CN105517950A - 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 - Google Patents

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 Download PDF

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Publication number
CN105517950A
CN105517950A CN201480048887.XA CN201480048887A CN105517950A CN 105517950 A CN105517950 A CN 105517950A CN 201480048887 A CN201480048887 A CN 201480048887A CN 105517950 A CN105517950 A CN 105517950A
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transport membrane
stream
reactor
oxygen
oxygen transport
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CN105517950B (en
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S.查克拉瓦蒂
I.C.斯图克特
R.F.德尔内维奇
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Praxair Technology Inc
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Praxair Technology Inc
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0446—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0457—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—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
    • 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
    • B01J8/067—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • 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
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    • C01—INORGANIC CHEMISTRY
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    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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    • 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
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1623—Adjusting the temperature

Abstract

A method and system for producing a synthesis gas in an oxygen transport membrane based reforming system is disclosed that carries out a primary reforming process within a reforming reactor, and a secondary reforming process within an oxygen transport membrane reactor and in the presence of heat generated from a oxygen transport membrane reactor and an auxiliary source of heat. The auxiliary source of heat is disposed within the reactor housing proximate the reforming reactors and may include an auxiliary reactively driven oxygen transport membrane reactor or a ceramic burner.

Description

For using the method and system of the reforming system production of synthetic gas in next life based on oxygen transport membrane with secondary reformation and auxiliary thermal source
Invention field
The present invention relates to the method and system for producing synthetic gas in based on the reforming system of oxygen transport membrane, and relate more specifically to for provide one-level to reform and secondary reformation and auxiliary thermal source based on the reforming system of oxygen transport membrane in produce the method and system of synthetic gas.
background
The synthetic gas of hydrogen and carbon monoxide is used for various industrial application, and the production of such as hydrogen, chemical and synthol are produced.Routinely, synthetic gas is produced in flame reformer, and Sweet natural gas and steam are reformed to produce synthetic gas in the reformer tubes of nickel-containing catalyst under high temperature (such as 850 DEG C to 1000 DEG C) and middle pressure (such as 16 to 30bar) wherein.Heat absorptivity demand for heat for the steam methane reforming reaction occurred in reformer tubes is by providing to the burner partly providing the smelting furnace of fuel to carry out lighting a fire by Sweet natural gas.For increasing the hydrogen richness of synthetic gas produced by steam methane reforming (SMR) method, synthetic gas can be made to stand water gas shift reaction to make residue vapor in synthetic gas and reaction of carbon monoxide.
The replacement scheme of the steam methane reforming well established is non-catalytic partial oxidation method (POx), allows the oxygen of substoichiometric amount and natural gas feed at high temperature to react thus and produces steam and carbonic acid gas.High temperature residual methane is by reforming with the reaction of high-temperature steam and carbonic acid gas.
Attractive alternative method for the production of synthetic gas is self-heating recapitalization (ATR) method, and described self-heating recapitalization method uses oxidation to produce heat, wherein uses catalyzer to occur under than Pox method low temperature to allow to reform.Be similar to Pox method, need oxygen to make the gas by partial oxidation of natural in burner to provide heat, high temperature carbon dioxide and steam with reformation residual methane.Need some steam to be added in Sweet natural gas and formed with the carbon controlled on catalyzer.But both ATR and Pox methods all need independent air gas separation unit (ASU) to produce hyperbaric oxygen, this increases the complicacy of whole method and fund and running cost.
When raw material (feedstock) is containing a large amount of heavy hydrocarbon, after SMR and ATR process is usually located at pre-reforming step.Pre-reforming is the technique based on catalyzer for higher hydrocarbon being changed into methane, hydrogen, carbon monoxide and carbonic acid gas.The reaction related in pre-reforming is generally heat absorption.Most of pre-reformer on natural gas steam operate in heat sink region, and adiabatically operate, and the raw material of therefore pre-reforming leaves with the temperature lower than the raw material entering pre-reformer.The other method of discussion is secondary reformation method by the present invention, and it is the autothermal process of the product be fed from SMR process in essence.Therefore, the charging of secondary reformation process is mainly from the synthetic gas of steam methane reforming.Depend on terminal applies, some Sweet natural gases can walk around SMR process, and are directly introduced in secondary reformation step.In addition, when being secondary reformation process after SMR process, SMR can operate under lesser temps (such as relative with 850 DEG C to 1000 DEG C 650 DEG C to 825 DEG C).
As will be appreciated, the ordinary method of the production synthetic gas such as discussed above is expensive and needs complicated equipment (installations).For overcoming complicacy and the expense of this kind equipment, propose: using oxygen transport membrane to produce synthetic gas in the reactor supplying oxygen, and thus produce the heat needed for heat absorptivity demand for heat supporting steam methane reforming reaction.Typical oxygen transport membrane has tight zone, although described tight zone air proof, when the service temperature making it stand rising and cross-film oxygen partial pressure difference, will transmit oxonium ion.
Example for the synthesis of the reforming system based on oxygen transport membrane of the production of 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 there is operational problem in all these systems based on oxygen transport membrane, because this oxygen transport membrane needs to operate under the high temperature of about 900 DEG C to 1100 DEG C.When hydrocarbon (such as methane and higher hydrocarbon) stands this high temperature in oxygen transport membrane, especially under high pressure and low steam and carbon ratio, there is excessive carbon and formed.The prior art that carbon formation problem is pointed out is above based on especially serious in the system of oxygen transport membrane.At U.S. Patent number 8,349, a kind of different methods using the reforming system based on oxygen transport membrane in the production of synthetic gas is disclosed in 214, described method provides the reforming system based on oxygen transport membrane, the described reforming system based on oxygen transport membrane uses hydrogen and carbon monoxide as the part of reactant gas being fed to oxygen transport membrane pipe, and the hydrocarbon content of the charging of the per-meate side entering oxygen transport membrane pipe is minimized.The waste heat produced in oxygen transport membrane pipe transfers to the reformer tubes be made up of conventional material mainly through radiation.Use low hydrocarbon content height hydrogen and carbon monoxide are fed to many outstanding problems that oxygen transport membrane pipe solves oxygen transport membrane system comparatively early.
By prior art based on the other problems that the reforming system of oxygen transport membrane produces be the cost of oxygen transport membrane module and this reforming system based on oxygen transport membrane lower than required weather resistance, reliability and operational availability.These problems are major causes of the reforming system not yet successful commercialization based on oxygen transport membrane.The progress of oxygen transport membrane material has solved and the problem that oxygen flux, film fall and creep life is relevant, but from cost standpoint and operational reliability and operability viewpoint, for the reforming system based on oxygen transport membrane realizing commericially feasible leaves much work to be done.
The present invention by provide improvement for using the method driving the system of oxygen transport membrane to prepare synthetic gas based on reactivity to solve the problems referred to above, the described system based on reactivity driving oxygen transport membrane is made up of two reactors, and described two reactors can in form---reforming reactor and the oxygen transport membrane reactor of the pipe group containing catalyzer.Partial oxidation and some infiltration (namely containing catalyzer) sides occurring in oxygen transport membrane of reforming, and the reforming process promoted by reforming catalyst occurs in the reforming reactor of next-door neighbour's oxygen transport membrane reactor.Partial oxidation process (it is heat release) and reforming process (it is heat absorption) the two all occur in the reforming system based on oxygen transport membrane, and therefore there is the heat that high heat integration degree absorbs by reforming process to make the heat supply discharged in oxidising process.Specifically, driving the improvement of the system of oxygen transport membrane to comprise improvement drives the system of oxygen transport membrane to carry out the one-level reforming process in the reforming reactor of packed catalyst and the secondary reformation process in the oxygen transport membrane reactor containing catalyzer based on reactivity based on reactivity, and provides auxiliary thermal source with the reformation load between equilibrium oxygen transmission membrane reactor and auxiliary thermal source.
Summary of the invention
Feature of the present invention can be the method for producing synthetic gas in based on the reforming system of oxygen transport membrane, the described reforming system based on oxygen transport membrane can comprise at least two reactors, described two reactors can in the form of the pipe group containing catalyzer, comprise reforming reactor and oxygen transport membrane reactor, said method comprising the steps of: (i), under the existence of the reforming catalyst be arranged in reforming reactor and heat, hydrocarbon containing feed stream of reforming in reforming reactor is to produce reformed syngas stream; (ii) reformed syngas stream is fed to reactivity to drive and the reactant side containing the oxygen transport membrane reactor of catalyzer, wherein said oxygen transport membrane reactor comprises at least one oxygen transport membrane element, described oxygen transport membrane element is configured to when the service temperature standing to raise and the oxygen partial pressure difference across at least one oxygen transport membrane element, oxygen driven from reactivity and contains isolating containing oxygen stream of the oxidant side of the oxygen transport membrane reactor of catalyzer, and by oxygen ion transport, the oxygen of separation being transferred to reactant side; (iii) make the reformed syngas stream of a part react poor with the oxygen partial pressure produced across at least one oxygen transport membrane element with the oxygen infiltrating through at least one oxygen transport membrane element, and produce reaction product and heat; (iv), under the existence of the catalyzer contained in oxygen transport membrane reactor, reaction product and heat, the hydrocarbon gas of not reforming reformed in reformed syngas stream is to produce syngas product stream.The first part of the heat needed for initial or one-level reforming step is driven by reactivity and provides containing the oxygen transport membrane reactor of catalyzer, and is transmitted by the auxiliary thermal source near reforming reactor layout for the second section of one-level reforming step institute heat requirement.
Feature of the present invention also can be the reforming system based on oxygen transport membrane, and the described reforming system based on oxygen transport membrane comprises: (a) reactor enclosure; (b) reforming reactor, it to be arranged in reactor enclosure and to be configured under the existence of the reforming catalyst be arranged in reforming reactor and heat, and reformation hydrocarbon containing feed stream is to produce reformed syngas stream; C () reactivity drives oxygen transport membrane reactor, it is arranged in reactor enclosure near reforming reactor, and be configured to receive reformed syngas stream and make a part of reformed syngas stream and oxygen permeable react and produce reaction product and heat, described heat comprises the first part of reforming reactor institute heat requirement; (d) auxiliary thermal source, it is arranged in reactor enclosure near reforming reactor, and is configured to the second section of the heat supplied needed for reforming reactor generation reformed syngas stream.
The reactive oxygen transport membrane reactor driven is configured to reform any hydrocarbon gas do not reformed in reformed syngas stream further under one or more of catalyzer and the existence of some heats that produced by the reaction of reformed syngas stream and oxygen permeable, to produce syngas product stream.At the temperature of about 730 DEG C of the exit of reforming reactor and at the temperature of about 995 DEG C in the exit of OTM reactor, the modulus of syngas product stream about between 1.85 and 2.15 or larger, and depends on the amount of the heat being supplied to reforming reactor by auxiliary thermal source.More specifically, at the specified temperature, the maximum value of when modulus of syngas product stream is greater than about 85% from the minimum value of about 1.85 when being less than 15% when the per-cent of the heat being supplied to reforming reactor by the auxiliary thermal source per-cent be increased to when the heat being supplied to reforming reactor by auxiliary thermal source about 2.15.In other words, at the temperature of the exit of reforming reactor and OTM reactor about 730 DEG C and 995 DEG C respectively, when the second section of the heat being supplied to reforming reactor by auxiliary thermal source be to be supplied to reforming reactor total institute heat requirement 50% or less time, the modulus of syngas product stream can about between 1.85 and 2.00; And when the second section of the heat being supplied to reforming reactor by auxiliary thermal source exceed to be supplied to reforming reactor total institute heat requirement 50% time, the modulus of syngas product stream is about between 2.00 and 2.15.Point out as above-mentioned, the actual modulus of syngas product stream also depends on based on the reforming temperature in the reforming system of oxygen transport membrane, and the temperature in the especially exit of reforming reactor.Such as, if the temperature in reforming reactor exit is increased to the temperature between 800 DEG C and 900 DEG C, so according to the amount of heat being supplied to reforming reactor by auxiliary thermal source, the scope of the modulus of expection syngas product stream will be increased to may between about 1.90 to 2.25 or larger.
Except the modulus of syngas product stream divides (reformingdutysplit) based on the reformation load between the first part of the heat in the reforming system of oxygen transport membrane and the second section of heat and except changing based on being designed to enter, the hydrogen of syngas product stream and carbon monoxide ratio (H 2/ CO) about also slightly to change between 2.95 and 3.10 according to the amount of the heat being supplied to reforming reactor by auxiliary thermal source under the reforming reactor temperature out of about 730 DEG C.The carbon monoxide of syngas product stream and carbon dioxide ratio (CO/CO 2) divide under the temperature out of about 730 DEG C and according to the reformation load between the first part and the second section of heat of heat and about also changing between 2.50 and 3.30.
Auxiliary thermal source can be designed to the heat about between 15% and 85% be provided for needed for the reformation of hydrocarbon containing feed stream.Auxiliary thermal source can in be arranged in reactor enclosure and to be close to one or more auxiliary oxygen transport membrane reactor of reforming reactor or the form of one or more ceramic burner.
accompanying drawing is sketched
Although with clear, this specification sheets points out that applicant takes that the claim of its subject matter of an invention terminates as, think when considered in conjunction with the accompanying drawings, the present invention will be understood better, wherein:
Fig. 1 is the schematic diagram of the embodiment of reforming system based on oxygen transport membrane, and the described reforming system based on oxygen transport membrane is designed in oxygen transport membrane reactor, use the auxiliary thermal source comprising the second oxygen transport membrane reactor to carry out both one-level reforming process and secondary reformation process;
Fig. 2 is the schematic diagram of the reforming system based on oxygen transport membrane of the Fig. 1 being suitable for methanol production process and integrating with methanol production process;
Fig. 3 is the schematic diagram of the alternate embodiment of reforming system based on oxygen transport membrane, and the described reforming system based on oxygen transport membrane is designed in oxygen transport membrane reactor, use the auxiliary thermal source comprising one or more ceramic burner to carry out both one-level reforming process and secondary reformation process;
Fig. 4 is the modulus that is depicted in the synthetic gas produced in the reforming system based on oxygen transport membrane as the chart of function of per-cent of one-level reformation load being attributable to auxiliary thermal source;
Fig. 5 is the hydrogen and the carbon monoxide ratio (H that are depicted in the synthetic gas produced in the reforming system based on oxygen transport membrane 2/ CO) as the chart of function of per-cent of one-level reformation load being attributable to auxiliary thermal source; With
Fig. 6 is the carbon monoxide and the carbon dioxide ratio (CO/CO that are depicted in the synthetic gas produced in the reforming system based on oxygen transport membrane 2) as the chart of function of per-cent of one-level reformation load being attributable to auxiliary thermal source.
describe in detail
Fig. 1 provides the schematic diagram of the embodiment according to the reforming system 100 based on oxygen transport membrane of the present invention.Therefrom visible, in order to preheating will containing oxygen stream 110(such as air by means of gas blower (FD) 114 containing oxygen incoming flow 110) system of causing enters in interchanger 113.Interchanger 113 preferably with the high-level efficiency of arranging containing oxygen incoming flow 110 and oxygen deprivation retentate stream 124 operative association that heats, ring-type and the ceramic heat regenerator of continuous rotation.The air feed stream 110 entered be heated in ceramic heat regenerator 113 about 850 DEG C to the temperature within the scope of 1050 DEG C with produce heating air feed stream 115.
Oxygen-denuded air leaves oxygen transport membrane reformer tubes as the oxygen deprivation retentate stream 124 of heating at identical or slightly higher than the incoming flow 115 of heating temperature.Any temperature rising (being usually less than about 30 DEG C) is attributable to the oxidizing reaction in oxygen transport membrane pipe by hydrogen and carbon monoxide and produces and be passed to the portion of energy of oxygen deprivation retentate stream 124 by convection current.
The heating temperatures of this oxygen deprivation retentate stream 124 is returned the temperature between about 1050 DEG C and 1200 DEG C, then this oxygen deprivation retentate stream 124 is directed to interchanger or ceramic heat regenerator 113.This temperature of oxygen deprivation retentate stream 124 increases preferably by using pipe burner 126 to complete, and this pipe burner 126 uses some residual oxygen in retentate stream 124 as oxygenant to promote the burning of make-up fuel stream 128.Although not shown, alternative approach is by the discrete air streams burning make-up fuel stream 128 in pipe burner 126, and then makes hot flue gas mix with oxygen deprivation retentate stream 124.In ceramic heat exchanger or heat regenerator 113, the oxygen deprivation retentate stream 124 of heating provides energy so that the temperature of the feed air stream entered 110 is increased to temperature between about 850 DEG C to 1050 DEG C from envrionment temperature.The cold retentate stream (usually containing the oxygen being less than about 5%) leaving ceramic heat exchanger of gained leaves the reforming system 100 based on oxygen transport membrane as waste gas 131 at the temperature of about 150 DEG C.
Although not shown in Fig. 1, pipe burner and make-up fuel stream can be arranged in the upstream of the reactor in intake ducting (intakeduct) 116 by the alternate embodiment based on the reforming system 100 of oxygen transport membrane.This arrangement (arrangement) will allow to use less ceramic heat regenerator 113 and for the not too harsh operational condition of ceramic heat regenerator 113.
Usually by preferred for hydrocarbon containing feed stream 130(to be reformed Sweet natural gas) mix to be formed with a small amount of hydrogen or hydrogen-rich gas 132 and combine hydrocarbon charging 133, and in the interchanger 134 serving as feed preheater, be preheated to about 370 DEG C subsequently, as described in more detail below.Because Sweet natural gas is usually containing unacceptable high-level sulfur material, so add a small amount of hydrogen or hydrogen-rich gas 132 to promote desulfurization.Preferably, the incoming flow 136 of heating experiences sweetening process via device 140, such as hydrotreatment, so that sulfur material is reduced into H 2s, uses the material of such as ZnO and/or CuO to be removed subsequently in protection bed.Hydrotreating step also makes any olefin saturated be present in hydrocarbon containing feed stream.In addition because Sweet natural gas is generally containing higher hydrocarbon, higher hydrocarbon forms unexpected carbon laydown by high temperature decomposing, it adversely affects reforming process, natural gas feed stream is pre-reforming in adiabatic pre-reformer preferably, and higher hydrocarbon is changed into methane, hydrogen, carbon monoxide and carbonic acid gas by this pre-reformer.In addition consider but unshowned be such embodiment, wherein pre-reformer be heating pre-reformer, it can with the reforming system thermal coupling (thermallycoupled) based on oxygen transport membrane.
Superheated vapour 150 is added into as required pre-treatment Sweet natural gas and hydrogen incoming flow 141 with production mixed feed stream 160, wherein steam and carbon ratio are about between 1.0 and 2.5, and more preferably about between 1.2 and 2.2.Superheated vapour 150 is preferably about between 15bar and 80bar and between about 300 DEG C and 600 DEG C, and the source of operation steam 172 produces in fired heater 170.As shown in Figure 1, fired heater 170 is configured to use air 175, as oxygenant, process steam 172 is heated into superheated vapour 150 to a part for burn make-up fuel stream 174 and the tail gas 229 produced by the reforming system based on oxygen transport membrane that optionally burns.In Illustrative Embodiment, in fired heater 170, heat air source 175 to produce the airflow 176 of heating to be used as the oxygenant in fired heater 170.Also in fired heater 170, heat mixed feed stream 160, thus produce the mixed feed stream 180 of heating.The mixed feed stream 180 of heating has the temperature preferably between about 450 DEG C and 650 DEG C, and the temperature more preferably between about 500 DEG C and 600 DEG C.
Illustrative Embodiment based on the reforming system 100 of oxygen transport membrane comprises three reactors (200,210,220) be arranged in single reactor enclosure 201.First reactor is reforming reactor 200, it comprises containing reforming catalyst pipe, and the mixed feed stream 180 of the heating containing hydrocarbon charging and steam that is configured to reform under the existence of the conventional reforming catalyst be arranged in reformer tubes and heat is to produce reformed syngas stream 205.The temperature of reformation hydrogen-rich synthetic gas stream is designed between 650 DEG C and 850 DEG C usually.
Reformed syngas stream 205 is fed to the second reactor as inflow subsequently, and this second reactor is oxygen transport membrane reactor 210.More specifically, reformed syngas stream 205 is fed to reactivity to drive and the reactant side containing the oxygen transport membrane reactor 210 of catalyzer.The reactive oxygen transport membrane reactor 210 that drives comprises one or more oxygen transport membrane element or pipe (having oxidant side and reactant side separately), and it is arranged near reformer tubes.Each oxygen transport membrane element or pipe are configured to, by oxygen ion transport, oxygen is separated to reactant side from the containing oxygen stream 115 of heating of catalytic oxidation agent side.When oxygen transport membrane element or pipe stand the service temperature of rising and there is oxygen partial pressure difference across oxygen transport membrane element or pipe, there is oxygen ion transport.
The part being fed to the reformed syngas stream 205 of the reactant side of oxygen transport membrane reactor 210 reacts poor with the oxygen partial pressure produced across oxygen transport membrane element or pipe with the oxygen permeated by oxygen transport membrane element or pipe immediately, and it drives oxygen ion transport and is separated.This reaction produces reaction product and heat.
A part for the heat produced with the reaction of oxygen permeable by reformed syngas stream 205 is passed to oxygen deprivation retentate stream via convection current, and another part of described heat via radiation delivery to reforming reactor 200.
Oxygen transport membrane reactor 210 is configured to the hydrocarbon gas do not reformed in reformed syngas stream 205 of reforming further, and produces syngas product stream 215.Under the existence of the Part III of the one or more of reforming catalysts contained in oxygen transport membrane element or pipe, reaction product (such as from the reaction of the part in reformed syngas stream 205 and Oxygen permeation thing) and the energy produced by same reaction or heat, there is this secondary reformation.At the temperature that the syngas product stream 215 leaving oxygen transport membrane reactor 210 is preferably between about 900 DEG C and 1050 DEG C.
The 3rd reactor in Illustrative Embodiment is auxiliary oxygen transport membrane reactor 220, and it is configured to auxiliary radiation thermal source to be provided to reforming reactor 200.This auxiliary reactor 220 or thermal source preferably provide the heat about between 15% and 85% needed for initial reformate of the mixed feed stream 180 of the heating occurred in reforming reactor 200.Auxiliary oxygen transport membrane reactor 220 or reactively drive oxygen transport membrane reactor 220, it comprises near reforming reactor 200 or with relative to reforming reactor 200 and column direction and multiple oxygen transport membrane element of arranging or pipe.Auxiliary oxygen transport membrane reactor 220 is also configured to by oxygen ion transport, by oxygen from the oxidant side of contact oxygen transport membrane element or pipe containing the reactant side being separated or infiltrating into oxygen transport membrane element or pipe oxygen stream 115.Oxygen permeable is preferably less than about 3bar with the hydrogeneous 222(of stream of low pressure being fed to the reactant side of oxygen transport membrane element or pipe via valve 221) react with the oxygen partial pressure difference produced across oxygen transport membrane element and produce assisted reaction product stream 225 and heat.
In Illustrative Embodiment, the hydrogeneous stream 222 of low pressure is the stream of hydrogen and light hydrocarbon, and it preferably includes recycling part 226 and the optionally postcombustion 224 of syngas product stream.The part left in the reacting product stream 225 of the oxygen transport membrane element of oxygen transport membrane reactor 220 or the reactant side of pipe is tail gas 227, and this tail gas 227 can be mixed to pipe burner 126 with supplemental natural gas fuel 228.The another part left in the reacting product stream 225 of the reactant side of oxygen transport membrane element or pipe is tail gas 229, and this tail gas 229 can be mixed to fired heater 170 with supplemental natural gas fuel 174.
Preferably, reforming reactor 200 and oxygen transport membrane reactor 210 arrange as the pipe group of the closely packed be closely adjacent to each other.Reforming reactor 200 is generally made up of reformer tubes.Oxygen transport membrane reactor 210 and auxiliary oxygen transport membrane reactor 220 comprise multiple ceramic oxygen transport membrane pipe.Oxygen transport membrane pipe be preferably configured to can under the service temperature raised the multi-layered ceramic tube of conduct oxygen ions, wherein the oxidant side of oxygen transport membrane pipe is the outside surface of the vitrified pipe containing oxygen stream being exposed to heating, and reactant side or permeate side are the internal surfaces of vitrified pipe.The one or more of catalyzer (if applicable) promoting partial oxidation and/or reformation in each oxygen transport membrane pipe.Although only three reformer tubes are in close proximity to six secondary reformation oxygen transport membrane elements or pipe and four auxiliary oxygen transport membrane elements or pipe shown in Fig. 1, but as those skilled in the art can expect, many this oxygen transport membrane pipes and many reformer tubes can be there is in each reformation subsystem based on oxygen transport membrane or assembly.Similarly, can exist for the multiple reformation subsystem based on oxygen transport membrane in the industrial application of the reforming system 100 based on oxygen transport membrane or assembly.
The oxygen transport membrane element used in embodiment disclosed herein or pipe preferably comprise the composite structure combining tight zone, porous supporting body and the intermediate porous layer between tight zone and porous supporting body.Tight zone and intermediate porous layer separately can raise service temperature under conduct oxygen ions and electronics, so that oxygen is separated from the airflow entered.Porous supporting body layer can therefore forming reactions thing side or permeate side.Tight zone and intermediate porous layer preferably comprise respectively conduct oxygen ions and the ion-conductive material of electronics and the mixture of electrically conductive material.Intermediate porous layer preferably has the perviousness lower than porous supporting body layer and little mean pore size, distributes towards porous supporting body layer with the oxygen will be separated by tight zone.Preferred oxygen transport membrane pipe also comprises mixed phase oxygen-ion conductive ceramic of compact separating layer, and described separating layer comprises the mixture of the Perovskite Phase based on zirconic oxygen ion conduction phase and main conduction electronics.This thin dense separation layers is implemented on thicker inertia porous supporting body.
The solution of oxidation catalyst particles or the precursor containing oxidation catalyst particles is optionally positioned at the thicker inertia porous supporting body of intermediate porous layer and/or contiguous intermediate porous layer.Select containing the oxidation catalyst particles of oxide catalyst (such as Gd2 O3 cerium dioxide), with in the hole on the side relative with intermediate porous layer being introduced in porous supporting body time, under oxygen permeable exists, promote the oxidation of the synthesis air-flow through partial conversion.
The heat absorptivity demand for heat of the reforming process occurred in reforming reactor 200 is together supplied by the radiation of some heats from oxygen transport membrane reactor 210 and auxiliary oxygen transport membrane reactor 220 and the convective heat transfer that provided by the oxygen deprivation retentate stream heated.Must make in the design of this reforming system the ceramic oxygen transport membrane pipe of heat release and heat absorption containing catalyzer reformer tubes between can thermal coupling or heat trnasfer fully.A part in heat trnasfer between pottery oxygen transport membrane pipe and vicinity or the reformer tubes containing reforming catalyst arranged side by side is the radiation pattern by heat trnasfer, nonlinear temperature difference (the such as T wherein between surface-area, surperficial viewing factor (surfaceviewfactor), emissivity and pipe otm 4-T reformer 4) be the key element realizing required thermal coupling.Emissivity and temperature generally require domination by tube material and reaction.Surface-area and surperficial viewing factor are generally arranged by the pipe in each module and whole reactor or structure (configuration) is arranged.Although exist and numerous can meet the pipe arrangement or structure that the thermal coupling between oxygen transport membrane pipe and reformer tubes requires, but key challenge realizes relatively high per unit volume productivity, it depends on again the amount of the active oxygen transmission membrane area contained in unit volume conversely.The additional challenge realizing optimum coupling performance is the size optimizing making ceramic oxygen transport membrane pipe and the reformer tubes containing catalyzer, and makes the effective surface area ratio A of respective tube more specifically reformer/ A otmoptimizing.Certainly, this optimized performance must require with the manufacturability of module and reactor, cost and reliability, maintainability, operational availability weigh.
Advantageously, have been found that the modulus of the syngas product stream produced by the open embodiment of the reforming system based on oxygen transport membrane changes according to the amount of the heat leaving stream temperature and be supplied to reforming reactor by auxiliary thermal source.Such as, as described in Fig. 4, when the temperature in the exit of reforming reactor be about 730 DEG C and the temperature in the exit of OTM reactor for about 995 DEG C time, the modulus of the syngas product stream produced by open embodiment about between 1.85 and 2.15 or larger, and be supplied to by auxiliary thermal source reforming reactor heat amount (total representing with the per-cent of the one-level reformation load from auxiliary thermal source) and change.Similarly, as shown in Figure 5, under the reforming reactor temperature out of about 730 DEG C, according to the amount of heat being supplied to reforming reactor by auxiliary thermal source, the hydrogen of syngas product stream and carbon monoxide ratio (H 2/ CO) maintain generally in the segment about between 2.95 and 3.10.In addition, the amount being supplied to the heat of reforming reactor by auxiliary thermal source is expressed as the per-cent of the total one-level reformation load from auxiliary thermal source in Figure 5.Finally, as shown in Figure 6 and under the reforming reactor temperature out of about 730 DEG C, according to the amount of heat being supplied to reforming reactor by auxiliary thermal source, the carbon monoxide of syngas product stream and carbon dioxide ratio (CO/CO 2) scope is between about between 2.50 and 3.30.
The actual modulus of syngas product stream, H 2/ CO ratio and CO/CO 2ratio depends on based on the temperature out realized in the reforming system of oxygen transport membrane to a great extent.The temperature of about 730 DEG C in the exit of the graphical presentation reforming reactor of Fig. 4-Fig. 6.If this temperature is increased to the temperature between about 800 DEG C and 900 DEG C, so according to the amount or the per-cent that to be supplied to the reformation load heat of reforming reactor by auxiliary thermal source, the scope of the modulus of expection syngas product stream also can be increased to may between about 1.90 to 2.25 or larger.The temperature increasing the exit of OTM reactor causes the modulus of synthetic gas to reduce usually.
Point out as above-mentioned, auxiliary thermal source is configured or more preferably designs the total heat about between 15% and 85% needed for one-level reformation of the hydrocarbon containing feed stream provided in reforming reactor.Auxiliary thermal source for auxiliary oxygen transport membrane reactor as shown in Figures 1 and 2 or can comprise hereafter one or more ceramic burner as shown for example in figure 3 in greater detail.At the low side of 15% to 85% scope, the modulus of syngas product stream is about 1.90, but in the higher-end of described scope, and the modulus of syngas product stream is about between 2.10 and 2.15 or larger.The chart of phenogram 4 and be by the alternative of disclosed syngas product of producing based on the reforming system of oxygen transport membrane at present: when the heat being supplied to reforming reactor by auxiliary thermal source be to be supplied to reforming reactor total institute heat requirement 50% or less time, the modulus of syngas product stream is about between 1.85 and 2.00, and when the heat being supplied to reforming reactor by auxiliary thermal source exceedes 50% of total institute heat requirement of reforming reactor, the modulus of syngas product stream is about between 2.00 and 2.15 or larger.Point out as above-mentioned, if the temperature in reforming reactor exit raises, so the modulus of expection syngas product is increased to 2.25 or larger according to the amount of the heat being supplied to reforming reactor by auxiliary thermal source is corresponding.
Therefore, likely design and/or make the reforming system that the present invention is based on oxygen transport membrane be applicable to heat load division by regulating simply or change between oxygen transport membrane reactor and auxiliary thermal source and temperature out produces the synthetic gas with desired characteristic.Synthetic gas characteristic that is required or target must will depend on the application of synthetic gas and other system variable such as spout temperature, Methane slip (methaneslip), reactor pressure etc.
Again get back to Fig. 1, the synthesis air-flow 215 produced by oxygen transport membrane reactor 210 is generally containing hydrogen, carbon monoxide, unconverted methane, steam, carbonic acid gas and other components.Major portion from the sensible heat of synthesis air-flow 215 can use heat exchanging segment or reclaim row (recoverytrain) 250 and reclaim.Heat exchanging segment 250 is designed to cool the synthesis air-flow 215 produced leaving oxygen transport membrane reactor 210.In this Illustrative Embodiment, heat exchanging segment 250 is also designed to make while cooling syngas stream 215, produces process steam 172, hydrocarbon incoming flow 133 255 and water inlet 259 and heating boiler is intake of preheating combination.
For minimum metal dirt problem, in process gas (PG) boiler 252 by hot synthesis gas product stream 215(preferably at the temperature between about 900 DEG C and 1050 DEG C) be cooled to about 400 DEG C or less temperature.Use the mixture of initial cooling syngas product stream 254 preheating Sweet natural gas and hydrogen incoming flow 133 in feed preheater 134 subsequently, and preboiler water inlet 255 in economizer 256 subsequently, and heat feed water flow 259.In Illustrative Embodiment, boiler feed water stream 255 preferably uses the pumping of intake pump (not shown), heats and be sent to steamdrum 257 in economizer 256, and the feed water flow of heating is sent to the degasser (not shown) providing boiler feed water 255.The synthetic gas leaving feed water heater 258 is preferably about 150 DEG C.Use wing fan formula water cooler 261 and by the syngas cooler 264 of water coolant 266 charging, described synthetic gas be cooled to about 40 DEG C.Cooling syngas 270 enters separating tank (knock-outdrum) 268 subsequently, wherein water removes from bottom as process condensate logistics 271, described process condensate logistics recirculation is used as water inlet (although not shown), and cooling syngas 272 is in recovered overhead.
Final syngas product 276 is obtained by the compression of cooling syngas stream 273 in synthesic gas compressor 274.Depend on application, may stage compression be needed.Interstage cooling and condensate separation are not shown in Figure 1.But before this compression, a part for cooling syngas stream 226 optionally can be recycled to reactor enclosure to form all or part of of the hydrogeneous stream of low pressure 222.Depend on the working pressure of the reforming system based on oxygen transport membrane, the pressure of the synthetic gas of recovery preferably in the scope of about 10bar and 35bar, and more preferably in the scope of 12bar and 30bar.The modulus of the final syngas product of producing in the embodiment described in which is generally about 1.8 to 2.3.
Fig. 2 is the schematic diagram of the reforming system based on oxygen transport membrane of the Fig. 1 being applicable to methanol production process and integrating with methanol production process.In many aspects, the embodiment in the similar Fig. 1 of this embodiment, and for simplicity's sake, the description of the common aspect of two embodiments will no longer repeat herein, and following discussion concentrates in difference.Synthetic gas is compressed into about between 80 and 100bar usually in synthesic gas compressor 274.Shown in figure 2 in embodiment, final syngas product 276 mixes with methyl alcohol re-circulates stream 310.This mixed flow 320 of compressed synthesis gas and methyl alcohol re-circulates in interchanger 322 by synthesizing methanol stream 324 indirect heating to the temperature between about 175 DEG C and 300 DEG C.The stream 326 of heating is guided in methanol sythesis reactor 330.Definite heat of joining is by the method for the type according to methanol sythesis reactor, technology suppliers and whole process integration (be namely integrated with front end or synthetic gas produces section) change.In this methanol sythesis reactor 330, consume hydrogen, carbon monoxide and carbonic acid gas with in exothermic process through following reaction methanol and water:
The heat produced in methanol-fueled CLC reaction is for production of steam and/or for pre-heated synthesis gas charging.The temperature in the exit of methanol reactor is usually between about 200 DEG C and about 260 DEG C.This methanol-fueled CLC stream 324 was cooled to about 38 DEG C before entering separator 334 in interchanger 322 and water cooler 332, in separator 334 main other materials (such as dme, ethanol and higher alcohols) containing methyl alcohol, water and trace crude carbinol stream 340 bottom part from, and be sent to further distilation steps for final purifying.Most of overhead streams 336 from separator 334 is methyl alcohol re-circulates stream 344, and it returns to methanol sythesis reactor 330 to increase the transformation efficiency of carbon to methyl alcohol via recycle compressor 345.Recycle compressor 345 is needed to compensate pressure drop across methanol sythesis reactor 330 and relevant device (such as interchanger and water cooler).
The small portion (usually about between 1% and 5%) of (purged) overhead streams 336 is discharged to prevent from accumulating inert substance methanol synthesis loop 300 from methanol synthesis loop 300.The typical case of discharging current 350 is composed as follows: 75% hydrogen, 3% carbonic acid gas, 12% carbonic acid gas, 3% nitrogen and 7% methane, and the higher thermal value with about 325BTU/scf.Then methyl alcohol loop discharging current 350 splits into two streams, that is: methyl alcohol discharging current 350A, and it gets back to auxiliary oxygen transport membrane reactor 220 as hydrogeneous charging is directed; With methyl alcohol discharging current 350B, it forms hydrogen-rich gas, and this hydrogen-rich gas and hydrocarbon containing feed stream combine and combine hydrocarbon charging 133 to be formed.In Illustrative Embodiment, the hydrogeneous stream of low pressure 222 is mixtures of a part of methyl alcohol discharging current 350A and supplemental natural gas flow in fuel 224.
Fig. 3 is the schematic diagram of the alternate embodiment of reforming system based on oxygen transport membrane, and the described reforming system based on oxygen transport membrane is designed in oxygen transport membrane reactor, use the auxiliary thermal source comprising one or more ceramic burner to carry out one-level reforming process and secondary reformation process.In many aspects, this embodiment is similar to the embodiment of Fig. 2, and for simplicity's sake, the description of the common aspect of two embodiments will no longer repeat herein, and following discussion is only concentrated in difference.
Embodiment shown in Fig. 2 and the Main Differences between the embodiment of Fig. 3 are disposed near reforming reactor 200 by: the 3rd reactor driving oxygen transport membrane reactor to form by reactivity and reactively drive and one or more porous ceramic combustor (i.e. flameless burner) contained in the reactor enclosure 201 of the oxygen transport membrane reactor 210 of catalyzer is replaced.One or more ceramic burner 555 is preferably configured to use air or enriched air to burn containing lightweight hydrocarbon stream as oxygenant.When using porous ceramic combustor as auxiliary thermal source, importantly design the spatial disposition of ceramic burner relative to oxygen transport membrane reactor and reforming reactor to maximize thermal coupling and system efficiency, the mechanical complexity of minimization system simultaneously.Different from the purposes of oxygen transport membrane reactor, the purposes of the porous ceramic combustor in reactor enclosure need other design challenge and to the improvement of system to make burner fully integrated for auxiliary thermal source.This challenge and improvement can comprise provides independent oxidant stream and/or the independent fuel source for porous ceramic combustor.In addition, the start-up routine (start-upprocedures) between the embodiment using Low Pressure Oxygen transmission membrane reactor and those embodiments using one or more porous ceramic combustor and exhaust manifold (exhaustmanifolding) difference may be significant and must take in.
Although not shown in figure 3, porous ceramics or flameless burner can be preferably radiant tube type burner, and it has the tubulose similar to the oxygen transport membrane reactor tube described in Fig. 1 with Fig. 2 (wherein burning in the inside of pipe) or cylindrical structure.Another kind of ceramic burner structure is the multiple perforated tubular ceramic burner of arrangement, and wherein fuel is from the internal transmission of pipe to outside surface, and uses oxygen deprivation retentate stream to burn on the outer surface as oxygenant.Other arrangement still under consideration of auxiliary thermal source can comprise the annular array of radial direction or ring-shaped pottery burner arrangement or possibility or even burner.
Another difference between the embodiment illustrated in figs. 2 and 3 is, pipe burner 126A is arranged in the upstream of the reactor enclosure 201 in intake ducting 116 and is coupled with make-up fuel stream and/or recirculation methyl alcohol discharging current 350B.In this arrangement, the operational condition for ceramic heat regenerator 113 is not too harsh, and uses less ceramic heat regenerator 113 to save capital outlay by by permission.If necessary, then pipe burner 126A can be placed in the downstream of reactor enclosure 201 on the contrary as in fig. 2.
Although adopted various ways to show characteristic sum of the present invention describe the present invention for preferred embodiment, but as the skilled person would expect, many interpolations, changes and improvements can be carried out to it when not deviating from as claims the spirit and scope of the present invention set forth.

Claims (20)

1., for producing the method for synthetic gas in based on the reforming system of oxygen transport membrane, said method comprising the steps of:
Under the existence of the reforming catalyst be arranged in reforming reactor and heat, hydrocarbon containing feed stream of reforming in described reforming reactor is to produce reformed syngas stream;
Described reformed syngas stream is fed to reactivity to drive and the reactant side containing the oxygen transport membrane reactor of catalyzer, wherein said oxygen transport membrane reactor comprises at least one oxygen transport membrane element, described oxygen transport membrane element is configured to, when the service temperature standing to raise and the oxygen partial pressure difference across at least one oxygen transport membrane element described, by oxygen ion transport, oxygen is separated to reactant side from reactivity driving and containing the containing oxygen stream of oxidant side of the oxygen transport membrane reactor of catalyzer;
The reformed syngas stream of a part is made to react poor with the oxygen partial pressure produced across at least one oxygen transport membrane element described with the oxygen penetrating at least one oxygen transport membrane element described, and produce reaction product and heat, described heat comprises the first part of the heat needed for the reformation of described hydrocarbon containing feed stream; With
Under the existence of the one or more of catalyzer contained in described oxygen transport membrane reactor, described reaction product and described heat, the hydrocarbon gas of not reforming reformed in described reformed syngas stream is to produce syngas product stream;
The second section of the heat wherein needed for initial reformate step is by the auxiliary thermal source transmission of arranging near described reforming reactor.
2. method according to claim 1, wherein due to the reaction of described reformed syngas stream and oxygen permeable and the heat produced be passed to: (i) is present in containing the reformed syngas stream in the oxygen transport membrane reactor of catalyzer; (ii) described reforming reactor; (iii) oxygen deprivation retentate stream.
3. method according to claim 1, wherein said auxiliary thermal source is provided as the heat about between 15% and 85% needed for the initial reformate of the described hydrocarbon containing feed stream in described reforming reactor.
4. method according to claim 1, wherein said auxiliary thermal source is one or more reactive oxygen transport membrane reactor driven.
5. method according to claim 4, the oxygen transport membrane reactor that wherein said reactivity drives comprises multiple oxygen transport membrane element, described multiple oxygen transport membrane element is arranged near described reforming reactor and is configured to: (i) by oxygen ion transport, by oxygen from the oxidant side of the described oxygen transport membrane element of contact containing being separated oxygen stream and transferring to the reactant side of described oxygen transport membrane element; (ii) hydrogeneous stream is received at described reactant side joint; And (iii) make described hydrogeneous stream and the oxygen permeable in reactant side react with the oxygen partial pressure difference produced across described oxygen transport membrane element and produce assisted reaction product stream and heat.
6. method according to claim 5, wherein said hydrogeneous stream comprises the stream of hydrogen and light hydrocarbon, and by the assisted reaction product stream leaving described reactant side as a supplement fuel-feed to pipe burner or fired heater or be somebody's turn to do both.
7. method according to claim 5, one or more reactive oxygen transport membrane reactor driven wherein said is configured to receive the hydrogeneous stream of low pressure at described reactant side joint, and the pressure of described hydrogeneous stream is about 3bar or less.
8. method according to claim 5, its comprise further a part for described syngas product stream is fed to described oxygen transport membrane element reactant side to form the step of all or part of hydrogeneous stream.
9. method according to claim 5, is wherein used for methanol-fueled CLC equipment by produced synthetic gas, and described hydrogeneous stream comprises further from the part in the discharging current of described methanol-fueled CLC equipment.
10. method according to claim 1, wherein said hydrocarbon containing feed stream is pre-reforming incoming flow.
11. methods according to claim 10, wherein said hydrocarbon containing feed stream in the pre-reformer of adiabatic pre-reformer or heating by pre-reforming.
12. methods according to claim 1, wherein said auxiliary thermal source is one or more ceramic burner, the oxygen transport membrane reactor of one or more ceramic burner described near described reforming reactor and described reactivity driving and containing catalyzer is arranged, one or more ceramic burner described is configured to the stream using air or enriched air to burn containing light hydrocarbon as oxygenant.
13. based on the reforming system of oxygen transport membrane, and described reforming system comprises:
Reactor enclosure;
Reforming reactor, it is arranged in described reactor enclosure, and is configured under the existence of the reforming catalyst be arranged in described reforming reactor and heat, and reformation hydrocarbon containing feed stream is to produce reformed syngas stream;
The reactive oxygen transport membrane reactor driven, it is arranged in described reactor enclosure near described reforming reactor, and be configured to receive described reformed syngas stream and make a part for described reformed syngas stream and oxygen permeable react and produce reaction product and heat, described heat comprises the first part of the heat needed for described reforming reactor;
Any hydrocarbon gas do not reformed reformed in described reformed syngas stream under the existence of heat and described reaction product described in some that what wherein said reactivity drove be configured to produce in the reaction by described reformed syngas stream and oxygen permeable containing the oxygen transport membrane reactor of catalyzer further, with production syngas product stream; With
Auxiliary thermal source, it is arranged in described reactor enclosure near described reforming reactor, and is configured to supply the second section that described reforming reactor produces the heat needed for described reformed syngas stream;
The modulus of wherein said syngas product stream about between 1.85 and 2.15 or larger, and depends on reforming reactor temperature out and is supplied to the amount of heat of described reforming reactor by described auxiliary thermal source.
14. systems according to claim 13, the oxygen transport membrane reactor that wherein said reactivity drives comprises multiple oxygen transport membrane pipe containing catalyzer further, oxidant side and reactant side are determined in described oxygen transport membrane area within a jurisdiction, and be configured to, when the service temperature standing to raise and the oxygen partial pressure difference across at least one oxygen transport membrane pipe described, by oxygen ion transport, oxygen is separated to described reactant side from containing oxygen stream of the described oxidant side of contact; With
The oxygen transport membrane reactor that wherein said reactivity drives be configured to further one or more of catalyzer and produced by described reformed syngas stream and the reaction of oxygen permeable on described reactant side some described in heat existence under the hydrocarbon gas do not reformed reformed in described reformed syngas stream, to produce described syngas product stream.
15. systems according to claim 13, the hydrogen of wherein said syngas product stream and carbon monoxide ratio (H 2/ CO) about between 2.95 and 3.10 or larger, and depend on temperature in the exit of described reforming reactor and be supplied to the amount of heat of described reforming reactor by described auxiliary thermal source.
16. systems according to claim 13, the carbon monoxide of wherein said syngas product stream and carbon dioxide ratio (CO/CO 2) about between 2.50 and 3.30 or larger, and depend on temperature in the exit of described reforming reactor and be supplied to the amount of heat of described reforming reactor by described auxiliary thermal source.
17. systems according to claim 13, wherein said auxiliary thermal source comprises one or more auxiliary oxygen transport membrane reactor further, and described auxiliary oxygen transport membrane reactor is configured to the heat about between 15% and 85% needed for reformation of the described hydrocarbon containing feed stream be provided as in described reforming reactor.
18. systems according to claim 13, wherein said auxiliary thermal source comprises one or more ceramic burner further, one or more ceramic burner described is configured to use air or enriched air to burn containing the stream of light hydrocarbon as oxygenant, and is provided as the heat about between 15% and 85% needed for reformation of the described hydrocarbon containing feed stream in described reforming reactor.
19. systems according to claim 13, wherein when the second section of the heat being supplied to described reforming reactor by described auxiliary thermal source be to be supplied to described reforming reactor total institute heat requirement 50% or less time, the modulus of described syngas product stream is about between 1.85 and 2.00; And when the second section of the heat being supplied to described reforming reactor by described auxiliary thermal source exceed to be supplied to described reforming reactor total institute heat requirement 50% time, the modulus of described syngas product stream depends on that the temperature in the exit of described reforming reactor is about between 2.00 and 2.15 or larger.
20. systems according to claim 13, described system comprises pre-reformer further, described pre-reformer is arranged in described reforming reactor upstream, and is configured to hydrocarbon containing feed stream described in pre-reforming, and wherein said pre-reformer is the pre-reformer of adiabatic pre-reformer or heating.
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