CN105517950B - For using the method and system of the reforming system next life production of synthetic gas based on oxygen transport membrane with secondary reformation and auxiliary thermal source - Google Patents
For using the method and system of the reforming system next life production of synthetic gas based on oxygen transport membrane with secondary reformation and auxiliary thermal source Download PDFInfo
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- CN105517950B CN105517950B CN201480048887.XA CN201480048887A CN105517950B CN 105517950 B CN105517950 B CN 105517950B CN 201480048887 A CN201480048887 A CN 201480048887A CN 105517950 B CN105517950 B CN 105517950B
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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
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- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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Abstract
Disclose the method and system for producing synthesis gas in the reforming system based on oxygen transport membrane, the reforming system based on oxygen transport membrane carries out the level-one reforming process in reforming reactor, and the secondary reformation process in oxygen transport membrane reactor and carries out in the presence of by oxygen transport membrane reactor and the heat of auxiliary thermal source generation.The auxiliary thermal source is arranged in reactor enclosure close to reforming reactor, and may include assisted reaction driving oxygen transport membrane reactor or ceramic burner.
Description
Invention field
The present invention relates to the method and systems for producing synthesis gas in the reforming system based on oxygen transport membrane, and more
More particularly to for providing the reformation system based on oxygen transport membrane of both level-one reformation and secondary reformation and auxiliary thermal source
The method and system of synthesis gas is produced in system.
Background
The synthesis gas of hydrogen and carbon monoxide is used for various industrial applications, such as production, chemicals and the synthesis of hydrogen
Fuel production.Routinely, synthesis gas produces in flame reformer, wherein natural gas and steam nickel-containing catalyst reformation
It reforms in device pipe under high temperature (such as 850 DEG C to 1000 DEG C) and middle pressure (such as 16 to 30 bar) to produce synthesis gas.
Heat absorptivity demand for heat for the steam methane reforming reaction in reformer tubes occurs is by partly by natural gas
The burner lighted a fire of smelting furnace of fuel is provided to provide.It is synthesized to increase by what steam methane reforming (SMR) method produced
The hydrogen content of gas can make synthesis gas be subjected to water gas shift reaction so that residue vapor and carbon monoxide in synthesis gas are anti-
It answers.
The alternative solution of well established steam methane reforming is non-catalytic partial oxidation method (POx), is thus allowed sub-
The oxygen of the amount of stoichiometry reacts at high temperature with natural gas feed generates steam and carbon dioxide.High temperature residual methane by with
The reaction of high-temperature steam and carbon dioxide is reformed.
Attractive alternative for producing synthesis gas is self-heating recapitalization (ATR) method, the self-heating recapitalization side
Method generates heat using oxidation, wherein being occurred under than Pox method low temperature using catalyst with allowing to reform.Similar to Pox
Method needs oxygen to make the gas by partial oxidation of natural in burner and provide heat, high temperature carbon dioxide and steam to reform remnants
Methane.It needs for some steam to be added in natural gas and be formed with the carbon controlled on catalyst.However, both ATR and Pox methods are all
Need individual air gas separation unit (ASU) to produce hyperbaric oxygen, this increases the complexity of entire method and fund and operation
Cost.
When raw material (feedstock) contains a large amount of heavy hydrocarbons, SMR and ATR process is usually located at after pre-reforming step.In advance
Reformation is the technique based on catalyst for higher hydrocarbon to be converted to methane, hydrogen, carbon monoxide and carbon dioxide.Pre-reforming
Involved in reaction be usually heat absorption.Most of pre-reformers on natural gas steam operate in heat sink region, and absolutely
It thermally operates, and therefore the raw material of pre-reforming is left with the temperature lower than the raw material for entering pre-reformer.The present invention is by discussion
Another method is secondary reformation method, is substantially the autothermal process for being fed the product from SMR process.Therefore, second level
The charging of reforming process is mainly the synthesis gas from steam methane reforming.Depending on terminal applies, some natural gases can be around
SMR process is crossed, and is introduced directly into secondary reformation step.In addition, when being secondary reformation process after SMR process, SMR
It can be operated under lower temperature (such as with 850 DEG C to 1000 DEG C opposite 650 DEG C to 825 DEG C).
As it would be appreciated, the conventional method of all production synthesis gas as already discussed above is expensive and needs multiple
Miscellaneous equipment (installations).For the complexity and expense for overcoming this kind of equipment, it has been suggested that: using oxygen transport membrane
Synthesis gas is generated in reactor to supply oxygen, to generate the heat absorptivity demand for heat institute for supporting steam methane reforming reaction
The heat needed.Typical oxygen transport membrane has compacted zone, although the compacted zone air proof, works as and is subjected to raised behaviour
When making temperature and cross-film oxygen partial pressure difference, oxonium ion will be transmitted.
The example of the reforming system based on oxygen transport membrane of production for synthesis gas is found in: U.S. Patent number 6,048,
472；6,110,979；6,114,400；6,296,686；7,261,751；8,262,755；With 8,419,827.All these bases
All there is operational problem in the system of oxygen transport membrane, because this oxygen transport membrane needs the height at about 900 DEG C to 1100 DEG C
The lower operation of temperature.In the case where hydrocarbon (such as methane and higher hydrocarbon) is subjected to this high temperature in oxygen transport membrane, especially in high pressure
Under low steam and carbon ratio, excessive carbon occurs and is formed.Carbon is formed problem and is passed in the prior art being indicated above based on oxygen
It is especially serious in the system of defeated film.Disclosed in U.S. Patent number 8,349,214 it is a kind of in the production of synthesis gas using base
In the distinct methods of the reforming system of oxygen transport membrane, the method provides the reforming system based on oxygen transport membrane, described to be based on oxygen
The reforming system of transmission film uses hydrogen and carbon monoxide as a part for the reactant gas for being fed into oxygen transport membrane pipe, and
And minimize the hydrocarbon content into the charging of the per-meate side of oxygen transport membrane pipe.The waste heat generated in oxygen transport membrane pipe mainly leads to
Overshoot is transmitted to the reformer tubes made of conventional material.Oxygen transport membrane is fed into using the high hydrogen of low hydrocarbon content and carbon monoxide
Pipe solves many outstanding problems of oxygen transport membrane system earlier.
By the prior art based on the other problems that the reforming system of oxygen transport membrane generates be the cost of oxygen transport membrane module with
And this reforming system based on oxygen transport membrane be lower than required durability, reliability and operational availability.These problems are
Reforming system based on oxygen transport membrane not yet successful commercialization the main reason for.The progress of oxygen transport membrane material solved with
Oxygen flux, the problem that film drops and creep life is related, but from the point of view of cost standpoint and operating reliability and availability viewpoint,
For realize commericially feasible based on the reforming system of oxygen transport membrane, there are many work to be done.
The present invention prepares synthesis gas by providing the improved system based on reactivity driving oxygen transport membrane that is used to use
Method solves the above problems, and the system based on reactivity driving oxygen transport membrane is by two reactor groups at described two
Reactor can be in the form of the pipe group containing catalyst --- reforming reactor and oxygen transport membrane reactor.Partial oxidation and some
Reform occur in infiltration (containing catalyst) side of oxygen transport membrane, and by reforming catalyst promote reforming process close to
Occur in the reforming reactor of oxygen transport membrane reactor.(it is heat absorption for partial oxidation process (it is exothermic) and reforming process
) the two all occurs in the reforming system based on oxygen transport membrane, and therefore has high fever degree of integration so that in oxidation process
The heat of release supplies the heat absorbed by reforming process.Specifically, the system based on reactivity driving oxygen transport membrane changes
Kind includes improving the system based on reactivity driving oxygen transport membrane to carry out the level-one in the reforming reactor that catalyst is filled
Reforming process and the secondary reformation process in the oxygen transport membrane reactor containing catalyst, and auxiliary thermal source is provided with flat
The reformation load weighed between oxygen transport membrane reactor and auxiliary thermal source.
Summary of the invention
Feature of the invention can be the method for producing synthesis gas in the reforming system based on oxygen transport membrane, the base
It may include at least two reactors in the reforming system of oxygen transport membrane, described two reactors can be in the pipe group containing catalyst
Form, including reforming reactor and oxygen transport membrane reactor the described method comprises the following steps: (i) be arranged in reform it is anti-
In the presence of answering the reforming catalyst and heat in device, hydrocarbon containing feed stream is reformed in reforming reactor to produce reformed syngas
Stream；(ii) reformed syngas stream is fed into the reactant side of reactivity driving and the oxygen transport membrane reactor containing catalyst,
Described in oxygen transport membrane reactor include at least one oxygen transport membrane element, the oxygen transport membrane element is configured to when being subjected to rising
When high operation temperature and oxygen partial pressure difference across at least one oxygen transport membrane element, oxygen is driven from reactivity and containing catalyst
It is isolated in the oxygen-containing stream of the oxidant side of oxygen transport membrane reactor, and isolated oxygen is transmitted to by reaction by oxygen ion transport
Object side；(iii) make a part reformed syngas stream reacted with the oxygen for infiltrating through at least one oxygen transport membrane element with generate across
The oxygen partial pressure difference of at least one oxygen transport membrane element, and generate reaction product and heat；(iv) is in oxygen transport membrane reactor
In in the presence of the catalyst, reaction product and the heat that contain, reformation does not reform the hydrocarbon gas in reformed syngas stream to generate
Syngas product stream.It is driven by reactivity and for the first part of heat needed for initial or level-one reforming step containing catalyst
Oxygen transport membrane reactor provides, and is the second part of level-one reforming step institute calorific requirement by arranging close to reforming reactor
Auxiliary thermal source transmit.
Feature of the invention also may be based on the reforming system of oxygen transport membrane, the reforming system packet based on oxygen transport membrane
It includes: (a) reactor enclosure；(b) reforming reactor is arranged in reactor enclosure and is configured to be arranged in reforming reactor
In reforming catalyst and heat in the presence of, reform hydrocarbon containing feed stream to generate reformed syngas stream；(c) reactivity driving oxygen
Transmit membrane reactor, be arranged in reactor enclosure close to reforming reactor, and be configured to receive reformed syngas stream and
Make a part of reformed syngas stream that reaction product and heat are reacted and generated with oxygen permeable, the heat includes reforming reactor
The first part of institute's calorific requirement；(d) auxiliary thermal source is arranged in reactor enclosure close to reforming reactor, and is configured
To supply the second part of heat needed for reforming reactor generates reformed syngas stream.
The oxygen transport membrane reactor of reactivity driving is further configured in one or more of catalyst and by reforming
Synthesis air-flow and oxygen permeable react some heats generated in the presence of any in reformed syngas stream of reformation do not reform
The hydrocarbon gas, to generate syngas product stream.About 730 DEG C of the exit of reforming reactor at a temperature of and OTM reactor
At a temperature of about 995 DEG C of exit, the modulus of syngas product stream is big between about 1.85 and 2.15 or more, and depends on
The amount of the heat of reforming reactor is supplied to by auxiliary thermal source.More specifically, at the specified temperature, the mould of syngas product stream
Several about 1.85 minimum values from when the percentage of the heat by auxiliary thermal source supplied to reforming reactor is less than 15% are increased to
About 2.15 maximum value when the percentage by auxiliary thermal source supplied to the heat of reforming reactor is greater than about 85%.In other words,
At a temperature of the exit of reforming reactor and OTM reactor respectively about 730 DEG C and 995 DEG C, it is supplied to when by auxiliary thermal source
When the second part of the heat of reforming reactor is 50% or less of total institute's calorific requirement to be supplied to reforming reactor, synthesis
The modulus of gas product stream can be between about 1.85 and 2.00；And when by auxiliary thermal source supplied to reforming reactor heat the
When two parts are more than 50% of total institute's calorific requirement to be supplied to reforming reactor, the modulus of syngas product stream about 2.00 with
Between 2.15.Such as above-mentioned point out, the practical modulus of syngas product stream is additionally depended in the reforming system based on oxygen transport membrane
Reforming temperature, and the temperature in the exit of especially reforming reactor.For example, if the temperature in reforming reactor exit
The temperature being increased between 800 DEG C and 900 DEG C, then according to the amount for the heat for being supplied to reforming reactor by auxiliary thermal source, in advance
The range of the modulus of phase syngas product stream will be increased to may be between about 1.90 to 2.25 or bigger.
Except the modulus of syngas product stream is based on the of the heat for being designed to enter in the reforming system based on oxygen transport membrane
Reformation load between a part and the second part of heat divides (reforming duty split) except change, synthesizes
The hydrogen and carbon monoxide ratio (H of gas product stream2/ CO) under about 730 DEG C of reforming reactor outlet temperature and according to by
The amount of auxiliary thermal source supplied to the heat of reforming reactor also slightly changes between about 2.95 and 3.10.Syngas product stream
Carbon monoxide and carbon dioxide ratio (CO/CO2) under about 730 DEG C of outlet temperature and according in heat first part with
Reformation load division between the second part of heat also changes between about 2.50 and 3.30.
Auxiliary thermal source can be designed to provide the heat between about 15% and 85% needed for the reformation for hydrocarbon containing feed stream
Amount.Auxiliary thermal source can be in being arranged in reactor enclosure and close to one or more auxiliary oxygen transport membranes of reforming reactor
The form of reactor or one or more ceramic burners.
Brief description
Although this specification thinks to work as to be expressly noted that applicant takes that the claim of the theme of its invention terminates as
When being considered in conjunction with the accompanying, it is better understood with the present invention, in which:
Fig. 1 is the schematic diagram of the embodiment of the reforming system based on oxygen transport membrane, the reformation based on oxygen transport membrane
System is designed to carry out level-one weight using the auxiliary thermal source including the second oxygen transport membrane reactor in oxygen transport membrane reactor
It has suffered both journey and secondary reformation process；
Fig. 2 is to be applicable in methanol production process and the reformation based on oxygen transport membrane with Fig. 1 of methanol production process integration
The schematic diagram of system；
Fig. 3 is the schematic diagram of the alternate embodiment of the reforming system based on oxygen transport membrane, described based on oxygen transport membrane
Reforming system be designed in oxygen transport membrane reactor use the auxiliary thermal source comprising one or more ceramic burners into
Both row level-one reforming process and secondary reformation process；
Fig. 4 is to be depicted in the modulus of the synthesis gas produced in the reforming system based on oxygen transport membrane as being attributable to assist
The level-one of heat source reforms the chart of the function of the percentage of load；
Fig. 5 is the hydrogen and carbon monoxide ratio for being depicted in the synthesis gas produced in the reforming system based on oxygen transport membrane
(H2/ CO) as be attributable to auxiliary thermal source level-one reform load percentage function chart；With
Fig. 6 is the carbon monoxide and carbon dioxide ratio for being depicted in the synthesis gas produced in the reforming system based on oxygen transport membrane
Rate (CO/CO2) as be attributable to auxiliary thermal source level-one reform load percentage function chart.
It is described in detail
Fig. 1 provides the schematic diagram of the embodiment of the reforming system 100 according to the present invention based on oxygen transport membrane.Therefrom may be used
See, in order to preheat oxygenate feed stream 110 by means of air blower (FD) 114 for oxygen-containing stream 110(such as air) it leads to system and enters
In heat exchanger 113.Heat exchanger 113, which is preferably, is associated with cloth with oxygenate feed stream 110 and the operation of the oxygen deprivation retentate stream 124 of heating
The ceramic heat regenerator of high efficiency, ring-type and the continuous rotation set.The air feed stream 110 of entrance is in ceramic heat regenerator
The temperature within the scope of about 850 DEG C to 1050 DEG C is heated in 113 to generate the air feed stream 115 of heating.
Oxygen denuded air is as the oxygen deprivation retentate stream 124 heated in identical or slightly higher the feeding flow 115 than heating temperature
Oxygen transport membrane reformer tubes are left under degree.Any temperature rises (generally less than about 30 DEG C) and is attributable to be existed by hydrogen and carbon monoxide
Oxidation reaction in oxygen transport membrane pipe generates and by the portion of energy of convection current to oxygen deprivation retentate stream 124.
The temperature of the oxygen deprivation retentate stream 124 is heated into back the temperature between about 1050 DEG C and 1200 DEG C, the then oxygen deprivation
Retentate stream 124 is directed to heat exchanger or ceramic heat regenerator 113.This temperature of oxygen deprivation retentate stream 124 increases excellent
Selection of land is completed by using pipe burner 126, which is made using some residual oxygens in retentate stream 124
Promote the burning of make-up fuel stream 128 for oxidant.Although being not shown, alternative approach is in pipe burner 126
Air stream burning make-up fuel stream 128 is separated, and mixes hot flue gas with oxygen deprivation retentate stream 124.In ceramics
In heat exchanger or heat regenerator 113, the oxygen deprivation retentate stream 124 of heating provides feed air stream 110 of the energy will enter
Temperature the temperature between about 850 DEG C to 1050 DEG C is increased to from environment temperature.More than the resulting cold infiltration for leaving ceramic heat exchanger
Logistics (usually containing the oxygen less than about 5%) as exhaust gas 131 about 150 DEG C at a temperature of leave the weight based on oxygen transport membrane
Whole system 100.
It is not seen in fig. 1, but the alternate embodiment of the reforming system 100 based on oxygen transport membrane pipeline can be fired
Burner and make-up fuel stream are arranged in the upstream of the reactor in admission line (intake duct) 116.This arrangement
(arrangement) will allow using smaller ceramic heat regenerator 113 and less harsh for ceramic heat regenerator 113
Operating condition.
Usually by the preferred natural gas of hydrocarbon containing feed stream 130(to be reformed) mixed with a small amount of hydrogen or hydrogen-rich gas 132 with
Combination hydrocarbon charging 133 is formed, and is then preheated to about 370 DEG C in the heat exchanger 134 for serving as feed preheater, it is as follows
In greater detail.Because natural gas usually contains unacceptable high-level sulfur material, a small amount of hydrogen or hydrogen-rich are added
Gas 132 is to promote desulfurization.Preferably, the feeding flow 136 of heating via device 140 undergo sweetening process, such as hydrotreating,
Sulfur material is reduced into H2S is then removed in guard bed using the material of such as ZnO and/or CuO.Hydrotreating
Step is also saturated any alkene being present in hydrocarbon containing feed stream.Additionally since natural gas typically contains higher hydrocarbon, higher hydrocarbon
It will decompose at high temperature and form unexpected Carbon deposition, negatively affect reforming process, natural gas feed stream preferably exists
It is insulated pre-reforming in pre-reformer, which is converted to methane, hydrogen, carbon monoxide and carbon dioxide for higher hydrocarbon.Separately
It is outer consideration but it is unshowned be such a embodiment, wherein pre-reformer be heating pre-reformer, can be based on
The reforming system thermal coupling (thermally coupled) of oxygen transport membrane.
By superheated steam 150 on demand be added to pretreatment natural gas and hydrogen feeding flow 141 to produce mixed feed stream 160,
Wherein steam and carbon ratio be between about 1.0 and 2.5, and more preferably between about 1.2 and 2.2.Superheated steam 150 is preferred
Ground uses work between about 15 bar and 80 bar and between about 300 DEG C and 600 DEG C in fired heater 170
The source of skill steam 172 generates.As shown in Figure 1, fired heater 170 is configured to use air 175 as oxidant by work
Skill steam 172 be heated into superheated steam 150 burn make-up fuel stream 174 and optionally burning by the reformation based on oxygen transport membrane
The a part for the tail gas 229 that system generates.In Illustrative Embodiment, air-source 175 is heated in fired heater 170 with
The oxidant for generating the air stream 176 of heating to be used as in fired heater 170.Mixing is heated also in fired heater 170
Feeding flow 160, to generate the mixed feed stream 180 of heating.The mixed feed stream 180 of heating has preferably at about 450 DEG C
With the temperature between 650 DEG C, and the temperature more preferably between about 500 DEG C and 600 DEG C.
The Illustrative Embodiment of reforming system 100 based on oxygen transport membrane includes to be arranged in single reactor enclosure 201
Three reactors (200,210,220).First reactor is reforming reactor 200 comprising pipe containing reforming catalyst is configured
To reform the heating containing hydrocarbon charging and steam in the presence of the conventional reforming catalyst and heat being arranged in reformer tubes
Mixed feed stream 180 is to produce reformed syngas stream 205.Reform hydrogen-rich synthetic gas stream temperature be commonly designed 650 DEG C with
Between 850 DEG C.
Reformed syngas stream 205 is fed into second reactor consequently as inflow, which is oxygen transport membrane
Reactor 210.More specifically, reformed syngas stream 205 is fed into reactivity driving and oxygen transport membrane containing catalyst is anti-
Answer the reactant side of device 210.Reactivity driving oxygen transport membrane reactor 210 includes one or more oxygen transport membrane elements or pipe
(respectively having oxidant side and reactant side), arranges close to reformer tubes.Each oxygen transport membrane element or pipe are configured to pass through
Oxygen ion transport separates oxygen from the oxygen-containing stream 115 of the heating of catalytic oxidation agent side to reactant side.When oxygen transport membrane element
Or pipe is subjected to raised operation temperature and across oxygen transport membrane element or pipe are there are when oxygen partial pressure difference, and oxygen ion transport occurs.
Be fed into a part of the reformed syngas stream 205 of the reactant side of oxygen transport membrane reactor 210 immediately with pass through
Oxygen transport membrane element or the oxygen of pipe infiltration are reacted to generate the oxygen partial pressure difference of across oxygen transport membrane element or pipe, and driving oxonium ion passes
Defeated and separation.The reaction generates reaction product and heat.
It is seeped with a part for reacting the heat generated of oxygen permeable via convection current to oxygen deprivation by reformed syngas stream 205
Excess stream, and another part of the heat is transferred to reforming reactor 200 via radiation.
Oxygen transport membrane reactor 210 is further configured to reform the hydrocarbon gas that do not reform in reformed syngas stream 205,
And generate syngas product stream 215.One or more of reforming catalysts for containing in oxygen transport membrane element or pipe, reaction
Product (such as a part in reformed syngas stream 205 and Oxygen permeation object react) and the energy generated by same reaction
Or in the presence of the Part III of heat, the secondary reformation occurs.Leave the syngas product stream of oxygen transport membrane reactor 210
215 are preferably at a temperature of between about 900 DEG C and 1050 DEG C.
Third reactor in Illustrative Embodiment is auxiliary oxygen transport membrane reactor 220, is configured to that spoke will be assisted
It penetrates heat source and is provided to reforming reactor 200.The auxiliary reactor 220 or heat source preferably provide to be occurred in reforming reactor 200
Heating mixed feed stream 180 initial reformate needed for heat between about 15% and 85%.Assist oxygen transport membrane reactor
220 or reactivity driving oxygen transport membrane reactor 220, it includes close to reforming reactor 200 or relative to reforming reaction
200 parallel direction of device and the multiple oxygen transport membrane elements or pipe arranged.Auxiliary oxygen transport membrane reactor 220 is also configured to pass through
Oxygen is separated or is infiltrated into oxygen from the oxygen-containing stream 115 of the oxidant side of contact oxygen transport membrane element or pipe and passes by oxygen ion transport
The reactant side of defeated membrane component or pipe.Oxygen permeable is low with the reactant side that is fed into oxygen transport membrane element or pipe via valve 221
Hydrogeneous stream 222(is pressed to be preferably less than about 3 bar) it reacts to generate the oxygen partial pressure difference across oxygen transport membrane element and generate auxiliary
Reacting product stream 225 and heat.
In Illustrative Embodiment, the hydrogeneous stream 222 of low pressure is the stream of hydrogen and light hydrocarbon, preferably includes synthesis gas
The recycle sections 226 of product stream and optionally supplement fuel 224.Leave the oxygen transport membrane element of oxygen transport membrane reactor 220
Or a part in the reacting product stream 225 of the reactant side of pipe is tail gas 227, which can fire with supplemental natural gas
Material 228 is mixed to pipe burner 126.It leaves another in the reacting product stream 225 of the reactant side of oxygen transport membrane element or pipe
A part is tail gas 229, which can mix with supplemental natural gas fuel 174 to fired heater 170.
Preferably, reforming reactor 200 and oxygen transport membrane reactor 210 are arranged as the pipe group for the close dress being closely adjacent to each other
Column.Reforming reactor 200 is generally made of reformer tubes.Oxygen transport membrane reactor 210 and auxiliary oxygen transport membrane reactor 220 wrap
Containing multiple ceramic oxygen transport membrane pipes.Oxygen transport membrane pipe be preferably configured as can under raised operation temperature conductive oxonium ion
Multi-layered ceramic tube, wherein the oxidant side of oxygen transport membrane pipe be exposed to heating oxygen-containing stream ceramic tube outer surface, and
Reactant side or penetrant side are the inner surfaces of ceramic tube.It is to promote partial oxidation and/or reformation in each oxygen transport membrane pipe
One or more of catalyst (if applicable).Although showing only three reformer tubes in Fig. 1 is in close proximity to six secondary reformations
Oxygen transport membrane element or pipe and four auxiliary oxygen transport membrane elements or pipe, but as those skilled in the art will recognize that,
Many this oxygen transport membrane pipes and many reformer tubes may be present in each reformation subsystem or component based on oxygen transport membrane.Together
Sample, it can exist for multiple reformations based on oxygen transport membrane in the industrial application of the reforming system 100 based on oxygen transport membrane
Subsystem or component.
Oxygen transport membrane element or pipe used in embodiment disclosed herein, which preferably comprise, combines compacted zone, porous branch
The composite construction of support body and the intermediate porous layer between compacted zone and porous supporting body.Compacted zone and intermediate porous layer are respectively
Can under raised operation temperature conductive oxonium ion and electronics, oxygen is separated from the air stream of entrance.Porous supporting body
Therefore layer can form reactant side or penetrant side.Compacted zone and intermediate porous layer preferably comprise conductive oxonium ion and electronics respectively
Ion-conductive material and electrically conductive material mixture.Intermediate porous layer preferably has the infiltration lower than porous supporting body layer
Property and small average pore size, by the oxygen separated by compacted zone towards porous supporting body layer be distributed.Preferred oxygen transport membrane pipe is also
Including mixed phase oxygen-ion conductive ceramic of compact separating layer, the separating layer include oxygen ion conduction phase based on zirconium oxide and
The mixture of the Perovskite Phase of main conduction electronics.The thin dense separation layers are implemented on thicker inertia porous supporting body.
The solution of oxidation catalyst particles or the precursor containing oxidation catalyst particles is optionally disposed in intermediate porous layer
And/or in the thicker inertia open support body of neighbouring intermediate porous layer.Selection contains oxidation catalyst (such as Gd2 O3 dioxy
Change cerium) oxidation catalyst particles, when in the hole on the side opposite with intermediate porous layer for being introduced in porous supporting body,
Promote the oxidation of the synthesis air-flow through partial conversion in the presence of oxygen permeable.
The heat absorptivity demand for heat of the reforming process occurred in reforming reactor 200 is by coming from oxygen transport membrane reactor
The convection current that 210 radiation with some heats of auxiliary oxygen transport membrane reactor 220 and the oxygen deprivation retentate stream by heating provide
Heat transmitting is supplied together.Exothermic ceramic oxygen transport membrane pipe and containing for heat absorption must be made to urge in the design of this reforming system
It being capable of abundant Geothermal Coupling or heat transmitting between the reformer tubes of agent.Ceramic oxygen transport membrane pipe and neighbouring or arranged side by side containing are reformed
A part in heat transmitting between the reformer tubes of catalyst is the radiation mode of logical heat transfer, wherein surface area, surface
Nonlinear temperature difference (such as T between viewing factor (surface view factor), emissivity and pipeotm 4-TReformer 4)
It is the key element of thermal coupling needed for realizing.Emissivity and temperature generally are required to dominate by tube material and reaction.Surface area
It is generally arranged by the pipe in each module and entire reactor with surface viewing factor or construction (configuration) dominates.
Although being closed there are numerous pipe arrangements that can satisfy the thermal coupling requirement between oxygen transport membrane pipe and reformer tubes or construction
Key challenge is to realize relatively high per unit volume productivity, and the active oxygen for depending on containing in unit volume in turn again passes
The amount of defeated membrane area.The additional challenge for realizing optimum coupling performance is to make ceramic oxygen transport membrane pipe and the reformer containing catalyst
The size of pipe optimizes, and more specifically makes the effective surface area ratio A of respective tubeReformer/AotmIt optimizes.Certainly, this
Performance optimizes must be with module and the requirement of the manufacturability of reactor, cost and reliability, maintainability, operational availability
Weighed.
Advantageously, it has been found that, it is produced by the synthesis gas that the open embodiment of the reforming system based on oxygen transport membrane produces
The modulus of logistics according to leave stream temperature and by auxiliary thermal source supplied to reforming reactor heat amount change.For example, such as Fig. 4
Middle description, when the temperature in the exit that the temperature in the exit of reforming reactor is about 730 DEG C and OTM reactor is about
At 995 DEG C, the modulus by the syngas product stream of open embodiment production is between about 1.85 and 2.15 or bigger, and with
The percentage table of load (is reformed with total level-one from auxiliary thermal source by the amount of auxiliary thermal source supplied to the heat of reforming reactor
Show) and change.Similarly, as shown in figure 5, being supplied under about 730 DEG C of reforming reactor outlet temperature according to by auxiliary thermal source
To the amount of the heat of reforming reactor, the hydrogen and carbon monoxide ratio (H of syngas product stream2/ CO) it maintains and is typically in the range of
In segment between about 2.95 and 3.10.In addition, being stated in Fig. 5 by the amount of auxiliary thermal source supplied to the heat of reforming reactor
The percentage of load is reformed for total level-one from auxiliary thermal source.Finally, as shown in Figure 6 and in about 730 DEG C of reforming reaction
Under device outlet temperature, according to the amount for the heat for being supplied to reforming reactor by auxiliary thermal source, the carbon monoxide of syngas product stream
With carbon dioxide ratio (CO/CO2) range is between about 2.50 and 3.30.
Practical modulus, the H of syngas product stream2/ CO ratio and CO/CO2Ratio is heavily dependent on to be passed based on oxygen
The outlet temperature realized in the reforming system of defeated film.About 730 DEG C of the exit of the graph representation reforming reactor of Fig. 4-Fig. 6
Temperature.If the temperature is increased to the temperature between about 800 DEG C and 900 DEG C, according to anti-supplied to reforming by auxiliary thermal source
Answer the amount or percentage of the reformation load heat of device, it is contemplated that the range of the modulus of syngas product stream will also increase by may be between
It is between about 1.90 to 2.25 or bigger.The temperature for increasing the exit of OTM reactor typically results in the modulus reduction of synthesis gas.
It is pointed out Ru above-mentioned, auxiliary thermal source is configured or more preferably designs to provide the hydrocarbon containing feed stream in reforming reactor
Level-one reform needed for about 15% and 85% between total amount of heat.Auxiliary thermal source can be auxiliary oxygen as shown in Figures 1 and 2
Transmission membrane reactor may include one or more ceramic burners as shown for example in figure 3 being described in more below
Device.In the low side of 15% to 85% range, the modulus of syngas product stream is about 1.90, however in the higher-end of the range,
The modulus of syngas product stream is big between about 2.10 and 2.15 or more.The chart of phenogram 4 and by it is presently disclosed be based on oxygen
The alternative of the syngas product of the reforming system production of transmission film is: when the heat for being supplied to reforming reactor by auxiliary thermal source
When amount is 50% or less of total institute's calorific requirement to be supplied to reforming reactor, the modulus of syngas product stream about 1.85 with
Between 2.00, and when the heat by auxiliary thermal source supplied to reforming reactor is more than total institute's calorific requirement of reforming reactor
When 50%, the modulus of syngas product stream is big between about 2.00 and 2.15 or more.It is pointed out Ru above-mentioned, if reforming reactor goes out
Temperature at mouthful increases, then by the modulus of expected syngas product according to the heat for being supplied to reforming reactor by auxiliary thermal source
Amount increase accordingly to 2.25 or bigger.
Therefore, it is possible to design and/or make to be suitable for passing through the present invention is based on the reforming system of oxygen transport membrane simply to adjust
Section changes heat load division and outlet temperature between oxygen transport membrane reactor and auxiliary thermal source to produce with required spy
The synthesis gas of property.Required or target synthesis gas characteristic will necessarily depend on synthesis gas and other system variables such as outflux
The application of temperature, Methane slip (methane slip), reactor pressure etc..
Fig. 1 is turned again to, hydrogen, an oxidation are typically contained by the air-flow 215 that synthesizes that oxygen transport membrane reactor 210 produces
Carbon, unconverted methane, steam, carbon dioxide and other components.The major part of sensible heat from synthesis air-flow 215 can make
It is recycled with heat exchanging segment or recycling column (recovery train) 250.Heat exchanging segment 250 is designed to leave oxygen transport membrane reaction with cooling
The generated synthesis air-flow 215 of device 210.In the Illustrative Embodiment, heat exchanging segment 250 is also designed so as to be closed cooling
While at air-flow 215, generate process steam 172, preheat the hydrocarbon charging stream 133 of combination and heating boiler water inlet 255 and into
Water 259.
It is in process gas (PG) boiler 252 that hot synthesis gas product stream 215(is preferred to minimize Metal Dusting problem
At a temperature of between about 900 DEG C and 1050 DEG C) it is cooled to about 400 DEG C or smaller temperature.Then use initial cooling
Syngas product stream 254 to preheat the mixture of natural gas and hydrogen feeding flow 133 in feed preheater 134, and is then saving
Preboiler water inlet 255 in hot device 256, and heat feed water flow 259.In Illustrative Embodiment, boiler feed water stream 255 is preferred
The feed water flow quilt for being pumped using intake pump (not shown), heating and be sent to steamdrum 257 in economizer 256, and heated
It send to the degasser (not shown) of offer boiler feed water 255.The synthesis gas for leaving feed water heater 258 is preferably about 150 DEG C.
The synthesis gas is cooled to about 40 using fin-fan cooler 261 and the syngas cooler fed by cooling water 266 264
℃.Cooling syngas 270 subsequently enters knockout drum (knock-out drum) 268, and wherein water is from bottom as process condensate object
Stream 271 removes, and the process condensate logistics is recycled for use as into water (although being not shown), and cooling syngas 272 is in tower top
Recycling.
Final syngas product 276 is obtained by compression of the cooling syngas stream 273 in synthesic gas compressor 274.It takes
Certainly in application, it may be necessary to multi-stage compression.Cascade EDFA and condensate separation are not shown in FIG. 1.However, in this compression
Before, a part of of cooling syngas stream 226 can be recycled to reactor enclosure optionally to form the whole of the hydrogeneous stream 222 of low pressure
Or part.Depending on the operating pressure of the reforming system based on oxygen transport membrane, the pressure of the synthesis gas of recycling is preferably about 10
In the range of bar and 35 bar, and more preferably in the range of 12 bar and 30 bar.It produces in the embodiment described in which
The modulus of final syngas product be typically about 1.8 to 2.3.
Fig. 2 is the weight based on oxygen transport membrane suitable for methanol production process and with Fig. 1 of methanol production process integration
The schematic diagram of whole system.In many aspects, the embodiment is similar to the embodiment in Fig. 1, and for simplicity, two realities
The description for applying the common aspect of scheme will not be repeated again herein, and following discussion is concentrated in difference.Synthesis gas is usually synthesizing
It is compressed into air compressor 274 between about 80 and 100 bar.In embodiment shown in figure 2, final syngas product
276 mix with methanol circuit recirculation flow 310.Compressed synthesis gas and the mixed flow 320 of methanol circuit recycling are in heat exchanger
By 324 indirect heating of synthesizing methanol stream to the temperature between about 175 DEG C and 300 DEG C in 322.By the guidance of stream 326 of heating to first
In alcohol synthesis reaction device 330.It is exact with heat will be whole according to the type of methanol synthesis reactor, technology suppliers and entire technique
The method of conjunction (is integrated with front end or synthesis gas generates section) variation.In the methanol synthesis reactor 330, hydrogen, one are consumed
Carbonoxide and carbon dioxide are to produce first alcohol and water through following reaction in exothermic process:
The heat generated in methanol synthesis reaction is produced for steam and/or is fed for pre-heated synthesis gas.Methanol reaction
The temperature in the exit of device is usually between about 200 DEG C and about 260 DEG C.The methanol-fueled CLC stream 324 is before entering separator 334
It is cooled to about 38 DEG C in heat exchanger 322 and cooler 332, methanol, water and micro other are mainly contained in separator 334
The crude carbinol stream 340 of substance (such as dimethyl ether, ethyl alcohol and higher alcohol) is separated in bottom, and is sent to further distilation steps
For finally purifying.Most of tower top stream 336 from separator 334 is methanol circuit recirculation flow 344, via recycling
Compressor 345 return to methanol synthesis reactor 330 with increase carbon to methanol conversion ratio.Need recycle compressor 345
Compensate the pressure drop across methanol synthesis reactor 330 and relevant device (such as heat exchanger and cooler).
From methanol synthesis loop 300 be discharged (purged) tower top stream 336 fraction (usually between about 1% and 5%) with
It prevents from accumulating inert substance in methanol synthesis loop 300.The typical composition of discharge stream 350 is as follows: 75% hydrogen, 3% carbon dioxide,
12% carbon dioxide, 3% nitrogen and 7% methane, and the relatively high heating value with about 325 BTU/scf.Methanol circuit discharge stream 350
Then two streams are split into, it may be assumed that methanol discharge stream 350A is directed back into auxiliary oxygen transport membrane reactor as hydrogeneous charging
220；With methanol discharge stream 350B, formed hydrogen-rich gas, the hydrogen-rich gas combined with hydrocarbon containing feed stream with formed combine hydrocarbon into
Material 133.In Illustrative Embodiment, the hydrogeneous stream 222 of low pressure is a part of methanol discharge stream 350A and supplemental natural gas fuel stream
224 mixture.
Fig. 3 is the schematic diagram of the alternate embodiment of the reforming system based on oxygen transport membrane, described based on oxygen transport membrane
Reforming system be designed in oxygen transport membrane reactor use the auxiliary thermal source comprising one or more ceramic burners into
Row level-one reforming process and secondary reformation process.In many aspects, the embodiment which is similar to Fig. 2, and be
For the sake of simplicity, the description of the common aspect of two embodiments will not be repeated again herein, and following discussion is only concentrated in difference
On.
Main difference between embodiment shown in Figure 2 and the embodiment of Fig. 3 are as follows: by reactivity driving oxygen transmission
The third reactor of membrane reactor composition is disposed in close to reforming reactor 200 and reactivity driving and the oxygen containing catalyst passes
One or more porous ceramic combustors (i.e. flameless burner) in the reactor enclosure 201 of defeated membrane reactor 210 are replaced.
One or more ceramic burners 555, which are preferably configured to use air or enriched air as oxidant, to burn containing lightweight
Hydrocarbon stream.When using porous ceramic combustor as auxiliary thermal source, it is important that design ceramic burner is relative to oxygen transport membrane
The space arrangement of reactor and reforming reactor is to maximize thermal coupling and system effectiveness, while the machinery for minimizing system is multiple
Polygamy.Different from the purposes of oxygen transport membrane reactor, the purposes of the porous ceramic combustor in reactor enclosure needs others
Design challenge and to the improvement of system so that burner it is fully integrated be auxiliary thermal source.This challenge and improvement may include providing
Independent oxidant stream and/or the independent fuels sources for porous ceramic combustor.In addition, transmitting membrane reactor using Low Pressure Oxygen
Embodiment and use the startup program (start- between those of one or more porous ceramic combustors embodiment
Up procedures) and exhaust manifold (exhaust manifolding) difference may be significant and must be subject to
Consider.
Although being not shown in Fig. 3, porous ceramics or flameless burner can be preferably radiant tube type burner, tool
The similar tubulose of oxygen transport membrane reactor tube (wherein burning in the inside of pipe) or cylinder for having and describing in Fig. 1 and Fig. 2
Shape construction.Another ceramic burner construction is the multiple perforated tubular ceramic burners of arrangement, and wherein fuel is passed from the inside of pipe
Outer surface is transported to, and oxygen deprivation retentate stream is used to burn on the outer surface as oxidant.Auxiliary thermal source it is other still
Arrangement under consideration may include radial direction or ring-shaped pottery burner arrangement or may even burner annular array.
Another difference between the embodiment shown in figure 2 and figure 3 is that pipe burner 126A is arranged in air inlet pipe
The upstream of reactor enclosure 201 in road 116 and with make-up fuel stream and/or recycling methanol discharge stream 350B couple.At this
It is less harsh for the operating condition of ceramic heat regenerator 113 in kind arrangement, and will be by allowing using lesser ceramics
Heat regenerator 113 saves Capital expenditure.If it is necessary, then pipe burner 126A can be set as in fig. 2 instead
In the downstream of reactor enclosure 201.
Although various ways has been used to show feature of the invention and for the preferred embodiment description present invention, such as
Those skilled in the art will expect, without departing substantially from the spirit and scope of the present invention as described in appended claims the case where
Under can carry out many additions, changes and improvements to it.
Claims (20)
1. the method for producing synthesis gas in the reforming system based on oxygen transport membrane, the described method comprises the following steps:
In the presence of the reforming catalyst and heat being arranged in reforming reactor, reformed in the reforming reactor hydrocarbonaceous
Feeding flow is to produce reformed syngas stream；
The reformed syngas stream is fed into the reactant side of reactivity driving and the oxygen transport membrane reactor containing catalyst,
Described in oxygen transport membrane reactor include at least one oxygen transport membrane element, the oxygen transport membrane element is configured to when being subjected to rising
When high operation temperature and oxygen partial pressure difference across at least one oxygen transport membrane element, by oxygen ion transport by oxygen from reaction
Property driving and the oxygen-containing stream of the oxidant side of the oxygen transport membrane reactor containing catalyst in separation to reactant side；
React the reformed syngas stream of a part to generate across institute with the oxygen for penetrating at least one oxygen transport membrane element
The oxygen partial pressure difference of at least one oxygen transport membrane element is stated, and generates reaction product and heat, the heat includes containing to be described
The first part of heat needed for the reformation of hydrocarbon charging stream；With
One or more of catalyst, the reaction product and the heat contained in the oxygen transport membrane reactor is deposited
Under, reformation does not reform the hydrocarbon gas in the reformed syngas stream to generate syngas product stream；
It is wherein the second part of heat needed for initial reformate step by the auxiliary thermal source close to reforming reactor arrangement
Transmitting.
2. method described in claim 1, wherein the heat generated with reacting for oxygen permeable due to the reformed syngas stream
Be passed to: (i) is present in the reformed syngas stream in the oxygen transport membrane reactor containing catalyst；(ii) reforming reaction
Device；(iii) oxygen deprivation retentate stream.
3. method described in claim 1, wherein the auxiliary thermal source be provided as in the reforming reactor it is described it is hydrocarbonaceous into
Heat needed for the initial reformate of stream between 15% and 85%.
4. method described in claim 1, wherein the auxiliary thermal source is the oxygen transport membrane of one or more reactivity drivings
Reactor.
5. method as claimed in claim 4, wherein the oxygen transport membrane reactor of the reactivity driving includes multiple oxygen transport membranes
Element, the multiple oxygen transport membrane element are arranged and are configured to close to the reforming reactor: (i) is passed by oxonium ion
It is defeated, oxygen is separated from the oxygen-containing stream of oxidant side for contacting the oxygen transport membrane element and is transmitted to the oxygen transport membrane member
The reactant side of part；(ii) hydrogeneous stream is received in the reactant side；And (iii) makes the hydrogeneous stream and in reactant side
Oxygen permeable is reacted to generate the oxygen partial pressure difference across the oxygen transport membrane element and generate assisted reaction product stream and heat.
6. method described in claim 5 wherein the hydrogeneous stream includes the stream of hydrogen and light hydrocarbon, and will be left described
The assisted reaction product stream of reactant side as supplement fuel-feed to pipe burner or fired heater or the rwo.
7. method described in claim 5, wherein the oxygen transport membrane reactor of one or more reactivity driving is matched
It sets to receive the hydrogeneous stream of low pressure in the reactant side, the pressure of the hydrogeneous stream is 3bar or smaller.
8. method described in claim 5 further comprises that a part of the syngas product stream is fed into the oxygen
Transmit the step of reactant side of membrane component is to form all or part of hydrogeneous stream.
9. method described in claim 5, wherein generated synthesis gas is used for methanol-fueled CLC equipment, and the hydrogeneous stream
Further include a part in the discharge stream from the methanol-fueled CLC equipment.
10. method described in claim 1, wherein the hydrocarbon containing feed stream is pre-reforming feeding flow.
11. method described in any one of claim 10, wherein the hydrocarbon containing feed stream is in insulation pre-reformer or the pre-reformer of heating
It is middle by pre-reforming.
12. method described in claim 1, wherein the auxiliary thermal source is one or more ceramic burners, it is one
Or more ceramic burner close to the reforming reactor and it is described reactivity driving and containing catalyst oxygen transport membrane reaction
Device arrangement, one or more ceramic burner be configured to use air or enriched air as oxidant come burn containing
The stream of light hydrocarbon.
13. the reforming system based on oxygen transport membrane, the reforming system includes:
Reactor enclosure；
Reforming reactor is arranged in the reactor enclosure, and is configured in being arranged in the reforming reactor
In the presence of reforming catalyst and heat, hydrocarbon containing feed stream is reformed to produce reformed syngas stream；
The oxygen transport membrane reactor of reactivity driving, is arranged in the reactor enclosure close to the reforming reactor, and
Be configured to receive the reformed syngas miscarry and make a part of the reformed syngas stream reacted with oxygen permeable and
Raw reaction product and heat, the heat include the first part of heat needed for the reforming reactor；
Wherein the oxygen transport membrane reactor containing catalyst of the reactivity driving is further configured by the reformation
The reformation is reformed in the presence of synthesis air-flow and some heats for reacting generation of oxygen permeable and the reaction product to close
At any hydrocarbon gas that do not reform in air-flow, to produce syngas product stream；With
Auxiliary thermal source is arranged in the reactor enclosure close to the reforming reactor, and is configured to supply described heavy
The second part of heat needed for whole reactor generates the reformed syngas stream；
Wherein the modulus of the syngas product stream is between 1.85 and 2.15 or bigger, and depends on reforming reactor and export
Temperature and by the auxiliary thermal source supplied to the reforming reactor heat amount.
14. system described in claim 13, wherein the oxygen transport membrane reactor of the reactivity driving further include it is multiple
Oxidant side and reactant side are determined in oxygen transport membrane pipe containing catalyst, the oxygen transport membrane area within a jurisdiction, and be configured to when through
When by raised operation temperature and across the oxygen partial pressure difference of at least one oxygen transport membrane pipe, by oxygen ion transport by oxygen from contact institute
It states in the oxygen-containing stream of oxidant side and separates to the reactant side；With
Wherein it is described reactivity driving oxygen transport membrane reactor be further configured with one or more of catalyst and by
Weight in the presence of reacting some heats generated of the reformed syngas stream and the oxygen permeable in the reactant side
The hydrocarbon gas that do not reform in the whole reformed syngas stream, to generate the syngas product stream.
15. system described in claim 13, wherein the hydrogen of the syngas product stream and carbon monoxide ratio (H2/ CO)
It is between 2.95 and 3.10 or bigger, and depend in the temperature in the exit of the reforming reactor and by the auxiliary thermal source
Supplied to the amount of the heat of the reforming reactor.
16. system described in claim 13, wherein the carbon monoxide of the syngas product stream and carbon dioxide ratio (CO/
CO2) between 2.50 and 3.30 or bigger, and depend in the temperature in the exit of the reforming reactor and by described auxiliary
Help heat source supplied to the amount of the heat of the reforming reactor.
17. system described in claim 13, wherein the auxiliary thermal source further includes one or more auxiliary oxygen transmission
Membrane reactor, the auxiliary oxygen transport membrane reactor are configurable to provide as the hydrocarbon containing feed stream in the reforming reactor
Reformation needed for heat between 15% and 85%.
18. system described in claim 13, wherein the auxiliary thermal source further includes one or more ceramic burners,
One or more ceramic burner is configured to use air or enriched air as oxidant to burn containing light hydrocarbon
Stream, and the heat needed for the reformation for the hydrocarbon containing feed stream being provided as in the reforming reactor between 15% and 85%
Amount.
19. system described in claim 13, wherein when the heat for being supplied to the reforming reactor by the auxiliary thermal source
When second part is 50% or less of total institute's calorific requirement to be supplied to the reforming reactor, the syngas product stream
Modulus is between 1.85 and 2.00；And when the second part for the heat for being supplied to the reforming reactor by the auxiliary thermal source
More than total institute's calorific requirement to be supplied to the reforming reactor 50% when, the modulus of the syngas product stream depends on institute
It is between 2.00 and 2.15 or bigger to state the temperature in the exit of reforming reactor.
20. system described in claim 13, the system further includes pre-reformer, and the pre-reformer is arranged in described
Reforming reactor upstream, and it is configured to hydrocarbon containing feed stream described in pre-reforming, and wherein the pre-reformer is that insulation is pre-
Reformer or the pre-reformer of heating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361874077P | 2013-09-05 | 2013-09-05 | |
| US61/874077 | 2013-09-05 | ||
| US201361910697P | 2013-12-02 | 2013-12-02 | |
| US61/910697 | 2013-12-02 | ||
| PCT/US2014/035430 WO2015034556A1 (en) | 2013-09-05 | 2014-04-25 | Method and system for producing a synthesis gas using gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source |
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| CN105517950A CN105517950A (en) | 2016-04-20 |
| CN105517950B true CN105517950B (en) | 2018-12-14 |
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| US6296686B1 (en) | 1998-06-03 | 2001-10-02 | Praxair Technology, Inc. | Ceramic membrane for endothermic reactions |
| US6114400A (en) | 1998-09-21 | 2000-09-05 | Air Products And Chemicals, Inc. | Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products |
| US6783750B2 (en) * | 2001-08-22 | 2004-08-31 | Praxair Technology, Inc. | Hydrogen production method |
| US7261751B2 (en) | 2004-08-06 | 2007-08-28 | Conocophillips Company | Synthesis gas process comprising partial oxidation using controlled and optimized temperature profile |
| US7427368B2 (en) * | 2005-08-16 | 2008-09-23 | Praxair Technology, Inc. | Synthesis gas and carbon dioxide generation method |
| US8262755B2 (en) | 2007-06-05 | 2012-09-11 | Air Products And Chemicals, Inc. | Staged membrane oxidation reactor system |
| US8349214B1 (en) * | 2011-07-08 | 2013-01-08 | Praxair Technology, Inc. | Synthesis gas method and apparatus |
-
2014
- 2014-04-25 CA CA2920197A patent/CA2920197A1/en not_active Abandoned
- 2014-04-25 WO PCT/US2014/035430 patent/WO2015034556A1/en active Application Filing
- 2014-04-25 CN CN201480048887.XA patent/CN105517950B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0298525A1 (en) * | 1983-03-25 | 1989-01-11 | Imperial Chemical Industries Plc | Steam reforming |
| US6110979A (en) * | 1997-12-23 | 2000-08-29 | Air Products And Chemicals, Inc. | Utilization of synthesis gas produced by mixed conducting membranes |
| CN1131096C (en) * | 1998-06-03 | 2003-12-17 | 普莱克斯技术有限公司 | Syngas reactor with ceramic membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105517950A (en) | 2016-04-20 |
| WO2015034556A1 (en) | 2015-03-12 |
| CA2920197A1 (en) | 2015-03-12 |
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