CN1161934A - Method for generating hydrogen and energy and apparatus thereof - Google Patents
Method for generating hydrogen and energy and apparatus thereof Download PDFInfo
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- CN1161934A CN1161934A CN 96121971 CN96121971A CN1161934A CN 1161934 A CN1161934 A CN 1161934A CN 96121971 CN96121971 CN 96121971 CN 96121971 A CN96121971 A CN 96121971A CN 1161934 A CN1161934 A CN 1161934A
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- membrane separator
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 71
- 239000001257 hydrogen Substances 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 98
- 239000007789 gas Substances 0.000 claims abstract description 93
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000012466 permeate Substances 0.000 claims abstract description 13
- 239000012495 reaction gas Substances 0.000 claims abstract description 12
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 32
- 239000008246 gaseous mixture Substances 0.000 claims description 28
- 239000000376 reactant Substances 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 18
- 238000010248 power generation Methods 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 7
- 238000001764 infiltration Methods 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 230000005611 electricity Effects 0.000 abstract description 3
- 239000012465 retentate Substances 0.000 abstract 3
- 238000001179 sorption measurement Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 229910052786 argon Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000926 separation method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- -1 CO 2 Chemical compound 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- Y02T10/32—
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A process for the generation of energy and of a hydrogen-rich mixture (30), includes the following steps: a) a partial oxidation of an incoming hydrocarbon gas mixture (15) is carried out using an oxidant mixture (16) which contains oxygen, so as to obtain as output from the unit a reaction gas (17) which contains hydrogen and CO; b) the reaction gas produced at the end of step a) is passed into a membrane separator (24) which generates, as its permeate output, a permeate gas mixture (25) enriched in the more permeable components of the reaction gas and, as its retentate output, a retentate gas mixture (26) enriched in the less permeable components of the reaction gas; c) the retentate gas mixture (26) is treated in an electricity generation unit (27); d) the permeate gas mixture (25) is separated in a preferential adsorption separator (29) so as to obtain, as unadsorbed product gas, the desired hydrogen-rich gas mixture (30).
Description
The present invention relates to produce the field (usually this technology is referred to as " POX " in the literature, represents partial oxidation) of hydrogen with the partial oxidation of hydrocarbon mixture.This invention is particularly related to the method and apparatus that produces hydrogen and energy simultaneously.
Many methods that relevant hydrogen and/or energy produce have been reported in the literature, it is based on the partial oxidation of hydrocarbon mixture (for example coal, Sweet natural gas, oil and heavy fuel oil), and along with the variation of reaction conditions (composition of temperature, pressure and reactant gases) can cause that the composition of formed reactant gases sharply changes.Reference is many articles of publishing with the name of TEXACO SHELL or WESTINGHOUSE.
Reactant gases as the product of partial oxidation device comprises tens percent H usually
2/ CO mixture, and nitrogen, CO
2, argon gas or the like.
General flow process generally includes the following current of partial oxidation device and operates, a step or a polystep reaction gas cleanup step: discharge the CO that generates with the water vapour catalyzed reaction, discharge section or whole H
2S discharges COS (carbonyl sulfide) and discharges NOX (these purifying step are known for the personnel that are familiar with the partial oxidation field).
These purifying step following currents operation, the reactant gases of Jing Huaing is sent to usually and selects in the absorption extraction device in (for example PSA type) or other diaphragm type separator like this, so that flow according to the regulation generate energy of every kind of situation requirement or hydrogen stream or CO.
The most normal oxygenant of quoting is that air or oxygen-enriched content reach 35% even more air in the document about POX.
From these a lot of documents, mention document EP-A-217505, the document has been described generate energy and the mixture with at least 50% hydrogen simultaneously, this mixture has comprised the hydrogen that produces as " not absorbing product " air-flow from select the absorption extraction device, wherein treated as the POX device product and the reactant gases produced, and by absorbed gaseous mixture (rich CO, CO in separator
2, N
2, CH
4Or the like) in the feeder, then in gas turbine, expand through the mixture through catalytic burning and to generate electricity and produce energy more.
Because the purpose of this piece document provides a kind of mixture that is used for ammoniacal liquor synthetic hydrogen that comprises, the hydrogen of low concentration allows.Yet the author mentions the gas that is produced by the absorption extraction device comprises the argon gas (from for the argon gas that obtains the oxidant gas that uses) that quantity be can not ignore, the beyond all doubt permission of the disclosed argon gas of the document.
The successful work of being undertaken by the applicant in this field is verified, and these contain under the oxygen situation of argon gas in supply, have found a large amount of argon gas in the hydrogen rich gas mixture of being produced by this method.Yet, though use this hydrogen-rich mixture in many applications afterwards, the argon gas existence there is no inconvenience, (for example hydrogen sulfur method or hydrogen cleavage method) in other cases, argon gas has reduced the dividing potential drop of hydrogen in the gaseous mixture that uses, thereby causes side reaction significantly.
In the face of these problems, that at first considers is to use very pure oxygen (typically 99.5%), the further like this process cost that has increased device.
Another kind of technical feasibility scheme is to select absorption unit to constitute by the PSA that arranges, so that stop argon gas better, be not (the retained gas scale of construction that the hydrogen extraction yield reduces and low value low pressure absorbs increases) that does not have consequence still at equipment and its this arrangement of aspect of performance.
An object of the present invention is to provide a kind of method and apparatus of producing energy and hydrogen-rich mixture, it comprises as follows:
The mixture (as required, reach in case of necessity 99.9% or even 99.99% hydrogen) of producing energy simultaneously and having very high hydrogen purity;
Prepare in the process at partial oxidation, may use impure oxygen (according to original case, it can sharply change, and therefore they can comprise a large amount of argon gas in this case);
The ratio of density of hydrogen and generated energy approaches to be rich in flexible in the mixture that produces: purpose is to revise this ratio as requested herein, and, keep constant as required, although can suitably be modified in the hydrocarbon gas mixture characteristic that enters processed in the partial oxidation device (for example H/C ratio).
Production method according to energy of the present invention and hydrogen-rich mixture is made up of following implementation step:
A) in the partial oxidation device, use the oxidant mixture that comprises oxygen that the gaseous mixture that enters that comprises hydrocarbon or hydrocarbon mixture is carried out partial oxidation, so that obtain the reactant gases that comprises hydrogen and carbon monoxide CO as the product of this device;
B) pass through membrane separator at the terminal reactant gases that produces of step a), so that produce as it the infiltration product the multiple infiltration component of enrichment reaction gas mixtures permeate gas mixture and as the reservation gaseous mixture of the less permeable component of its enrichment reactant gases of retained product;
C) in power generation assembly, handle said reservation gaseous mixture;
D) in selecting the absorption extraction device, separate said permeate gas mixture, so that obtain satisfactory hydrogen-rich gaseous mixtures as unabsorbed gas products.
According to the present invention, be interpreted as in the series connection of suitable place with " membrane separator " and/or a semi-permeable membrane or the barrier film module of the characteristic with separating hydrogen gas from the reactant gases that enters separator are installed in parallel, or a cover semi-permeable membrane or a cover barrier film module.
According to the present invention, this method comprises membrane separator and selects the use of using and connect of uniting of absorption extraction device.Has H
2/ N
2, H
2/ CO and H
2/ Ar makes under optimum pressure than the optionally application of the membrane separator of high selectivity, might add hydrogen-rich gas in selecting the absorption extraction device, the reservation gaseous mixture (comprising CO, argon gas and nitrogen substantially) in the membrane separator can be admitted in the power generation assembly simultaneously.
As the relevant embodiment in back explains, according to the present invention, the possible one side of this method is by the characteristic of suitable selection membrane separator, produce very pure hydrogen (for example variation of from 99.5 to 99.9% purity), and the while is in the beginning of flow process, use impure oxygen, comprise the oxygen that contains remarkable concentration argon gas.
And, under low-down pressure (with the situation of low value), be reduced to minimumly by the quantity of the reservation gas after the absorption of selecting the absorption extraction device to produce, the two is inversely proportional to because enter the hydrogen amount of separator and its extraction output.
Here mention the principle of diaphragm type gas separator simply again, Here it is because the different effect of barrier film both sides dividing potential drop, the low pressure mixture that enrichment enters the more infiltration component of gas of membrane separator forms at the permeate side of membrane separator, and pressure forms on the reservation limit of separator near the input pressure of the mixture that enters and the mixture of the less infiltration component of enrichment.
For example, production about gas or CO, the mixture that obtains from certain enterprise begins to carry out lock out operation usually, make this mixture pass through membrane separation, this film has isolating characteristic (for example using the film of aramid type) in hydrogen other component from mixture, produce hydrogen-rich mixture at membranous permeate side,, produce the mixture of rich hydrocarbon or rich CO on membranous reservation limit simultaneously along with the difference of situation.
The performance of obvious this membrane separator depends on membranous working conditions greatly, and for example temperature, membranous air inlet are pressed or the content that enters mixture to be separated, wish the component content that extracts at permeate side.
About temperature, by increasing membranous service temperature, membranous perviousness and productivity increase usually, but impair its selection rate and efficient as everybody knows.The term of barrier film or barrier film module " service temperature " is generally understood as the temperature that forms in the barrier film module, because be used to heat the interference that adds of the external system barrier film module or insulation (thermostatic chamber) sometimes by the membranous temperature that enters gas.
Here mention some definition about the conventional situation of separation of nitrogen from air: membranous " output " representative exists the ratio of nitrogen, membranous O in the mixture that enters that the reservation outgoing side of film is found
2/ N
2The selection rate representative is by the rate of permeation or the infiltrative ratio (selection rate=oxygen permeability/nitrogen rate of permeation) of membranous oxygen permeability or perviousness and nitrogen.Use this same learning concept under the situation of Hydrogen Separation, this learning concept is opposite with discharge output, because the hope recovery is the infiltration mixture of enrichment hydrogen.
Hereinafter, use the simplification of terminology " selection rate of membrane separator " of relevant given gas, it should be understood to be in the mixture aspect of handling in this separator, and this separator is to the selection rate (above-mentioned selection rate is the notion of being correlated with) of the gas discussed.
Therefore the selection rate that changes the separator of relevant given gas (for example hydrogen) is possible, for example uses the barrier film with different qualities, or use same model module but under different operational conditions, particularly temperature condition.
According to one embodiment of the invention, in the oxidant gas mixture, change in oxygen concentration from 21% to 98% scope.
According to one embodiment of the invention, between partial oxidation step and membrane separation step, carry out at least a following cleansing operation:
Processing reaction gas in carbonyl sulfide (COS) conversion system;
Processing reaction gas in desulfurizer;
Processing reaction gas in carbon monoxide CO conversion system, wherein in reactant gases, at least some CO are by being converted into carbonic acid gas CO with the water vapour catalyzed reaction
2With hydrogen H
2
Preferentially sent in the steam-generating installation by the reservation gas after the absorption of separator selection absorption generation.
According to another embodiment, desulfurized step does not carry out in the upstream of membrane separator, and carries out between membrane separator and power generation assembly.Power generation assembly communicates with the reservation output terminal of separator by circuit.The investment of desulfurizer and process cost are in fact than higher.Therefore, according to the present invention, two separation configurations, promptly membrane separator/selection absorption extraction device might be in suitable place along the reservation line move operation of membrane separator, and this has benefited from the common good anti-H of polymer fiber that is seen
2S.These variations might suitably reduce the needed investment of desulfurization operations, and electricity and steam consumption, because the volume that desulfurizer is handled on the reservation limit of membrane separator must reduce.
And, penetrate on one side the H that has penetrated at membrane separator
2S part is collected in and comes from this and select in the low pressure retention in absorption extraction device every living (performance of this device can obviously not reduce) and it on selecting the absorption extraction device, it for example is compressed and turns back in the sulfurous combustion gases system of refinery (or other appropriate hydrocarbon gas supply department), or in other steam-generating installation.
And, according to prior art, discovery is opposite with the produced simultaneously equipment of energy with hydrogen, wherein the reactant gases that produces from the POX device in fact is divided into two kinds of air-flows, they are sent in two dedicated pipelines that optimum cooperation seldom is provided, according to the present invention, this method disposes the ratio between the electric weight that the concentration that may revise even be adjusted at hydrogen in the hydrogen-rich gaseous mixtures and power generation assembly produce, and for example changes one of following parameters:
The degree of conversion of CO conversion system in reactant gases (yes between POX device and membrane separator conversion system);
The hydrogen selection rate of membrane separator.
Such as previously mentioned, for example by change using the quantity and the characteristic of the barrier film module in membrane separator, or the hydrogen selection rate that the service temperature that selectively changes separator is revised separator is possible.
According to the present invention, " service temperature " is understood to be in the application's above-mentioned notion.
Revise or adjust H
2May becoming of/energy ratio is definitely important, so that in order to be complementary with the represented needs of user, and can handle and adapt in the partial oxidation device, effective modification of the pending quality that enters gaseous mixture (for example H/C ratio), for example because at industrial site partial production taking place changes, supply is the pending mixture that enters in the POX device.
The present invention also relates to produce the device of energy and hydrogen-rich mixture, it is particularly suitable for implementing above-mentioned method, and comprises:
The source of supply that enters gaseous mixture that comprises hydrocarbon or hydrocarbon mixture;
The source of supply that comprises the oxidant gas mixture of oxygen;
The partial oxidation device that is connected with source of supply is so that can produce the reactant gases that comprises hydrogen and carbon monoxide CO as its product;
Membrane separator, an one input terminus is connected on the output terminal of partial oxidation device by main gas tube;
Power generation assembly, it is connected on the retention output terminal of membrane separator by the second line;
Select to absorb gas separator, PSA type for example, an one input terminus is connected on the penetrant output terminal of membrane separator by the 3rd pipeline.
In suitable place, between partial oxidation device and membrane separator, equipment comprise at least a for those skilled in the art all known below gas-cleaning installation;
Use water vapor with carbon monoxide CO catalysis changing into carbonic acid gas CO
2With hydrogen H
2
The conversion system of carbonyl sulfide COS;
The desulfurizer of gas.
According to one embodiment of the invention, on the second line, this equipment is included in the desulfurizer of the gas between membrane separator and the power generation assembly.
Other features and advantages of the present invention are embodied by the description of the given embodiment that is used for illustrating rather than limits in back, about the description of accompanying drawing, wherein:
Fig. 1 is the equipment diagram of producing hydrogen and energy in the prior art simultaneously;
Fig. 2 is the equipment diagram that is fit to implement the inventive method;
Fig. 3 be fit to implement the inventive method and be included in the diagram that another equipment of desulfurization operations is carried out in the membrane separator upstream.
Fig. 1 produces the device of hydrogen and energy with graphic mode explanation prior art the time, wherein is divided into two kinds of air-flows from the reactant gases of partial oxidation POX device and is admitted in two dedicated pipelines.
Fig. 1 represents partial oxidation POX device 1, and on the one hand, hydrocarbon gas mixture 2 that enters and the oxidant mixture 3 that comprises oxygen are admitted in this device.
Reactant gases 4 by the partial oxidation operation produces reaches selection absorption extraction device 11 (it is under PSA type situation) before at it, carries out COS and transforms the operate continuously that (device 5), desulfurization (device 6) and portion C O transform (installing 9).
Here need CO conversion system 9 so that increase the hydrogen content in the mixture of the input terminus reach PSA type separator and reduce its CO content.This is that the output of PSA type separator will obviously reduce because there is not this CO conversion system, and in order to produce the hydrogen of equal amts, the amount of gas that the input limit of PSA type separator needs therefore meeting is obviously big
Some reactant gasess as the product that installs 6 produces by bay-line 7, are sent to energy and form device 8 places.
Arrive in the PSA separators 11 as the reactant gases after the purification of device 9 products generation 10, reservation gas 12 after forming unabsorbed hydrogen-rich gas product 13 and may being used in the absorption of output terminal in the steam-generating installation or that be recycled to partial oxidation device 1.
As for Fig. 2, its explanation be fit to be implemented the equipment of the inventive method, after it in series uses membrane separation, is then carried out the secondary operation that the PSA type is selected absorption extraction.
As noted above, the gaseous mixture that enters (rich hydrocarbon) composition can change bigger, for example methane, coal or the like.
In represented embodiment, the reactant gases from device 14, before it enters membrane separator 24, carry out twice cleansing operation: the COS in device 8 transforms and the desulfurization in device 20.
The reactant gases 23 of Jing Huaing enters in the membrane separator 24 like this, and wherein the retention product as membrane separator produces rich especially CO, CO
2And N
2Reservation gaseous mixture 26, they are sent in the power generation assembly 27.
What produce at the permeate side of separator 24 is the rich hydrogen permeate gas mixture 25 that under low pressure forms, it was compressed again by compressor 28 before arriving PSA type selection absorption extraction device 29, so that under high pressure produce the unabsorbed product gas 30 of rich hydrogen and under low pressure produce particularly rich CO
2Permeate gas 21 with the absorption of CO.
Then, gaseous mixture 30 can be sent to subscriber station 31 theres that may use this hydrogen-rich gaseous mixtures at any time.For low pressure mixture 21, for example it is sent in the steam-generating installation 22 or comes back to the source place of the rich appropriate hydrocarbon gas that enters, and for example, this place, source may be a refinery.
This application drawing of implementing the equipment of the inventive method illustrates by this method and according to the desired detailed description of each user, it is possible saving the CO step of converting.
Fig. 3 provides the accommodation of the equipment of describing in advance among a kind of Fig. 2 in front, wherein desulfurizer 20 no longer is put into the upstream of membrane separator 24 but is put into the downstream of this separator 24 herein, and the second pipeline is connected to the retention output terminal of membrane separator 24 on the power generation assembly 27.
In this case, carried out cleansing operation completely because arrive the reactant gases 19 of membrane separator 24, it is different from the complete cleansing operation of carrying out among in front Fig. 2, therefore the gas separated mixture is different from gas separated mixture in Fig. 2 in membrane separator 24, the gaseous mixture that different digitized representations is different, they enter the separator downstream, and arrive power generation assembly 27, PSA separator 29, subscriber station 31 respectively or kept the recovery point 22 of gaseous mixture by the low pressure that the PSA separator produces.
Table I, II and III explanation the following example:
Table I: comparative example illustrates with the equipment in the oxidant mixture application drawing 1 that comprises 99.5% oxygen;
Table II: comparative example illustrates with the impure oxidant mixture that comprises 95% oxygen to be applied in equipment among Fig. 1;
Table III: embodiments of the invention, in front the equipment among Fig. 2 in, use the oxidant mixture comprise 95% oxygen;
Therefore can see: in the embodiment of Table I (using purity is the scheme of 99.5% very pure oxygen), as the unabsorbed product mixture that PSA separator product produces, its hydrogen is very pure and has concentration and be about 0.1% remaining argon gas.
Because some reactant gasess that produce as device 6 products are sent in the power generation assembly by dedicated pipeline, therefore do not wrap umber and contain approximately equalised CO and hydrogen so this gas has had the lock out operation of selection and it.
About the comparative example of Table II, the scheme of equipment of the prior art is used in its explanation with low-purity oxidation agent composition (95% oxygen).In the product gas mixture that produces as PSA separator product thereby also contain the argon gas (about 1%) of significant amounts, the hydrogen partial pressure that it impairs in this mixture, the purpose that forms this mixture are for example to use it in hydrogen desulfurization or the hydrogen cracking in sensitive operation subsequently.
More than also can carry out herein about the statement of the composition of delivering to the gaseous mixture in the power generation assembly.
On the contrary, have a look at the result of the embodiment of Table III of the present invention, can see that described method can begin to produce the hydrogen with extremely pure (about 99.9%) of allowing residual argon concentration (about 0.1%) from the lower oxidant source material of product oxygen purity (comprising 5% remaining argon gas) as the PSA separator.
As mentioned above, according to the present invention, on the one hand, then select the secondary operation of absorption extraction might begin to form excellent hydrogen selection rate after the membrane separation from impure oxygen, and will deliver in the power generation assembly as the gaseous mixture that membrane separator retention product produces simultaneously, form very selective (in this case, being rich in CO) through determining this gaseous mixture.
Although described the present invention according to the specific technology scheme of counting, it is not limited to these, on the contrary can making, and for those skilled in the art, obviously be the modifications and variations in these claims scope.
Table I
| Liquid | Mixture " 2 " | Mixture " 3 " | Mixture " 4 " | Take-off equipment " 5 " | Take-off equipment " 6 " | Mixture " 10 " | Mixture " 13 " | Mixture " 12 " | Mixture " 7 " |
| Composition dry volume % | |||||||||
| ??N 2 | ??0.00 | ????0.00 | ????0.00 | ????00.0 | ??0.00 | ????0.00 | ??0.00 | ????0.00 | |
| ??O 2 | ??99.50 | ????0.00 | ????0.00 | ????00.0 | ??0?00 | ????0.00 | ??0.00 | ????0.00 | |
| ??Ar | ??0.50 | ????0.13 | ????0.13 | ????0.13 | ??0.09 | ????0.09 | ??0.09 | ????0.13 | |
| ??CO | ????48.17 | ????48.14 | ????49.59 | ??3.43 | ????0.00 | ??7.46 | ????49.59 | ||
| ??H 2 | ????42.82 | ????42.79 | ????44.08 | ??61.34 | ????99.91 | ??16.01 | ????44.08 | ||
| ??CO 2 | ????7.14 | ????7.20 | ????5.94 | ??34.96 | ????0.00 | ??76.05 | ????5.94 | ||
| ??CH 4 | ????0.25 | ????0.25 | ????0.26 | ??0.18 | ????0.00 | ??0.39 | ????0.26 | ||
| ??H 2S | ????1.43 | ????1.50 | ????0.00 | ??0.00 | ????0.00 | ??0.00 | ????0.00 | ||
| ??COS | ????0.07 | ????0.00 | ????00.0 | ??0.00 | ????0.00 | ??0.00 | ????0.00 | ||
| ????100.00 | ????100.00 | ????100.00 | ??100.00 | ????100.00 | ??100.00 | ????100.00 | |||
| ??kg/h | ??1000 | ??1000 | |||||||
| Master stream speed | ??709 | ????2803 | ????2805 | ????2722 | ??1853 | ????1001 | ??852 | ????1441 | |
| ??Nm 3/h | |||||||||
| ??N 2 | ??0 | ????0 | ????0 | ????0 | ??0 | ????0 | ??0 | ????0 | |
| ??O 2 | ??706 | ????0 | ????0 | ????0 | ??0 | ????0 | ??0 | ????0 | |
| ??Ar | ??4 | ????4 | ????4 | ????4 | ??1.67 | ????1 | ??1 | ????2 | |
| ??CO | ????1350 | ????1350 | ????1350 | ??64 | ????0 | ??64 | ????715 | ||
| ??H 2 | ????1200 | ????1200 | ????1200 | ??1136 | ????1000 | ??136 | ????635 | ||
| ??CO 2 | ????200 | ????202 | ????162 | ??648 | ??648 | ????86 | |||
| ??CH 4 | ????7 | ????7 | ????7 | ??3 | ??3 | ????4 | |||
| ??H 2S | ????40 | ????42 | ????0 | ??0 | ??0 | ????0 | |||
| ??COS | ????2 | ????0 | ????0 | ??0 | ??0 | ????0 |
Table II
| Liquid | Mixture " 2 " | Mixture " 3 " | Mixture " 4 " | Take-off equipment " 5 " | Take-off equipment " 6 " | Mixture " 10 " | Mixture " 13 " | Mixture " 12 " | Mixture " 7 " |
| Composition dry volume % | |||||||||
| ??N 2 | ??0.00 | ??0.00 | ????0.00 | ????00.0 | ????0.00 | ??0.00 | ????0.00 | ????0.00 | |
| ??O 2 | ??99.50 | ??0.00 | ????0.00 | ????00.0 | ????0.00 | ??0.00 | ????0.00 | ????0.00 | |
| ??Ar | ??5.0 | ??1.31 | ????1.31 | ????1.35 | ????0.94 | ??0.94 | ????0.93 | ????1.35 | |
| ??CO | ??47.60 | ????47.56 | ????48.99 | ????3.40 | ??0.00 | ????7.02 | ????48.99 | ||
| ??H 2 | ??42.31 | ????42.28 | ????43.54 | ????60.82 | ??99.06 | ????20.08 | ????43.54 | ||
| ??CO 2 | ??7.05 | ????7.12 | ????5.86 | ????34.67 | ??0.00 | ????71.59 | ????5.86 | ||
| ??CH 4 | ??0.25 | ????0.25 | ????0.25 | ????0.18 | ??0.00 | ????0.36 | ????0.25 | ||
| ??H 2S | ??1.41 | ????1.48 | ????0.00 | ????0.00 | ??0.00 | ????0.00 | ????0.00 | ||
| ??COS | ??0.07 | ????0.00 | ????00.0 | ????0.00 | ??0.00 | ????0.00 | ????0.00 | ||
| ??100.00 | ????100.00 | ????100.00 | ????100.00 | ??100.00 | ????100.00 | ????100.00 | |||
| ??kg/h | ??1000 | ??1050 | |||||||
| Master stream speed | ??745 | ??2836 | ????2836 | ????2756 | ????2958 | ??1010 | ????948 | ????1397 | |
| ??Nm 3/h | |||||||||
| ??N 2 | ??0 | ??0 | ????0 | ????0 | ????0 | ??0 | ????0 | ????0 | |
| ??O 2 | ??707 | ??0 | ????0 | ????0 | ????0 | ??0 | ????0 | ????0 | |
| ??Ar | ??37 | ??37 | ????37 | ????37 | ????18 | ??10 | ????9 | ????19 | |
| ??CO | ??1350 | ????1350 | ????1350 | ????67 | ??0 | ????67 | ????684 | ||
| ??H 2 | ??1200 | ????1200 | ????1200 | ????1191 | ??1000 | ????191 | ????608 | ||
| ??CO 2 | ??200 | ????202 | ????162 | ????679 | ????679 | ????82 | |||
| ??CH 4 | ??7 | ????7 | ????7 | ????3 | ????3 | ????4 | |||
| ??H 2S | ??40 | ????42 | ????0 | ????0 | ????0 | ????0 | |||
| ??COS | ??2 | ????0 | ????0 | ????0 | ????0 | ????0 |
Table III
| Liquid | Mixture " 2 " | Mixture " 3 " | Mixture " 4 " | Take-off equipment " 5 " | Take-off equipment " 6 " | Mixture " 10 " | Mixture " 13 " | Mixture " 12 " | Mixture " 7 " |
| Composition dry volume % | |||||||||
| ????N 2 | ????0.00 | ??0.00 | ????0.00 | ????00.0 | ????0.00 | ??0.00 | ??0.00 | ????0.00 | |
| ????O 2 | ????95.00 | ??0.00 | ????0.00 | ????00.0 | ????0.00 | ??0.00 | ??0.00 | ????0.00 | |
| ????Ar | ????5.00 | ??1.31 | ????1.31 | ????1.35 | ????0.10 | ??0.10 | ??0.10 | ????2.31 | |
| ????CO | ??47.60 | ????47.56 | ????48.99 | ????3.00 | ??0.00 | ??18.30 | ????84.30 | ||
| ????H 2 | ??42.31 | ????42.23 | ????43.54 | ????92.80 | ??99.90 | ??56.60 | ????5.72 | ||
| ????CO 2 | ??7.05 | ????7.12 | ????5.86 | ????4.00 | ??0.00 | ??24.40 | ????7.30 | ||
| ????CH 4 | ??0.25 | ????0.25 | ????0?25 | ????0.10 | ??0.00 | ??0.61 | ????0.37 | ||
| ????H 2S | ??1.41 | ????1.48 | ????0.00 | ????0.00 | ??0.00 | ??0.00 | ????0.00 | ||
| ????COS | ??0.07 | ????0.00 | ????00.0 | ????0.00 | ??0.00 | ??0.00 | ????0.00 | ||
| ??100.00 | ????100.00 | ????100.00 | ????100.00 | ??100.00 | ??100.00 | ????100.00 | |||
| ????kg/h | ??1000 | ????1050 | |||||||
| Master stream speed | ????745 | ??2836 | ????2836 | ????2756 | ????1197 | ??1001 | ??196 | ????1559 | |
| ????Nm 3/h | |||||||||
| ????N 2 | ????0 | ??0 | ????0 | ????0 | ????0 | ??0 | ??0 | ????0 | |
| ????O 2 | ????707 | ??0 | ????0 | ????0 | ????0 | ??0 | ??0 | ????0 | |
| ????Ar | ????37 | ??37 | ????37 | ????37 | ????1 | ??1 | ??0 | ????36 | |
| ????CO | ??1350 | ????1350 | ????1350 | ????36 | ??0 | ??36 | ????1314 | ||
| ????H 2 | ??1200 | ????1200 | ????1200 | ????2111 | ??1000 | ??111 | ????89 | ||
| ????CO 2 | ??200 | ????202 | ????162 | ????48 | ??48 | ????114 | |||
| ????CH 4 | ??7 | ????7 | ????7 | ????1 | ??1 | ????6 | |||
| ????H 2S | ??40 | ????42 | ????0 | ????0 | ??0 | ????0 | |||
| ????COS | ??2 | ????0 | ????0 | ????0 | ??0 | ????0 |
Claims (10)
1. energy and the hydrogen-rich mixture method of producing, form by the following step:
A) use oxidant mixture (16) in partial oxidation device (14), the gaseous mixture that enters (15) that comprises hydrocarbon or hydrocarbon mixture to be carried out partial oxidation, so that obtain the reactant gases (17) as this device product, it comprises hydrogen and carbon monoxide CO;
B) reactant gases that produces when step a) finishes enters in the membrane separator (24) so that produce permeate gas mixture (25) as its penetrant product, the multiple infiltration component of this mixture enrichment reactant gases, and produce retention gaseous mixture (26), the less infiltration component of this mixture enrichment reactant gases as its retention product.
C) in power generation assembly (27), handle said retention gaseous mixture (26);
D) in selecting absorption extraction device (29), separate said permeate gas mixture (25), so that obtain said hydrogen-rich gaseous mixtures (30) as unabsorbed gas products;
2. according to the method for claim 1, it is characterized in that the oxygen concentration of oxidant mixture changes in 21% to 90% scope.
3. according to the method for claim 1 or 2, it is characterized in that selecting absorption extraction device (29) to produce retention gas (21) after absorbing, this gas is sent in the steam generation device (22).
4. according to the method for one of claim 1-3, it is characterized in that carrying out at least a following purifying step between the two at the separating step of partial oxidation step (14) and membrane separator (24):
Processing reaction gas in carbonyl sulfide COS conversion system (18);
Processing reaction gas in desulfurizer (20);
Processing reaction gas in the carbon monoxide conversion system, wherein in reactant gases at least some CO by being converted into carbonic acid gas CO with the steam catalyzed reaction
2With hydrogen H
2
5. according to the method for one of claim 1-3, it is characterized in that producing said retention gaseous mixture (32), before it arrives in the power generation assembly (27), be sent in the desulfurizer (20) at said membrane separator retention output terminal.
6. according to the method for one of claim 1-3, it is characterized in that, be adjusted in the ratio of hydrogen and the electric weight that in step c), produces in the said hydrogen-rich gaseous mixtures by said power generation assembly by revising at least a following parameters:
The degree of conversion of CO conversion system;
The hydrogen selective of said membrane separator.
7. according to the method for claim 6, it is characterized in that revising the hydrogen selective of membrane separator by the performance characteristic of revising at least a following separator;
The quantity of the barrier film module that in separator, uses;
The service temperature of separator.
8. be particularly suitable for implementing the formation energy of method of one of claim 1-7 and the equipment of hydrogen-rich mixture, composed as follows:
Comprise hydrocarbon and hydrocarbon mixture send into gaseous mixture supply source (15);
The plenum system (16) that comprises the oxidant gas mixture of oxygen;
Partial oxidation device (14), it is connected to the supply source place, so that can produce the reactant gases that comprises hydrogen and carbon monoxide CO as its product;
Membrane separator (24), an one input terminus is connected on the output terminal of partial oxidation device by Trunk Line;
Power generation assembly (27) is connected to by the second pipeline on the retention output terminal of membrane separator;
Select to absorb gas separator (29), an one input terminus is connected on the penetrant output terminal of membrane separator by the 3rd pipeline.
9. according to the equipment of claim 8, it is characterized in that between partial oxidation device (14) and membrane separator (24), comprising at least a following gas-cleaning installation,
Use the steam catalytic convention design, its carbon monoxide CO is converted into carbonic acid gas CO
2With hydrogen H
2
The conversion system of carbonyl sulfide COS;
Desulfurizer.
10. according to the equipment of claim 8, it is characterized in that it is included on the second pipeline and the desulfurizer between membrane separator and power generation assembly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121971 CN1161934A (en) | 1995-10-26 | 1996-10-25 | Method for generating hydrogen and energy and apparatus thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9512631 | 1995-10-26 | ||
| CN 96121971 CN1161934A (en) | 1995-10-26 | 1996-10-25 | Method for generating hydrogen and energy and apparatus thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1161934A true CN1161934A (en) | 1997-10-15 |
Family
ID=5127038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96121971 Pending CN1161934A (en) | 1995-10-26 | 1996-10-25 | Method for generating hydrogen and energy and apparatus thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1161934A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459066A (en) * | 2009-04-06 | 2012-05-16 | 巴斯夫欧洲公司 | Method for electrochemically separating hydrogen from a reaction mixture |
| CN111420539A (en) * | 2020-05-07 | 2020-07-17 | 兰州理工大学 | Automobile exhaust purification system and method based on gas hydrate method |
-
1996
- 1996-10-25 CN CN 96121971 patent/CN1161934A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459066A (en) * | 2009-04-06 | 2012-05-16 | 巴斯夫欧洲公司 | Method for electrochemically separating hydrogen from a reaction mixture |
| CN102459066B (en) * | 2009-04-06 | 2014-08-13 | 巴斯夫欧洲公司 | Process for the electrochemical separation of hydrogen from a reaction mixture |
| CN111420539A (en) * | 2020-05-07 | 2020-07-17 | 兰州理工大学 | Automobile exhaust purification system and method based on gas hydrate method |
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