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WO2008016361A1 - Fuel processing of feedstocks having high olefin concentrations - Google Patents

Fuel processing of feedstocks having high olefin concentrations Download PDF

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Publication number
WO2008016361A1
WO2008016361A1 PCT/US2006/030658 US2006030658W WO2008016361A1 WO 2008016361 A1 WO2008016361 A1 WO 2008016361A1 US 2006030658 W US2006030658 W US 2006030658W WO 2008016361 A1 WO2008016361 A1 WO 2008016361A1
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WO
WIPO (PCT)
Prior art keywords
feedstock
hydrodesulfurizer
hydrogenator
hydrogen
gas
Prior art date
Application number
PCT/US2006/030658
Other languages
French (fr)
Inventor
Peter F. Foley
Stephen G. Pixton
John L. Preston
Antonio M. Vincitore
Derek W. Hildreth
Original Assignee
Utc Fuel Cells, Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Utc Fuel Cells, Llc filed Critical Utc Fuel Cells, Llc
Priority to PCT/US2006/030658 priority Critical patent/WO2008016361A1/en
Publication of WO2008016361A1 publication Critical patent/WO2008016361A1/en
Priority to US12/321,261 priority patent/US20090194459A1/en
Priority to US13/416,744 priority patent/US9745526B2/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • 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
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • 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
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1619—Measuring the temperature
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/169—Controlling the feed

Definitions

  • This invention relates to processing of conventional pipeline natural gas feedstock which contains high concentrations of olefins, such as ethylene and propylene, to convert the olefins to ethane and propane prior to desulfurization, in a system which reforms the feedstock and processes it to create reformate gas with a high hydrogen content.
  • olefins such as ethylene and propylene
  • Reformation of conventional natural gas feedstocks create reformate gas having a high concentration of hydrogen, usually with further processing to lower the concentrations of CO, to provide hydrogen fuel for fuel cells (and other purposes).
  • the processing typically begins with desulfurization in a catalytic hydrodesulfurizer (HDS).
  • HDS catalytic hydrodesulfurizer
  • Pipeline natural gas at times, is injected with concentrations as high as 15 volume percent of olefins (C n H 2n ) such as ethylene and/or propylene, such as, for instance, to maintain the heating value of the gas.
  • olefins react with hydrogen in the hydrodesulfurizer, raising the temperature of the catalyst bed to levels which reduce hydrodesulfurizer performance and may cause failure of the HDS.
  • a system controller In order to protect against such high temperature excursions, a system controller is typically programmed to reduce the power output of the fuel cell or other reformate consuming system (sometimes referred to as "foldback"), and if the problem is not thereby corrected, to shut down the fuel processing system.
  • Olefins react over the hydrodesulfurizer catalyst in the presence of hydrogen to form alkanes (C n H 2n + 2 ), generating heat.
  • alkanes C n H 2n + 2
  • ethylene (reaction 1) and propylene (reaction 2) react to form ethane and propane: (1) C 2 H 4 + H 2 ⁇ C 2 H 6 + heat (2) C 3 H 6 + H 2 ⁇ C 3 H 8 + heat
  • aspects of the invention include: providing a nearly olefin-free natural gas feedstock; reducing shut downs and foldbacks in apparatus employing reformate hydrogen generated from natural gas feedstock; more reliable reformation of natural gas to provide reformate; a simple system for dealing with olefins in natural gas feedstock; and improved reliability of desulfurization of natural gas feedstock.
  • This invention is predicated on realization that excessively exothermic reactions may not only be distanced from delicate, vulnerable catalysts, but may also be carried out in the presence of heat removal so as to avoid excessive temperature spikes that can harm a catalyst.
  • the catalytic bed in a catalytic, natural gas hydrodesulfurizer is maintained below a maximum temperature limit by reacting any olefins in the feedstock, such as ethylene or propylene, with hydrogen to form corresponding alkanes, such as ethane or propane, before the stream of feedstock reaches the hydrodesulfurizer.
  • the alkanes do not react in the hydrodesulfurizer, and thus do not cause a power plant shutdown or foldback.
  • the natural gas feedstock is reacted in a cooled reactor, such as a water cooled hydrogenator.
  • the cooling of the olefin/hydrogen reaction limits the temperature of the olefin reaction process, thereby avoiding damage to a vessel or catalyst. It also ensures conversion of a high percentage of the olefins in the feedstock to alkanes when operating at rated power.
  • the coolant may be pressurized hot water, which may be on the order of between about 180 0 C (325°F) and about 21O 0 C (375°F), or higher; the process is passive in that reaction of more olefins will simply boil more of the water (that is convert more water to steam), which is endothermic and retains the gas exit temperature in the range appropriate for a hydrodesulfurizer inlet temperature.
  • a post reaction cooler which may comprise an air cooled radiator or a liquid coolant heat exchanger, may cool the processed feedstock to an appropriate temperature, such as on the order of 9O 0 C (190 0 F), prior to entering the hydrodesulfurizer.
  • the invention may be practiced (a) with recycled reformate obtained at any point downstream of a reformer, a shift converter or a preferential oxidizer, fed by the hydrodesulfurizer, or (b) with hydrogen-containing gas from another source, such as a mini catalytic partial oxidizer.
  • the invention may be implemented as original equipment or conveniently as a retrofit, since it requires only a small adaptation with respect to providing reactors and hydrogen for the olefin reaction.
  • the process of the invention is very simple, allowing the components that perform the olefin reactions to remain within the feedstock stream without consequence, even when no olefins are in the feedstock.
  • FIG. 1 is a simplified, stylized, block diagram of a natural gas desulfurization and reforming system employing a first embodiment of the present invention.
  • Fig. 2 is a simplified, stylized, block diagram of a natural gas desulfurization and reforming system employing a second embodiment of the present invention.
  • Fig. 3 is a simplified, stylized, block diagram of a natural gas desulfurization and reforming system employing a third embodiment of the present invention.
  • a natural gas desulfurization and reformation system 11 includes a hydrodesulfurizer 12, which contains a conventional, commercially available catalyst and sorption material such as zinc oxide.
  • the desulfurized feed is mixed in an ejector 14 with steam from any suitable source 15 and enters an inlet of a reformer 16, which may also be a catalytic partial oxidizer, a non-catalytic partial oxidizer, or an autothermal device, but in this embodiment is a catalytic steam reformer, typically utilizing a noble metal, such as Platinum, Palladium, Rhodium, Ruthenium or alloys thereof, or a Nickel catalyst.
  • a process gas containing a high percentage of hydrogen, as well as carbon monoxide and carbon dioxide is fed over a conduit 19 to a conventional water gas shift reactor 20 that converts a substantial amount of CO and water into CO 2 and hydrogen.
  • the result is reformate gas in a conduit 28 which contains a high percentage of hydrogen, some CO 2 and other gases, possibly including unreformed hydrocarbons.
  • the hydrogen-containing reformate gas is fed by the conduit 28 through an orifice 30 to provide an adequate flow of hydrogen for desulfurization, when reaction of olefins is not required, and to provide additional hydrogen through a valve 31 when reaction of olefins is required.
  • the hydrogen and natural gas raw feedstock in a conduit 35 are provided to an inlet 36 of a water cooled hydrogenator 38, which may comprise a dual coil heat exchanger having catalysts disposed on the surfaces of a primary coil 39, with high pressure hot water in lines 42 from a source 43 circulating through a secondary coil 40.
  • the hydrogenator 38 can be considered a passive device in terms of controlling operating temperature. Coolant flow from the source 43 is set to control the reactor temperature within an acceptable range given any possible olefin content in the natural gas raw feedstock.
  • a controller 46 adjusts H 2 flow through the valve 31 in response to variations in reactor temperature, within that range of temperature, as indicated by a temperature sensor 47. As the reactor temperature increases, the H 2 flow is increased according to a predetermined schedule. As a result, the system feeds enough H 2 to the hydrogenator to assure conversion of all the olefins, while minimizing the H 2 flow when olefin content is low or zero.
  • the temperature of the pressurized hot water from the source may be greater than 18O 0 C (325°F), but is in the liquid phase because of being at a pressure on the order of 103OkPa (150 psi).
  • 103OkPa 150 psi
  • This also provides passive control on the temperature within the cooled hydrogenator 38, so that the catalyst is not harmed and there is no danger to the structural integrity of the vessel. Maintaining catalyst temperature is a critical function of the water cooled reactor design.
  • the cooled reactor is designed to maintain the catalyst above the light off temperature required by the selected catalyst to initiate the hydrogenation reaction after long term exposure to non-olefin bearing feedstocks .containing poisons, such as sulfur, which may inhibit the reaction at room temperature.
  • the light off temperature for the preferred embodiment of the design is 100 0 C.
  • a second critical function of the cooled reactor design is to limit the maximum temperature within the catalyst bed to prevent catalyst damage or deactivation and to limit the thermodynamic equilibrium olefin slip to acceptable levels.
  • the cooled reactor design for the preferred embodiment maintains the catalyst temperature between 100 0 C and 310 0 C by using cooling water at an inlet temperature between 160° and 17O 0 C.
  • the cooling capacity of the cooled reactor must be sized to absorb the heat release associated with at least this minimum olefin conversion.
  • the maximum olefin limit for the down stream equipment is set by both the inlet feedstock gas temperature to the HDS, and the maximum HDS catalyst bed temperature limit.
  • the minimum required olefin conversion is 80%, and the cooled reactor is sized to convert 100% of the olefins and to absorb all of the heat release associated with that conversion level.
  • the outflow from the cooled hydrogenator 38 in a conduit 50 may exceed the desired inlet temperature of downstream equipment.
  • a heat exchanger is used to cool the feedstock, in those instances.
  • the exit temperature of the hydrogenator 38 may exceed 215°C (419°F), which exceeds the desired inlet temperature of the hydrodesulfurizer 12.
  • a heat exchanger 52 is employed in the preferred embodiment of the design to reduce the temperature of the olefin depleted feedstock to about 100 0 C.
  • the heat exchanger may comprise an air cooled radiator in most cases, but if necessary, can comprise a heat exchanger cooled by a liquid coolant in a conduit 55.
  • heat exchanger 52 is required to cool the feedstock in order to achieve the desired inlet HDS temperature.
  • Heat exchanger 52 may be omitted for those instances where alternate hydrogenator catalysts or operating conditions are used, which result in an inlet HDS feedstock temperature low enough so that the HDS catalyst bed will not exceed the maximum temperature limit.
  • conduit sizing may be used to reduce flow OfH 2 when reaction of olefins is not required.
  • another valve, controllable by the controller 46 may be employed. Or, both functions may be performed by appropriate control of a single valve.
  • the refo ⁇ ned gas is fed in a conduit 28a to a preferential carbon monoxide oxidizer 58 where additional CO is converted to CO 2 .
  • the reformate with higher H 2 concentrations is available for utilization in the conduit 28 as well as being applied to the orifice 30 and valve 31.
  • a mini-catalytic partial oxidizer 65 receives non-desulfurized natural gas through a valve 68 and humidified air through a valve 69 to produce sufficient hydrogen in a conduit 71 for both hydrogenation of the olefins and hydrodesulfurization of the feedstock.
  • a valve 75 may control the flow of feedstock from the conduit 35 to the inlet 36 of the hydrogenator 38.
  • Hydrogen may be provided to the processes herein from other sources, if desired. Since the mini CPO fuel and air are controlled by the controller 46 via valves 68 and 69, orifice 30 and valve 31 are not needed in this embodiment.
  • the term "olefm-depleted" means having the olefins reduced sufficiently so as to not have excessive temperatures in the hydrodesulfurizer as a result of reactions therewith, which typically requires conversion of at least about 80% of the olefins to alkanes.
  • the natural gas feedstock in conduit 35 is allowed to flow through the hydrogenator 38 at all times (even when not needed to convert olefins) for mechanical and control simplicity, and to support quicker response to excessive temperatures.
  • the amount of hydrogen is varied for beneficial olefin removal in accordance to a pre-determined operating temperature range within the hydrogenator catalyst bed.
  • the hydrogenator operating temperature range is set at 149 0 C (30O 0 F) to 177 0 C (35O 0 F).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A reformer system (11) having a hydrodesulfurizer (12) provides desulfurized natural gas feedstock to a catalytic steam reformer (16), the outflow of which is treated by a water gas shift reactor (20) and optionally a preferential CO oxidizer (58) to provide reformate gas (28, 28a) having high hydrogen and moderate carbon dioxide content. To avoid damage to the hydrodesulfurizer from overheating, any olefins in the non-desulfurized natural gas feedstock (35) are reacted (38) with hydrogen (28, 28a; 71) to convert them to alkanes (e.g., ethylene and propylene to ethane and propane) in a hydrogenator (38) cooled (46), below a temperature which would damage the hydrogenator, by evaporative cooling with pressurized hot water (42). Hydrogen for the desulfurizer and the olefin reaction may be provided as recycle reformate (28, 28a) or from a mini-CPO (67), or from other sources.

Description

Fuel Processing of Feedstocks Having High Olefin Concentrations
Technical Field
This invention relates to processing of conventional pipeline natural gas feedstock which contains high concentrations of olefins, such as ethylene and propylene, to convert the olefins to ethane and propane prior to desulfurization, in a system which reforms the feedstock and processes it to create reformate gas with a high hydrogen content.
Background Art
Reformation of conventional natural gas feedstocks create reformate gas having a high concentration of hydrogen, usually with further processing to lower the concentrations of CO, to provide hydrogen fuel for fuel cells (and other purposes). The processing typically begins with desulfurization in a catalytic hydrodesulfurizer (HDS). Pipeline natural gas, at times, is injected with concentrations as high as 15 volume percent of olefins (CnH2n) such as ethylene and/or propylene, such as, for instance, to maintain the heating value of the gas. These olefins react with hydrogen in the hydrodesulfurizer, raising the temperature of the catalyst bed to levels which reduce hydrodesulfurizer performance and may cause failure of the HDS. In order to protect against such high temperature excursions, a system controller is typically programmed to reduce the power output of the fuel cell or other reformate consuming system (sometimes referred to as "foldback"), and if the problem is not thereby corrected, to shut down the fuel processing system.
Olefins react over the hydrodesulfurizer catalyst in the presence of hydrogen to form alkanes (CnH2n+2), generating heat. For example, ethylene (reaction 1) and propylene (reaction 2) react to form ethane and propane: (1) C2H4 + H2 → C2H6 + heat (2) C3H6 + H2 → C3H8 + heat
These reactions are highly exothermic, generating temperature rises of up to 28°C (5O0F) per percent of olefin concentration in the feedstock.
Disclosure of Invention Aspects of the invention include: providing a nearly olefin-free natural gas feedstock; reducing shut downs and foldbacks in apparatus employing reformate hydrogen generated from natural gas feedstock; more reliable reformation of natural gas to provide reformate; a simple system for dealing with olefins in natural gas feedstock; and improved reliability of desulfurization of natural gas feedstock. This invention is predicated on realization that excessively exothermic reactions may not only be distanced from delicate, vulnerable catalysts, but may also be carried out in the presence of heat removal so as to avoid excessive temperature spikes that can harm a catalyst.
According to the present invention, the catalytic bed in a catalytic, natural gas hydrodesulfurizer (HDS) is maintained below a maximum temperature limit by reacting any olefins in the feedstock, such as ethylene or propylene, with hydrogen to form corresponding alkanes, such as ethane or propane, before the stream of feedstock reaches the hydrodesulfurizer. The advantage of this process is that the alkanes do not react in the hydrodesulfurizer, and thus do not cause a power plant shutdown or foldback. According further with the invention, the natural gas feedstock is reacted in a cooled reactor, such as a water cooled hydrogenator. the cooling of the olefin/hydrogen reaction limits the temperature of the olefin reaction process, thereby avoiding damage to a vessel or catalyst. It also ensures conversion of a high percentage of the olefins in the feedstock to alkanes when operating at rated power. In further accord with the invention, the coolant may be pressurized hot water, which may be on the order of between about 1800C (325°F) and about 21O0C (375°F), or higher; the process is passive in that reaction of more olefins will simply boil more of the water (that is convert more water to steam), which is endothermic and retains the gas exit temperature in the range appropriate for a hydrodesulfurizer inlet temperature.
In still further accord with the invention, when deemed necessary or desirable, a post reaction cooler, which may comprise an air cooled radiator or a liquid coolant heat exchanger, may cool the processed feedstock to an appropriate temperature, such as on the order of 9O0C (1900F), prior to entering the hydrodesulfurizer.
The invention may be practiced (a) with recycled reformate obtained at any point downstream of a reformer, a shift converter or a preferential oxidizer, fed by the hydrodesulfurizer, or (b) with hydrogen-containing gas from another source, such as a mini catalytic partial oxidizer. The invention may be implemented as original equipment or conveniently as a retrofit, since it requires only a small adaptation with respect to providing reactors and hydrogen for the olefin reaction. The process of the invention is very simple, allowing the components that perform the olefin reactions to remain within the feedstock stream without consequence, even when no olefins are in the feedstock.
Other aspects, features and advantages of the present invention will become more apparent in the light of the following detailed description of exemplary embodiments thereof, as illustrated in the accompanying drawing.
Brief Description of the Drawings Fig. 1 is a simplified, stylized, block diagram of a natural gas desulfurization and reforming system employing a first embodiment of the present invention.
Fig. 2 is a simplified, stylized, block diagram of a natural gas desulfurization and reforming system employing a second embodiment of the present invention.
Fig. 3 is a simplified, stylized, block diagram of a natural gas desulfurization and reforming system employing a third embodiment of the present invention.
Mode(s) for Carrying Out the Invention
Referring to Fig. 1, a natural gas desulfurization and reformation system 11 includes a hydrodesulfurizer 12, which contains a conventional, commercially available catalyst and sorption material such as zinc oxide. The desulfurized feed is mixed in an ejector 14 with steam from any suitable source 15 and enters an inlet of a reformer 16, which may also be a catalytic partial oxidizer, a non-catalytic partial oxidizer, or an autothermal device, but in this embodiment is a catalytic steam reformer, typically utilizing a noble metal, such as Platinum, Palladium, Rhodium, Ruthenium or alloys thereof, or a Nickel catalyst. From the reformer 16, a process gas containing a high percentage of hydrogen, as well as carbon monoxide and carbon dioxide is fed over a conduit 19 to a conventional water gas shift reactor 20 that converts a substantial amount of CO and water into CO2 and hydrogen.
The result is reformate gas in a conduit 28 which contains a high percentage of hydrogen, some CO2 and other gases, possibly including unreformed hydrocarbons. The hydrogen-containing reformate gas is fed by the conduit 28 through an orifice 30 to provide an adequate flow of hydrogen for desulfurization, when reaction of olefins is not required, and to provide additional hydrogen through a valve 31 when reaction of olefins is required.
The hydrogen and natural gas raw feedstock in a conduit 35 are provided to an inlet 36 of a water cooled hydrogenator 38, which may comprise a dual coil heat exchanger having catalysts disposed on the surfaces of a primary coil 39, with high pressure hot water in lines 42 from a source 43 circulating through a secondary coil 40. In accordance with the invention, the hydrogenator 38 can be considered a passive device in terms of controlling operating temperature. Coolant flow from the source 43 is set to control the reactor temperature within an acceptable range given any possible olefin content in the natural gas raw feedstock. A controller 46 adjusts H2 flow through the valve 31 in response to variations in reactor temperature, within that range of temperature, as indicated by a temperature sensor 47. As the reactor temperature increases, the H2 flow is increased according to a predetermined schedule. As a result, the system feeds enough H2 to the hydrogenator to assure conversion of all the olefins, while minimizing the H2 flow when olefin content is low or zero.
The temperature of the pressurized hot water from the source may be greater than 18O0C (325°F), but is in the liquid phase because of being at a pressure on the order of 103OkPa (150 psi). When the reaction of an olefin with hydrogen raises the temperature above about 1800C (325°F), the hot water will boil, producing steam, which keeps the temperature from rising above the vaporization temperature at the pressure of the hot water. This also provides passive control on the temperature within the cooled hydrogenator 38, so that the catalyst is not harmed and there is no danger to the structural integrity of the vessel. Maintaining catalyst temperature is a critical function of the water cooled reactor design. Virgin hydrogenator catalyst and in-service catalysts that have been subjected to short term exposure to a non-olefm bearing feedstock containing catalyst poisons, such as sulfur, will initiate the hydrogenation reaction upon exposure to olefin bearing feedstock at temperatures less than room temperature (210C) . Some hydrogenator catalysts when subjected to long term exposure to non-olefm bearing feedstock containing poisons require an elevated temperature to initiate the hydrogenation reaction upon re-introduction of an olefin bearing feedstock containing poisons. This minimum temperature is defined, herein, as the light off temperature. The light-off temperature is functionally dependent on the inlet gas conditions and the inherent physical/chemical properties of the catalyst. The cooled reactor is designed to maintain the catalyst above the light off temperature required by the selected catalyst to initiate the hydrogenation reaction after long term exposure to non-olefin bearing feedstocks .containing poisons, such as sulfur, which may inhibit the reaction at room temperature. The light off temperature for the preferred embodiment of the design is 1000C. A second critical function of the cooled reactor design is to limit the maximum temperature within the catalyst bed to prevent catalyst damage or deactivation and to limit the thermodynamic equilibrium olefin slip to acceptable levels. The cooled reactor design for the preferred embodiment maintains the catalyst temperature between 1000C and 3100C by using cooling water at an inlet temperature between 160° and 17O0C.
Another critical design feature of the cooled reactor is that it reduces the olefin content of the feedstock to a level which is consistent with the maximum olefin limits for the down stream equipment. The cooling capacity of the cooled reactor must be sized to absorb the heat release associated with at least this minimum olefin conversion. Typically, the maximum olefin limit for the down stream equipment is set by both the inlet feedstock gas temperature to the HDS, and the maximum HDS catalyst bed temperature limit. In the preferred embodiment of the cooled reactor design the minimum required olefin conversion is 80%, and the cooled reactor is sized to convert 100% of the olefins and to absorb all of the heat release associated with that conversion level.
The outflow from the cooled hydrogenator 38 in a conduit 50 may exceed the desired inlet temperature of downstream equipment. A heat exchanger is used to cool the feedstock, in those instances. In the preferred embodiment of the design, the exit temperature of the hydrogenator 38 may exceed 215°C (419°F), which exceeds the desired inlet temperature of the hydrodesulfurizer 12. A heat exchanger 52 is employed in the preferred embodiment of the design to reduce the temperature of the olefin depleted feedstock to about 1000C. The heat exchanger may comprise an air cooled radiator in most cases, but if necessary, can comprise a heat exchanger cooled by a liquid coolant in a conduit 55. These and other details are selected as may be suitable for any given implementation of the present invention.
Under most power plant operating conditions, heat exchanger 52 is required to cool the feedstock in order to achieve the desired inlet HDS temperature. Heat exchanger 52 may be omitted for those instances where alternate hydrogenator catalysts or operating conditions are used, which result in an inlet HDS feedstock temperature low enough so that the HDS catalyst bed will not exceed the maximum temperature limit. A number of other variations may be made in the details of implementation, when incorporating the invention into a system. For instance, instead of the orifice 30, conduit sizing may be used to reduce flow OfH2 when reaction of olefins is not required. In place of the orifice 30, another valve, controllable by the controller 46, may be employed. Or, both functions may be performed by appropriate control of a single valve.
As shown in Fig. 2, in some applications, such as when the reformate will fuel a proton exchange membrane fuel cell, the refoπned gas is fed in a conduit 28a to a preferential carbon monoxide oxidizer 58 where additional CO is converted to CO2 . The reformate with higher H2 concentrations is available for utilization in the conduit 28 as well as being applied to the orifice 30 and valve 31.
Another embodiment of the invention, illustrated in Fig. 3, does not use recycle hydrogen either for desulfurization or for hydrogenation of olefins. Instead, a mini-catalytic partial oxidizer 65 (mini CPO) receives non-desulfurized natural gas through a valve 68 and humidified air through a valve 69 to produce sufficient hydrogen in a conduit 71 for both hydrogenation of the olefins and hydrodesulfurization of the feedstock. A valve 75 may control the flow of feedstock from the conduit 35 to the inlet 36 of the hydrogenator 38. Hydrogen may be provided to the processes herein from other sources, if desired. Since the mini CPO fuel and air are controlled by the controller 46 via valves 68 and 69, orifice 30 and valve 31 are not needed in this embodiment.
As used herein, the term "olefm-depleted" means having the olefins reduced sufficiently so as to not have excessive temperatures in the hydrodesulfurizer as a result of reactions therewith, which typically requires conversion of at least about 80% of the olefins to alkanes. The natural gas feedstock in conduit 35 is allowed to flow through the hydrogenator 38 at all times (even when not needed to convert olefins) for mechanical and control simplicity, and to support quicker response to excessive temperatures. The amount of hydrogen is varied for beneficial olefin removal in accordance to a pre-determined operating temperature range within the hydrogenator catalyst bed. In this preferred embodiment, the hydrogenator operating temperature range is set at 1490C (30O0F) to 1770C (35O0F).

Claims

Claims
1. A gas clean up method characterized by: catalytically reacting (38) hydrocarbon feedstock (35), before said feedstock is fed to a hydrodesulfurizer (12), with hydrogen-containing gas (28, 71) to convert olefins in the feedstock to alkanes to provide olefin-depleted feedstock; and feeding (50, 52) the olefin-depleted feedstock to the hydrodesulfurizer (12).
2. A method according to claim 1 further characterized by: said step of feeding including cooling (55) the olefin-depleted feedstock before said feedstock is fed to the hydrodesulfurizer (12).
3. A gas clean up apparatus, comprising: a hydrodesulfurizer (12); said gas clean up apparatus characterized by: means (38) for catalytically reacting hydrocarbon feedstock (35), before said feedstock is fed to the hydrodesulfurizer (12), with hydrogen-containing gas (28, 71) to convert olefins in the feedstock to corresponding alkanes to provide olefin-depleted feedstock; and means (50, 52) for feeding olefin-depleted feedstock to said hydrodesulfurizer.
4. Apparatus according to claim 3 further characterized by: said means for feeding comprising means (52, 55) for cooling the olefin- depleted feedstock before said feedstock is fed to the hydrodesulfurizer (12).
5. A gas clean up method characterized by: catalytically reacting in a temperature controlled hydrogenator (38) hydrocarbon feedstock (35), before said feedstock is fed to a hydrodesulfurizer (12), with hydrogen-containing gas (28, 65, 71) to convert olefins in the feedstock to corresponding alkanes to provide olefin-depleted feedstock; and feeding (50, 52) the olefin-depleted feedstock to the hydrodesulfurizer (12).
6. A gas clean up apparatus, comprising: a hydrodesulfurizer (12); said gas clean up apparatus characterized by. a temperature controlled hydrogenator (38) for catalytically reacting hydrocarbon gas feedstock (35) before said feedstock is fed to the hydrodesulfurizer, with hydrogen containing gas (28, 71) to convert olefins in the feedstock to corresponding alkanes to provide olefϊn-depleted feedstock; and means (50, 52) for feeding the olefm-depleted feedstock to said hydrodesulfurizer.
7. A gas clean up method characterized by: flowing hydrocarbon feedstock (35) and a predetermined flow (30; 68, 69) of hydrogen-containing gas (28, 71) through a temperature controlled hydrogenator (38) to a hydrodesulfurizer (12); monitoring (46, 47) temperature of said hydrogenator; and in response (37) to an indication (46, 47) of temperature of said hydrogenator being above a predetermined operating temperature, providing (31; 68, 69) additional flow of said hydrogen-containing gas to said hydrogenator to increase conversion of olefins in the feedstock to alkanes.
8. A method according to claim 7 further characterized by: said step of flowing comprising cooling (52, 55) the flow from said hydrogenator (38) to said hydrodesulfurizer (12).
9. A gas clean up apparatus, comprising: a source (35) of hydrocarbon feedstock; a hydrodesulfurizer (12); a source of hydrogen-containing gas (28, 71); said gas clean up apparatus characterized by: a temperature controlled hydrogenator (38) connected between said source of feedstock and said hydrodesulfurizer; means (30; 68, 69) for providing a predetermined flow of said hydrogen- containing gas to said hydrogenator; means (46, 47) for monitoring temperature of the hydrogenator; and means (31; 68, 69) responsive to said monitoring means indicating temperature of the hydrogenator being above a predetermined operating temperature for providing additional flow of said hydrogen-containing gas to said hydrogenator to increase conversion of olefins in the feedstock to alkanes.
10. Apparatus according to claim 9 further characterized by: said hydrogenator (38) connected to said hydrodesulfurizer (12) through a cooler (52).
11. Apparatus according to claim 9 further characterized by: said temperature controlled hydrogenator (38) being cooled (39, 46) by coolant (43) having a pressure at which the coolant boils at a temperature near said predetermined operating temperature.
12. Apparatus according to claim 9 further characterized by: said source of hydrogen-containing gas (28) including a steam reformer (16) receiving desulfurized, olefin-depleted natural gas from said hydrodesulfurizer.
13. Apparatus according to claim 9 further characterized by: said source (65, 71) of hydrogen gas comprising a catalytic partial oxidizer (65) operated on non-desulfurized hydrocarbon gas from said source (35, 68) and a humid, oxygen-containing gas (69).
PCT/US2006/030658 2006-08-03 2006-08-03 Fuel processing of feedstocks having high olefin concentrations WO2008016361A1 (en)

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US12/321,261 US20090194459A1 (en) 2006-08-03 2009-01-16 Fuel processing of feedstocks having components harmful to hydrodesulfurization
US13/416,744 US9745526B2 (en) 2006-08-03 2012-03-09 Fuel processing of feedstocks having components harmful to hydrodesulfurization

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