U.S. patent application number 10/055074 was filed with the patent office on 2002-08-01 for production of hydrogen from a gaseous hydrocarbon and system used in said procedure.
Invention is credited to Colombani, Piero, Cremonesi, Ernesto.
Application Number | 20020100216 10/055074 |
Document ID | / |
Family ID | 11446600 |
Filed Date | 2002-08-01 |
United States Patent
Application |
20020100216 |
Kind Code |
A1 |
Colombani, Piero ; et
al. |
August 1, 2002 |
Production of hydrogen from a gaseous hydrocarbon and system used
in said procedure
Abstract
Procedure and system for the production of hydrogen from methane
or other gaseous hydrocarbon, in which the methane is decomposed at
high temperature in the presence of a catalyst supplying hydrogen
and carbon. The carbon which would pollute the catalyst is
eliminated by means of a catalyst regeneration phase with steam,
which generates a reaction gas that can be re-used as a source of
energy
Inventors: |
Colombani, Piero; (Milan,
IT) ; Cremonesi, Ernesto; (Fara Gera D'adda (BG),
IT) |
Correspondence
Address: |
LERNER, DAVID, LITTENBERG,
KRUMHOLZ & MENTLIK
600 SOUTH AVENUE WEST
WESTFIELD
NJ
07090
US
|
Family ID: |
11446600 |
Appl. No.: |
10/055074 |
Filed: |
January 23, 2002 |
Current U.S.
Class: |
48/197R ; 48/119;
48/127.1; 48/199R; 48/61; 48/76 |
Current CPC
Class: |
B01J 2208/00548
20130101; B01J 2208/00203 20130101; C01B 2203/1241 20130101; C01B
2203/066 20130101; C01B 2203/1052 20130101; Y02P 20/584 20151101;
B01J 2208/00495 20130101; C01B 3/26 20130101; B01J 8/065 20130101;
C01B 2203/0883 20130101; C01B 2203/0277 20130101; C01B 2203/0811
20130101; C01B 2203/169 20130101; B01J 8/062 20130101; C01B 2203/84
20130101; C01B 2203/1642 20130101; B01J 2208/00504 20130101 |
Class at
Publication: |
48/197.00R ;
48/199.00R; 48/127.1; 48/119; 48/61; 48/76 |
International
Class: |
C10K 003/00; C10K
003/02; C10B 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 26, 2001 |
IT |
MI2001A000138 |
Claims
1. Procedure for the production of hydrogen from a gaseous
hydrocarbon, characterised in that it comprises a hydrogen
generation phase in which the hydrocarbon is decomposed in the
presence of a catalyst at high temperature, according to the
following reaction: C.sub.nH.sub.m.fwdarw.n- C+m/2H.sub.2 and a
catalyst regeneration phase with steam or water with elimination of
the carbon deposited on the catalyst, according to the reaction:
C+H.sub.2O.fwdarw.CO+H.sub.2 in which the reaction gas (CO+H.sub.2)
from the catalyst regeneration phase is re-used as a source of
energy.
2. Procedure according to claim 1, characterised in that the
reaction gas from the catalyst regeneration phase is re-used as a
source of energy in the process itself.
3. Procedure according to claim 1 or 2, characterised in that the
two phases are performed, at least for a certain amount of time,
parallel, in at least two retorts which operate alternatively
generating hydrogen and regenerating the catalyst.
4. Procedure according to claim 1, 2 or 3, characterised in that
the temperature of the cracking phase is between 1000.degree. C.
and 1100.degree. C.
5. Procedure according to claim 1, 2 or 3, characterised in that
the retort(s) are filled or coated with catalyst supported on a
ceramic material.
6. Procedure according to claim 5, characterised in that the
catalyst is nickel-based.
7. Procedure according to claim 6, in which the catalyst contains
nickel at 4% or more.
8. Procedure according to claim 1, 2 or 3, characterised in that
the hydrogen obtained is cooled and stored or used in fuel
cells.
9. Procedure according to claim 2, characterised in that the
reaction gas from the regeneration phase is used for generating
steam and/or for heating the retort(s).
10. System for the production of hydrogen from a gaseous
hydrocarbon according to the procedure of claim 1 or 2,
characterised in that it comprises: a retort (A or B) a hot chamber
(C) enclosing the retort; means for supplying the hydrocarbon
(a.sub.1, a.sub.2) to the retort; means for supplying the steam
(b.sub.1, b.sub.2) to the retort; means for supplying combustible
gas (f.sub.1) to a burner (g.sub.1) of the hot chamber; means for
supplying the regeneration gas to an external heat generator and/or
to a steam generator and/or to a burner (g2) in the hot
chamber.
11. System for the production of hydrogen from a gaseous
hydrocarbon according to the procedure of claim 3, characterised in
that it comprises: two retorts(A and B); a hot chamber (C)
enclosing the retorts; means for supplying hydrocarbon (a.sub.1,
a.sub.2) alternatively to the retorts; means for supplying steam
alternatively (b.sub.1, b.sub.2) to the retorts; means for
supplying combustible gas (f.sub.1) to a burner (g.sub.1) of the
hot chamber; means for supplying the regeneration gas to an
external heat generator and/or to a steam generator and/or to a
burner (92) in the hot chamber.
12. System, according to claim 10 or 11, characterised in that the
retort(s) use a catalyst supported on a ceramic material.
13. System according to claim 10 or 11, characterised in that the
hot chamber (C) is provided with a heat exchanger (11) connected to
a steam generator (13).
14. System according to claim 10 or 11, characterised in that it
comprises, at the outlet of the retort(s), a heat exchanger (12)
for cooling the gases produced.
Description
FIELD OF THE INVENTION
[0001] This invention concerns a procedure and a system for the
production of hydrogen by means of catalytic decomposition of
methane or other gaseous hydrocarbon.
[0002] In particular the invention concerns a procedure and a
system for the production of hydrogen by means of catalytic
decomposition of methane and subsequent regeneration of the
catalyst in one or more retorts. The catalyst used is porous,
impregnated with nickel at 7%.
BACKGROUND
[0003] Hydrogen is used in large quantifies to produce energy and
heat and is the only fuel which, during combustion, produces
non-polluting substances. Furthermore, it is used in the synthesis
of organic compounds.
[0004] The best-known and most widely used chemical procedure for
the is industrial production of hydrogen is reforming of natural
gaseous hydrocarbons (for example methane) or liquefied oil gases
with steam, according to the following reaction.
C.sub.nH.sub.m+nH.sub.2O.fwdarw.(n+m/2)H.sub.2+nCO
[0005] For methane the above equation becomes:
CH.sub.4+H.sub.2O.fwdarw.CO+3H.sub.2(106.degree. C.)
[0006] The reaction gas (CO+3H.sub.2) requires separation of the CO
from the hydrogen, which is performed by reducing the temperature
(preferably in a retort at a temperature between 300.degree. C. and
600.degree. C.), according to the following reaction:
2CO.fwdarw.CO.sub.2+C
[0007] The carbon dioxide is then eliminated via molecular sieves
or by means of other difficult, uncertain and costly
techniques.
[0008] The carbon produced is deposited in the form of soot on the
bottom of the retort and must be continuously eliminated by means
of an auger or by periodically cleaning the retort.
SUMMARY
[0009] The aim of the present invention, therefore, is to provide a
procedure and a system for the production of hydrogen from methane
which permits economic problem-free production as regards
separation of the CO and hydrogen gases and also, possibly, without
interruptions due to cleaning of the retort.
[0010] According to the present invention, this aim has been
achieved by catalytic decomposition (cracking) of the methane and
regeneration of the catalyst using one or more retorts, with re-use
of the reaction gases produced by regeneration of the catalyst.
[0011] The procedure for the production of hydrogen according to
the present invention comprises catalytic decomposition of natural
gaseous hydrocarbons or liquefied oil gases at high temperature,
according to the following reaction:
C.sub.nH.sub.m.fwdarw.nC+m/2H.sub.2
[0012] (for methane CH.sub.4.fwdarw.C+2H.sub.2)
[0013] and regeneration of the catalyst with steam or water
preferably at the same cracking temperature (and in a CO.sub.2
stream), involving elimination of the carbon deposited on the
catalyst according to the equation:
C+H.sub.2O.fwdarw.CO+H.sub.2
[0014] (in a CO.sub.2 stream CO.sub.2+C.fwdarw.2 CO).
[0015] The catalyst regeneration phase may be also obtained with a
N.sub.2/CO.sub.2 stream saturated with water (or steam).
[0016] Advantageously cracking of the methane occurs at a
temperature between 1000.degree. C. and 1100.degree. C., in a
retort filled with a nickel based catalyst carried on a ceramic
material support.
[0017] The hydrogen generated during cracking can be cooled and
stored or used in fuel cells.
[0018] The carbon, in the form of very fine powder, is deposited on
the ceramic support for the catalyst, gradually covering the
ceramic support and thus reducing its effectiveness.
[0019] The activity of the catalyst is controlled during the
procedure by detection and measurement of the non-cracked
hydrocarbon at the retort outlet. When a maximum pre-set amount of
hydrocarbon is recorded at the retort outlet, the retort switches
to the regeneration phase.
[0020] In the catalyst regeneration phase, steam is introduced into
the retort which reacts with the carbon deposited according to the
following reaction:
C+H.sub.2O.fwdarw.CO+H.sub.2
[0021] This reaction continues until all the carbon deposited on
the support of catalyst during cracking is transformed into CO, or
until the analyser detects the presence of CO in the gases emitted
by the retort. Subsequently the retort containing the regenerated
catalyst returns to the hydrogen production phase.
[0022] The reaction gas (CO+H.sub.2) of the catalyst regeneration
phase is reused without separation of the components as fuel, for
example for heating the generator itself. In the procedure
according to the present invention, preferably two retorts are
used, kept at the reaction temperature in one single hot chamber
provided with self-recovery burners powered by methane.
[0023] Each of the two retorts is provided with a flow meter for
measuring the methane flow and a flow rate regulator for the
steam.
[0024] The retorts operate alternatively generating hydrogen and
regenerating the catalyst, thus permitting a continuous production
of hydrogen. According to the operating mode of each retort, the
valve supplying the methane (for the retort generating hydrogen) or
the steam (for the retort regenerating the catalyst) is opened.
[0025] A heat exchanger is provided in the hot chamber used for
generation of the steam necessary in the catalyst regeneration
phase. This heat exchanger can be a coil, for example. In this way,
the heat generated is used to heat the retorts in the hot chamber,
thus obtaining additional energy saving.
[0026] The two ends of the retorts are thermally insulated by means
of a plug.
BRIEF DESCRIPTION OF THE DRAWING
[0027] A system diagram according to the present invention is shown
in the only FIGURE attached, provided purely as a non-restrictive
example.
DETAILED DESCRIPTION
[0028] In the FIGURE, A and B indicate two retorts filled with
ceramic material which supports a catalyst at 7% nickel (but a
catalyst at 4%-5% nickel--minimum--has also been tested).
[0029] C indicates the hot chamber which encloses the two retorts A
and B. The chamber is heated by combustible gas which enters via
the supply elements f.sub.1 and f.sub.2, provided with burners
g.sub.1 and g.sub.2.
[0030] The retorts A and B are supplied with a flow of a gaseous
hydrocarbon (for example methane) via the pipe (supply element)
a.sub.1 or a.sub.2, or with a flow of steam via pipe b.sub.1 or
b.sub.2, according to their operating mode (generation of hydrogen
or regeneration of the catalyst).
[0031] The flow of gaseous hydrocarbon (for example methane)
entering the retort during the cracking phase is measured with a
flow meter 9, while the quantity of steam entering for regeneration
of the catalyst is regulated by means of a flow rate regulator
10.
[0032] Valve 1 or 3 connects the retort (A or B) to the flow of
methane for the generation phase, while valve 2 or 4 connects the
retort (A or B) to the steam flow for the catalyst regeneration
phase.
[0033] The hydrocarbon and the steam enter the retort via a
diffuser provided with holes.
[0034] The valve 5 or 7 controls outlet of the hydrogen generated
via the pipe c.sub.1 or c.sub.2. The valve 6 or 8 controls outlet
of the gas (CO+H.sub.2), from the catalyst regeneration phase, via
the pipe d.sub.1 or d.sub.2 for re-use, preferably in the procedure
according to the present invention, as a source of energy.
[0035] 12 indicates a heat exchanger for cooling the gases produced
in the procedure according to the present invention. The cooling
water that circulates in the heat exchanger 12 enters via the
supply pipes e.sub.1 and exits from the heat exchanger via the
conveying pipes e.sub.2.
[0036] In an alternative preferred embodiment of the system
according to the present invention, said system is also provided
with a heat exchanger 11 connected to the steam generator 13 used
for regenerating the catalyst.
[0037] For illustrative purposes, some results obtained according
to a pilot embodiment of the present invention are given below,
with one single retort operating alternatively in the production
and regeneration phase.
[0038] The production of hydrogen obtainable by using one single
retort is 10 m.sup.3/h with a methane supply of 5 m.sup.3/h.
Cracking temperature was maintained around 1000.degree. C. to
increase process yield.
[0039] Hydrogen is produced for one hour; the system then switches
to the regeneration phase which can be considered terminated when
the CO analyser shows a value of below 1%.
[0040] Surprisingly, nickel based catalyst supported on a ceramic
material didn't quickly degrade at a cracking temperature set above
1000.degree. C. This means that a high yield of the process and a
long life of the catalyst may be attained at the same time.
[0041] Therefore, even if any suitable catalyst may be used--for
instance cubes of refractory material soaked in nickel--a nickel
based catalyst carried on a ceramic support is preferred since it
is easy--and consequently cheap--to obtain.
[0042] Nickel based catalyst supported on other inorganic materials
was also successfully tested.
[0043] By using two retorts it is possible to produce hydrogen from
gaseous hydrocarbon--such as methane--without interruption; while
one is producing hydrogen, the other is--at least for a certain
amount of time--in regeneration mode.
[0044] The present invention, furthermore, permits energy saving by
reusing the gas (CO+H.sub.2) from the catalyst regeneration phase
as fuel for maintaining the temperature in the hot chamber.
[0045] As the skilled person can appreciate, hydrogen produced in
the catalyst regeneration phase is not further separated from CO,
since the high temperature cracking phase results in a high yield
of the process (i.e. a great amount of hydrogen is produced at a
cracking temperature greater or equal to 1000.degree. C.).
* * * * *