WO2010109106A1 - Method and apparatus for producing hydrogen - Google Patents

Method and apparatus for producing hydrogen Download PDF

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WO2010109106A1
WO2010109106A1 PCT/FR2010/050367 FR2010050367W WO2010109106A1 WO 2010109106 A1 WO2010109106 A1 WO 2010109106A1 FR 2010050367 W FR2010050367 W FR 2010050367W WO 2010109106 A1 WO2010109106 A1 WO 2010109106A1
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hydrogen
step
gas
membrane reactor
separation
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PCT/FR2010/050367
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French (fr)
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Benoît DAVIDIAN
François Fuentes
Raphaelle Imbault
Solène VALENTIN
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L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04POSITIVE DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04FPUMPING OF FLUID BY DIRECT CONTACT OF ANOTHER FLUID OR BY USING INERTIA OF FLUID TO BE PUMPED; SIPHONS
    • F04F5/00Jet pumps, i.e. devices in which flow is induced by pressure drop caused by velocity of another fluid flow
    • F04F5/54Installations characterised by use of jet pumps, e.g. combinations of two or more jet pumps of different type
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/48Production 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 followed by reaction of water vapour with carbon monoxide
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505Membranes containing palladium
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04POSITIVE DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04FPUMPING OF FLUID BY DIRECT CONTACT OF ANOTHER FLUID OR BY USING INERTIA OF FLUID TO BE PUMPED; SIPHONS
    • F04F5/00Jet pumps, i.e. devices in which flow is induced by pressure drop caused by velocity of another fluid flow
    • F04F5/44Component parts, details, or accessories not provided for in, or of interest apart from, groups F04F5/02 - F04F5/42
    • F04F5/46Arrangements of nozzles
    • F04F5/462Arrangements of nozzles with provisions for cooling the fluid
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04POSITIVE DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04FPUMPING OF FLUID BY DIRECT CONTACT OF ANOTHER FLUID OR BY USING INERTIA OF FLUID TO BE PUMPED; SIPHONS
    • F04F5/00Jet pumps, i.e. devices in which flow is induced by pressure drop caused by velocity of another fluid flow
    • F04F5/44Component parts, details, or accessories not provided for in, or of interest apart from, groups F04F5/02 - F04F5/42
    • F04F5/46Arrangements of nozzles
    • F04F5/465Arrangements of nozzles with supersonic flow
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405Purification by membrane separation
    • C01B2203/041In-situ membrane purification during hydrogen production
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    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042Purification by adsorption on solids
    • C01B2203/043Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0475Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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    • C01B2203/0495Composition of the impurity the impurity being water
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0872Methods of cooling
    • C01B2203/0888Methods of cooling by evaporation of a fluid
    • C01B2203/0894Generation of steam
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
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    • C01B2203/1258Pre-treatment of the feed
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    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
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    • C01B2203/14Details of the flowsheet
    • C01B2203/148Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas

Abstract

In a method for producing hydrogen from a hydrocarbon feedstock that includes at least the steps of generating (32a, 33) a hot raw synthetic gas, optionally enriching (53a) the hot raw synthetic gas with hydrogen, separating hydrogen (32b, 53b) from the synthetic gas (raw or enriched) so as to obtain at least hydrogen (82, 83) and a residual gas (112, 113), compressing the hydrogen (82, 83) from the separation to produce the hydrogen (10), wherein two consecutive steps are combined in a diaphragm reactor (32, 53), the second step being the step c) for separating the hydrogen contained in the synthetic gas (32, 53) and being carried out on a dedicated diaphragm, the hydrogen compression step (82, 83), directly following the separation step c), is at least partially carried out in a thermokinetic compressor (9a) that simultaneously compresses and cools the hydrogen obtained from the separation (82, 83) to produce compressed cooled hydrogen (102a, 103a) using cooling water (12).

Description

Process and apparatus for producing hydrogen cooled and compressed

The present invention relates to a method and a plant for the production of hydrogen cooled and compressed. The process for producing hydrogen from hydrocarbons or fossil compounds comprises two main steps.

The first step is the synthesis gas generation, known as syngas (mixture of hydrogen, carbon monoxide, and other impurities) cans etc. by reforming or autothermal reforming or partial oxidation. It is followed by a second step of purification, generally via an adsorption process called PSA which provides hydrogen

The main stages of this process may themselves include other steps, depending on the nature and / or certain characteristics of the reactants and products, or according to various constraints whether internal or external to the process.

Thus for a light hydrocarbon feedstock, typically natural gas, conventionally be found, and as illustrated in Figure 1, at least the following steps:

• a stage hydrodesulfurization of the feed, • a pre-reforming step (optional)

• a methane reforming step with steam,

(these three steps constituting the generation of synthesis gas (or syngas), gas mixture mainly containing hydrogen (H 2), carbon monoxide (CO), carbon dioxide (CO 2) and methane ( CH 4) in smaller amounts, as well as water, nitrogen, and other gases in trace), then

• a CO conversion step (or shift) during which reacting water with CO syngas to enrich one of hydrogen; This reaction occurs in a reactor usually called shift reactor, is carried out at high, medium or low temperature (High Temperature Shift or HTS, Medium Temperature Shift or MTS, Low Temperature Shift or LTS); the product gas is syngas enriched in CO 2 and H 2, and strongly depleted in CO.

• a step of hydrogen purification by pressure swing adsorption (or Pressure Swing Adsorption) which produces hydrogen and at least one residual gas which is commonly referred to the syngas generation step, (the latter stages constituting the main steps implemented in a hydrogen purification via the PSA adsorption process). Recently, developments have been made that combine in a single reactor the production of syngas and its purification to produce hydrogen via a membrane reactor. In this type of multifunctional reactor, the syngas product is immediately in contact with a membrane letting through of hydrogen. Particularly appealing for this membrane palladium, used for their barrier properties to hydrogen at high temperatures. Two types of membrane reactors have been developed: The first type of membrane reactor combines considered cans etc. reforming reaction and purification of the syngas. Thus, according to this method, illustrated in Figure 2, for a light hydrocarbon feedstock, typically natural gas, there are for example at least the following steps:

• a hydrodesulfurization stage of the load,

• a pre-reforming step (optional)

• a step of generating the synthesis gas by steam reforming of methane cans etc., coupled to a step of hydrogen separation palladium membrane in a membrane reactor,

• an optional step of adiabatic compression of the hydrogen produced (as requested by the client).

The second type of membrane reactor combines considered meanwhile the conversion reaction of CO contained in the syngas and the separation of hydrogen over palladium membrane. Thus, according to this method, and as illustrated by Figure 3, for a light hydrocarbon feedstock, typically natural gas, there are for example, at least the following steps:

• a stage hydrodesulfurization of the feed, • a pre-reforming step (optional)

• Spray a step -reformage steam methane,

• a shift step, carried out at moderate or high temperatures, coupled with a step of hydrogen separation palladium membrane in a membrane reactor, • an optional step of adiabatic compression of the hydrogen produced (as requested by the client).

The technology of this membrane reactors the advantage of considerably simplifying the steps of the hydrogen production process. At least the shift reactor and the PSA are indeed removed. However, the hydrogen produced at the outlet of membrane reactor is at low pressure. Typically, the hydrogen output pressure is at most 1 bar abs. The customer who mostly need hydrogen at high pressure, so it is necessary to compress hydrogen.

An implementation known solution is to use an adiabatic compressor. However, this equipment represents a significant investment, and subsequently a significant operating cost. Compressing the hydrogen of one to twenty bar, via this type of compressor, induced by effect of high power consumption. Typically, to compress 50 000Nm3 / hydrogen H from 1 to 4 bar, the power consumption reaches 3 MW. In addition, the hydrogen at the outlet of membrane reactor is warm. An implementation known solution is to recover this heat for producing steam. However, the steam production is almost systematically associated with the process generally exceeds widely the needs of the process, and it is necessary to find a Steam user client to enhance the heat hydrogen and synthesis gas . There is therefore a need for a recovery of the heat of the hydrogen exiting a membrane reactor other than the production of steam associated with the method.

The object of the present invention is therefore to propose a method for compressing the purified hydrogen product in which power consumption is greatly reduced compared to the prior art, and a hydrogen-cooling method which enhances the heat Release otherwise.

The invention proposes for this purpose to realize a compression of hydrogen (very) hot available at the output of the membrane reactor - whether of the 1st type, that is to say involving a reforming step and a step of separating hydrogen, or 2 πd type, that is to say involving a shift step and a step of separating hydrogen-by direct injection of liquid water with the aid of a compressor that will thermokinetic allow to compress hydrogen while being cooled abruptly.

This step allows to partially compress hydrogen, 2 to 5 bar depending on the temperature of the hydrogen stream may be between 32O 0 C and 55O 0 C, and thus limit the costs of adiabatic compression.

Moreover, the partial cooling hydrogen which accompanies this compression can limit or eliminate the subsequent cooling steps.

The residual gas from the membrane separation, consisting of CH 4, CO, H 2 O,

CO 2 at high pressure and high temperature can in turn be directly used as fuel in the "fired heater" that provides the heat required for preheating the feed (natural gas and steam) for the 1-type reactor where the vapo - reforming is combined with the purification or directly in the furnace for reforming cans etc. 2 πd type reactor or recycled as a reactant in the reformer.

It thus combines two simultaneous effects particularly advantageous:

• an increase in the pressure of the hydrogen, • quench hydrogen.

The thermokinetic compressor allows the consumption of thermal energy by the hydrogen itself, thus ensuring its immediate recovery.

Indeed, a thermokinetic compressor compresses a gas by accelerating it to a high velocity, preferably greater than the speed of sound (typically around 330 m / s), while cooling it, for example by direct contact with water droplets, and slowing.

Cooling can take place before, during or after the acceleration.

The acceleration can be produced by forcing the gas to pass through a collar, for example a neck Laval. Similarly to decelerate the gas, it happened in a second pass, such as a collar of Laval.

The energy required by the thermokinetic compressor is provided by the hydrogen produced at the outlet of membrane reactor; the preferred coolant is water, which is the more advantageously separated and recycled as a cooling liquid. An example of a thermokinetic compressor is described in patent application FR-A-2805008. The principle is based on cooling a hot gas by vaporization of liquid water into fine droplets, followed by its compression, while using an array of convergent and divergent nozzle. 4 shows a compressor thermokinetic model according to this concept. According to its first object, the invention provides a method for producing hydrogen from a hydrocarbon feedstock comprising at least a) a step of generating a hot raw synthesis gas, b) an optional enrichment step hydrogen in the hot raw synthesis gas for obtaining an enriched synthesis gas, c) a step of separating hydrogen from the raw synthesis gas (or enriched) for obtaining at least of hydrogen and a residual gas, d) a step of compressing the hydrogen from the separation to produce hydrogen at the required pressure, wherein two consecutive stages, the second being the separation step c) of hydrogen contained in the synthesis gas and being formed on dedicated membrane are combined in a membrane reactor, characterized in that the compression step d) of the hydrogen from the separation step c) is performed at least partly in a compressed Eur thermokinetic which compresses and cooled simultaneously hydrogen from c) to produce compressed and cooled hydrogen, this by means of a coolant. According to a particular embodiment of the invention, steps a) and c) are combined in the membrane reactor to produce a hydrogen flow at a temperature between 450 0 C and 600 0 C, preferably between 500 0 C and 550 0 C and a pressure of the order of a few bar absolute or less, preferably less than or equal to 1 bar abs. According to another embodiment of the invention, the gas flowing into the membrane reactor being the raw synthesis gas from step a), the first two steps performed in the membrane reactor is the enrichment step of synthesis gas in hydrogen, the second step being the step of separation of the hydrogen contained in said enriched synthesis gas, hydrogen from the separation step is at a temperature between 300 0 C and 450 0 C, preferably between 320 ° This 44O 0 C and a pressure of the order of a few bar absolute or less, preferably less than or equal to 1 bar abs.

Preferably, the compressed and cooled hydrogen exiting the thermodynamic compressor is subjected to an additional compression step to produce pure hydrogen to the required final pressure.

The coolant is preferably liquid water. Advantageously, the hydrogen separation is carried out using a palladium membrane.

Also advantageously, the hydrocarbon feedstock fed to step a) is previously desulphurized and optionally pre-reformed.

According to another object of the invention, it relates to a hydrogen production facility comprising at least a hydrocarbon feedstock, a membrane reactor to produce hydrogen, thermokinetic compressor, means for feeding the membrane reactor in the hydrocarbon feed, means for sending the gas to the membrane reactor thermokinetic compressor, means for feeding the thermokinetic compressor coolant.

Alternatively, the plant for producing hydrogen according to the invention comprises at least a hydrocarbon feedstock, a reformer, a membrane reactor to produce hydrogen, thermokinetic compressor, means for supplying the reformer in the hydrocarbon feedstock, the means for sending the gas reformer to the membrane reactor, means for sending the gas to the membrane reactor thermokinetic compressor, means for feeding the thermokinetic compressor coolant.

The invention will be described in more detail in connection with Figures 1 to 3 and 5 and 6, in which Figures 1 to 3 illustrate basic patterns of known hydrogen production processes, Figures 5 and 6 illustrating for their basic diagrams corresponding to the hydrogen production methods of the invention. Figure 4 showing a thermokinetic compressor as described in the prior art

According to Figure 1, a light hydrocarbon feed, in this case natural gas (NG) fed to a hydrodesulfurization reactor 1. The desulfurized load, to which was added water vapor, feeding a pre-reformer 2 (optional), and then the desulfurized load (and optionally pre-reformed) is introduced into a methane steam reformer 3 producing synthesis gas 4 containing as major constituents mainly H 2, CO, CO 2.

The syngas 4 thus generated is then processed to produce hydrogen; for this it passes through the shift reactor 5 where the carbon monoxide reacts with steam (not numbered) in the presence of a catalyst adapted to generate hydrogen, and the carbon dioxide and supplying a gas synthesis 6 highly enriched in hydrogen and carbon dioxide and depleted in carbon monoxide.

The hydrogen-rich syngas 6 is then introduced into a PSA unit 7 where the individual components are separated to provide purified hydrogen 10 and at least one waste gas 1 1 which is recycled to the reforming step.

According to the diagram in Figure 2, which incorporates the latest developments known, the light hydrocarbon feedstock undergoes the same steps known until the hydrocarbon feedstock desulphurized and optionally pre-reformed. It is then introduced into the membrane reactor 3 2 which is 1 type according to the terms of the invention, that is to say that it combines a steam reforming reaction 3 2 a and a step of separation of hydrogen over palladium membrane in a membrane reactor 3 2b, to provide purified hydrogen 8 2 a temperature T82 and pressure P82 and a residual gas 1 1 which is recycled to the inlet of the membrane reactor 3 2.

Hydrogen 8 2 then undergoes a compression step in an adiabatic compressor 9 2 for hydrogen 1 Y 2 to the required pressure, depending on the customer's request.

According to the diagram in Figure 3, which also incorporates the recent developments known, the charge undergoes the same steps until the hydrocarbon feedstock desulfurized output from the pre-reformer optional 2. The hydrocarbon feedstock is then introduced into a reformer steam to methane of 3 3 to produce a synthesis gas fired 4 3 containing mainly H 2, CO, CO 2.

The synthesis gas thus generated is then introduced into a membrane reactor 5 3, which is the 2nd type according to the terms of the invention, that is to say that it combines a shift reaction 5 3 a and a step of hydrogen separation palladium membrane in a membrane reactor 5 3 b, to provide purified hydrogen 8 3 at a temperature T83 and pressure P83 and a residual gas 1 "I 3 which is recycled to the steam reforming in the feed stream entering process, and / or in the reformer 3 3, as a fuel which provides heat for the reaction. hydrogen March 8 then undergoes an adiabatic compression step in an adiabatic compressor 93 to obtain hydrogen 1 O 3 to the pressure required by the customer.

According to Figure 5, according to the invention, the light hydrocarbon feedstock undergoes all the steps of producing hydrogen as described in Figure 2 for obtaining purified hydrogen 8 2 at a temperature T82 and P82 pressure and a residual gas 1 1 2. This purified hydrogen exits the hot membrane reactor, and a pressure of about atmospheric pressure. In order to comply with customer requirements, the hydrogen then passes through the thermokinetic 8a compressor where it is compressed and quenched by direct injection of liquid water 12. output is obtained from the compressor thermokinetic a stream of hydrogen February 10 was cooled to a temperature T102a, compressed to a pressure P102a and having an increased water content of the quantity of water injected cooling. The water is recovered, it is then recycled as cooling as water 12. The hydrogen 102a is then subjected, depending on the final needs an additional stage of compression 9b, in an adiabatic compressor, designed to bring it to P102 required pressure, for example slightly higher than the line pressure which it is intended.

According to Figure 6, according to the invention, the light hydrocarbon feedstock undergoes all the steps of producing hydrogen as described in Figure 2 for obtaining purified hydrogen 8 3 a T83 temperature and pressure P83 and a residual gas 1 1 3. This purified hydrogen exits the hot membrane reactor, and a pressure of about atmospheric pressure. In order to comply with customer requirements, the hydrogen then passes through the thermokinetic 8a compressor where it is compressed and quenched by direct injection of liquid water 12. output is obtained from the compressor thermokinetic a hydrogen flow March 10 was cooled to a temperature T103a, compressed to a pressure P103A and having an increased water content of the quantity of water injected cooling. The water is recovered, it is then recycled as cooling as water 12. The hydrogen 103a is then subjected, as required an additional step of compression 9b, in an adiabatic compressor, designed to bring it to the P103 required pressure, for example slightly higher than the line pressure which it is intended.

The portion of the hydrogen exiting the membrane reactor into the thermokinetic compressor 12 for increasing the hydrogen pressure provides among other advantages:

• a reduction of the compression energy required to bring hydrogen to the network pressure,

• reduced costs of adiabatic compression, both in terms of investment, as operating costs, including energy consumption

• cooling of the hot hydrogen exiting the membrane reactor, • use of the heat contained in the exhaust of the hydrogen membrane reactor in the same process.

The basic patterns above are given for steam methane reformers (SMR). The patterns with the membrane reactor of 2 πd type where the CO conversion reaction is combined with the hydrogen purification may be extended to other types of reactors. Are, inter alia the partial oxidation reactor

(POX) and auto thermal reforming reactor (ATR).

Claims

1. A process for producing hydrogen from a hydrocarbon feedstock comprising at least a) a step of generating (3 2a, 3 3) of a hot raw synthesis gas, b) an optional enrichment step (5 3 a) hydrogen hot raw synthesis gas for obtaining an enriched synthesis gas, c) a step of hydrogen separation (3 2b 5 3b) from the raw synthesis gas (or enriched) for obtaining at least hydrogen (8 2, 8 3) and a residual gas (H 2, H 3), d) a compression step of the hydrogen (8 2, 8 3 ) from the separation to produce hydrogen (10), wherein two consecutive stages, the second being the separation step c) of the hydrogen contained in the synthesis gas (3 2, 5 3), and being carried out on dedicated membrane are combined in a membrane reactor (3 2, 5 3), characterized in that the compression of step d) hydrogen (8 2, 8 3) from the separation step c) e st performed at least partly in a thermokinetic compressor 9a which simultaneously compressed and cooled hydrogen from c) to produce hydrogen (10 2 a, 10 3 A) compressed and cooled, this using a coolant (12).
2. The method of claim 1 wherein step b) is not implemented, and steps a) and c) are combined in the membrane reactor 3 2 to produce a hydrogen stream (8 2) P82 a pressure of the order of a few bar absolute or less, preferably less than or equal to 1 bar absolute, and a T82 temperature of between 45O 0 C and 600 0 C, preferably between 500 0 C and 55O 0 C.
3. The method of claim 1 wherein the gas flowing into the membrane reactor 5 3 being the summary 4 3 Gross gas from step a), the first two steps performed in the membrane reactor is step 5 3 has enrichment of hydrogen in the synthesis gas by conversion of CO, the second step being the step of separation vessel 5 3b of the hydrogen contained in said enriched synthesis gas, wherein the hydrogen obtained from stage separation is a T83 temperature of between 300 0 C and 450 0 C, preferably between 320 ° This 44O 0 C and a pressure P83 of the order of a few bar absolute or less, preferably less than or equal to 1 bar abs.
4. Method according to one of the preceding claims wherein the compressed and cooled hydrogen (10 2 a, 10 3 A) is subjected to an additional compression step to produce pure hydrogen to the final pressure required P102.
5. Method according to one of the preceding claims wherein the coolant (12) is water.
6. Method according to one of the preceding claims wherein said hydrogen separation is carried out using a palladium membrane.
7. Method according to one of the preceding claims wherein the hydrocarbon feed to step a) is previously desulphurized and optionally pre-reformed.
8. hydrogen production facility capable of implementing the method of claim 2 comprising at least a hydrocarbon feedstock, a membrane reactor (3 2) to produce hydrogen (8 2), a thermokinetic compressor (9a ), means for feeding the membrane reactor the hydrocarbon feedstock, means for sending the gas to the membrane reactor thermokinetic compressor, means for feeding the thermokinetic compressor coolant.
9. hydrogen production facility capable of implementing the method of claim 3 comprising at least a hydrocarbon feedstock, a reformer (3 3), a membrane reactor (5 3) to produce hydrogen (8 3 ), a thermokinetic compressor (9a), means for supplying the reformer in the hydrocarbon feedstock, means for supplying the gas from the reformer to the membrane reactor, means for sending the gas membrane reactor thermokinetic compressor, means for feeding the thermokinetic compressor coolant
PCT/FR2010/050367 2009-03-25 2010-03-04 Method and apparatus for producing hydrogen WO2010109106A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2805008A1 (en) * 2000-02-16 2001-08-17 Joseph Haiun termocinetique compressor
WO2002070402A2 (en) * 2001-03-05 2002-09-12 Shell Internationale Research Maatschappij B.V. Apparatus and process for the production of hydrogen
US20040224396A1 (en) * 2003-01-29 2004-11-11 Maston Valerie A. Self-contained and streamlined methane and/or high purity hydrogen generation system
US20050281735A1 (en) * 2001-03-02 2005-12-22 Chellappa Anand S Hydrogen generation apparatus and method for using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2805008A1 (en) * 2000-02-16 2001-08-17 Joseph Haiun termocinetique compressor
US20050281735A1 (en) * 2001-03-02 2005-12-22 Chellappa Anand S Hydrogen generation apparatus and method for using same
WO2002070402A2 (en) * 2001-03-05 2002-09-12 Shell Internationale Research Maatschappij B.V. Apparatus and process for the production of hydrogen
US20040224396A1 (en) * 2003-01-29 2004-11-11 Maston Valerie A. Self-contained and streamlined methane and/or high purity hydrogen generation system

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