CA2412328C - Process for catalytic autothermal steam reforming of alcohols - Google Patents
Process for catalytic autothermal steam reforming of alcohols Download PDFInfo
- Publication number
- CA2412328C CA2412328C CA2412328A CA2412328A CA2412328C CA 2412328 C CA2412328 C CA 2412328C CA 2412328 A CA2412328 A CA 2412328A CA 2412328 A CA2412328 A CA 2412328A CA 2412328 C CA2412328 C CA 2412328C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- process according
- alcohols
- hydrocarbons
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1023—Catalysts in the form of a monolith or honeycomb
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1029—Catalysts in the form of a foam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a process for catalytic autothermal steam reforming of alcohols having two or more carbon atoms by directing a preheated educt or reactant mixture of the alcohols, oxygen and water or steam over a catalyst. The process is conducted in an adiabatic manner wherein the catalyst comprises at least one platinum group metal on an oxidic support selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide or mixed oxides thereof and zeolites, and that the educt or reactant mixture contains additional hydrocarbons, which are reformed at the same time as the alcohols.
Description
OMG ftef.: 01 U313 l~Y Iaacket:13 ~ S 9 22772.1 ~'~-ocess far cat~a~ytic autothe~~nal steam refo~r~nnng of alcolhols FIFlLri O~' T'H~ I~NTIUIY
The invention provides a process for hydz~oge~n production. More specifically, a pxocess for catalytic autothercaaal steam reforxx~,ing of aIcohols, which have two or mare carbon atoms, by directing a preheated educt or reactant mixture of alcohols, oxygen and water or steam over a catalyst. T'ixxs process is conducted in an adiabatic manner. The catalyst in the present i~avention comprises at Ieast one ptatiz~uzn group metal on an oxidic support selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide or mixed oxides thereof and zeolites, and wherein the educt or reactant mixture contaizts additional hydrocarbons, which are reformed at the saxzre time as the alcohols.
IS
BACII~GR~I3~ ~F ~ INVENTI(~~T
The present invention xelates to a pxocess For catalytic autothermal stearxi reforming of alcohois having two or more carbon atoms, in particular ethanol, by directing a preheated eduet or reactant mixture of the alcohols, oxygen and water' or steam over a catalyst.
for the production of hydrogen, as is 1<xtown, that alcohols can be converted to hydrogen, carbon monoxide and carbon dioxide in the presence of steam and a suitable catalyst. The reaction is highly endothermic and proceeds fox example according to the following reaction equation;
CZHSOH + I3E20 .,.- 2 CO + 4 H~ ~~ ~ + 29S l~.Ilrnole (1) The so-called steam to carbon ratio S!C i.s characteristic of this reaction.
In equation (I), Sly equals 0.5.
Another koowni rlxetl~od for producing hydrogen is catalytic partial oxidation (GI'O). During Ck'D, especlall~r hydrocaxb~ns are converted to carbon monoxide and.
hydrogen in the presence of oxyge~a and a catalyst, fax example according to reaction equation (2). in the case of alcohols, the energetic situation is different;
~or instance, in the case of ethanol, pure partial oxidation is endotherrnio, i.e. a process that will not proceed without energy input (3a). If the amount of oxygen is increased (3b-3a), a selectiv$ catalyst is necessary which preferably oxidizes CO and nvt hydrogen.
An.
iruportant paranr~eter of partial oxidation is the air coefficient ~,, which is defined as the ratio t~etween tlae number of moles of oxygen used to the rxumber of moles of oxygen xe.~uired for cornptete oxidation {see reaction equation (4)):
C81~1$ + 4 OZ . 8 CO -~ 9 H~ 7. = 4.3~ 4H = - 685 krlmole CxH~OH ~- I/2 02 » 2 CO + 3 fIz ~, 0.17 ~H = + 57 k3'Irraole {3a) C2HSUl'I + 1 Q2 . Ci~z + CO + 3 I-i2 ~. = 0.33 AH = - 226 kJ~amole (3b) C2I-I~OI-I + 3l2 OZ ~ 2 Cue. + 3 H~ ~. = 0..50 dH = - 5U9 kJ/mole (3c) C~I~~OH + 3 Q2 . 2 COz + 3 HZC9 ~. = 1 ~,H = - I368 kJlmole (4) The present inwerniQr~ relates to another method of hydrogen production, the so-called catalytic autotlaexmal steam reforming. Thi$ process combines catalytic part'sal, oxidation and stearx~ reforrnin~, wherein the exothermic oxidation supplies the. wcessary reaction heat for the subsequent endothermic steam reforix~zxtg_ For this purpose, the educt or reactant mixture ca:n be preheated to a preheat tenxp~;rature. At the ~te~perature prevailing at the reactor outlet, the product mixture is in the thermodynamic eduilibrium of the water-gas shill reaction. Ae~totherFnal steam reforrr~ittg corxabines the advantages of catalytic (partial) oxidation (good start-up behavior) and steam reforming (high hydrogen yields).
A catalyst for use in an autothermal reformer has been disclosed in tire art.
This catalyst comprises O.U'I% to 6% rhodium and 1.0 to 35% calcium oxide o~, an alumina support, which is furthermore promoted wvith 3 to 15% rnagnesitun, The catalyst is used in~
the form of pellets and in particular has a lovv tendency to cake at low oxygenlcarbon ratios. Azx example of a typical catalyst system far autntherrnal reloxrning comprises art iron oxide catalyst for partial oxidation fir about one-third of fits length, and the described rhodium catalyst ~or abort two-thirds of its length.
A bifunctiox~.al catalyst for the partial oxidation of Lrydrocaxbons has also bset~
disclosed in the art. This catalyst exhibits dehydrogenatiozt activity for dehydrogenating the hydrocarbons az~d is capable of selectively oxidizing the hydrocarbon chain. 'the dehydrogenation activity is prr~vided by metals of the eigbth group of the periodic table, while selective o~.idation is effeoted by ionized oxygen. °fhe sources for the ionized oxygen are oxides that crystallize in a ~iuorite or perovskite structure, such as far example zirconium oxide, cerium oxide, bismuth oxide etc. An example of a preferred catalyst is TtlCeGd~. This is used iwt(ae form; of pellets with diameters of I . I25 to 1.5 inches.
It in known in that art that a process ~or tl~e catalytic production of hydrogen by means of a self sustaining partial a~xidation and steam reformuig of hydrocarbons, whereitu I S a mixture of the hydrocarbons and an oaryger~..containing gas and optiorxally steam is reacted in the presence of a catalyst comprising rhodium dispersed on a suipport, which contains cerium and zirconium as rations. The catalyst is used in granular form.
It is also known in the , art that a process and an apparatus for autotherma( reforming ofhydrocarbons wherein the ~uei is added to a.two-stage refoamex via a feeding unit. In a heat exchanger in coun~texourrent and in a heat-exchanging manner, the resulting reformats is fed to the educt or reactant of the reforming process, which is Led from the outside to the inside. The fuel added via the feeding uzait, together with the educt or reactant, is directly provided to the reaction zone comprising a catalyst, where the combustion and reforming or catalysis is carried out. 'The re~orzxa,er comprises a 3~oneycomb carrier coated ~xYith a catalyst in an upper part, and a bed coated with catalyst in a Lower part. A honeycomb carrier can also be used ixxstead of the bed.
Catalytic autothermal stearr~, refoxnning of aloohols seems to be a suitable process for the production of I~ydxogem in a vehicle powered by fuel eeIls sirtee by means of this process the hydrogen needed to operate the fast cells can be obtained from e.g. renewable resources such as bio-et(xanol, which in some countries is a9lready used in conventional corinbustzon engines. For this held of application, the hydrogen productivity is of declsme importance. ~t can either be expressed based on the volume of catalyst, see equation (S), or ~~; the mass of the employed noble z~netal, see equation (6):
3' Nri'1 ~.~at ~ ~ _ _ (~) ~K~t't i~t'h pE~ w V~zz ~?n (~) BEM - t ° J~~ ~ h t'~at: Hydrogen productivity based on the volume VK~ of the catalyst i'~: Hydrogen productivity based ozI the mass of the noble rnetai 1 il 'V: 'Volume of hydrogen produced under standard conditions t: ~ilne One problem. in connection with th;e use of alcohols for the production df hydrogen by means c~f autotherrnai reforming is the fact that .for providing the alcohols, the existing 15 zz~frastructure in place for gasoline and diesel fuel is used, i.e. the biological alcohol. is transported in the carne truck~trailers and stored in the sataae tanks as the otlxer engine fuels so that a contamination off' the alcohols by gasoline and diesel fuel cannot be prevented.
Examinations o~ the purity of alcohols stored in vessels. in which gasoline or diesel fuel had been previously stored have shown that these alcohols may contain between ~.5 and 20 10 wt...°J° of these hydrocarboxls, based on the tote! weight of alcohols anal hydrocarbons.
lJsualIy, the contamination of the alcohols by hydrocarbons, lie: between a.5 and 5 cwt...°J°.
Based on the forgoing, there is a need in the art for a process for catalytic autotherlnal steam. reforming that allows the simultaneous refozxning of alcohols and ? 5 hydrocarbons with a very high hydrogen productivity, whiclh is well suited for use in mobile systems.
The invention provides a process for hydz~oge~n production. More specifically, a pxocess for catalytic autothercaaal steam reforxx~,ing of aIcohols, which have two or mare carbon atoms, by directing a preheated educt or reactant mixture of alcohols, oxygen and water or steam over a catalyst. T'ixxs process is conducted in an adiabatic manner. The catalyst in the present i~avention comprises at Ieast one ptatiz~uzn group metal on an oxidic support selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide or mixed oxides thereof and zeolites, and wherein the educt or reactant mixture contaizts additional hydrocarbons, which are reformed at the saxzre time as the alcohols.
IS
BACII~GR~I3~ ~F ~ INVENTI(~~T
The present invention xelates to a pxocess For catalytic autothermal stearxi reforming of alcohois having two or more carbon atoms, in particular ethanol, by directing a preheated eduet or reactant mixture of the alcohols, oxygen and water' or steam over a catalyst.
for the production of hydrogen, as is 1<xtown, that alcohols can be converted to hydrogen, carbon monoxide and carbon dioxide in the presence of steam and a suitable catalyst. The reaction is highly endothermic and proceeds fox example according to the following reaction equation;
CZHSOH + I3E20 .,.- 2 CO + 4 H~ ~~ ~ + 29S l~.Ilrnole (1) The so-called steam to carbon ratio S!C i.s characteristic of this reaction.
In equation (I), Sly equals 0.5.
Another koowni rlxetl~od for producing hydrogen is catalytic partial oxidation (GI'O). During Ck'D, especlall~r hydrocaxb~ns are converted to carbon monoxide and.
hydrogen in the presence of oxyge~a and a catalyst, fax example according to reaction equation (2). in the case of alcohols, the energetic situation is different;
~or instance, in the case of ethanol, pure partial oxidation is endotherrnio, i.e. a process that will not proceed without energy input (3a). If the amount of oxygen is increased (3b-3a), a selectiv$ catalyst is necessary which preferably oxidizes CO and nvt hydrogen.
An.
iruportant paranr~eter of partial oxidation is the air coefficient ~,, which is defined as the ratio t~etween tlae number of moles of oxygen used to the rxumber of moles of oxygen xe.~uired for cornptete oxidation {see reaction equation (4)):
C81~1$ + 4 OZ . 8 CO -~ 9 H~ 7. = 4.3~ 4H = - 685 krlmole CxH~OH ~- I/2 02 » 2 CO + 3 fIz ~, 0.17 ~H = + 57 k3'Irraole {3a) C2HSUl'I + 1 Q2 . Ci~z + CO + 3 I-i2 ~. = 0.33 AH = - 226 kJ~amole (3b) C2I-I~OI-I + 3l2 OZ ~ 2 Cue. + 3 H~ ~. = 0..50 dH = - 5U9 kJ/mole (3c) C~I~~OH + 3 Q2 . 2 COz + 3 HZC9 ~. = 1 ~,H = - I368 kJlmole (4) The present inwerniQr~ relates to another method of hydrogen production, the so-called catalytic autotlaexmal steam reforming. Thi$ process combines catalytic part'sal, oxidation and stearx~ reforrnin~, wherein the exothermic oxidation supplies the. wcessary reaction heat for the subsequent endothermic steam reforix~zxtg_ For this purpose, the educt or reactant mixture ca:n be preheated to a preheat tenxp~;rature. At the ~te~perature prevailing at the reactor outlet, the product mixture is in the thermodynamic eduilibrium of the water-gas shill reaction. Ae~totherFnal steam reforrr~ittg corxabines the advantages of catalytic (partial) oxidation (good start-up behavior) and steam reforming (high hydrogen yields).
A catalyst for use in an autothermal reformer has been disclosed in tire art.
This catalyst comprises O.U'I% to 6% rhodium and 1.0 to 35% calcium oxide o~, an alumina support, which is furthermore promoted wvith 3 to 15% rnagnesitun, The catalyst is used in~
the form of pellets and in particular has a lovv tendency to cake at low oxygenlcarbon ratios. Azx example of a typical catalyst system far autntherrnal reloxrning comprises art iron oxide catalyst for partial oxidation fir about one-third of fits length, and the described rhodium catalyst ~or abort two-thirds of its length.
A bifunctiox~.al catalyst for the partial oxidation of Lrydrocaxbons has also bset~
disclosed in the art. This catalyst exhibits dehydrogenatiozt activity for dehydrogenating the hydrocarbons az~d is capable of selectively oxidizing the hydrocarbon chain. 'the dehydrogenation activity is prr~vided by metals of the eigbth group of the periodic table, while selective o~.idation is effeoted by ionized oxygen. °fhe sources for the ionized oxygen are oxides that crystallize in a ~iuorite or perovskite structure, such as far example zirconium oxide, cerium oxide, bismuth oxide etc. An example of a preferred catalyst is TtlCeGd~. This is used iwt(ae form; of pellets with diameters of I . I25 to 1.5 inches.
It in known in that art that a process ~or tl~e catalytic production of hydrogen by means of a self sustaining partial a~xidation and steam reformuig of hydrocarbons, whereitu I S a mixture of the hydrocarbons and an oaryger~..containing gas and optiorxally steam is reacted in the presence of a catalyst comprising rhodium dispersed on a suipport, which contains cerium and zirconium as rations. The catalyst is used in granular form.
It is also known in the , art that a process and an apparatus for autotherma( reforming ofhydrocarbons wherein the ~uei is added to a.two-stage refoamex via a feeding unit. In a heat exchanger in coun~texourrent and in a heat-exchanging manner, the resulting reformats is fed to the educt or reactant of the reforming process, which is Led from the outside to the inside. The fuel added via the feeding uzait, together with the educt or reactant, is directly provided to the reaction zone comprising a catalyst, where the combustion and reforming or catalysis is carried out. 'The re~orzxa,er comprises a 3~oneycomb carrier coated ~xYith a catalyst in an upper part, and a bed coated with catalyst in a Lower part. A honeycomb carrier can also be used ixxstead of the bed.
Catalytic autothermal stearr~, refoxnning of aloohols seems to be a suitable process for the production of I~ydxogem in a vehicle powered by fuel eeIls sirtee by means of this process the hydrogen needed to operate the fast cells can be obtained from e.g. renewable resources such as bio-et(xanol, which in some countries is a9lready used in conventional corinbustzon engines. For this held of application, the hydrogen productivity is of declsme importance. ~t can either be expressed based on the volume of catalyst, see equation (S), or ~~; the mass of the employed noble z~netal, see equation (6):
3' Nri'1 ~.~at ~ ~ _ _ (~) ~K~t't i~t'h pE~ w V~zz ~?n (~) BEM - t ° J~~ ~ h t'~at: Hydrogen productivity based on the volume VK~ of the catalyst i'~: Hydrogen productivity based ozI the mass of the noble rnetai 1 il 'V: 'Volume of hydrogen produced under standard conditions t: ~ilne One problem. in connection with th;e use of alcohols for the production df hydrogen by means c~f autotherrnai reforming is the fact that .for providing the alcohols, the existing 15 zz~frastructure in place for gasoline and diesel fuel is used, i.e. the biological alcohol. is transported in the carne truck~trailers and stored in the sataae tanks as the otlxer engine fuels so that a contamination off' the alcohols by gasoline and diesel fuel cannot be prevented.
Examinations o~ the purity of alcohols stored in vessels. in which gasoline or diesel fuel had been previously stored have shown that these alcohols may contain between ~.5 and 20 10 wt...°J° of these hydrocarboxls, based on the tote! weight of alcohols anal hydrocarbons.
lJsualIy, the contamination of the alcohols by hydrocarbons, lie: between a.5 and 5 cwt...°J°.
Based on the forgoing, there is a need in the art for a process for catalytic autotherlnal steam. reforming that allows the simultaneous refozxning of alcohols and ? 5 hydrocarbons with a very high hydrogen productivity, whiclh is well suited for use in mobile systems.
S1C~MARY 4F THC ~1'VEl~iTIUN
The present in~entiun provides a process for catalytic autothermal steam refantning that allows the simultaneous reforming of alcohols and hydrorarbans with high hydrogen productivity. This process is appropriate for use in mobile systems.
In one embodiment, the present invention provides a process for catalytic autothermaI steam refozzxxing of alcohols having two or more carbon atoms by directing a preheated educt or reactant mixture of the alcahols, oxygen and water or steaaa over a catalyst. The process is conducted in an adiabatic manner wherein the catalyst comprises at least one platinum group metal on an oxidic support selected fro~nn. the group consisting of aluminum oxide, silicon dioxide, titanium dioxide or rr~i~ed oxides thereof and zeolites, and that the eduat or reactant mixture contains additional hydrocarbons, which are reformed at the same time as the alcoltols.
1.5 par a. better understanding of the present invention together with other and further advantages and embodiments, reference is made to the following description;
taken in oonjunction with flee examples, the scope of which is set forth vin the appended claims.
DETAICE1E~ DESCRIPTION ~F 'Z'Z'HC 1NVENTIUN
The invention will now be described in conn.ectioza with preferred embodiments.
ThesE embodiments are presented to aid in a~a understanding of the present invention and are not xute~aded to, and shauld z~ot $e construc;d to, limit the invention in any way. ,A~.11 alternatives, modil_ications and equivalents, which . may become obvious to those o;F
ordinary skill o~ reading the disclosure are included within' the spirit and scope of the invention.
This disclosure is not a primer on process for preparing platinuru ox platinum alloy powders, basic concepts known to those skilled in the art have not been set forth in detail.
The process according to the invention is achieved by a single.stage prac~ss, l.c.
the educt or reaotant mixture is directed over a single catalyst capable of providi~ag the energy requirEd for the endothermic steam reforming by catalytic oxidation of part of the b eduet or reactant mixture in the inlet section of the catalyst. This causes an increase in the tezxzperature of the educt or reactant ~.ixture from the pxeheat t~ernperature to the necessary reaction temperature between 600 and 800°C. i~xidatian and steam reforming then xxzerge into one another.
S
The catalyst to be used according to the present invention comprises, oza a carrier, a catalyst composition, which has been applied in the form of a coating onto the geometric surfacxs o~ the carrier. Preferred carriers are monolithic ceramic or metal honeycomb carriers, open-cell eera~zxzic or metallic foam carriers, metal sheets or irregularly shaped 20 elements. The thiclmess of the catalytic coating is usually bctweez~ about 20 and about 100 p,rn.
Qne advantage of this catalyst set-up is its relatively low heat capacity.
Furthexznore, the entire catalyst composition is very accessible for the reactants since it is 15 spz~ead out in the form of a coating. This results in a high spe~.cific catalyst activity and a high dynamic of the catalytic process, which means that the process can easily adapt to the changixag demands for hydrogen production in a motor vehicle. it is also important that the process is an adiabatic process. That is, no heat is removed fxozn the catalytic process by zneazzs of a heat exchanger. The process according to the present invention therefore 20 has a very short start-up tixxze after cold start of the motor vehicle since no unnecessary components have to be heated to the operating tem~pexature.
The catalyst composition comprises at least one platinum group metal on a fine oxidic support. Thus, the catalyst composition is a catalyst on a support or supported 2S catalyst, The term supported catalyst as it is used izz the present invention only refers to the catalyst corrzposition and is distitzguished from the catalyst, which consists of 'the carrier and the supported catalyst applied thereon in the ~ozxrz of a coating.
Possible oa.idie supports for the platz>«utz~: group metals include oxides selected 30 from the group consisting of aluzxzinum oxide, silicon dioz~ide, titanium oxide or mixed oxides thereof and zeolites. Preferably, materials with a speeifnc sz3rface area of more than 1 t? zn2/g are used in order to allow as highly disperse a distributiozx of the catalytica,Ily active components as possible on this large surface. The techruques for producing such a supported catalyst and for coating an inert carrier therewith are knorwn~ to the person skilled in the art.
For thermal stabilization and as promoters, the catalyst com~pasitiou can additionally comprise at least one oxide selected ~rozn the group consisting of baF~c oxide, bismuth oxide, gallium o~cide, alkali metal oxides, alkaline earCh~ metal oxides, oxides of subgroup elements an,d rare earth metal oxides in a concentration ot°
up to about 40 wt:
based a~n the total weight ofthe catalyst composition.
As a noble metal, the. catalyst coznxposition preferably comprises about 0.1 ttr about 2 rill.-°/o rhodium, based azt its total weight. Rhodium exhibits a high steam reforming activity, while at the same tame its oxidation activity is low compared to that of platinum.
This way, the partial oxidation of the educt or reactant mixture at the inlet of the catalyst is attenuated and high terrxperature peaks are avoided which might destroy the catalyst. In.
order to adjust the oxidation activity to the process requirements, the catalyst caznposition raay additionally comprise platinum andlor palladium in a ratio of rhodium to platinum andlor palladium between about 20:1 axed about 2:1, preferably about 10:1 to about 3:1, In this connection, it is in ~porEant that the amount by weight of platin~arnt andlor palladium is lower than that ofrhodium in order to avoid overly vigorous oxidation at the catalyst inlet.
l~t'efv~rably, a catalyst composition is used that comprises rhodium and aptiana'lly platinum and/or palladium on an active aluminum oxide. This catalyst composition ~nn~y additionally cotxtp~se cerium oxide to reduce carbon black deposits and increase sulfur resistance.
It has been found that the catalyst to 'be used in accordance with the present invention is capable of sirr~ulta~epusly re~orz~aing a mixture of different alcohols and hydrocarbons. The process rnay be carried out with limear or branched alcohc~ls or alcohol mixtures. Depez~tling oz~ the alcohol used, steam to carbon ratios SIC
ofbetween about 0.5 a~cxd about 4 can be applied. The air coefficient ~, of the educt or reactant mixture and its preheat temperature are selected such that at the outlet of the catalyst a temperature between about 600 and about 800°C is eskablished.
According to tl~e present invention, these alcohols or alcohol mixtures comprise about 0.5 to about 10 cwt.-% of hydrocarbons, based on the total weight of alcohols and hydrocarbons, pre~exably, the amount of hydrocarlaons lies beriween about U.5 and about 5 wt.%. ' The hydrocarbons may be diesel fuel or gasoline. In addition to long-chain hydrocarbons, these fuels rnay also contain aromatic hydrocarbo~as, which are also simultaneously refonaaed together with the atcohols card tXae other hydrocarbotas, Gasoline and particularly diesel fuels usually contain trice amounts of sulfur compounds that can poison tlae reforming catalysts. ~Iowever, it has been found tb;at the catalysts suggested for the process of the present invention are relativety resistant to sulfur poisoning. I~urkhermore, another advantage of the process is that the product gas txiixture of the re~ornrxing process has a very low methane content of less than 0.5 vol.-%.
The suggested process only represents part o~the overall process for the pmductivn a~ hydrogen in a vehicle equipped with I'uel cells. In addition to autothenm;al reforming, this overall process also coxx~prises process steps for the removal of carbon monoxide from the refarmate, for example by means of one or zn,oz~e water~gas shi$ stages.
Furrhermc~re, the overall process also invalaes the catalytic combustion of the anode e~chaust gets of the fuel cell. The reaction in the watex gas shift stages and the catalytic coxrabustion are exothermic, and provide the necessary annount o~l~eat for preheating the educt or reactant rnuxture to a suitable preheat temperature o~ between about 15U and about 350°C during the continuous operation of the vehicle.
~7uring cold starting of the vehicle, the catalyst i5 briefly operated writh a educt or reactant mixture not containing az~y water or steam in order i:o quicl~ly heat the entire system to the operating temperature by catalytic oxidation at the catalyst, After the 3Q operating temperatures have been reached, catalytic autothermai reforming is staxted by adding steam to the educt or reactant mixture. Alternatively, the operating temperatures can also be adausted by ;means of other preheating measures.
Having ~owv generally described the iztvention, the same may be more readily understood through reference to the following e~.ample, which are provided by way of illustration and are not intended to lin~i~ the present invention unless spacifed.
EXAMpI~l~
The invention is explained in more detail by the fallowin,g example.
Example 1:
,A, catalyst useful for the process according to the izwention was prepared in the following way: Finely divided aluzznina with a specific surface area ~B~'f-surface) of 100 m2dg and beug doped with S wt. °Jo of la~zthanum oxide {La2t~) was dispersed in water. A
conventional ceramic t~aneycomb carrier was dipped irno the dispersion to eaat the walls of the flow channels with the stabilized alumina. The coated carrier was then dried anal calained at S00 °G. The concentration of the alumina coating was x50 gil of honeycomb carrier. Subsequently the coated carrier was impregnated witlx an aqueous solution of RhCl3 as a precursor compound for rhodiuzta. The impregnates! carrier was then dried, calcined at 500 °C and finally treated in a stream of fonm,xng ~,as {95 voL-% N2; S vol: °Jo H2) at 400 °C to claezxxically reduce the rhadiam precursor compound.
The concentration of rhodium in the i;inxshed catalyst was 1 gll afthe honeycomb caxtiet.
The catalyst was used to aut~,thermally reform ethan4l. ,~, mixture of etha~aolg air and steam was heated to S00 °C and then conducted through the flow channels of tlae catalyst. The r~aass flow of ethanol was 200 blku, ~eforzning was done with an air cc~e~~cient of 7~ = 0.2z and varying steam to carbon ratios (SIC). The following table lists the dry composition of the product gas mixture (reformats) at the catalyst outlet.
Table: Composition o~ reformats at varying SIC ratios Composition of reformatsSIC = I S!C = SIC = 3 SIC ~
.3 2 3.S
H2 [voi.~%~ 35.1 36.4 37.8 38.7 CQz jvol. lo] 14.0 15.4 17.0 17.G
CQ [vol.-%~ 8.7 7.2 5.1 4,4 CH4 ~vol. l] 0.23 0.22 0.22 0.21 Catalyst outlet temperat~.ane649 644 G37 G31 [Cj The results show that according to the present process k~~h hydrogen; outpr~t can be obtained at relatively low catalyst outlet te~;nperat~tres.
While the invention has been described in connection with specific embodir~aenis thereof, it will he understood that it is capaf~le of further rnodificatioz~s and this application in ix~tendeci to cover any variation, uses, or adaptations of the iztwention folio~uving, in '1 D general, the principiss of the ir~ven~tion and including such departures from the present l'~I5G105L11"e as come within known or custvxnary practice rnithin~ tlxe arrr to which the invention pertains and as rnay be applied to the essential featums herein6efore set forth anal as follows in the scope of the appended claims.
The present in~entiun provides a process for catalytic autothermal steam refantning that allows the simultaneous reforming of alcohols and hydrorarbans with high hydrogen productivity. This process is appropriate for use in mobile systems.
In one embodiment, the present invention provides a process for catalytic autothermaI steam refozzxxing of alcohols having two or more carbon atoms by directing a preheated educt or reactant mixture of the alcahols, oxygen and water or steaaa over a catalyst. The process is conducted in an adiabatic manner wherein the catalyst comprises at least one platinum group metal on an oxidic support selected fro~nn. the group consisting of aluminum oxide, silicon dioxide, titanium dioxide or rr~i~ed oxides thereof and zeolites, and that the eduat or reactant mixture contains additional hydrocarbons, which are reformed at the same time as the alcoltols.
1.5 par a. better understanding of the present invention together with other and further advantages and embodiments, reference is made to the following description;
taken in oonjunction with flee examples, the scope of which is set forth vin the appended claims.
DETAICE1E~ DESCRIPTION ~F 'Z'Z'HC 1NVENTIUN
The invention will now be described in conn.ectioza with preferred embodiments.
ThesE embodiments are presented to aid in a~a understanding of the present invention and are not xute~aded to, and shauld z~ot $e construc;d to, limit the invention in any way. ,A~.11 alternatives, modil_ications and equivalents, which . may become obvious to those o;F
ordinary skill o~ reading the disclosure are included within' the spirit and scope of the invention.
This disclosure is not a primer on process for preparing platinuru ox platinum alloy powders, basic concepts known to those skilled in the art have not been set forth in detail.
The process according to the invention is achieved by a single.stage prac~ss, l.c.
the educt or reaotant mixture is directed over a single catalyst capable of providi~ag the energy requirEd for the endothermic steam reforming by catalytic oxidation of part of the b eduet or reactant mixture in the inlet section of the catalyst. This causes an increase in the tezxzperature of the educt or reactant ~.ixture from the pxeheat t~ernperature to the necessary reaction temperature between 600 and 800°C. i~xidatian and steam reforming then xxzerge into one another.
S
The catalyst to be used according to the present invention comprises, oza a carrier, a catalyst composition, which has been applied in the form of a coating onto the geometric surfacxs o~ the carrier. Preferred carriers are monolithic ceramic or metal honeycomb carriers, open-cell eera~zxzic or metallic foam carriers, metal sheets or irregularly shaped 20 elements. The thiclmess of the catalytic coating is usually bctweez~ about 20 and about 100 p,rn.
Qne advantage of this catalyst set-up is its relatively low heat capacity.
Furthexznore, the entire catalyst composition is very accessible for the reactants since it is 15 spz~ead out in the form of a coating. This results in a high spe~.cific catalyst activity and a high dynamic of the catalytic process, which means that the process can easily adapt to the changixag demands for hydrogen production in a motor vehicle. it is also important that the process is an adiabatic process. That is, no heat is removed fxozn the catalytic process by zneazzs of a heat exchanger. The process according to the present invention therefore 20 has a very short start-up tixxze after cold start of the motor vehicle since no unnecessary components have to be heated to the operating tem~pexature.
The catalyst composition comprises at least one platinum group metal on a fine oxidic support. Thus, the catalyst composition is a catalyst on a support or supported 2S catalyst, The term supported catalyst as it is used izz the present invention only refers to the catalyst corrzposition and is distitzguished from the catalyst, which consists of 'the carrier and the supported catalyst applied thereon in the ~ozxrz of a coating.
Possible oa.idie supports for the platz>«utz~: group metals include oxides selected 30 from the group consisting of aluzxzinum oxide, silicon dioz~ide, titanium oxide or mixed oxides thereof and zeolites. Preferably, materials with a speeifnc sz3rface area of more than 1 t? zn2/g are used in order to allow as highly disperse a distributiozx of the catalytica,Ily active components as possible on this large surface. The techruques for producing such a supported catalyst and for coating an inert carrier therewith are knorwn~ to the person skilled in the art.
For thermal stabilization and as promoters, the catalyst com~pasitiou can additionally comprise at least one oxide selected ~rozn the group consisting of baF~c oxide, bismuth oxide, gallium o~cide, alkali metal oxides, alkaline earCh~ metal oxides, oxides of subgroup elements an,d rare earth metal oxides in a concentration ot°
up to about 40 wt:
based a~n the total weight ofthe catalyst composition.
As a noble metal, the. catalyst coznxposition preferably comprises about 0.1 ttr about 2 rill.-°/o rhodium, based azt its total weight. Rhodium exhibits a high steam reforming activity, while at the same tame its oxidation activity is low compared to that of platinum.
This way, the partial oxidation of the educt or reactant mixture at the inlet of the catalyst is attenuated and high terrxperature peaks are avoided which might destroy the catalyst. In.
order to adjust the oxidation activity to the process requirements, the catalyst caznposition raay additionally comprise platinum andlor palladium in a ratio of rhodium to platinum andlor palladium between about 20:1 axed about 2:1, preferably about 10:1 to about 3:1, In this connection, it is in ~porEant that the amount by weight of platin~arnt andlor palladium is lower than that ofrhodium in order to avoid overly vigorous oxidation at the catalyst inlet.
l~t'efv~rably, a catalyst composition is used that comprises rhodium and aptiana'lly platinum and/or palladium on an active aluminum oxide. This catalyst composition ~nn~y additionally cotxtp~se cerium oxide to reduce carbon black deposits and increase sulfur resistance.
It has been found that the catalyst to 'be used in accordance with the present invention is capable of sirr~ulta~epusly re~orz~aing a mixture of different alcohols and hydrocarbons. The process rnay be carried out with limear or branched alcohc~ls or alcohol mixtures. Depez~tling oz~ the alcohol used, steam to carbon ratios SIC
ofbetween about 0.5 a~cxd about 4 can be applied. The air coefficient ~, of the educt or reactant mixture and its preheat temperature are selected such that at the outlet of the catalyst a temperature between about 600 and about 800°C is eskablished.
According to tl~e present invention, these alcohols or alcohol mixtures comprise about 0.5 to about 10 cwt.-% of hydrocarbons, based on the total weight of alcohols and hydrocarbons, pre~exably, the amount of hydrocarlaons lies beriween about U.5 and about 5 wt.%. ' The hydrocarbons may be diesel fuel or gasoline. In addition to long-chain hydrocarbons, these fuels rnay also contain aromatic hydrocarbo~as, which are also simultaneously refonaaed together with the atcohols card tXae other hydrocarbotas, Gasoline and particularly diesel fuels usually contain trice amounts of sulfur compounds that can poison tlae reforming catalysts. ~Iowever, it has been found tb;at the catalysts suggested for the process of the present invention are relativety resistant to sulfur poisoning. I~urkhermore, another advantage of the process is that the product gas txiixture of the re~ornrxing process has a very low methane content of less than 0.5 vol.-%.
The suggested process only represents part o~the overall process for the pmductivn a~ hydrogen in a vehicle equipped with I'uel cells. In addition to autothenm;al reforming, this overall process also coxx~prises process steps for the removal of carbon monoxide from the refarmate, for example by means of one or zn,oz~e water~gas shi$ stages.
Furrhermc~re, the overall process also invalaes the catalytic combustion of the anode e~chaust gets of the fuel cell. The reaction in the watex gas shift stages and the catalytic coxrabustion are exothermic, and provide the necessary annount o~l~eat for preheating the educt or reactant rnuxture to a suitable preheat temperature o~ between about 15U and about 350°C during the continuous operation of the vehicle.
~7uring cold starting of the vehicle, the catalyst i5 briefly operated writh a educt or reactant mixture not containing az~y water or steam in order i:o quicl~ly heat the entire system to the operating temperature by catalytic oxidation at the catalyst, After the 3Q operating temperatures have been reached, catalytic autothermai reforming is staxted by adding steam to the educt or reactant mixture. Alternatively, the operating temperatures can also be adausted by ;means of other preheating measures.
Having ~owv generally described the iztvention, the same may be more readily understood through reference to the following e~.ample, which are provided by way of illustration and are not intended to lin~i~ the present invention unless spacifed.
EXAMpI~l~
The invention is explained in more detail by the fallowin,g example.
Example 1:
,A, catalyst useful for the process according to the izwention was prepared in the following way: Finely divided aluzznina with a specific surface area ~B~'f-surface) of 100 m2dg and beug doped with S wt. °Jo of la~zthanum oxide {La2t~) was dispersed in water. A
conventional ceramic t~aneycomb carrier was dipped irno the dispersion to eaat the walls of the flow channels with the stabilized alumina. The coated carrier was then dried anal calained at S00 °G. The concentration of the alumina coating was x50 gil of honeycomb carrier. Subsequently the coated carrier was impregnated witlx an aqueous solution of RhCl3 as a precursor compound for rhodiuzta. The impregnates! carrier was then dried, calcined at 500 °C and finally treated in a stream of fonm,xng ~,as {95 voL-% N2; S vol: °Jo H2) at 400 °C to claezxxically reduce the rhadiam precursor compound.
The concentration of rhodium in the i;inxshed catalyst was 1 gll afthe honeycomb caxtiet.
The catalyst was used to aut~,thermally reform ethan4l. ,~, mixture of etha~aolg air and steam was heated to S00 °C and then conducted through the flow channels of tlae catalyst. The r~aass flow of ethanol was 200 blku, ~eforzning was done with an air cc~e~~cient of 7~ = 0.2z and varying steam to carbon ratios (SIC). The following table lists the dry composition of the product gas mixture (reformats) at the catalyst outlet.
Table: Composition o~ reformats at varying SIC ratios Composition of reformatsSIC = I S!C = SIC = 3 SIC ~
.3 2 3.S
H2 [voi.~%~ 35.1 36.4 37.8 38.7 CQz jvol. lo] 14.0 15.4 17.0 17.G
CQ [vol.-%~ 8.7 7.2 5.1 4,4 CH4 ~vol. l] 0.23 0.22 0.22 0.21 Catalyst outlet temperat~.ane649 644 G37 G31 [Cj The results show that according to the present process k~~h hydrogen; outpr~t can be obtained at relatively low catalyst outlet te~;nperat~tres.
While the invention has been described in connection with specific embodir~aenis thereof, it will he understood that it is capaf~le of further rnodificatioz~s and this application in ix~tendeci to cover any variation, uses, or adaptations of the iztwention folio~uving, in '1 D general, the principiss of the ir~ven~tion and including such departures from the present l'~I5G105L11"e as come within known or custvxnary practice rnithin~ tlxe arrr to which the invention pertains and as rnay be applied to the essential featums herein6efore set forth anal as follows in the scope of the appended claims.
Claims (15)
1. A process for catalytic autothermal steam reforming of alcohols having two or more carbon atoms comprising directing a preheated reactant mixture of the alcohols, oxygen and water or steam over a catalyst, in which the process is conducted in an adiabatic manner, wherein the catalyst comprises at least one platinum group metal on an oxidic support selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide or a mixed oxide comprising two or more of said oxides and zeolites, and wherein the reactant mixture contains about 0.5 to about 10 wt%
hydrocarbons, based on the total weight of alcohols and hydrocarbons, which are reformed at the same time as the alcohols.
hydrocarbons, based on the total weight of alcohols and hydrocarbons, which are reformed at the same time as the alcohols.
2. The process according to claim 1, wherein the hydrocarbons are diesel fuels.
3. The process according to claim 1, wherein the hydrocarbons are gasoline.
4. The process according to claim 1, wherein the hydrocarbons also comprise aromatic hydrocarbons in addition to long-chain hydrocarbons.
5. The process according to claim 1, wherein the alcohols are linear or branched alcohols or alcohol mixtures.
6. The process according to claim 1, wherein the alcohols consist of ethanol.
7. The process according to claim 1, wherein the catalyst additionally comprises at least one oxide selected from the group consisting of boric oxide, bismuth oxide, gallium oxide, alkali metal oxides, alkaline earth metal oxides, oxides of subgroup elements and rare earth metal oxides in a concentration of up to about 40 wt.% based on the total weight of the catalyst composition.
8. The process according to claim 1, wherein the catalyst comprises rhodium in a concentration of about 0.1 to about 2 wt.-%, based on total weight of the catalyst composition.
9. The process according to claim 8, wherein the catalyst additionally comprises at least one or both of platinum or palladium in a ratio of rhodium to the at least one or both of platinum or palladium of between about 20:1 to about 2:1 by weight.
10. The process according to claim 8, wherein the active aluminum oxide is used as support for rhodium and optionally platinum/palladium.
11. The process according to claim 10, wherein the catalyst additionally comprises cerium oxide.
12. The process according to claim 11, wherein the catalyst is coated on a carrier.
13. The process according to claim 12, wherein the carrier is a monolithic honeycomb ceramic or metal carrier, open-cell ceramic or metallic foam body or a metal sheet.
14. The process according to claim 1, wherein the preheated reactant mixture is selected such that at the outlet of the catalyst the temperature is between about 600 and about 800°C.
15. The process according to claim 13, wherein the reactant mixture has a steam to carbon ratio that is adjusted to between about 0.5 and about 4 by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10157155A DE10157155A1 (en) | 2001-11-22 | 2001-11-22 | Process for the catalytic autothermal steam reforming of higher alcohols, especially ethanol |
| DE10157155.0-41 | 2001-11-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2412328A1 CA2412328A1 (en) | 2003-05-22 |
| CA2412328C true CA2412328C (en) | 2011-03-22 |
Family
ID=7706480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2412328A Expired - Fee Related CA2412328C (en) | 2001-11-22 | 2002-11-21 | Process for catalytic autothermal steam reforming of alcohols |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6949683B2 (en) |
| EP (1) | EP1314688B1 (en) |
| JP (1) | JP2003183002A (en) |
| KR (1) | KR100908401B1 (en) |
| AT (1) | ATE388119T1 (en) |
| BR (1) | BR0204774B1 (en) |
| CA (1) | CA2412328C (en) |
| DE (2) | DE10157155A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10136768B4 (en) * | 2001-07-27 | 2012-03-01 | Robert Bosch Gmbh | Fuel cell system with two transformation units for catalytic decomposition and method for catalytic decomposition |
| DE10157155A1 (en) | 2001-11-22 | 2003-06-12 | Omg Ag & Co Kg | Process for the catalytic autothermal steam reforming of higher alcohols, especially ethanol |
| US7274043B2 (en) * | 2003-04-15 | 2007-09-25 | Luminus Devices, Inc. | Light emitting diode systems |
| JP4875295B2 (en) * | 2003-10-29 | 2012-02-15 | 株式会社日本触媒 | Reforming catalyst for partial oxidation and reforming method |
| US7585339B2 (en) * | 2004-09-15 | 2009-09-08 | Haldor Topsoe A/S | Process for reforming ethanol to hydrogen-rich products |
| KR100647331B1 (en) * | 2005-08-02 | 2006-11-23 | 삼성에스디아이 주식회사 | Shift reactor, fuel cell system employing the same, and operating method of the same |
| FR2892323B1 (en) * | 2005-10-20 | 2008-08-15 | Cie D Etudes Des Technologies | CATALYST FOR THE PRODUCTION OF HYDROGEN RICH GAS |
| US7951350B1 (en) | 2007-01-26 | 2011-05-31 | West Biofuels, Llc | Fuel-gas reforming systems and methods |
| US8153027B2 (en) * | 2007-07-09 | 2012-04-10 | Range Fuels, Inc. | Methods for producing syngas |
| WO2009009388A2 (en) * | 2007-07-09 | 2009-01-15 | Range Fuels, Inc. | Methods and apparatus for producing syngas |
| US20090014689A1 (en) * | 2007-07-09 | 2009-01-15 | Range Fuels, Inc. | Methods and apparatus for producing syngas and alcohols |
| US8142530B2 (en) * | 2007-07-09 | 2012-03-27 | Range Fuels, Inc. | Methods and apparatus for producing syngas and alcohols |
| US20090093555A1 (en) * | 2007-07-09 | 2009-04-09 | Range Fuels, Inc. | Methods and apparatus for producing syngas |
| US20090165368A1 (en) * | 2007-12-28 | 2009-07-02 | Yunquan Liu | Process and apparatus for reforming gaseous and liquid fuels |
| WO2009136909A1 (en) * | 2008-05-06 | 2009-11-12 | West Biofuels, Llc | Fuel-gas reforming systems and methods |
| JP5376222B2 (en) * | 2009-05-14 | 2013-12-25 | 独立行政法人産業技術総合研究所 | Ethanol steam reforming catalyst |
| US8207084B2 (en) * | 2009-06-23 | 2012-06-26 | Ford Global Technologies, Llc | Urea-resistant catalytic units and methods of using the same |
| US9611437B2 (en) * | 2010-01-12 | 2017-04-04 | Lummus Technology Inc. | Producing low methane syngas from a two-stage gasifier |
| KR101463543B1 (en) * | 2014-02-13 | 2014-11-19 | 고천일 | Improved apparatus and method for manufacturing reforming fuel |
| JP6541339B2 (en) * | 2014-12-01 | 2019-07-10 | クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Steam reforming catalyst for hydrocarbon-containing gas, hydrogen production apparatus, and hydrogen production method |
| KR101581235B1 (en) * | 2015-04-14 | 2015-12-30 | 고천일 | Apparatus and method for manufacturing reforming fuel |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5815013B2 (en) | 1980-07-17 | 1983-03-23 | 株式会社豊田中央研究所 | Steam reforming catalyst and its manufacturing method |
| US4415484A (en) * | 1982-04-26 | 1983-11-15 | United Technologies Corporation | Autothermal reforming catalyst |
| DE3382193D1 (en) | 1982-09-30 | 1991-04-11 | Engelhard Corp | METHOD FOR PRODUCING HYDROGEN-rich GAS FROM HYDROCARBONS. |
| DE3340569A1 (en) | 1983-11-09 | 1985-05-23 | Sued Chemie Ag | CATALYST FOR THE PRODUCTION OF SYNTHESIS GAS OR FROM HYDROGEN AND METHOD FOR THE PRODUCTION THEREOF |
| US4755498A (en) | 1986-04-30 | 1988-07-05 | International Fuel Cells Corporation | Steam reforming catalyst |
| EP0303438A3 (en) * | 1987-08-14 | 1989-12-27 | DAVY McKEE CORPORATION | Production of synthesis gas from hydrocarbonaceous feedstock |
| US5112527A (en) | 1991-04-02 | 1992-05-12 | Amoco Corporation | Process for converting natural gas to synthesis gas |
| DE4427665A1 (en) * | 1994-08-04 | 1996-02-08 | Sued Chemie Ag | Catalyst for methane steam reforming and / or methane oxidation |
| US6293979B1 (en) | 1994-12-19 | 2001-09-25 | Council Of Scientific & Industrial Research | Process for the catalytic conversion of methane or natural gas to syngas or a mixture of carbon monoxide and hydrogen |
| US6376423B2 (en) | 1997-04-11 | 2002-04-23 | Chiyoda Corporation | Catalyst for preparation of synthesis gas and process for preparing carbon monoxide |
| US5883138A (en) | 1997-04-25 | 1999-03-16 | Exxon Research And Engineering Company | Rapid injection catalytic partial oxidation process and apparatus for producing synthesis gas (law 562) |
| US6267912B1 (en) | 1997-04-25 | 2001-07-31 | Exxon Research And Engineering Co. | Distributed injection catalytic partial oxidation process and apparatus for producing synthesis gas |
| US6110861A (en) | 1997-06-02 | 2000-08-29 | The University Of Chicago | Partial oxidation catalyst |
| DE19727841A1 (en) | 1997-06-24 | 1999-01-07 | Fraunhofer Ges Forschung | Method and device for the autothermal reforming of hydrocarbons |
| US20020007595A1 (en) | 1997-06-24 | 2002-01-24 | Uli Maier-Roeltgen | Method for reforming hydrocarbons autothermally |
| DE19753738A1 (en) * | 1997-12-04 | 1999-06-10 | Degussa | Process for producing a catalyst |
| GB9806199D0 (en) | 1998-03-24 | 1998-05-20 | Johnson Matthey Plc | Catalytic generation of hydrogen |
| GR1003235B (en) * | 1998-05-22 | 1999-10-13 | Process for the production of hydrogen and electricity generation by bio-ethanol reforming with the use of fuel cells and without emission of pollutants | |
| US6146472A (en) * | 1998-05-28 | 2000-11-14 | The Timken Company | Method of making case-carburized steel components with improved core toughness |
| EP1481729B1 (en) | 1998-06-09 | 2006-08-16 | Idemitsu Kosan Company Limited | Process for the autothermal reforming of a hydrocarbon feedstock |
| CA2282948A1 (en) | 1998-09-16 | 2000-03-16 | University Technologies International, Inc. | Low temperature autothermal steam reformation of methane in a fluidized bed |
| US6524550B1 (en) | 1999-05-03 | 2003-02-25 | Prashant S. Chintawar | Process for converting carbon monoxide and water in a reformate stream |
| AU2001231082A1 (en) | 2000-01-24 | 2001-07-31 | International Fuel Cells, Llc | Autothermal fuel gas reformer assemblage |
| US6458334B1 (en) | 2000-03-02 | 2002-10-01 | The Boc Group, Inc. | Catalytic partial oxidation of hydrocarbons |
| DE10025032A1 (en) | 2000-05-20 | 2001-11-29 | Dmc2 Degussa Metals Catalysts | Process for the autothermal, catalytic steam reforming of hydrocarbons |
| US6436363B1 (en) | 2000-08-31 | 2002-08-20 | Engelhard Corporation | Process for generating hydrogen-rich gas |
| US7025903B2 (en) | 2001-02-15 | 2006-04-11 | Delphi Technologies, Inc. | Reformer system process |
| DE10157155A1 (en) | 2001-11-22 | 2003-06-12 | Omg Ag & Co Kg | Process for the catalytic autothermal steam reforming of higher alcohols, especially ethanol |
-
2001
- 2001-11-22 DE DE10157155A patent/DE10157155A1/en not_active Ceased
-
2002
- 2002-11-20 US US10/300,173 patent/US6949683B2/en not_active Expired - Fee Related
- 2002-11-21 CA CA2412328A patent/CA2412328C/en not_active Expired - Fee Related
- 2002-11-21 JP JP2002338654A patent/JP2003183002A/en not_active Withdrawn
- 2002-11-22 AT AT02026344T patent/ATE388119T1/en not_active IP Right Cessation
- 2002-11-22 BR BRPI0204774-8A patent/BR0204774B1/en not_active IP Right Cessation
- 2002-11-22 EP EP02026344A patent/EP1314688B1/en not_active Expired - Lifetime
- 2002-11-22 KR KR1020020073164A patent/KR100908401B1/en not_active IP Right Cessation
- 2002-11-22 DE DE60225404T patent/DE60225404T2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE10157155A1 (en) | 2003-06-12 |
| CA2412328A1 (en) | 2003-05-22 |
| KR100908401B1 (en) | 2009-07-21 |
| US6949683B2 (en) | 2005-09-27 |
| EP1314688A3 (en) | 2003-12-17 |
| EP1314688B1 (en) | 2008-03-05 |
| ATE388119T1 (en) | 2008-03-15 |
| BR0204774B1 (en) | 2011-03-09 |
| JP2003183002A (en) | 2003-07-03 |
| US20030116472A1 (en) | 2003-06-26 |
| DE60225404D1 (en) | 2008-04-17 |
| KR20030042433A (en) | 2003-05-28 |
| BR0204774A (en) | 2003-09-16 |
| DE60225404T2 (en) | 2009-03-12 |
| EP1314688A2 (en) | 2003-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2412328C (en) | Process for catalytic autothermal steam reforming of alcohols | |
| US7150866B2 (en) | Catalyst for autothermal reforming of hydrocarbons with increased water gas shift activity | |
| KR101052385B1 (en) | Use of Metal Supported Copper Catalysts for Alcohol Reforming | |
| US6790247B2 (en) | Compact fuel processor | |
| US6585940B2 (en) | Reformer | |
| US6576203B2 (en) | Reformer | |
| US20020090334A1 (en) | Method for reducing the carbon monoxide content of a hydrogen rich gas | |
| CA2348120C (en) | A process for the autothermal catalytic steam reforming of hydrocarbons | |
| CA2477852A1 (en) | Steam-reforming catalytic structures | |
| CN101712461A (en) | Hydrogen purification device and fuel cell power generation system | |
| CA2629078C (en) | Process conditions for pt-re bimetallic water gas shift catalysts | |
| US7972394B2 (en) | Selective methanation reactor for reducing carbon monoxide in a reformate stream | |
| US20030012719A1 (en) | Catalyst and process for removing carbon monoxide from a reformate gas | |
| JP3574469B2 (en) | Method for oxidizing CO to CO2 and method for producing hydrogen-containing gas for fuel cell | |
| US20060168887A1 (en) | Method for producing a fuel gas containing hydrogen for electrochemical cells and associated device | |
| JPH07309603A (en) | Production of hydrogen-containing gas for fuel cell | |
| EP1391240A1 (en) | Method for preparing a catalyst for preferential oxidation to remove carbon monoxide from a hydrogen-rich gas, a process for preferential oxidation to remove carbon monoxide from hydrogen-rich gas and a method for operating a fuel cell system | |
| WO2004004895A1 (en) | Method for preparing a catalyst for preferential oxidation and a process thereof | |
| JPH0834601A (en) | Production of hydrogen-containing gas for fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20151123 |