said evacuation circuit generating unit in the equipment of claim 31 is comprising a kind of partial oxidation device.
35, said evacuation circuit generating unit in the equipment of claim 31 is comprising a kind of coal gasification device.
36, the equipment of claim 31 comprises a kind of additional PSA system and is diverted to the used conduit means of said additional PSA system to a part of waste gas of the said PSA of major general system.
37, the equipment of claim 31 is included as a discharging part from the used conduit means of the waste gas of PSA system.
38, the equipment of claim 36 comprises as the extra difficult absorption product gas that contains hydrogen production that had purified already and is reclaimed used conduit means.
39, the equipment of claim 31, wherein said conduit means are fit to be used for compressed exhaust gas is sent back to said conversion system recirculation.
40, the equipment of claim 31, wherein said conduit means are fit to be used for compressed exhaust gas is sent back to the recirculation of said evacuation circuit generating unit.
41, power is planted 31 the equipment that requires, comprise exhaust emission device, said waste gas is the gas that is discharged when said PSA system is in the countercurrent depressurization final stage and reduces desorption pressures, said device is fit to hydrogen-rich gas and carries out the used Exhaust gas recirculation device of recirculation, and said hydrogen-rich gas is that the countercurrent depressurization process from said PSA system is in unique hydrogen-rich gas that the initial high pressure stage is discharged.
42, the equipment of claim 41, comprising the gas re-circulation device, said gas is the gas that final stage discharged of removing step from said PSA system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85109166 CN85109166A (en) | 1984-02-07 | 1985-10-24 | Improve the recovery of hydrogen by exhaust jet stream |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/577,802 US4553981A (en) | 1984-02-07 | 1984-02-07 | Enhanced hydrogen recovery from effluent gas streams |
| CN 85109166 CN85109166A (en) | 1984-02-07 | 1985-10-24 | Improve the recovery of hydrogen by exhaust jet stream |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85109166A true CN85109166A (en) | 1987-04-29 |
Family
ID=25742144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85109166 Pending CN85109166A (en) | 1984-02-07 | 1985-10-24 | Improve the recovery of hydrogen by exhaust jet stream |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85109166A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465094C (en) * | 2007-01-27 | 2009-03-04 | 营口三征有机化工股份有限公司 | Method of synthesizing ammonia by hydrogen gas purified by tail gas of sodium cyanide and alkali-chloride production |
| CN105939772A (en) * | 2014-01-30 | 2016-09-14 | 巨石材料公司 | Integration of plasma and hydrogen process with combined cycle power plant, simple cycle power plant and steam reformers |
| CN107074536A (en) * | 2014-10-22 | 2017-08-18 | 环球油品公司 | Hydrogen is reclaimed from the waste gas of fractionation zone |
| US11760884B2 (en) | 2017-04-20 | 2023-09-19 | Monolith Materials, Inc. | Carbon particles having high purities and methods for making same |
| US11866589B2 (en) | 2014-01-30 | 2024-01-09 | Monolith Materials, Inc. | System for high temperature chemical processing |
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| WO2024107639A1 (en) * | 2022-11-18 | 2024-05-23 | Uop Llc | Process for increasing hydrogen recovery by chilling hydrogen with product co2 stream |
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1985
- 1985-10-24 CN CN 85109166 patent/CN85109166A/en active Pending
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| CN100465094C (en) * | 2007-01-27 | 2009-03-04 | 营口三征有机化工股份有限公司 | Method of synthesizing ammonia by hydrogen gas purified by tail gas of sodium cyanide and alkali-chloride production |
| US11866589B2 (en) | 2014-01-30 | 2024-01-09 | Monolith Materials, Inc. | System for high temperature chemical processing |
| CN105939772A (en) * | 2014-01-30 | 2016-09-14 | 巨石材料公司 | Integration of plasma and hydrogen process with combined cycle power plant, simple cycle power plant and steam reformers |
| CN115463513A (en) * | 2014-01-30 | 2022-12-13 | 巨石材料公司 | Integration of plasma and hydrogen processes with combined cycle power plants and steam reformers |
| US11939477B2 (en) | 2014-01-30 | 2024-03-26 | Monolith Materials, Inc. | High temperature heat integration method of making carbon black |
| US12144099B2 (en) | 2014-01-31 | 2024-11-12 | Monolith Materials, Inc. | Plasma torch design |
| CN107074536B (en) * | 2014-10-22 | 2019-04-30 | 环球油品公司 | Hydrogen is recycled from the exhaust gas of fractionation zone |
| CN107074536A (en) * | 2014-10-22 | 2017-08-18 | 环球油品公司 | Hydrogen is reclaimed from the waste gas of fractionation zone |
| US11998886B2 (en) | 2015-02-03 | 2024-06-04 | Monolith Materials, Inc. | Regenerative cooling method and apparatus |
| US12250764B2 (en) | 2015-07-29 | 2025-03-11 | Monolith Materials, Inc. | DC plasma torch electrical power design method and apparatus |
| US12119133B2 (en) | 2015-09-09 | 2024-10-15 | Monolith Materials, Inc. | Circular few layer graphene |
| US12012515B2 (en) | 2016-04-29 | 2024-06-18 | Monolith Materials, Inc. | Torch stinger method and apparatus |
| US11760884B2 (en) | 2017-04-20 | 2023-09-19 | Monolith Materials, Inc. | Carbon particles having high purities and methods for making same |
| US12030776B2 (en) | 2017-08-28 | 2024-07-09 | Monolith Materials, Inc. | Systems and methods for particle generation |
| WO2024107639A1 (en) * | 2022-11-18 | 2024-05-23 | Uop Llc | Process for increasing hydrogen recovery by chilling hydrogen with product co2 stream |
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