CA1334124C - Process and apparatus for producing hydrogen - Google Patents
Process and apparatus for producing hydrogenInfo
- Publication number
- CA1334124C CA1334124C CA000551904A CA551904A CA1334124C CA 1334124 C CA1334124 C CA 1334124C CA 000551904 A CA000551904 A CA 000551904A CA 551904 A CA551904 A CA 551904A CA 1334124 C CA1334124 C CA 1334124C
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- Prior art keywords
- gas
- hydrogen
- zone
- combustion zone
- pressure
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
A process for producing hydrogen comprising the following steps:
(a) converting a hydrocarbonaceous feed (e.g. natural gas) in a reaction zone at elevated temperature and pressure at least partly into a gas mixture containing hydrogen and carbon monoxide, (b) removing hydrogen (e.g. by means of pressure swing adsorption) from product gas obtained from step (a), and (c) combusting hydrogen-depleted off gas obtained from step (b) with an oxygen-containing gas in a combustion zone and employing energy thus produced in at least one step of the process (e.g. for convective heating of the reaction zone or gas compression).
The invention further relates to an apparatus suitable for said process.
(a) converting a hydrocarbonaceous feed (e.g. natural gas) in a reaction zone at elevated temperature and pressure at least partly into a gas mixture containing hydrogen and carbon monoxide, (b) removing hydrogen (e.g. by means of pressure swing adsorption) from product gas obtained from step (a), and (c) combusting hydrogen-depleted off gas obtained from step (b) with an oxygen-containing gas in a combustion zone and employing energy thus produced in at least one step of the process (e.g. for convective heating of the reaction zone or gas compression).
The invention further relates to an apparatus suitable for said process.
Description
PROCESS AND APPARATUS FOR PRODUCING HYDROGEN
The invention relates to a process for producing hydrogen and to an apparatus suitable for carrying out such a process.
It is well known to prepare a hydrogen-containing gas such as synthesis gas (which mainly contains hydrogen and carbon monoxide, and in addition carbon dioxide, nitrogen and (unconverted) hydrocarbons and steam) by means of steam reforming or (non) catalytic partial oxidation of a hydrocarbonaceous feed.
It is furthermore known to remove hydrogen from a hydrogen-containing product gas, e.g. by means of pressure swing adsorption, thus obtaining substantially pure hydrogen and in addition hydrogen-depleted off-gas.
It has now been found that said hydrogen-preparation and -separation steps can be efficiently integrated by employing energy produced by combusting in a combustion zone hydrogen-depleted off-gas obtained from the latter step in at least one of the steps of the integrated process itself, e.g. for the compression of oxygen-containing gas required in at least the former step of the process.
The invention therefore provides a method for integrating hydrogen-preparation and hydrogen-separation steps comprising the steps of:
a) preparing a gas mixture containing hydrogen and carbon-monoxide by means of 1) steam reforming in a convective reformer _1 ~IF
1 1 3 3 4 l6234293 2883 containing a reforming zone and a combustion zone at a temperature from 600C to 1600C and a pressure from 2 to 200 bar or by means of 2) (non)catalytic partial oxidation of a hydrocarbonaceous feed in a (non)catalytic partial oxidation zone at a temperature from 600C to 1600C and a pressure from 1 to 250 bar;
b) optionally catalytically converting at least part of the carbon-monoxide present in the said gas mixture in the presence of steam at carbon-manoxide conversion conditions into carbon-dioxide and hydrogen in a conversion zone which is maintained at a temperature from 180 to 450C and at a pressure from 2 to 200 bar;
c) removing hydrogen from the obtained product gas by passing the hydrogen-containing gas to a pressure swing adsorption (P.S.A.) unit from which separately a substantially pure hydrogen gas stream and a stream of hydrogen-depleted P.S.A. off-gas are withdrawn; wherein the said hydrogen-depleted P.S.A. off-gas obtained in step (c) is combusted with an oxygen-containing gas in at least one of the steps of the said integrated process itself:
in the said combustion zone of the said convective reformer for convective heating of the said reforming zone or in the combustion chamber of a gas turbine driving a compressor providing oxygen-containing gas to the said combustion chamber of the said gas turbine.
The process according to the present invention will be elucidated hereinafter with the use of the Figures in which various preferred options of the process have been incorporated without having the 1 334 t 24 intent of limiting said process to those partinllAr Pmho~imP~ts as depicted in the Figures.
Figure l relates to a ~Lefe-l~d ~rha~imPnt of the present process wherein h~dloy~-depleted off gas is heat .~ An.~ with flue gas, before use as fuel gas in a convective rPf~rmin~ zone.
Figure 2 relates to another preferred ~mko~ nt of the process according to the invention in which off gas is used as fuel gas in a gas ~lrhinP.
R~Le.~e numerals relating to similAr process steps andtor equipment are the same in the two Figures.
In Figure l the essential process steps (a), (b) and (c) are carried out in reforming zone (l) of convective reformpr (2), in pressure swing adsorption unit (3), and in combustion zone (4), Le:j~Lively.
A h~Lu~.h).. A~ feed, ~LefeL~bly containing ~rmAlly liquid and/or ~cy~l~ hydrocArhnn~, in parti~llAr Cl-C4 hydrocArhnn~
such as those present in natural gas, is introduced via line (5) into L~fo..,;ng zone (l) Loy~Lher with steam introduced via line (6).
In zone (l) step (a) of the present process is suita-hly carried out at a L~.~eLa~re fl~.l 600 to 1600 C and a pressure from 2 to 200 h~r. The refQrming zone preferably comprises catalyst in order to ~eLaLe said zone at a relatively low L~.~e1~LuLe from 600 to 1100 C and at a pressure from 5-50 bar.
The reactor which contains said ref~rming zone (l) and option-ally combustion zone (4) (which may also be spaced apart from the ref~rming zone and be located outside the reactor) preferably contains internals in order to improve heat exchange between said zones and ensure optimal use of catalyst, if any.
The reactor intPrnAl~ suitably comprise double concentric tubes with catalyst in the annular space between the tubes. The outer tubes are suitably mLunted s~sL~ILially vertically in a horizontal inlet manifold for hydrocArhnn/steam feed distribution.
The lower ends of the outer tubes are preferably closed in order to re~tlse the flow of gas having passed downwardly ~1L~U~11 the AnmllAr catalyst bed. The inner tubes into which the h~L~y~--_ 3 _ l 3341 24 containing product gas is sllhse~l~ntly passed, are suitably connected to a product outlet mAn;fold. AdvantA~e~lcly, the oombustion gas (having a ~ ~eJ~LuLe of e.g. 900-1200 C) enters the ,-f~..,;ng reactor below or n~Ar the lower ends of the ~lh~ r reaction zone and leaves the reactor below the hor;7~ntAl inlet manifold, situated at the relatively cold (e.g. 500-800 C) upper part of the reactor. When the concentxic tubes are mDunted in the above-descr;h~ l,Yu~lel, their hot lower ends can expand freely and ~hPrmAl ~x~An~;~n in the m nifolds is kept to a m;n;mllm.
A gas mixture oon~A;n;ng hyd~uy~ and carbon m~,nx;~ is L~.JV~ from reform;ng zone ~1) through line (7). In order to produ oe a~;tional h~koy~n, at least part and ~ere~hly all of said gas mixture is ~rerelably directed to carbon mnnnx;~
~llv~l~ion zone (8) in which at least part of the carbon mn~nx;~
present in the gas mixture is catalytically O~llV~3d in the presenoe of steam at the a~lu~iate ~ .x;~P ~ullv~lsion conditions in one or mDre steps into carbon ~;~x;~. C~l~v~ ion zone (8) is sui W ly m~intained at a ~ e~a~re from 180 to 450 C
and a pressure from 2 to 200 bar.
H~d~y~,-contA;n;ng product gas obtained from wl~v~ion zone (8) and/or l~r~ ng zone (1) is directed via line (9) to pres Æ e swing adsorption unit (3) from which a suLs~ ;A11Y pure h~koy~. gas stream is wi~h~rAwn via line (10). Unit (3) ~le~lably comprises a plurality of vessels oont~;n;ng molP~llAr sieve beds which are sequentially in the adsorption-, desorption- and purge-stage. Hcwever, it is also poss;hlQ to substitute a liquid absorption unit (wherein carbon mnnox;~p and/or ~Arbon ~;nx;~P are selectively Ahsorhe~ by a liquid which is subsequently ~y~ ~la~ed) or a h~kuy~l pPn~PAhle II~I~LaUle unit for pressure swing adsorption unit (3) in order to recover h~dl~y~ from the product gas ob~;ned via line (9).
H~koy~l-depleted off gas (which may still oontain up to 5 or even up to 30% by volume of h~kuy~l, ~PpPn~;ng on th~ type of adsorption unit and pressure employed) obtained fl~.l unit (3) is - \ -~ 4 ~ l 3341 24 eL~bly directed via line (11) to oompressor (15) and e~ ntly via line (14) to heat ~x~h~n~r (12) wherein heat is ~x~h~n~e~ with the effltlent gas stream (13) from oombustion zone (4) which gas stream generally has a higher l~ ~ Lure (e.g.
from 150 to 1000 C) than the off gas. Accordingly, the energy eff;~ cy of the process according to the invention is subst~nt;~lly ill~Luv~d, thus Pn~hl;ng optimal use of the h~L~ -depleted off-gas in one or more process steps.
The heat e~ my~d off-gas is directed via line (16) to combustion zone (4). As the energy-cvllL~lL of the off-gas is in many cases not ~lff;c;~nt to employ said gas as the only fuel saur oe for a cc~bustion zone, additional fuel is ~LereLobly provided via line (18).
In a preferred ~mho~;m~nt of the pro oe ss according to the invention as depicted in Figure 1 the combustion zone (4) as applied in step (c) provides ~h~rm~l energy for the læfo.~
reaction zone (1) of step (a) by means of o~llv~Live heat transfer.
A main a~v~-L~y~ of such an aLl~ J - ~L is that the reaction zone will as a result he heated substantially lm;formly instead of risking local overheating by a number of burners located in the reaction zone, as in previous reform;ng process~s.
~fflll~nt gas from combustion zone (4) ~rpl;f~ in steps (a) and (c) as ~ se~ her~inhefore is suitably (after heat eXchAn~e) dil}YiJ2d via line (19) to a separate cc~bustion zone (20) to be used as ~ LCL gas LoyeL~leL with fuel gas supplied via line (21). Cp~;on~lly, part of the heat-px~-h~e~ effluent gas is recycled via line (17) to oombustion zone (4). ~ff~ nt gas emanating from the. latter oombustion zone (20) is preferably dlrecbed via line (30) to turbo-~xL~I~Pr (22) wherein the gas is ~x~ to provide mp~hAn;cAl energy to ~ SS oxygen-con~A;n;ng gas (e.g. air) supplied via line (23) to ~ SS~L (24). In some cases ~lff;~;,Pnt oxygen is present in the e~x~ded efflu~nt gas obtained via line (27) from turbo-Px~ , (22) to enable the use of said gas as oxygen-containing gas for the oombustion zone (not depicted in Figure 1).
_ ~ 334 1 ~
Thrbo-PxpAn~r (22), ~AI~L~SsoL (24) and ~eraLoL (33) are pr~r~ y coupled (e.g. by means of axis (25)) and opt;nnAlly cnmh;nf~ with one or mDre other compressors (15).
Ccmpressed oxygen-contA;n;ng gas (e.g. the gas provided via line (26)) is pref~rAhly employed in at least one of the steps (a) and (c) of the present process, in part;~llAr in combustion zone (4) (via line (28)) _nd via line (29) in oombustion zone (20). me use of compressed, and LheL~LY preheated, oxygen-containing gas is ~L~feLL~d in the process according to the invention in order to improve the thPnnAl eff;~;~ncy of the combustion zone(s) and thus of the entire process.
The process and d~aLaLus which are ~ a~ically depicted in Figure 2 will be described hereinafter only in so far as features diffeL~l~ from those depicted in Figure 1 are in~
A 5;gn;f;rAnt differ~e is the use of a catalytic or non-catalytic partial oxidation zone (31) in the ~mho~;mpnt depicted in Figure 2. &ch a zone is generally ~eLaLed at a L~l~eLaLure from 600 to 1600 C and preferably at a ~ Lure from 1000 to 1500 C, whereas the pressure in said zone is generally from 1 to 250 bar and ~L~feLably from 10 to 100 bar. Zone (31) constitutes the reaction zone employed in step (a) as well as a combustion zone as employed in step (c) of the process according to the invention.
A further difference with the process and a~aLa~us as depicted in Figure 1 is that in Figure 2 the h~dkoy~l-depleted off gas obtained from h~L~y~l separation unit (3) through line (11) is used as fuel gas in combustion zone (20) of a gas ~llrh;n~ instead of in a ccmbustion zone (4) of a r~form;ng a~aLaL~s. F~ P~
eff~lent gas from turbo-P~pAn~er (22) is opt;~nAlly at least partly used in a combustion zone (not depicted in Figure 2).
O~ygen-cnnt~;ning gas is advant~qeal~ly provided by oompressor (24) via line (26) to oombustion zone (20). S~bstantially pure oxygen gas is supplied via line (34) to compressor (32) and sllhsec~ently diracbed via line (35) to partial oxidation zone (31).
The invention further relates to an apparatus suitable for producing h~loy~l which oomprises a reactor having feed inlet means and product outlet means cYnT~m;cAting with heat ~x~hAn~Pr reactor intPrnAl~, a combustor which is in heat exchAn~ relation with said intPrnAl~ a pressure swing adsorption unit cY~T~micAting with the product outlet means and having separate h~rvy~l and off-gas outlet means, and a gastllrh;n~ which is in oommunication with the conbustor and/or the off-gas outlet mPans.
The process according to the invention is ill~sL~aLed hy way of th~ following Example.
EX~E
me process su~hstA-ntially as depicted in Figure 2 is carried out by intro~l~;ng 872 tons/day of feed gas (contA;n;ng su~sLanLially methane) at a L~.~elaLure of 50 C and a pressure of 51 bar in catAlytic partial oxidation zone (31) and reacting the feed gas with 2490 tons/day of su~LallLially pure oxygen gas introduced via line (35) at a L~,~elàL~re of 100 C and a ~Les~u of 48 bar.
The h~dL~yt~ ntA;n;ng synthesis gas ohtained via line (7) at 380 C and 30 h~r is subjected in carbon m~nnx;~ veLsion zone (8) to a catalytic steam shift together with steam having a L~,~elaL~re of 380 C and a pres OE e of 61 bar. 2160 tons/day of mainly h~dLuy~l- and carbon ~;nX;~-contA;n;ng product gas from zone (8) is led to Pressure Swing AdsoL~Lion unit (3) at a L~.~elaL~re of 40 C and a pressure of 26 bar; fram unit (3) 200 tons/day of suhs~A~t;Ally pure h~dL~y~n is obtAined at 40 C and 25 bar in addition to 1960 tons/day offgas oontA;n;~ carbon dioxide and h~dL~y~l as major r~5~ Ls at 40 C and 1.6 bar. & id offgas is led via line (11) to compressor (15) from which an outlet gas stream (14) is obtained at a L~,~eLaL~re of 310 C and a pressure of 17 hur and cnmh;ne~ with 344 tons/day of methane-contA;n;ng gas at a pressure of 51 bar and a L~~ ature of 50 C having a S;m;lAr c~m~os;tion as the feed gas to zone (31).
The cnmh;n~ gas stream (16) is directed to a gas tllrh;n~
oomprising oo~bustion zone (20), ccmpressor (24) and turbo ~
(22). In said gas tllrh;n~ 76 Megawatt electric power is y~leLdLed by generator (33) of which 18 Megawdtt is required for operating _ 7 _ l 3341 2~
compressors (15) and (32), leaving 58 Megawatt nett power export, excluding additional electricity y~ ~a~ion by means of waste heat recovery from the ~X~ f~ efflll~nt gas stream (27).
The invention relates to a process for producing hydrogen and to an apparatus suitable for carrying out such a process.
It is well known to prepare a hydrogen-containing gas such as synthesis gas (which mainly contains hydrogen and carbon monoxide, and in addition carbon dioxide, nitrogen and (unconverted) hydrocarbons and steam) by means of steam reforming or (non) catalytic partial oxidation of a hydrocarbonaceous feed.
It is furthermore known to remove hydrogen from a hydrogen-containing product gas, e.g. by means of pressure swing adsorption, thus obtaining substantially pure hydrogen and in addition hydrogen-depleted off-gas.
It has now been found that said hydrogen-preparation and -separation steps can be efficiently integrated by employing energy produced by combusting in a combustion zone hydrogen-depleted off-gas obtained from the latter step in at least one of the steps of the integrated process itself, e.g. for the compression of oxygen-containing gas required in at least the former step of the process.
The invention therefore provides a method for integrating hydrogen-preparation and hydrogen-separation steps comprising the steps of:
a) preparing a gas mixture containing hydrogen and carbon-monoxide by means of 1) steam reforming in a convective reformer _1 ~IF
1 1 3 3 4 l6234293 2883 containing a reforming zone and a combustion zone at a temperature from 600C to 1600C and a pressure from 2 to 200 bar or by means of 2) (non)catalytic partial oxidation of a hydrocarbonaceous feed in a (non)catalytic partial oxidation zone at a temperature from 600C to 1600C and a pressure from 1 to 250 bar;
b) optionally catalytically converting at least part of the carbon-monoxide present in the said gas mixture in the presence of steam at carbon-manoxide conversion conditions into carbon-dioxide and hydrogen in a conversion zone which is maintained at a temperature from 180 to 450C and at a pressure from 2 to 200 bar;
c) removing hydrogen from the obtained product gas by passing the hydrogen-containing gas to a pressure swing adsorption (P.S.A.) unit from which separately a substantially pure hydrogen gas stream and a stream of hydrogen-depleted P.S.A. off-gas are withdrawn; wherein the said hydrogen-depleted P.S.A. off-gas obtained in step (c) is combusted with an oxygen-containing gas in at least one of the steps of the said integrated process itself:
in the said combustion zone of the said convective reformer for convective heating of the said reforming zone or in the combustion chamber of a gas turbine driving a compressor providing oxygen-containing gas to the said combustion chamber of the said gas turbine.
The process according to the present invention will be elucidated hereinafter with the use of the Figures in which various preferred options of the process have been incorporated without having the 1 334 t 24 intent of limiting said process to those partinllAr Pmho~imP~ts as depicted in the Figures.
Figure l relates to a ~Lefe-l~d ~rha~imPnt of the present process wherein h~dloy~-depleted off gas is heat .~ An.~ with flue gas, before use as fuel gas in a convective rPf~rmin~ zone.
Figure 2 relates to another preferred ~mko~ nt of the process according to the invention in which off gas is used as fuel gas in a gas ~lrhinP.
R~Le.~e numerals relating to similAr process steps andtor equipment are the same in the two Figures.
In Figure l the essential process steps (a), (b) and (c) are carried out in reforming zone (l) of convective reformpr (2), in pressure swing adsorption unit (3), and in combustion zone (4), Le:j~Lively.
A h~Lu~.h).. A~ feed, ~LefeL~bly containing ~rmAlly liquid and/or ~cy~l~ hydrocArhnn~, in parti~llAr Cl-C4 hydrocArhnn~
such as those present in natural gas, is introduced via line (5) into L~fo..,;ng zone (l) Loy~Lher with steam introduced via line (6).
In zone (l) step (a) of the present process is suita-hly carried out at a L~.~eLa~re fl~.l 600 to 1600 C and a pressure from 2 to 200 h~r. The refQrming zone preferably comprises catalyst in order to ~eLaLe said zone at a relatively low L~.~e1~LuLe from 600 to 1100 C and at a pressure from 5-50 bar.
The reactor which contains said ref~rming zone (l) and option-ally combustion zone (4) (which may also be spaced apart from the ref~rming zone and be located outside the reactor) preferably contains internals in order to improve heat exchange between said zones and ensure optimal use of catalyst, if any.
The reactor intPrnAl~ suitably comprise double concentric tubes with catalyst in the annular space between the tubes. The outer tubes are suitably mLunted s~sL~ILially vertically in a horizontal inlet manifold for hydrocArhnn/steam feed distribution.
The lower ends of the outer tubes are preferably closed in order to re~tlse the flow of gas having passed downwardly ~1L~U~11 the AnmllAr catalyst bed. The inner tubes into which the h~L~y~--_ 3 _ l 3341 24 containing product gas is sllhse~l~ntly passed, are suitably connected to a product outlet mAn;fold. AdvantA~e~lcly, the oombustion gas (having a ~ ~eJ~LuLe of e.g. 900-1200 C) enters the ,-f~..,;ng reactor below or n~Ar the lower ends of the ~lh~ r reaction zone and leaves the reactor below the hor;7~ntAl inlet manifold, situated at the relatively cold (e.g. 500-800 C) upper part of the reactor. When the concentxic tubes are mDunted in the above-descr;h~ l,Yu~lel, their hot lower ends can expand freely and ~hPrmAl ~x~An~;~n in the m nifolds is kept to a m;n;mllm.
A gas mixture oon~A;n;ng hyd~uy~ and carbon m~,nx;~ is L~.JV~ from reform;ng zone ~1) through line (7). In order to produ oe a~;tional h~koy~n, at least part and ~ere~hly all of said gas mixture is ~rerelably directed to carbon mnnnx;~
~llv~l~ion zone (8) in which at least part of the carbon mn~nx;~
present in the gas mixture is catalytically O~llV~3d in the presenoe of steam at the a~lu~iate ~ .x;~P ~ullv~lsion conditions in one or mDre steps into carbon ~;~x;~. C~l~v~ ion zone (8) is sui W ly m~intained at a ~ e~a~re from 180 to 450 C
and a pressure from 2 to 200 bar.
H~d~y~,-contA;n;ng product gas obtained from wl~v~ion zone (8) and/or l~r~ ng zone (1) is directed via line (9) to pres Æ e swing adsorption unit (3) from which a suLs~ ;A11Y pure h~koy~. gas stream is wi~h~rAwn via line (10). Unit (3) ~le~lably comprises a plurality of vessels oont~;n;ng molP~llAr sieve beds which are sequentially in the adsorption-, desorption- and purge-stage. Hcwever, it is also poss;hlQ to substitute a liquid absorption unit (wherein carbon mnnox;~p and/or ~Arbon ~;nx;~P are selectively Ahsorhe~ by a liquid which is subsequently ~y~ ~la~ed) or a h~kuy~l pPn~PAhle II~I~LaUle unit for pressure swing adsorption unit (3) in order to recover h~dl~y~ from the product gas ob~;ned via line (9).
H~koy~l-depleted off gas (which may still oontain up to 5 or even up to 30% by volume of h~kuy~l, ~PpPn~;ng on th~ type of adsorption unit and pressure employed) obtained fl~.l unit (3) is - \ -~ 4 ~ l 3341 24 eL~bly directed via line (11) to oompressor (15) and e~ ntly via line (14) to heat ~x~h~n~r (12) wherein heat is ~x~h~n~e~ with the effltlent gas stream (13) from oombustion zone (4) which gas stream generally has a higher l~ ~ Lure (e.g.
from 150 to 1000 C) than the off gas. Accordingly, the energy eff;~ cy of the process according to the invention is subst~nt;~lly ill~Luv~d, thus Pn~hl;ng optimal use of the h~L~ -depleted off-gas in one or more process steps.
The heat e~ my~d off-gas is directed via line (16) to combustion zone (4). As the energy-cvllL~lL of the off-gas is in many cases not ~lff;c;~nt to employ said gas as the only fuel saur oe for a cc~bustion zone, additional fuel is ~LereLobly provided via line (18).
In a preferred ~mho~;m~nt of the pro oe ss according to the invention as depicted in Figure 1 the combustion zone (4) as applied in step (c) provides ~h~rm~l energy for the læfo.~
reaction zone (1) of step (a) by means of o~llv~Live heat transfer.
A main a~v~-L~y~ of such an aLl~ J - ~L is that the reaction zone will as a result he heated substantially lm;formly instead of risking local overheating by a number of burners located in the reaction zone, as in previous reform;ng process~s.
~fflll~nt gas from combustion zone (4) ~rpl;f~ in steps (a) and (c) as ~ se~ her~inhefore is suitably (after heat eXchAn~e) dil}YiJ2d via line (19) to a separate cc~bustion zone (20) to be used as ~ LCL gas LoyeL~leL with fuel gas supplied via line (21). Cp~;on~lly, part of the heat-px~-h~e~ effluent gas is recycled via line (17) to oombustion zone (4). ~ff~ nt gas emanating from the. latter oombustion zone (20) is preferably dlrecbed via line (30) to turbo-~xL~I~Pr (22) wherein the gas is ~x~ to provide mp~hAn;cAl energy to ~ SS oxygen-con~A;n;ng gas (e.g. air) supplied via line (23) to ~ SS~L (24). In some cases ~lff;~;,Pnt oxygen is present in the e~x~ded efflu~nt gas obtained via line (27) from turbo-Px~ , (22) to enable the use of said gas as oxygen-containing gas for the oombustion zone (not depicted in Figure 1).
_ ~ 334 1 ~
Thrbo-PxpAn~r (22), ~AI~L~SsoL (24) and ~eraLoL (33) are pr~r~ y coupled (e.g. by means of axis (25)) and opt;nnAlly cnmh;nf~ with one or mDre other compressors (15).
Ccmpressed oxygen-contA;n;ng gas (e.g. the gas provided via line (26)) is pref~rAhly employed in at least one of the steps (a) and (c) of the present process, in part;~llAr in combustion zone (4) (via line (28)) _nd via line (29) in oombustion zone (20). me use of compressed, and LheL~LY preheated, oxygen-containing gas is ~L~feLL~d in the process according to the invention in order to improve the thPnnAl eff;~;~ncy of the combustion zone(s) and thus of the entire process.
The process and d~aLaLus which are ~ a~ically depicted in Figure 2 will be described hereinafter only in so far as features diffeL~l~ from those depicted in Figure 1 are in~
A 5;gn;f;rAnt differ~e is the use of a catalytic or non-catalytic partial oxidation zone (31) in the ~mho~;mpnt depicted in Figure 2. &ch a zone is generally ~eLaLed at a L~l~eLaLure from 600 to 1600 C and preferably at a ~ Lure from 1000 to 1500 C, whereas the pressure in said zone is generally from 1 to 250 bar and ~L~feLably from 10 to 100 bar. Zone (31) constitutes the reaction zone employed in step (a) as well as a combustion zone as employed in step (c) of the process according to the invention.
A further difference with the process and a~aLa~us as depicted in Figure 1 is that in Figure 2 the h~dkoy~l-depleted off gas obtained from h~L~y~l separation unit (3) through line (11) is used as fuel gas in combustion zone (20) of a gas ~llrh;n~ instead of in a ccmbustion zone (4) of a r~form;ng a~aLaL~s. F~ P~
eff~lent gas from turbo-P~pAn~er (22) is opt;~nAlly at least partly used in a combustion zone (not depicted in Figure 2).
O~ygen-cnnt~;ning gas is advant~qeal~ly provided by oompressor (24) via line (26) to oombustion zone (20). S~bstantially pure oxygen gas is supplied via line (34) to compressor (32) and sllhsec~ently diracbed via line (35) to partial oxidation zone (31).
The invention further relates to an apparatus suitable for producing h~loy~l which oomprises a reactor having feed inlet means and product outlet means cYnT~m;cAting with heat ~x~hAn~Pr reactor intPrnAl~, a combustor which is in heat exchAn~ relation with said intPrnAl~ a pressure swing adsorption unit cY~T~micAting with the product outlet means and having separate h~rvy~l and off-gas outlet means, and a gastllrh;n~ which is in oommunication with the conbustor and/or the off-gas outlet mPans.
The process according to the invention is ill~sL~aLed hy way of th~ following Example.
EX~E
me process su~hstA-ntially as depicted in Figure 2 is carried out by intro~l~;ng 872 tons/day of feed gas (contA;n;ng su~sLanLially methane) at a L~.~elaLure of 50 C and a pressure of 51 bar in catAlytic partial oxidation zone (31) and reacting the feed gas with 2490 tons/day of su~LallLially pure oxygen gas introduced via line (35) at a L~,~elàL~re of 100 C and a ~Les~u of 48 bar.
The h~dL~yt~ ntA;n;ng synthesis gas ohtained via line (7) at 380 C and 30 h~r is subjected in carbon m~nnx;~ veLsion zone (8) to a catalytic steam shift together with steam having a L~,~elaL~re of 380 C and a pres OE e of 61 bar. 2160 tons/day of mainly h~dLuy~l- and carbon ~;nX;~-contA;n;ng product gas from zone (8) is led to Pressure Swing AdsoL~Lion unit (3) at a L~.~elaL~re of 40 C and a pressure of 26 bar; fram unit (3) 200 tons/day of suhs~A~t;Ally pure h~dL~y~n is obtAined at 40 C and 25 bar in addition to 1960 tons/day offgas oontA;n;~ carbon dioxide and h~dL~y~l as major r~5~ Ls at 40 C and 1.6 bar. & id offgas is led via line (11) to compressor (15) from which an outlet gas stream (14) is obtained at a L~,~eLaL~re of 310 C and a pressure of 17 hur and cnmh;ne~ with 344 tons/day of methane-contA;n;ng gas at a pressure of 51 bar and a L~~ ature of 50 C having a S;m;lAr c~m~os;tion as the feed gas to zone (31).
The cnmh;n~ gas stream (16) is directed to a gas tllrh;n~
oomprising oo~bustion zone (20), ccmpressor (24) and turbo ~
(22). In said gas tllrh;n~ 76 Megawatt electric power is y~leLdLed by generator (33) of which 18 Megawdtt is required for operating _ 7 _ l 3341 2~
compressors (15) and (32), leaving 58 Megawatt nett power export, excluding additional electricity y~ ~a~ion by means of waste heat recovery from the ~X~ f~ efflll~nt gas stream (27).
Claims (5)
1. A method for integrating hydrogen-preparation and hydrogen-separation steps comprising the steps of:
a) preparing a gas mixture containing hydrogen and carbon-monoxide by means of 1) steam reforming in a convective reformer containing a reforming zone and a combustion zone at a temperature from 600°C to 1600°C and a pressure from 2 to 200 bar or by means of 2) (non)catalytic partial oxidation of a hydrocarbonaceous feed in a (non)catalytic partial oxidation zone at a temperature from 600°C to 1600°C and a pressure from 1 to 250 bar;
b) optionally catalytically converting at least part of the carbon-monoxide present in the said gas mixture in the presence of steam at carbon-monoxide conversion conditions into carbon-dioxide and hydrogen in a conversion zone which is maintained at a temperature from 180 to 450°C and at a pressure from 2 to 200 bar;
c) removing hydrogen from the obtained product gas by passing the hydrogen-containing gas to a pressure swing adsorption (P.S.A.) unit from which separately a substantially pure hydrogen gas stream and a stream of hydrogen-depleted P.S.A. off-gas are withdrawn; wherein the said hydrogen-depleted P.S.A. off-gas obtained in step (c) is combusted with an oxygen-containing gas in at least one of the steps of the said integrated process itself:
in the said combustion zone of the said convective reformer for convective heating of the said reforming zone or in the combustion chamber of a gas turbine driving a compressor providing oxygen-containing gas to the said combustion chamber of the said gas turbine.
a) preparing a gas mixture containing hydrogen and carbon-monoxide by means of 1) steam reforming in a convective reformer containing a reforming zone and a combustion zone at a temperature from 600°C to 1600°C and a pressure from 2 to 200 bar or by means of 2) (non)catalytic partial oxidation of a hydrocarbonaceous feed in a (non)catalytic partial oxidation zone at a temperature from 600°C to 1600°C and a pressure from 1 to 250 bar;
b) optionally catalytically converting at least part of the carbon-monoxide present in the said gas mixture in the presence of steam at carbon-monoxide conversion conditions into carbon-dioxide and hydrogen in a conversion zone which is maintained at a temperature from 180 to 450°C and at a pressure from 2 to 200 bar;
c) removing hydrogen from the obtained product gas by passing the hydrogen-containing gas to a pressure swing adsorption (P.S.A.) unit from which separately a substantially pure hydrogen gas stream and a stream of hydrogen-depleted P.S.A. off-gas are withdrawn; wherein the said hydrogen-depleted P.S.A. off-gas obtained in step (c) is combusted with an oxygen-containing gas in at least one of the steps of the said integrated process itself:
in the said combustion zone of the said convective reformer for convective heating of the said reforming zone or in the combustion chamber of a gas turbine driving a compressor providing oxygen-containing gas to the said combustion chamber of the said gas turbine.
2. The method as claimed in claim 1 wherein hydrogen-depleted off-gas from the pressure swing adsorption unit is compressed and subsequently is heat exchanged with effluent gas from the combustion zone of the convective reformer.
3. The method as claimed in claims 1 or 2, wherein effluent gas from the combustion zone of the convective reformer is used as moderator gas for a different combustion zone and effluent gas emanating from the latter combustion zone is expanded to provide mechanical energy to compress oxygen-containing gas which is provided to the combustion zone of the convective reformer.
4. The method as claimed in claim 1 wherein substantially pure oxygen gas is supplied via a compressor to the said partial oxidation zone.
5. An apparatus for carrying out the process as claimed in claim 1, 2 or 4 comprising a reactor having feed inlet means and product outlet means communicating with heat exchanger reactor internals, a combustor which is in heat exchange relation with said internals, a pressure swing adsorption unit communicating with the product outlet means and having separate hydrogen- and off-gas outlet means, and a gas turbine which is in communication with the combustor and/or the off-gas outlet means.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8629031 | 1986-12-04 | ||
| GB868629031A GB8629031D0 (en) | 1986-12-04 | 1986-12-04 | Producing hydrogen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334124C true CA1334124C (en) | 1995-01-31 |
Family
ID=10608464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000551904A Expired - Fee Related CA1334124C (en) | 1986-12-04 | 1987-11-16 | Process and apparatus for producing hydrogen |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU595405B2 (en) |
| CA (1) | CA1334124C (en) |
| DE (1) | DE3740865A1 (en) |
| GB (2) | GB8629031D0 (en) |
| MY (1) | MY102725A (en) |
| NL (1) | NL8702706A (en) |
| NZ (1) | NZ222775A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4003210A1 (en) * | 1990-02-01 | 1991-08-14 | Mannesmann Ag | METHOD AND APPARATUS FOR GENERATING MECHANICAL ENERGY |
| GB2307008A (en) * | 1995-11-13 | 1997-05-14 | Fred Moseley | Gas turbine engine with two stage combustion |
| DE10122016A1 (en) * | 2001-05-07 | 2002-11-28 | Viessmann Werke Kg | Apparatus for generating hydrogen and method for allothermic steam reforming |
| EP1944268A1 (en) | 2006-12-18 | 2008-07-16 | BP Alternative Energy Holdings Limited | Process |
| RU2599407C1 (en) * | 2015-06-09 | 2016-10-10 | Федеральное государственное унитарное предприятие "Центральный институт авиационного моторостроения имени П.И. Баранова" | Method of continuous operation gas turbine plant action |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930915B1 (en) * | 1967-07-15 | 1974-08-16 | ||
| US4132065A (en) * | 1977-03-28 | 1979-01-02 | Texaco Inc. | Production of H2 and co-containing gas stream and power |
| DE2911669A1 (en) * | 1979-03-24 | 1980-10-02 | Linde Ag | Hydrogen mfr. from hydrocarbon(s) by steam reforming and adsorption - with combustion and/or recirculation of purging gas after carbon di:oxide sepn. |
| ES507688A0 (en) * | 1980-12-09 | 1982-11-01 | Linde Ag | ABSORPTION PROCEDURE TO DECOMPOSE AT LEAST TWO RAW GAS STREAMS. |
| EP0115752B1 (en) * | 1981-08-07 | 1986-12-10 | Union Carbide Corporation | Improved process and apparatus for the production of ammonia |
| DE3310902A1 (en) * | 1983-03-25 | 1984-09-27 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR HEATING HYDROGEN PRESSURE FROM 200 TO 400 BAR |
| US4592860A (en) * | 1984-02-07 | 1986-06-03 | Union Carbide Corporation | Process and apparatus for ammonia synthesis gas production |
| GB8520892D0 (en) * | 1985-08-21 | 1985-09-25 | Ici Plc | Ammonia synthesis gas |
| DE3571797D1 (en) * | 1984-03-02 | 1989-08-31 | Ici Plc | Process for producing ammonia synthesis gas |
| GB8513997D0 (en) * | 1985-06-04 | 1985-07-10 | Ici Plc | Technical hydrogen |
| EP0167300A1 (en) * | 1984-06-06 | 1986-01-08 | Humphreys & Glasgow Limited | Process for the production of alcohols |
| US4919844A (en) * | 1984-08-16 | 1990-04-24 | Air Products And Chemicals, Inc. | Enhanced heat transfer reformer and method |
| DE3566878D1 (en) * | 1984-10-18 | 1989-01-26 | Ici Plc | Production of ammonia synthesis gas |
| AU573439B2 (en) * | 1985-03-25 | 1988-06-09 | Schick, J.H. | Process for the production of heat energy from synthetic gas |
-
1986
- 1986-12-04 GB GB868629031A patent/GB8629031D0/en active Pending
-
1987
- 1987-11-12 NL NL8702706A patent/NL8702706A/en not_active Application Discontinuation
- 1987-11-16 CA CA000551904A patent/CA1334124C/en not_active Expired - Fee Related
- 1987-12-02 NZ NZ222775A patent/NZ222775A/en unknown
- 1987-12-02 DE DE19873740865 patent/DE3740865A1/en not_active Withdrawn
- 1987-12-02 MY MYPI87003142A patent/MY102725A/en unknown
- 1987-12-02 AU AU82007/87A patent/AU595405B2/en not_active Ceased
- 1987-12-03 GB GB8728276A patent/GB2198429B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| NL8702706A (en) | 1988-07-01 |
| NZ222775A (en) | 1989-07-27 |
| AU8200787A (en) | 1988-06-09 |
| AU595405B2 (en) | 1990-03-29 |
| DE3740865A1 (en) | 1988-06-16 |
| GB8728276D0 (en) | 1988-01-06 |
| GB8629031D0 (en) | 1987-01-14 |
| MY102725A (en) | 1992-09-30 |
| GB2198429B (en) | 1990-12-19 |
| GB2198429A (en) | 1988-06-15 |
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