CN103249815B

CN103249815B - The hydrogenation methanation of carbon containing feed

Info

Publication number: CN103249815B
Application number: CN201180052570.XA
Authority: CN
Inventors: P.K.拉曼; V.吉拉迪罗克; E.T.罗宾逊; A.瑟德什潘德
Original assignee: Greatpoint Energy Inc
Current assignee: Shunguan Investment Co., Ltd
Priority date: 2010-11-01
Filing date: 2011-10-28
Publication date: 2016-08-24
Anticipated expiration: 2031-10-28
Also published as: KR20130109173A; JP2013541622A; WO2012061238A1; CN103249815A; US20120102837A1; EP2635660A1; CA2814201A1; AU2011323648A1

Abstract

The method that the present invention relates to carbon containing feed hydrogenation methane is melted into the synthesis gas of methane rich, wherein gas stream and the carbon containing feed of oxygen rich air are inputted in fluidized-bed hydrogenation methanator, and wherein when inputting this hydrogenation methanator, this carbon containing feed has high water capacity, it is therefore an objective to such as contribute to the heat management in this hydrogenation methanator.

Description

The hydrogenation methanation of carbon containing feed

Invention field

The method that the present invention relates to carbon containing feed hydrogenation methane is melted into the synthesis gas of methane rich, wherein by the gas of oxygen rich air In body stream and carbon containing feed input fluidized-bed hydrogenation methanator, and wherein when inputting this hydrogenation methanator This carbon containing feed has high water capacity, it is therefore an objective to such as contribute to the heat management in this hydrogenation methanator.

Background of invention

Due to the most higher energy prices of factors and environmental concern, low fuel the carbon containing feed being worth is (such as Petroleum coke, Residual oil, asphalitine, coal and biomass) produce value-added product (such as pipeline quality substitute natural gas, hydrogen, first Alcohol, higher hydrocarbon, ammonia and electric energy) again it is of concern.

Such low fuel is worth carbon containing feed and can gasify at high temperature and pressure production of synthetic gas stream in next life, and it subsequently may be used To change into such value-added product.

A kind of favourable gasification process is hydrogenation methanation, wherein by carbon containing feed at fluidized-bed hydrogenation methanator In, directly it is converted in the presence of the catalyst source being in suitable high temperature and high pressure and steam and produces the synthesis air-flow of methane rich (middle BTU synthesizes air-flow) crude product.This differs markedly from the gasification process of routine, such as based on carbon source at high temperature and pressure Those methods (thermal evaporation, it is typical that non-catalytic) of part burning/oxidation, wherein synthesis gas (carbon monoxide+hydrogen) is Primary product (little or no direct generation methane), then it can be further processed to produce methane (via catalytic methane Change, see following reaction (III)) perhaps other higher hydrocarbon products many.

The synthesis air-flow of the methane rich that hydrogenation methanation process and conversion/utilization are formed is disclosed in produce value-added product Such as US3828474, US3958957, US3998607, US4057512, US4092125, US4094650, US4204843, US4243639, US4468231, US4500323, US4541841, US4551155, US4558027, US4606105, US4617027, US4609456, US5017282, US5055181, US6187465, US6790430, US6894183, US6955695, US2003/0167961A1, US2006/0265953A1, US2007/000177A1, US2007/083072A1, US2007/0277437A1, US2009/0048476A1, US2009/0090056A1, US2009/0090055A1, US2009/ 0165383A1, US2009/0166588A1, US2009/0165379A1, US2009/0170968A1, US2009/ 0165380A1, US2009/0165381A1, US2009/0165361A1, US2009/0165382A1, US2009/ 0169449A1, US2009/0169448A1, US2009/0165376A1, US2009/0165384A1, US2009/ 0217582A1, US2009/0220406A1, US2009/0217590A1, US2009/0217586A1, US2009/ 0217588A1, US2009/0218424A1, US2009/0217589A1, US2009/0217575A1, US2009/ 0229182A1, US2009/0217587A1, US2009/0246120A1, US2009/0259080A1, US2009/ 0260287A1, US2009/0324458A1, US2009/0324459A1, US2009/0324460A1, US2009/ 0324461A1, US2009/0324462A1, US2010/0071235A1, US2010/0071262A1, US2010/ 0120926A1, US2010/0121125A1, US2010/0168494A1, US2010/0168495A1, US2010/ 0179232A1, US2010/0287835A1, US2011/0031439A1, US2011/0062012A1, US2011/ 0062722A1, US2011/0062721A1, US2011/0064648A1, US2011/0088896A1, US2011/ 0088897A1, US2011/0146978A1, US2011/0146979A1, US2011/0207002A1, US2011/0217602A1 With in GB1599932.Referring also to Chiaramonte et al., " Upgrade Coke by Gasification ", Hydrocarbon Processing, nineteen eighty-two JIUYUE the 255-257 page；With Kalina et al., " Exxon Catalytic Coal Gasification Process Predevelopment Program, Final Report ", Exxon Research And Engineering Co., Baytown, TX, FE236924,1978 year December.

The hydrogenation methanation of carbon source typically comprises four reactions the most separate:

Steam carbon: C+H₂O → CO + H₂ (I)

Water-gas shift: CO+H₂O →H₂ + CO₂ (II)

CO methanation: CO+3H₂ → CH₄ + H₂O (III)

Hydrogasification: 2H₂ + C → CH₄ (IV)

In this hydrogenation methanation reaction, before three reactions (I-III) mainly resulted in following W-response:

2C +2H₂O → CH₄ + CO₂ (V)。

This entirety hydrogenation methanation reaction is the most thermally equilibrated；But, owing to process heat loss and other energy Demand (such as evaporates the energy needed for the dampness entering in reactor with feed), it is necessary to adds some heat and keeps heat flat Weighing apparatus.

This reaction is also (produces and consume synthesis gas) that essentially synthetic gas (hydrogen and carbon monoxide) balances；So, When carbon monoxide and hydrogen take out together with product gas, it is necessary to as required carbon monoxide and hydrogen are joined in reaction To avoid deficiency.

In order to keep the clean hot as close possible to neutral (only marginally heat release or heat absorption) of reaction, and keep synthesis gas Balance, often inputs the overheated gas stream of steam, carbon monoxide and hydrogen in this hydrogenation methanator.Often, an oxygen Change carbon and hydrogen stream is the recirculation flow separated from product gas, and/or the product first by a reformation/partial oxidation part Alkane provides.See for example US4094650, US6955595 and the US2007/083072A1 being previously incorporated.

In a kind of variant of this hydrogenation methanation process, required carbon monoxide, hydrogen and heat energy can also pass through will Oxygen input hydrogenation methanator to produce in situ at least in part.See for example the US2010/ being previously incorporated 0076235A1 and US2010/0287835A1 and US patent application 13/211476 (attorney docket FN-owned together 0063 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock), its applying date is On August 17th, 2011；With own together US provisional application 13/228821 (attorney docket FN-0064 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock), it is that JIUYUE in 2011 is applied on the 9th.

Result is that the crude product gas stream of " directly " methane rich also contains a large amount of hydrogen, carbon monoxide and carbon dioxide, its Can such as be directly used as the middle BTU energy, maybe can process and produce multiple high value products stream, alternative such as pipeline quality Natural gas, high-purity hydrogen, methanol, ammonia, higher hydrocarbon, carbon dioxide (for the oil recovery rate improved and industrial use) and electricity Energy.

In the variant of above-mentioned hydrogenation methanation process, wherein oxygen input reactor will produce a required oxidation Carbon, hydrogen and heat energy are used for this hydrogenation methanation reaction, and main focus is to form focus, and control and distribution by The heat energy that oxidation reaction produces.It (is sometimes calamity that the heat management of the difference in hydrogenation methanator such as can cause too early Difficulty) failure of apparatus, and the caking of carbonaceous material.

Therefore, the problem of heat management in hydrogenation methanator that solves is correct operation and optimization hydrogenation methanation process A key issue, the invention provides a kind of solution for this heat management problems.

Summary of the invention

On the one hand, the present invention provides the side of a kind of crude product gas stream being produced methane rich by on-gaseous carbonaceous material Method, the method comprising the steps of:

A () supplies in hydrogenation methanator

(1) derived from the carbon containing feed of described on-gaseous carbonaceous material,

(2) hydrogenation methanation catalyst,

(3) flow of superheated steam, and

(4) the gas stream of oxygen rich air,

Wherein this hydrogenation methanator comprises fluid bed, and described fluid bed has the top higher than bottom, and wherein The gas stream of this flow of superheated steam and oxygen rich air is incorporated into this bottom of this fluid bed；

B (), at a temperature of object run, in the presence of hydrogenation methanation catalyst, carbon monoxide, hydrogen and steam, makes This carbon containing feed of a part in this hydrogenation methanator reacts, burnt with the thick gas and solid by-product producing methane rich Compound, wherein the thick gas of this methane rich comprises methane, carbon monoxide, hydrogen, carbon dioxide, hydrogen sulfide, steam, heat energy and folder The fines of band；With

C () makes a part of carbon containing feed and oxygen reaction to produce carbon monoxide, hydrogen and heat energy；

Wherein:

I the reaction of () step (b) accounts for leading on fluid bed top；

(ii) reaction of step (c) accounts for leading in fluid bed bottom；With

(iii) this carbon containing feed comprises from more than 10wt% to about 25wt% when being supplied to and being hydrogenated with methanator The high water capacity of (gross weight based on this carbon containing feed), it reaches such degree, i.e. making this carbon containing feed is substantially Free-pouring.

The method of the present invention may be used for such as by various carbonaceous materials to produce high value products and by-product.

In addition to heat management problems, the ability inputted by the carbon containing feed of higher water capacity in hydrogenation methanation improves The whole efficiency of described method, this is owing to such as decreasing necessary in feed preparation being dried, as will be detailed below further As discussing in detail.

These and other embodiments of the present invention, feature and advantage will be by reading detailed description below for these Become more clearly understood from for skilled person.

Brief Description Of Drawings

Fig. 1 is a kind of embodiment of the method for the crude product gas stream for producing methane rich of the present invention.

Fig. 2 is for being processed further the crude product stream of methane rich to produce one or more value-added product, such as hydrogen, generation With natural gas and/or electric energy, a kind of embodiment.

Describe in detail

The present invention relates to the method for on-gaseous carbonaceous material being eventually converted into one or more increment gaseous products. Provide below further details.

In the context of the present specification, point out without outer, whole open source literature the most mentioned herein, specially Profit application, patent and other lists of references are all expressly incorporated herein with their totality, for all mesh explicitly by introducing Just as illustrating completely as.

Unless otherwise defined, whole scientific and technical terminology used herein has the technology people with the application art The identical implication that member is generally understood.In the case of contradiction, it is as the criterion with the application documents (including definition) of the application.

Unless the most dated, otherwise trade mark represents with capitalization.

Unless otherwise stated, what whole percentage rate, number, ratio etc. were by weight.

Unless otherwise stated, the pressure be given with psi unit is gauge pressure, the pressure represented with kPa unit is absolute Value.

When a certain amount, concentration or other values or parameter are to be given with scope, or when string higher limit and lower limit are given, This is understood to specifically disclose by any pair of whole scope formed of any upper and lower bound, irrespective of whether point Do not disclose described scope.In place of here refer to a range of numerical value, unless otherwise directed, the most described scope is intended to Including its end points, and whole integers in such range and mark.When the range of definition, its purpose is not intended to the present invention Scope be limited to described occurrence.

When term " about " is for representing the end points of value or scope, the present invention should be understood to include described occurrence Or end points.

As used herein, term " comprises ", " comprising ", " including ", " including ", " having ", " having " or Its other change any is intended to cover non-exclusive inclusions.Such as, a kind of processing, method, the goods of string key element are comprised Or equipment need not be limited only to those key elements, but other key element being not expressly set out or these processing, side can be included The key element that method, goods or equipment are intrinsic.

Additionally, unless the contrary is expressly indicated otherwise, otherwise "or" and "and/or" refer to a kind of inclusive or, rather than Exclusiveness.Such as, condition A or B, or A and/or B meet following any one: A and be genuine (or existence) and B is False (or non-existent), A is false (or non-existent) and B is genuine (or existence), and A and B both are all It it is genuine (or existence).

" one " or " a kind of " that is used for describing various key elements herein and component is only used to conveniently, and provides one As open in implication.This description should be read as including one or at least one, and unless its implication is it is obvious that no Then this odd number the most also includes plural number.

As used herein, unless the most defined otherwise, otherwise term " substantially " represents being carried more than about 90% And material, the mentioned material of preferably above about 95%, and the mentioned material of more preferably greater than about 97%.Without rule Fixed, then percentage ratio when mentioning molecule (such as methane, carbon dioxide, carbon monoxide and hydrogen sulfide) based on mole, otherwise Based on weight (such as the fines carried secretly).

As used herein, unless the most defined otherwise, otherwise term " major part " represent more than 50% mentioned Material.Without regulation, then percentage ratio is mentioning molecule (such as hydrogen, methane, carbon dioxide, carbon monoxide and sulfuration Hydrogen) time based on mole, otherwise based on weight (such as to the fines carried secretly).

Term " lean " declines synonym with from the amount of being initially present.From fluid, such as remove most a kind of material will produce The stream of lean material, its leanest described material.Contrary, term " rich " be more than the amount of being initially present synonym.

As used herein, term " carbon containing " and hydrocarbon synonym.

As used herein, term " carbonaceous material " is the material containing organic hydrocarbon composition.According to definition here, contain Material with carbon element can be divided into biomass or abiotic material.

As used herein, term " biomass " refers to derive from the organic of (such as passing by 100 years) work recently The carbonaceous material of body, including plant base biomass and animal based biomass.For the sake of clarity, biomass do not include that fossil base contains Material with carbon element such as coal.For example, see US2009/0217575A1, US2009/0229182A1 and US2009/ of being previously incorporated 0217587A1。

As used herein, term " plant base biomass " represents and derives from material below: green plants, farming Thing, algae and tree, such as but not limited to sugar grass, bagasse, Caulis Sacchari sinensis, bamboo, Hybrid poplar, hybridization willow, silk tree (albizia Tree), Eucalyptus, Herba Medicaginis, Herba Medicaginis, Elaeis guineensis Jacq., switchgrass, arabian cron (sudangrass), Semen setariae, Jatropha curcas (jatropha) and awns Grass (miscanthus) (the huge awns of such as triploid (miscanthus xgiganteus)).Biomass farther include from agriculture Industry plantation, the refuse processed and/or degrade, such as corncob and skin, corn stalk, Caulis et Folium Oryzae, shuck, vegetable oil, Canola oil (canola oil), rapeseed oil, biodiesel, bark, wood flour, sawdust and plant waste.

As used herein, term " animal based biomass " represents by animal cultivation and/or utilizes produced refuse. Such as biomass include but not limited to refuse such as animal manure, birds droppings, poultry garbage, Animal fat from livestock culturing and processing With municipal solid waste (such as effluent sewerage).

As used herein, within term " abiotic matter " represents not included in term defined here " biomass " Those carbonaceous materials.The most abiotic matter include but not limited to anthracite, bituminous coal, ub-bituminous coal, brown coal, petroleum coke, asphalitine, Liquid petroleum residue or its mixture.For example, see US2009/0166588A1, US2009/0165379A1, US2009/ 0165380A1, US2009/0165361A1, US2009/0217590A1 and US2009/0217586A1.

" liquid heavy hydrocarbon material " is viscous liquid or semisolid material, and it is the most flowable or can be at height Flowing is produced under the conditions of temperature.These materials are the residues typically processed from hydrocarbon material (such as crude oil).Such as in crude oil essence In refining, first step is typically distillation so that complicated hydrocarbon mixture is separated into different volatile fraction.Typically first step Distillation needs under atmospheric pressure heating evaporation hydrocarbon as much as possible composition to be less than the actual temperature of about 650 °F, because relatively High temperature can cause thermal decomposition.The fraction the most not distilled is commonly referred to as " air petroleum residues ".This level Dividing and can distill the most under vacuo, the actual temperature of the highest about 650 °F can evaporate more material.Remaining Pot liquor is not referred to as " vacuum petroleum residues ".Both air petroleum residues and vacuum petroleum residues are at this Liquid heavy hydrocarbon material it is considered as in bright.

The not limiting example of liquid heavy hydrocarbon material includes vacuum resid；Air Residual oil；The oil of heavy and reduction is former Oil；Colophonium, pitch and Colophonium (naturally occurring and formed by petroleum refining scheme)；Tar sand oils；Shale oil；Catalysis is split The residue of change method；Coal liquefaction residue；With other hydrocarbon feed streams containing substantial amounts of heavy or cohesive material, such as pertroleum wax Fraction.

As used herein, term " asphalitine " is the aromatic carbonaceous solid when room temperature, and can be derived from example As crude oil and crude oil Tar sands are processed.Asphalitine can also be considered as liquid heavy feed hydrocarbon.

This liquid heavy hydrocarbon material can comprise a small amount of solid carbon-containing material, such as petroleum coke and/or solid inherently Asphalitine, it is usually dispersed in liquid heavy hydrocarbon substrate, and in the hot conditions of the feeding conditions as the inventive method Under remain solid.

As used herein, term " petroleum coke " includes consolidating of the high boiling hydrocarbon fraction that (i) obtain in PETROLEUM PROCESSING Body heat catabolite (heavy residue " Residual oil petroleum coke ")；(ii) the solid thermal catabolite (tar sand of prepared tar sand Or oil-sand " Tar sands petroleum coke ") the two.Such carbonized product includes the most unprocessed, calcining, needle-like and fluid bed Petroleum coke.

Residual oil petroleum coke can also be derived from crude oil, such as by for upgrading heavy-gravity residual crude oil (such as liquid Petroleum residues) coking method derive, this petroleum coke comprises ash as microcomponent, the most about 1.0wt% or more Little, the most about 0.5wt% or less, weight based on coke.Typically, the ash master in such low ash coke Metal to be comprised, such as nickel and vanadium.

Tar sands petroleum coke can be derived from oil-sand, such as by deriving for the coking method of upgrading oil-sand.Tar Sandstone oil coke comprises ash as less component, it is typical that about 2wt%-about 12wt%, and the most about 4wt%-about 12wt%, gross weight based on Tar sands petroleum coke.Typically, in such high ash coke, ash mainly wraps Containing material such as silicon dioxide and/or aluminium oxide.

Petroleum coke can comprise at least about 70wt% carbon, at least about 80wt% carbon, or at least about 90wt% carbon, based on The gross weight of petroleum coke.Typically, petroleum coke comprises the inorganic compound less than about 20wt%, weight based on petroleum coke.

As used herein, term " coal " represents mud coal, brown coal, ub-bituminous coal, bituminous coal, anthracite or its mixture.? In some embodiment, the carbon content of this coal is less than about 85%, or less than about 80%, or less than about 75%, or less than about 70%, or less than about 65%, or less than about 60%, or less than about 55%, or less than about 50% weight, based on total coal weight Amount.In other embodiments, the carbon content height of this coal to about 85%, or high to about 80% or high to about 75% weight, Based on total coal weight.The example of available coal includes but not limited to Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon and Powder River Basin (PRB) coal.Anthracite, bituminous coal, ub-bituminous coal and brown coal can be distinguished Comprise about 10wt%, about 5-about 7wt%, about 4-about 8wt% and the ash of about 9-about 11wt%, based on coal total Dry weight.But, the content of ashes in any concrete coal source will depend upon which grade and the source of coal, and this is that those skilled in the art know 's.See for example " Coal Data:A Reference ", Energy Information Administration, Office Of Coal, Nuclear, Electric and Alternate Fuels, U.S.Department of Energy, DOE/ EIA-0064 (93), February nineteen ninety-five.

Ash produced by coal combustion typically comprises both flying dust and bottom ash, and this is well known to those skilled in the art. Flying dust from bituminous coal can comprise the silicon dioxide of about 20-about 60wt% and the aluminium oxide of about 5-about 35wt%, base Gross weight in flying dust.Flying dust from ub-bituminous coal can comprise the silicon dioxide of about 40-about 60wt% and about 20-is big The aluminium oxide of about 30wt%, based on flying dust gross weight.Flying dust from brown coal can comprise the titanium dioxide of about 15-about 45wt% The aluminium oxide of silicon and about 20-about 25wt%, gross weight based on flying dust.See for example Meyers et al. " Fly Ash. A Highway Construction Material, " Federal Highway Administration, Report No.FHWA-IP-76-16, Washington, DC, 1976.

Bottom ash from bituminous coal can comprise the silicon dioxide of about 40-about 60wt% and about 20-about 30wt%'s Aluminium oxide, gross weight based on bottom ash.Bottom ash from ub-bituminous coal can comprise about 40-about 50wt% silicon dioxide and The aluminium oxide of about 15-about 25wt%, gross weight based on bottom ash.Bottom ash from brown coal can comprise about 30-about The silicon dioxide of 80wt% and the aluminium oxide of about 10-about 20wt%, gross weight based on bottom ash.See for example Moulton, Lyle K. " Bottom Ash and Boiler Slag, " Proceedings of the Third International Ash Utilization Symposium, U.S.Bureau of Mines, Information Circular No.8640, Washington, DC, 1973.

Under superincumbent definition, according to its source, material (such as methane) can be biomass or abiotic matter.

" on-gaseous " material is substantially liquid, semisolid, solid or mixture at ambient conditions.Such as coal, oil Jiao, asphalitine and liquid petroleum residue are non-gaseous material, and methane and natural gas are gaseous materials.

Term " unit " refers to unit operation.When describe existence more than one " unit " time, unless otherwise directed, that A little unit run in a parallel manner.But, single " unit " can comprise the series connection more than or parallel units, this Depend on context.Such as, sour gas removal unit can comprise hydrogen sulfide removal unit, is in series with carbon dioxide subsequently and goes Except unit.As another example, pollutant removal unit could be included for the first removal unit of first pollution thing, goes here and there subsequently It is associated with the second removal unit for the second pollutant.As another example, compressor can comprise the first compressor and will flow Body is compressed to the first pressure, is in series with the second compressor subsequently, comes further by fluid compression to second (higher) pressure.

Term " a part of carbon containing feed " refers to the carbon component of the feed of unreacted and partial reaction, and can Completely or partially derived from other components (such as carbon monoxide, hydrogen and methane) of this carbon containing feed.Such as " a part of carbon containing Feed " include the carbon component that is likely to be present in the fines of by-product carbonizing matter and recirculation, this carbonizing matter fundamentally derived from Initial carbon containing feed.

In the context of the present invention, term " superheated steam " refers to the most incoagulable steam stream.

Term " synthesis gas demand " refers to keep synthesis in the hydrogenation methanator of the reaction for step (b) Gas balances.As it has been described above, be hydrogenated with methanation reaction (seeing above equation (I), (II) and (III)) in the stable state that entirety is desirable In, hydrogen and carbon monoxide be relative equilibrium produce and consume.Because hydrogen and carbon monoxide both of which are as gaseous state A part for product is taken out, and therefore at least to need to be kept substantially the amount of this molecular balance, joins and/or at hydrogenation Methanator situ produces (as described below, burning/oxidation reaction) via with the oxygen supplied hydrogen and an oxygen Change carbon.In the present invention, it is necessary to join and/or result from the hydrogen and one in hydrogenation methanation reaction (step (b)) in situ The amount of carbonoxide is " synthesis gas demand ".

Term " steam demand " refers to the amount that must be added to be hydrogenated with the steam in methanator.At hydrogenation methane Change and reaction consumes steam, it is therefore necessary in this hydrogenation methanator, add some steam.For 2mol every in feed Carbon produce 1mol methane and 1mol carbon dioxide for, it is 2mol formula V such as () seeing that steam theoretical consumes.In reality In practice, steam consumption not optimum efficiency, and steam taken out together with product gas；It is therefore desirable to will be greater than theory The steam of amount joins in hydrogenation methanator, and this addition is " steam demand ".Steam can be such as via overheated steaming The gas stream of steam flow and oxygen rich air adds.Steam addition (and source) is discussed in further detail below.By carbon containing feed The steam that produces in situ (such as come from the evaporation of any dampness of carbon containing feed, or come from carbon containing feed in exist or The oxidation reaction of the hydrogen, methane and/or other hydrocarbon that produce) can help to meet steam demand；However, it is to be noted that Will less than resulting from or input any steam in hydrogenation methanator at a temperature of hydrogenation methanation reaction temperature in situ Hydrogenation methanation reaction " heat demand " can be affected.

Term " heat demand " refers to must be added to be hydrogenated with methanator and produce (such as via step in situ The reaction of (c)) reaction of step (b) is maintained at the most thermally equilibrated thermal energy its, as discussed above and following As being discussed in further detail.

Although may be used for practice or the test of the present invention similar or equivalent to those described herein method and material In, but there is described herein suitable method and material.Material, method and embodiment the most herein are merely exemplary , and except there being clear stipulaties, be otherwise non-determinate.

General machining information

In one embodiment of the present invention, the crude product gas stream (50) of methane rich is fundamentally by on-gaseous carbon containing Material (10) produces, as shown in Figure 1.

According to a kind of embodiment of the present invention, on-gaseous carbonaceous material (10) is added in feedstock preparation unit (100) Work, to produce carbon containing feed (32), is inputted catalyst applying unit (350), here applies hydrogenation methanation catalyst Produce the carbon containing feed (31+32) of catalysis.This hydrogenation methanation catalyst typically comprises from recycle catalyst stream (57) catalyst recycle and the supplementary catalyst from supplementary catalyst stream (56).Further details are presented below.

By the carbon containing feed (31+32) of this catalysis and flow of superheated steam (12), the gas stream (14) of oxygen rich air and optionally Cross hot synthesis gas feed streams (16) to input together in hydrogenation methanator (200).This flow of superheated steam (12) and optional Crossing hot synthesis gas feed streams (16) can be that (it comprises steam and heat energy, and optionally hydrogen and an oxidation to single feed streams Carbon) or multiple feed streams (its gas stream (14) with oxygen rich air and heat energy, synthesis gas and the steam combination of generation in situ, comprise Steam and heat energy, and optionally hydrogen and carbon monoxide), as desired at least substantially meet or at least meet at hydrogenation The hydrogenation synthesis gas of methanation reaction, steam and the heat demand carried out in methanator (200).

In one embodiment, such as US patent application 13/211476 (the attorney docket FN-0063 US owned together NP1, entitled Hydromethanation of a Carbonaceous Feedstock, filing date on August 17th, 2011) Disclosed, there is not optional hot synthesis gas feed streams (16) of crossing, and be catalyzed carbon containing feed (31+32), superheated steam The gas stream (14) of stream (12) and oxygen rich air all inputs at a temperature of the object run temperature less than hydrogenation methanation reaction In hydrogenation methanator (200).

According to the present invention, carbon containing feed (32), such as the carbon containing feed (31+32) of catalysis, it is the most free-pouring, and And be hydrogenated with in methanator (200) with the input of high water capacity, as discussed in further detail below.

This hydrogenation methanator (200) comprises fluid bed (202), and this fluid bed has top (202b) and bottom (202c) reaction of step (b) and step (c), is carried out wherein.It is not only restricted to any concrete theory, the reaction of step (b) (hydrogenation methanation reaction) accounts for leading at top (202b), and the reaction (oxidation reaction) of step (c) accounts for master at bottom (202c) Lead.It is believed that the boundary that there is not clear stipulaties, and be as oxygen consumption in bottom (202c) (with And heat energy and the generation of synthesis gas), there is transition.It is also believed that under the conditions of present in hydrogenation methanator (200) Oxygen consumes quickly；So, the major part of fluid bed (202) will be top (202b).

The gas stream (14) of this flow of superheated steam (12) and oxygen rich air can input hydrogenation methanator (200) respectively In, but typically merged before the bottom (202c) of input fluid bed (202).In one embodiment, introducing During to lower area (202c) of fluid bed (202), the temperature of two kinds of fluids (individually and in combination) will be less than step (b) The object run temperature of reaction.

This carbon containing feed at least some of in fluid bed (202) bottom (202c) by with the gas stream from oxygen rich air (14) oxygen reaction produces heat energy, and hydrogen and carbon monoxide (synthesis gas), presents in an amount at least sufficient to ideally meet step (b) The hydrogenation heat of methanation reaction and synthesis gas demand (do not used in the steady-state operation of the method ideally and individually crossed heat seal Become gas feed streams (16)).This includes coming from unreacted (fresh) feed, the feed of partial reaction (such as carbonizing matter and follows again Ring fines) solid carbon, and the gas (one in the bottom (202c) that can be produced from or be carried by feed and recirculation fines Carbonoxide, hydrogen, methane and higher hydrocarbon) reaction.Some water (steam), and other by-products such as dioxy would generally be produced Changing carbon, this depends on the degree of burning/oxidation.

In hydrogenation methanator (200) (mainly in the top (202b) of fluid bed (202)), carbon containing feed, Steam, hydrogen and carbon monoxide react in the presence of hydrogenation methanation catalyst, produce the crude product of methane rich, and it is finally made Crude product stream (50) for methane rich is taken out from hydrogenation methanator (200).

The reaction in fluid bed (202) of the carbon containing feed also creates by-product carbonizing matter, its comprise come from carbon containing to The unreacted carbon of material (including being hydrogenated with methanation catalyst) and non-carbon components, as described in further detail below. In order to prevent residue accumulation in hydrogenation methanator (200), take out pipeline (58) by by-product via carbonizing matter The purge of solids (solid purge) of carbonizing matter is customary takes out (occurs either periodically or continuously).

In one embodiment of the present invention, as own together and be in previously incorporated US provisional application _ _/_ _ _, _ _ _ (attorney docket FN-0065 US PRV, entitled Hydromethanation of a Carbonaceous Feedstock, Application simultaneously) disclosed in, carbon containing feed (32) (or carbon containing feed (31+32) of catalysis) is also entered into fluid bed (202) Bottom (202c).Because the carbon containing feed (31+32) of catalysis is introduced in the bottom (202c) of fluid bed (202), therefore burnt Compound is taken out pipeline (58) and be will be located in a bit, so that by-product carbonizing matter is in the confession of the carbon containing feed (31+32) higher than catalysis One or more on material position take out from fluid bed (202), typically take from the top (202b) of fluid bed (202) Go out.

In such an implementation, the carbon containing feed (31+32) owing to catalysis enters hydrogenation methanator (200) Relatively low confession shots, and the off-take point that by-product carbonizing matter is higher from hydrogenation methanator (200), be hydrogenated with methanation Reactor (200) will be in flowing up structure as discussed below.

Hydrogenation methanator (200) also typically comprises the region (206) being positioned under fluid bed (202), and These two regions separate typically via Turbogrid plates (208) or spacer.Can not fluidize in fluidized bed region (202) too greatly Particle, the biggest particle byproducts carbonizing matter and the most flowable aggregate are typically collected in the bottom of fluid bed (202) (202c), and in region (206).Such particle typically comprises carbon component (and ash and catalyst component), and can To take out pipeline (58) and (58a) from hydrogenation methanator via the carbonizing matter reclaimed for catalyst as described below (200) periodically remove in.

Typically, before taking out from hydrogenation methanator (200), the crude product of this methane rich is passed through fluidisation Initially-separate district (204) more than bed region (202).Disengagement zone (204) is optional comprises the most one or more inside Cyclone separator and/or other carry separate particles mechanism secretly.The crude product gas of " taking-up " (discussion seen below) methane rich Stream (50) typically comprises at least methane, carbon monoxide, carbon dioxide, hydrogen, hydrogen sulfide, steam, heat energy and the fines carried secretly.

First the crude product gas stream (50) of this methane rich carry out processing the most fines carried secretly of removing, the most logical Cross cyclone separator component (360) (the most one or more internally and/or externally cyclone separator) to carry out, if it is desired, The other process of choosing can be taken over after it, such as Venturi scrubber, as discussed in greater detail.It is somebody's turn to do " taking-up " The crude product gas stream (50) of methane rich be therefore considered as fines separate before crude product, regardless of be hydrogenation methanation Reactor (200) internally and/or externally carry out fines separation.

As Fig. 1 clearly shown in, the crude product stream (50) of methane rich is delivered to whirlwind is divided from hydrogenation methanator (200) The particle carried secretly is separated from device assembly (360).Although in order to concisely, in FIG cyclone separator component (360) is expressed as Single external cyclone, but cyclone separator component (360) as above can be that internally and/or externally whirlwind divides From device, and it can also be a series of multiple internally and/or externally cyclone separator.

The crude product gas stream (50) of this methane rich is processed in cyclone separator component (360) and produces lean fines richness The crude product gas stream (52) of methane and the fines stream (362) of recovery.

The fines stream (362) reclaimed can be hydrogenated with for defeated time in methanator (202), such as via fines recirculation pipe Defeated time fluid bed (202) top (202b) of line (364), and/or via defeated time fluid bed (202) of fines recirculation line (366) Bottom (202c) (the US provisional application 13/228821 such as owned together (attorney docket FN-0064 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock, 2011 applyings date JIUYUE 9 days) disclosed in).? In the case of the most defeated time fluid bed (202), the fines stream (362) of recovery can such as be recycled back into feedstock preparation unit (100) and/or in catalyst recovery unit (300).

The crude product gas stream (52) of lean fines methane rich typically comprises at least methane, carbon monoxide, carbon dioxide, hydrogen Gas, hydrogen sulfide, steam, ammonia and heat energy and a small amount of pollutant, the fines carried secretly such as remaining residual, and other are likely to be present in Volatilization in carbon containing feed and/or the material (such as hydrargyrum) that carries.Typically at the crude product gas stream of lean fines methane rich (52) there's almost no (total amount is typically less than about 50ppm) coagulable (at ambient conditions) hydrocarbon in.

The crude product gas stream (52) of this lean fines methane rich can process in one or more down stream processing steps, with Reclaim heat energy, purify and convert, produce one or more value added product, such as substitute natural gas (pipeline quality), hydrogen, an oxygen Change carbon, synthesis gas, ammonia, methanol, other syngas-derived products and electric energy, as carried in following " hydrogenation methanation " part And many documents disclosed in as, and as discussed in greater detail.

Provide below other details and embodiment.

Hydrogenation methanation

Catalytic gasification/hydrogenation methanation and/or crude product method for transformation and condition are typically published in such as US3828474, US3998607, US4057512, US4092125, US4094650, US4204843, US4468231, US4500323, US4541841, US4551155, US4558027, US4606105, US4617027, US4609456, US5017282, US5055181, US6187465, US6790430, US6894183, US6955695, US2003/0167961A1 and US2006/ 0265953A1, and US2007/0000177A1, US2007/0083072A1, the US2007/0277437A1 owned together, US2009/0048476A1, US2009/0090056A1, US2009/0090055A1, US2009/0165383A1, US2009/ 0166588A1, US2009/0165379A1, US2009/0170968A1, US2009/0165380A1, US2009/ 0165381A1, US2009/0165361A1, US2009/0165382A1, US2009/0169449A1, US2009/ 0169448A1, US2009/0165376A1, US2009/0165384A1, US2009/0217582A1, US2009/ 0220406A1, US2009/0217590A1, US2009/0217586A1, US2009/0217588A1, US2009/ 0218424A1, US2009/0217589A1, US2009/0217575A1, US2009/0229182A1, US2009/ 0217587A1, US2009/0246120A1, US2009/0259080A1, US2009/0260287A1, US2009/ 0324458A1, US2009/0324459A1, US2009/0324460A1, US2009/0324461A1, US2009/ 0324462A1, US2010/0076235A1, US2010/0071262A1, US2010/0121125A1, US2010/ 0120926A1, US2010/0179232A1, US2010/0168494A1, US2010/0168495A1, US2010/ 0292350A1, US2010/0287836A1, US2010/0287835A1, US2011/0031439A1, US2011/ 0062012A1, US2011/0062722A1, US2011/0062721A1, US2011/0064648A1, US2011/ 0088896A1, US2011/0088897A1, US2011/0146978A1, US2011/0146979A1, US2011/0207002A1 And US2011/0217602A1, and US patent application 13/094438 (attorney docket FN-0061 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock with Vanadium Recovery), its applying date It it is on April 26th, 2011；US patent application 13/211476 (attorney docket FN-0063 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock, August 17 2011 applying date)；With US patent Shen Please 13/228821 (attorney docket FN-0064 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock, 2011 applyings date JIUYUE 9 days) in.

In a kind of embodiment of the present invention shown in Fig. 1, by carbon containing feed (31+32), the flow of superheated steam of catalysis (12) it is incorporated in hydrogenation methanator (200) with optional hot synthesis gas feed streams (16) of crossing.It addition, also by a certain amount of The gas stream (14) of oxygen rich air be incorporated in hydrogenation methanator, for producing heat energy and synthesis gas in situ, as above As briefly discussing and in the most introduced many lists of references disclosed as (see for example and be previously incorporated US2010/0076235A1, US2010/0287835A1, US2011/0062721A1 and US patent application 13/211476).

Flow of superheated steam (12), the gas stream (14) of oxygen rich air and hot synthesis gas feed streams (16) (if present) excessively are desirable Ground is incorporated in hydrogenation methanator at a temperature of the object run temperature less than hydrogenation methanation reaction.Although Under the conditions of those, the heat demand of hydrogenation methanation reaction can be had adverse effect on (before the reaction of step (c)) by this, but It is that this actually enables the method to complete steam/heat and integrates, and does not use superheater that fuel heats (steady in the method During state is run), it typically provides fuel with a part of product from described method.Typically, there will be no Hot synthesis gas feed streams (16).

Step (b) and (c) are carried out in hydrogenation methanator (200).

Hydrogenation methanator (200) is fluidized-bed reactor.Hydrogenation methanator (200) can be e.g. The reverse flow configuration that " flows downward ", wherein the carbon containing feed (31+32) of this catalysis is introduced at higher point, so that particle court Fluid bed (202) bottom (202c) and flow down fluid bed (202), and gas flows in an upward direction and higher than fluid bed (202) point removes.

Or, that hydrogenation methanator (200) has " flowing up " and flow structure, wherein the carbon containing of this catalysis is given Material (31+32) in relatively low point (bottom (202c) of fluid bed (202)) input so that particle in fluid bed (202) with Gas flows upward to carbonizing matter by-product together and removes district, such as approaching or at the top on fluid bed (202) top (202b), Flow to the top of fluid bed (202).In one embodiment, carbon containing feed (the carbon containing feed (31+32) being such as catalyzed) Should produce for shots and to the greatest extent rationally be incorporated into close to oxygen (coming from the gas stream (14) of oxygen rich air) introducing point possibly In fluid bed (200).See for example US patent application that is that own together and that be previously incorporated _ _/_ _ _, _ _ _ (attorney docket FN-0065 US NP1, entitled Hydromethanation of a Carbonaceous Feedstock, simultaneously application).

Hydrogenation methanator (200), typically in high pressure and the hot operation of moderate, needs (such as to urge efflux of solids The carbon containing feed (31+32) changed and recirculation fines (if present)) it is incorporated in the reative cell of reactor, keep fluid simultaneously Required temperature, pressure and flow velocity.Those skilled in the art know for solid input is had high pressure and/or hot environment The feed inlet of reative cell, including planetary loader, screw feeder, rotary-piston and lock hopper.Should be appreciated that feed inlet Can include two or more pressure compensation element, such as lock hopper, it will be used alternatingly.In some cases, this contains Carbon feed can prepared higher than the pressure condition of reactor operating pressure, and therefore can be sent directly into instead by microparticle compositions Answer in device, it is not necessary to pressurize further.Gas for pressurization can be noble gas such as nitrogen, or more typically titanium dioxide Carbon stream, it can such as be recycled from by carbon-dioxide flow produced by acid gas removal unit.

It is appreciated that hydrogenation methanator (200) runs in moderate temperature (compared with traditional gasification method), and Object run temperature is at least about 1000 °F (about 538 DEG C), or at least about 1100 °F (about 593 DEG C) are to about 1500 °F (about 816 DEG C), or to about 1400 °F (about 760 DEG C), or arrive about 1300 °F (704 DEG C)；Pressure is of about 250psig (about 1825 kPa, absolute pressure), or about 400psig (about 2860kPa), or about 450psig is (about 3204 kPa), to about 800psig (about 5617 kPa), or to about 700psig (about 4928 kPa), or to about 600psig (about 4238 kPa), or arrive about 500psig (about 3549 kPa).

In hydrogenation methanator (200), typically gas flow rate is from about 0.5 ft/s (about 0.15m/s), or From about 1 ft/s (about 0.3m/s), to about 2.0ft/s (about 0.6m/sec), or to about 1.5 ft/s (about 0.45m/s)。

When the gas stream (14) of oxygen rich air inputs hydrogenation methanator (200), a part of carbon containing feed is (preferably Come from the carbon of the fines of the feed of partial reaction, by-product carbonizing matter and recirculation) will consume in oxidation/combustion reaction, Produce heat energy and the most certain amount of carbon monoxide and hydrogen (with typically other gases such as carbon dioxide and steam). The change of the amount of the oxygen of input hydrogenation methanator (200) provides favourable machining control, keeps synthesis with final Gas and thermal balance.Raising is aoxidized/burning by the amount improving oxygen, and therefore increases in-situ heat generation.On the contrary, the reduction of amount of oxygen In-situ heat will be reduced produce.The amount of produced synthesis gas finally will depend upon which the consumption of oxygen, and the oxygen meeting of higher amount Cause burning/be oxidized to more completely carbon dioxide and water rather than more part burn into carbon monoxide and hydrogen.

The carbon containing feed that amount of oxygen in input hydrogenation methanator (200) must enough burn/aoxidize enough, comes Produce enough heat energy and synthesis gas, to meet heat and the synthesis gas demand of stable state hydrogenation methanation reaction.

In one embodiment, it is provided that the amount to the molecular oxygen being hydrogenated with methanator (200) (is included in oxygen rich air Gas stream (14) in) can be from about 0.10, or from about 0.20, or from about 0.25, to about 0.6, or to about 0.5, or to about 0.4, or arrive about 0.35 pound of O₂/ every pound of carbon containing feed.

This hydrogenation methanation and oxidation/combustion reaction will occur simultaneously.Depend on the structure being hydrogenated with methanator (200) Making, said two step accounts for leading in region respectively, hydrogenation methanation on the top (202b) of fluid bed (202), oxidation/ Burn in the bottom (202c) of fluid bed (202).The gas stream (14) of this oxygen rich air typically mixes with flow of superheated steam (12), And by this mixture at the bottom of fluid bed (202) bottom (202c) or close to it in place of introduce, to avoid in reaction Device forms focus, with the gaseous products burning avoiding (minimizing) to obtain mutually.According to the present invention, input has high water capacity The carbon containing feed (31+32) of catalysis, in particular into fluid bed (202) bottom (202c), additionally aid the dissipation of heat and keep away Exempt to be formed focus in reactor (200).

If there is overheated synthesis gas feed streams (16), then this stream will be typically as the mixture with steam stream (12) Introduce, and the gas stream (14) of oxygen rich air is introduced separately into fluid bed (202) bottom (202c), the most preferentially to consume synthesis gas group Point.

The gas stream (14) of oxygen rich air can be hydrogenated with in methanator (200) by the input of any suitable means, Such as the oxygen of purification, oxygen-air mixture, oxygen-steam mixture or oxygen-inert gas mixture are directly injected into In reactor.See for example US4315753 and Chiaramonte et al., Hydrocarbon Processing, nineteen eighty-two 9 Month, the 255-257 page.

The gas stream (14) of oxygen rich air typically produces via conventional air-separating technology, and will be with steam Mixing supply, and be higher than about 250 °F (about 121 DEG C), arriving about 400 °F (about 204 DEG C) or (big to about 350 °F About 177 DEG C) or to the temperature of about 300 °F (about 149 DEG C) with in being at least slightly above hydrogenated with methanator (200) Introduce under the pressure of the pressure existed.Steam in the gas stream (14) of oxygen rich air is transferred to be hydrogenated with first at the stream (14) of oxygen rich air Should be incoagulable during alkylation reactors (200), the stream (14) of such oxygen rich air may require that and passes at relatively low pressure Defeated, carry out, before being introduced into the most shortly being hydrogenated with in methanator (200), pressurize (compression).

As it has been described above, this hydrogenation methanation reaction has steam demand, heat demand and synthesis gas demand.The group of these conditions Close the key factor of the service condition of the remainder determining that hydrogenation methanation reaction and the method.

Such as, the steam demand of hydrogenation methanation reaction needs steam to be at least about 1 with the mol ratio of carbon (in feed). But typically, this mol ratio is greater than about 1, or about 1.5 (or higher), to about 6 (or less), or to about 5 (or Less), or to about 4 (or less), or to about 3 (or less), or to about 2 (or less).The carbon containing feed (31 of catalysis + 32) water capacity, by dampness produced by the carbon containing feed in hydrogenation methanator (200) be included in superheated steam Steam in stream (12), the gas stream (14) of oxygen rich air and recirculation fines stream (crossing hot synthesis gas feed streams (16) with optional) Should be enough at least substantially meet the steam demand of (or the most satisfied) hydrogenation methanation reaction.

As it has been described above, this hydrogenation methanation reaction (step (b)) is the most thermally equilibrated, but due to process heat loss With other energy requirements (such as dampness evaporation on feed), it is necessary to produce some heat in hydrogenation methanation reaction, to protect Hold thermal balance (heat demand).Carbon is at the oxygen being incorporated in hydrogenation methanator (200) from the gas stream (14) of oxygen rich air In the presence of part burning/oxidation should be enough at least substantially to meet heat and the conjunction of (or the most satisfied) hydrogenation methanation reaction Become both gas demands.

The pressurization of the carbon containing feed (31+32) for catalysis used in hydrogenation methanator (200) and reaction The gas gas stream (14) (crossing hot synthesis gas feed streams (16) with optional) that comprises flow of superheated steam (12) and oxygen rich air and Optional other nitrogen, air or noble gas (such as argon), it can be defeated according to method known to those skilled in the art Enter to be hydrogenated with methanator (200).As a result, the gas stream (14) of this flow of superheated steam (12) and oxygen rich air must be with higher Pressure provides, and this pressure allows them to enter in hydrogenation methanator (200).

It is desirable that whole fluids all should be with the temperature input of the object run temperature less than hydrogenation methanator In hydrogenation methanator (200), such as, it is disclosed in the US provisional application 13/211476 being previously incorporated.

Flow of superheated steam (12) may be at the temperature of the saturation point under as little as feed pressure, but is desirable to Supply higher than this temperature, to avoid occurring the probability of any condensation.The typical feed temperature of flow of superheated steam (12) be from About 500 °F (about 260 DEG C) or from about 600 °F (about 316 DEG C) or from about 700 °F (about 371 DEG C), to about 950 °F (about 510 DEG C) or to about 900 °F (about 482 DEG C).The temperature of flow of superheated steam (12) will ultimately depend on from The level of the heat that described method reclaims, as discussed below.In any case, should not use in the steady-state operation of described method The superheater of fuel heating comes steam stream (12) described in superheated.

When stream (14) combination of flow of superheated steam (12) and oxygen rich air inputs the lower area (202c) of fluid bed (202) Time, the temperature of this combination stream will be typically from about 500 °F (about 260 DEG C) or from about 600 °F (about 316 DEG C) or From about 700 °F (about 371 DEG C), arrive about 900 °F (about 482 DEG C) or arrive about 850 °F (about 454 DEG C).

Temperature in hydrogenation methanator (200) can be such as by controlling amount and the temperature of flow of superheated steam (12) And the amount of the oxygen of input hydrogenation methanator (200) controls.

Advantageously, the steam for this hydrogenation methanation reaction is to be produced by process hot trapping from other process operations Raw (such as producing in waste heat boiler, so-called " process vapor " or " steam that process produces "), and real at some Execute in scheme, be that the steam produced separately as process provides.Such as produced by heat exchanger unit or waste heat boiler Raw process vapor stream can be as the flow of superheated steam (12) of part, in input hydrogenation methanator (200), as open In US2010/0287835A1 and the US patent application 13/211476 being such as previously incorporated like that, and as discussed below that Sample.

In certain embodiments, (the steam that whole processing described herein the most substantially steam is neutral Neutral), so that can be via heat exchange for being hydrogenated with the steam demand (pressure and amount) of methanation reaction, with being in it The process heat of middle different phase meets, or (the steam positive) of steam positivity, so produces unnecessary steam, And can such as be used for generating electricity.It is desirable that the steam that process produces accounts for being more than about of hydrogenation methanation reaction steam demand 95wt% or more than about 97wt% or more than about 99wt% or about 100wt% or higher.

The result of hydrogenation methanation reaction is the crude product of a kind of methane rich, as the crude product stream (50) of methane rich Taking out from hydrogenation methanator (200), the crude product stream (50) of this methane rich typically comprises CH₄、CO₂、H₂、CO、 H₂S, unreacted steam and optionally other pollutant (fines such as carried secretly, NH₃, COS, HCN and/or elemental mercury from vapor), this Depend on the character of carbonaceous material for being hydrogenated with methanation.

If hydrogenation methanation reaction runs with synthesis gas balance, the crude product stream (50) of this methane rich is passed through Leave hydrogenation methanator (200), at least about 15mol% or at least about 18mol% or the biggest will be typically comprised The methane of about 20mol%, rubbing of methane, carbon dioxide, carbon monoxide and the hydrogen in crude product stream (50) based on this methane rich That number.It addition, the methane typically comprising at least about 50mol% is added carbon dioxide by the crude product stream of this methane rich (50), The molal quantity of methane, carbon dioxide, carbon monoxide and hydrogen in crude product stream (50) based on this methane rich.

If hydrogenation methanation reaction runs with synthesis gas excess, such as, contain higher than or need beyond synthesis gas The carbon monoxide of the excess asked and/or hydrogen are (such as due to the gas of the oxygen rich air in input hydrogenation methanator (200) Flow the amount of (14) and create carbon monoxide and/or the hydrogen of excess), then can be to the methane in the crude product stream (50) of methane rich Some dilution effect is produced with the molar percentage of carbon dioxide.

In these methods can on-gaseous carbonaceous material (10) include the most wide variety of biomass and abiotic Material.Carbon containing feed (32) is derived from one or more on-gaseous carbonaceous materials (10), and it is to prepare region (100) at feed Middle processing, as described below.

Hydrogenation methanation catalyst (31) can comprise one or more catalyst materials, as described below.

Before hydrogenation methanator (200) is provided to, carbon containing feed (32) and hydrogenation methanation catalyst (31) Typically by closely mixing (that is, to provide the carbon containing feed (31+32) of catalysis).

Further gas processing

Fines is removed

The hot gas effluent of the reative cell leaving hydrogenation methanator (200) can be through fines remover unit (such as cyclone separator component (360)), this unit is incorporated among hydrogenation methanator (200) and/or outside it, fills When Disengagement zone.By overweight and can not be returned by the particle (that is, fines) that carry secretly of gas leaving hydrogenation methanator (200) Return to be hydrogenated with methanator (200), such as, return to reative cell (such as fluid bed (202)).

The fines carried secretly of residual is removed basically by any suitable device, the most internally and/or externally whirlwind Splitter, is optionally followed by Venturi scrubber.As it has been described above, via recirculation line (366) by least one These fineves are divided to return to fluid bed (202) lower area (202c).A part can also return via recirculation line (364) To fluid bed (202) top (202b).The fines of any remaining recovery can be processed and reclaim base metal catalysts, or directly It is recycled and returned to feed prepare, as described in the US2009/0217589A1 being previously incorporated.

Remove " most of " fines to represent and remove a certain amount of fines from the gas stream formed, so that Downstream processing It is not adversely affected；Therefore, most fines should at least be removed.The super-fine material of some reduced levels can be in institute The gas stream formed remains to such degree, i.e. Downstream processing is not affected by significant adverse.Typically, the most greatly The granularity of about 90wt% or at least about 95wt% or at least about 98wt% is more than about 20 μm or more than about 10 μm or big Fines in about 5 μm is removed.

Heat exchange

Depending on being hydrogenated with methanation condition, the crude product stream (52) of lean fines methane rich can be temperature about 1000 °F (about 538 DEG C)-about 1500 °F (about 816 DEG C), and the most about 1100 °F (about 593 DEG C)-about 1400 °F (about 760 DEG C), pressure about 50psig (about 446 kPa)-about 800psig (about 5617 kPa), the most greatly About 400psig (about 2860kPa)-about 600psig (about 4238 kPa) and speed about 0.5 ft/s (about 0.15m/ S)-about 2.0ft/s (about 0.61m/s), the most about 1.0ft/s (0.30m/s)-about 1.5 ft/s is (about 0.46m/s) get off generation.

The crude product stream (52) of lean fines methane rich can such as provide heat recovery units, such as first shown in Fig. 2 Heat exchanger unit (400).First heat exchanger unit (400) eliminate from the crude product stream (52) of lean fines methane rich to At least part of heat energy, and the temperature reducing the crude product stream (52) of lean fines methane rich is rich less than lean fines to produce temperature The crude product stream (70) of the methane rich of the cooling of the crude product stream (52) of methane.Reclaimed by the second heat exchanger unit (400) Heat energy may be used for producing the first process vapor stream (40), the most at least one of first process vapor stream (40) is permissible The most defeated returning to is hydrogenated with in methanator (200).

In one embodiment, as in figure 2 it is shown, the first heat exchanger unit (400) has steam boiler region (400b) both superheat regions (400a) and before it.Boiler water supply stream (39a) can be through steam boiler region (400b) producing the first process vapor stream (40), it is then passed through steam superheater (400a) and produces suitable temperature and pressure Superheating process steam stream (25) of power, is used for being incorporated in hydrogenation methanator (200).Steam superheater (400a) also may be used For other recycled vapour streams of superheated (the such as second process vapor stream (43)) to input hydrogenation methanator (200) degree needed for.

The crude product stream (70) of the methane rich of the cooling formed will typically be in temperature about 450 °F (about 232 DEG C)- About 1100 °F (about 593 DEG C), the most about 550 °F (about 288 DEG C)-about 950 °F (about 510 DEG C), pressure About 50psig (about 446 kPa)-about 800psig (about 5617 kPa), the most about 400psig is (about 2860kPa)-about 600psig (about 4238 kPa), and speed about 0.5 ft/s (about 0.15m/s)-about 2.0ft/ S (about 0.61m/s), leaves under the most about 1.0ft/s (0.30m/s)-about 1.5 ft/s (about 0.46m/s) Two heat exchangers unit (400).

Gas purification

Product cleanup can include that such as water-gas shift method (700), dehydration (450) and sour gas remove (800), Remove (500) with optional contaminant trace species and optional ammonia is removed and reclaims (600).

Contaminant trace species removes (500)

As well known to the skilled person, the pollutant water of the crude product stream (70) of the methane rich that gas stream such as cools down The character of the flat carbonaceous material that will depend upon which for preparing carbon containing feed.Such as some coal (such as Illinois #6) can have height Sulfur content, which results in higher COS pollute；Other coals such as Powder River Basin coal may comprise higher amount Hydrargyrum, it can volatilization in hydrogenation methanator (200).

COS can remove from the crude product stream (70) of the methane rich that gas stream such as cools down as follows: is hydrolyzed by COS (seeing US3966875, US4011066, US4100256, US4482529 and US4524050), flowed a gas through microgranule Calx Stone (sees US4173465), acidic buffer CuSO₄Solution (sees US4298584), containing the alkane of tetramethylene sulfone (sulfolane) Hydramine absorbent (such as methyl diethanolamine, triethanolamine, dipropanolamine or diisopropanolamine (DIPA)) (seeing US3989811)；Or use Freezing liquid CO₂Second gas stream (seeing US4270937 and US4609388) of this cooling of backwash.

HCN such as can get off removing from the crude product stream (70) of the methane rich that gas stream such as cools down: by with sulfuration Ammonium or ammonium polysulfide reaction response produce CO₂、H₂S and NH₃(seeing US4497784, US4505881 and US4508693), or use Formaldehyde, cleans (seeing US4572826) by the two-stage of ammonium polysulfide or sodium polysulphide subsequently, absorbs with water and (sees US4189307), and/or by the such as MoO of the hydrolyst through alumina load₃、TiO₂And/or ZrO₂And decompose (ginseng See US4810475, US5660807 and US5968465).

Element mercury can be removed from the crude product stream (70) of the methane rich that gas stream such as cools down the most as follows: passes through The absorption (seeing US3876393) of sulfuric acid activated carbon, by the absorption (seeing US4491609) of the carbon that sulfur is filled, by containing H₂The absorption (seeing US4044098) of the amine solvent of S, by the absorption (seeing US4892567) of the zeolite that silver or gold are filled, uses Hydrogen peroxide and methanol are oxidized to HgO (seeing US5670122), at SO₂In the presence of (see with the compound oxidation containing bromine or iodine US6878358), with the plasma oxidation (seeing US6969494) containing H, Cl and O, and/or with chloride oxidizing gas oxygen Change (such as ClO, see US7118720).

When using aqueous solution to remove any or all of COS, HCN and/or Hg, in contaminant trace species removal unit Produced waste water can import in treatment unit for waste water (not shown).

When it is present, the contaminant trace species of concrete contaminant trace species is removed and (such as should be cooled down from handled gas stream The crude product stream (70) of methane rich) in remove at least most of (or substantially all of) contaminant trace species, typically remove To the level specifying boundary at or below desired product stream.Typically, contaminant trace species removal should be from the first of cooling Gas stream removes COS, HCN and/or the hydrargyrum of at least 90% or at least 95% or at least 98%, based on the weight of pollutant before processing Amount.

Ammonia is removed and reclaims (600)

As well-known to those skilled in the art, biomass, some coal, the gasification of some petroleum coke and/or utilization sky Gas can produce the ammonia of pronounced amount as the source of oxygen being used for being hydrogenated with methanator (200) in product stream.Optionally, gas The crude product stream (70) of the methane rich that stream such as cools down can be removed at one or more ammonia and wash with water in recovery unit (600) Remove and reclaim ammonia.

Recovery ammonia processes can be such as in the crude product stream of methane rich of the cooling arising directly from heat exchanger (400) (70) carry out on, or carry out after one or two following process: the contaminant trace species removal unit that (i) is one or more (500), and (ii) one or more acid converting unit (700).

After washing, the crude product stream (70) of the methane rich that this gas stream such as cools down will typically comprise at least H₂S、 CO₂、CO、H₂And CH₄.When the crude product stream (70) of the methane rich of this cooling is in advance through peracid converting unit (700), then exist After washing, this gas stream will typically comprise at least H₂S、CO₂、H₂And CH₄。

Ammonia can reclaim from scrubber's water according to method known to those skilled in the art, can be typically as water-soluble Liquid (61) (such as 20wt%) reclaims.Scrubber waste can forward treatment unit for waste water (not shown) to.

When it is present, ammonia removal process should be removed from the stream (crude product stream (70) of the methane rich such as cooled down) of washing Remove the ammonia of at least most of (with substantially all).In ammonia removes context, " most of " removes and represents that removing is sufficiently high The component of percentage ratio, so as to produce desired end product.Typically, ammonia removal process will remove at least about 95% or The ammonia composition of the first gas stream of the washing of at least about 97%, weight based on the ammonia in described stream before processing.

Water-gas shift (700)

The crude product stream (crude product stream (70) of the methane rich such as cooled down) of some or all of methane rich is inputted Water-gas shift reactor (such as acid conversion reactor (700)).

In acid conversion reactor (700), gas experiences acid conversion reaction in the presence of water-bearing media (such as steam) (also referred to as water-gas shift reaction), so that (most or substantially all of) CO of major general's major part changes into CO₂ And improve H₂Mark.The generation of the hydrogen content improved is used for such as Optimization of Hydrogen and produces, or is used for as downstream methanation Optimize H₂/ CO ratio.

Water-gas shift processes can be in the crude product stream (70) of the methane rich cooled down directly from heat exchanger (400) Carry out, or the methane rich in the cooling that passes through contaminant trace species removal unit (500) and/or ammonia removal unit (600) Crude product stream is carried out on (70).

A kind of acid conversion method is described in detail in such as US7074373.The method includes adding water, or uses in gas The water comprised, and the water-gas mixture adiabatic reaction on steam reforming catalyst that will be formed.Typically steam reformation is urged One or more group VIII metal that agent is included in heat-resistant carriers.

It is that those skilled in the art are public for carrying out method and the reactor of acid gas conversion reaction on the gas stream containing CO Know.Suitably reaction condition and suitable reactor can be according to the amount of the CO of dilution changing from gas stream. In some embodiments, the conversion of this acid gas can be arrived big from about 100 DEG C or from about 150 DEG C or from about 200 DEG C About 250 DEG C or to about 300 DEG C or carry out to single-stage at a temperature of about 350 DEG C.In these embodiments, conversion reaction Can be catalyzed by any suitable catalyst well known by persons skilled in the art.Such catalyst includes but not limited to Fe₂O₃Base catalyst is (such as Fe₂O₃-Cr₂O₃Catalyst), and other transition metal bases and transition metal oxide base catalyst.? In other embodiments, acid gas conversion can be carried out in multistage.In a kind of specific embodiment, this acid gas is changed two Carry out in Ji.This two-stage approach uses high temperature sequence (sequence), is followed by low temperature sequence.For high temperature shift reaction Gas temperature is about 350 DEG C-about 1050 DEG C.Typically high temperature catalyst includes but not limited to ferrum oxide, optionally in combination with There is lesser amount of chromium oxide.Gas temperature for low temperature conversion is about 150 DEG C-about 300 DEG C, or about 200 DEG C-about 250℃.Low-temperature shift catalyst includes but not limited to Cu oxide, and it can be supported on zinc oxide or aluminium oxide.For acid The appropriate method of transformation process is described in the US2009/0246120A1 being previously incorporated.

This acid conversion reaction is heat release, and therefore it comes through conventional heat exchanger the such as second heat exchanger unit (401) Carry out, effectively utilize heat energy.The conversion reactor using these features is to well known to a person skilled in the art.Suitably turn Change in the US7074373 that an example of reactor is in previously incorporated and be illustrated, although be well known by persons skilled in the art Other designs are also effective.

After acid gas converse routine, the crude product stream (72) of the hydrogen rich gas formed generally comprises CH₄、CO₂、H₂、H₂S、 Steam, optional CO and optional other pollutant a small amount of.

As it has been described above, the crude product stream of hydrogen rich gas (72) can be provided to heat recovery units the such as second heat exchanger unit (401).And the second heat exchanger unit (401) is expressed as single unit in fig. 2, it can so exist and/or integrate In acid conversion reactor (700), it is possible to cool down this acid conversion reactor (700) and the crude product stream (72) from hydrogen rich gas At least one of heat energy of middle removing, reduces temperature and produces the stream of cooling.

The heat energy of this recovery at least some of can be used for being produced the second process vapor stream by water/vapour source.

In the specific embodiment shown in Fig. 2, the crude product stream (72) of hydrogen rich gas is leaving acid conversion reactor (700) it is introduced in after in superheater (401a), is followed by boiler water supply preheater (401b).Superheater (401a) can be used Carry out such as superheated stream (42a) (it can be the part of crude product stream (70) of methane rich for cooling), overheated to produce Stream (42b), then it reconsolidate into the crude product stream (70) of methane rich of cooling.Or, the methane rich of whole coolings Product stream can preheat in superheater (401a), consequently as in superheat flow (42b) input acid conversion reactor (700).Pot Stove may be used for such as preboiler water supply (46) for water preheater (401b) and produces the boiler water feed streams (39) of preheating, uses One or more in the first heat exchanger unit (400) and the 3rd heat exchanger unit (403), and other steam generations Operation.

If it is desire to some carbon monoxide contents of the crude product stream (50) being to maintain methane rich, then can provide and the The gas bypassing loop (71) that one heating recovery unit (400) communicates, so that some leave the first heat exchanger unit (400) The crude product stream (70) of methane rich of cooling can be once around peracid conversion reactor (700) and the second heat exchanger unit (401) upper thick with hydrogen rich gas of some points, and before dewatering unit (450) and/or sour gas removal unit (800) Product stream (72) combines.When desirably reclaiming single methane production, this is useful especially, is protected because as described below The carbon monoxide held can be subsequently by methanation.

Dehydration (450)

After acid conversion reactor (700) and the second heat exchanger unit (401) and in sour gas removal unit (800) before, typically by the crude product stream (72) of this hydrogen rich gas via knock-out drum (knock-out drum) or similar water Segregation apparatus (450) is processed to reduce water content.The waste water stream (47) (it will be acidic aqueous stream) formed can be sent to Treatment unit for waste water (not shown), for further processing.The crude product stream (72a) of the hydrogen rich gas of the dehydration formed is delivered to Sour gas removal unit (800) as described below.

Sour gas removes (800)

Use sour gas removal unit (800) subsequently to come from the crude product stream (72a) of the hydrogen rich gas of dehydration to remove Most H₂S and most CO₂And produce the gas stream (80) of depriving hydrogen sulphide.

Sour gas minimizing technology typically comprises and makes gas stream and solvent (such as monoethanolamine, diethanolamine, methyl diethyl Hydramine, diisopropylamine, diglycolamine, amino acid whose sodium salt solution, methanol, hot potassium carbonate etc.) contact, produce and be full of CO₂With/ Or H₂The absorbent of S.A kind of method can include using Selexol^®(UOP LLC, Des Plaines, IL USA) or Rectisol^®(Lurgi AG, Frankfurt am Main, Germany) solvent, it has two series；Each series contains H₂S Absorbent and CO₂Absorbent.

A kind of method for removing sour gas is described in and is previously incorporated in US2009/0220406A1.

At least most of (the most substantially all of) CO₂And/or H₂S (with other remaining contaminant trace species) should Remove via sour gas removal process.In sour gas removes context, " substantially " removes expression and eliminates sufficiently high The component of percentage ratio, so as to produce desired end product.Actual removal amount therefore may be between component and component Different.For " pipeline quality natural gas ", only can there is the H of trace (at most)₂S, although may allow higher (but It is still few) CO that measures₂。

Typically, at least about 85% or at least about 90% or the CO of at least about 92%₂Should be by the hydrogen-rich from dehydration The crude product stream (72a) of gas removes.Typically, at least about 95% or at least about 98% or the H of at least about 99.5%₂S Should be removed from the crude product stream (72a) of the hydrogen rich gas of dehydration.

In sour gas removing step, the loss of conceivable product (hydrogen and/or methane) should minimize, so that The gas stream (80) obtaining depriving hydrogen sulphide comprises at least most of (with substantially all of) crude product from the hydrogen rich gas of dehydration The methane of stream (72a) and hydrogen.Typically, such loss should be about 2mol% or less respectively, or about 1.5mol% Or less, or the methane of the crude product stream (72a) of the hydrogen rich gas from dehydration of about 1mol% or less and hydrogen.

The gas stream (80) of the depriving hydrogen sulphide formed generally will comprise CH₄、H₂With optional CO (for downstream methane Change), and the most a small amount of CO₂And H₂O。

The H of any recovery of (with other processes such as sour water stripping (SWS)) is removed from sour gas₂S (78) can be by this Any method (including Claus method) known to the skilled person changes into elementary sulfur.Sulfur can as melted liquid back and forth Receive.

CO from any recovery that sour gas is removed₂(79) can be by compression at CO₂Transmit in pipeline, industry should With and/or detain storage or other processes (as strengthen recovery of oil).

The gas stream (80) of the depriving hydrogen sulphide formed can such as be directly used as medium/high BTU fuel source, or as fuel The feed of battery, such as, be disclosed in US2011/0207002A1 and US2011/0217602A1 being previously incorporated, or following institute State and be processed further.

Hydrogen separation unit (850)

Hydrogen can to separate from the gas stream (80) of depriving hydrogen sulphide according to method known to those skilled in the art, as Low temperature distillation, use molecular sieve, gas separate (such as pottery) film and/or pressure-variable adsorption (PSA) technology.Before see for example The US2009/0259080A1 introduced.

In one embodiment, PSA device is used for Hydrogen Separation.For from containing methane (with an optional oxidation Carbon) admixture of gas in separate the PSA technique of hydrogen and be typically well known to a person skilled in the art, be disclosed in such as US6379645 (quotes document with other are wherein mentioned).PSA device is typically commercially available, such as based on available from Air The technique of Products and Chemicals Inc. (Allentown, PA), UOP LLC (Des Plaines, IL) etc..

In an alternate embodiment, it is possible to use hydrogen membrane separator, it is followed by PSA device.

Such separation provides the gas stream (82) of the depriving hydrogen sulphide of high-purity hydrogen product stream (85) and hydrogen-depleted gas.

Hydrogen gas product stream (85) the preferably purity reclaimed is at least about 99mol%, or at least 99.5mol%, or at least About 99.9mol%.

Hydrogen gas product stream (85) can serve as the such as energy and/or reactant.Such as hydrogen can serve as hydrogen base fuel The energy of battery, it is used for producing power and/or produces steam (seeing 980 in Fig. 2,982 and 984) and/or for subsequently Hydrogenation methanation process.Hydrogen is also used as the reactant in different method for hydrogenation, such as in chemistry and petroleum refining work Method for hydrogenation in industry.

The gas stream (82) of the depriving hydrogen sulphide of hydrogen-depleted gas will mainly comprise methane, and has optional a small amount of carbon monoxide (depending primarily on degree and the bypass of acid conversion reaction), carbon dioxide (depending primarily on the efficiency of sour gas minimizing technology) With hydrogen (depending primarily on degree and the efficiency of Hydrogen Separation technique).The gas stream (82) of the depriving hydrogen sulphide of hydrogen-depleted gas can be straight Connect use, and/or can be processed further with as described below/use.

Methanation (950)

The gas stream (82) of the gas stream (80) of all or part of depriving hydrogen sulphide or the depriving hydrogen sulphide of hydrogen-depleted gas can be straight Connect as methane product stream (99), or all or part of those streams can be processed further/purify producing methane production Stream (99).

In one embodiment, by the gas stream (80) of depriving hydrogen sulphide or the gas stream (82) of the depriving hydrogen sulphide of hydrogen-depleted gas Input supplements in (trim) methanator (950), produces separately with carbon monoxide that may be present and hydrogen in being flowed by those Outer methane, produces the product stream (97) of methane rich.

If there is hydrogen separation unit (850), the gas stream (80) of the most a part of depriving hydrogen sulphide can be via shunt valve Hydrogen separation unit (850) walked around by line (86), to adjust the hydrogen content of the gas stream (82) of the depriving hydrogen sulphide of hydrogen-depleted gas, optimizes H for methanation₂/ CO ratio.

This methanation reaction can be carried out in any suitable reactor, such as single-stage methanator, series connection Single-stage methanator or multistage reactor.Methanator includes but not limited to that fixed bed, moving bed or fluid bed are anti- Answer device.See for example US3958957, US4252771, US3996014 and US4235044.Methanator and catalyst lead to It is often commercially available.Catalyst and methanation condition for methanation are typically known to various equivalent modifications, and will Depend on the temperature of gas stream, pressure, flow velocity and the composition such as introduced.

Owing to methanation reaction is highly exothermic, therefore in different embodiments, the product gas stream of methane rich (97) heat recovery units can be such as further provided to, the such as the 3rd heat exchanger unit (403).Although the 3rd heat exchanger Unit (403) represents as separate unit, but it can so exist and/or be incorporated into methanator (950) in, therefore, it is possible to cool down methanator unit and remove at least one of heat energy from the gas stream of methane rich, with Reduce the temperature of the gas stream of this methane rich.The heat energy reclaimed may be used for being produced the second mistake by water and/or vapour source (39b) Journey steams steam flow (43).Although the most so representing in Fig. 2, but the 3rd heat exchanger unit (403) can comprise superheat region, It is followed by boiler area, as above for described in the first heat exchanger unit (400).Because methanation reaction is highly exothermic Property, it is the most overheated that the second process streams (43) will typically need not, and all or part of can be with all or part of Superheating process steam stream (25) combines, as flow of superheated steam (12).But if it is required, superheater (990) may be used for by Flow of superheated steam (12) superheated, to desired temperature, inputs hydrogenation methanator (200).

The product gas stream (97) of methane rich can serve as methane product stream (99), or it can add further when needed Work, is separated by any suitable gas separating method well known by persons skilled in the art and is reclaimed CH₄, include but not limited to Low temperature distillation separates (such as pottery) film with use molecular sieve or gas.Other method for gas purification includes such as producing methane Hydrate, as in US2009/0260287A1, US2009/0259080A1 and US2009/0246120A1 of being previously incorporated, institute is public As opening.

Pipeline quality natural gas

In certain embodiments, the present invention provides and can be produced " pipe by the hydrogenation methanation of on-gaseous carbonaceous material Line quality natural gas " method and system of (or " pipeline quality substitute natural gas ")." pipeline quality natural gas " typically refers to The stream containing methane, its: (1) pure methane calorific value ± 5% in (methane calorific value under standard atmospheric conditions is 1010btu/ft³), (2) are substantially free of water (typically dew point is about-40 DEG C or lower), and (3) are substantially free of toxicity Or corrosive contaminants.In some embodiments of the present invention, the methane product stream (99) described in above method meets Such requirement.

Waste water processes

Removed by contaminant trace species, acid is changed, ammonia is removed, sour gas is removed and/or appointing in catalyst recovery process In what one or more formed waste water, the pollutant of residual can remove in treatment unit for waste water, enables to follow again Water that ring reclaims in factory and/or process the water from factory process according to any method well known by persons skilled in the art. Depend on that feed and reaction condition, such residual contaminants can comprise such as aromatic hydrocarbons, CO, CO₂、H₂S, COS, HCN, ammonia and hydrargyrum. Such as H₂S and HCN can be such as removing of getting off: waste water is acidified to pH about 3, uses inert gas treatment spent acidic in stripper Water, and pH is increased to about 10, and this waste water of second time inert gas treatment removes ammonia (seeing US5236557).H₂S Can remove as follows: with this waste water of oxidizer treatment in the presence of the coke particle of residual, with by H₂S changes into insoluble sulphuric acid Salt, it can pass through flotation or be filtered to remove (seeing US4478425).Aromatic hydrocarbons can remove as follows: by waste water with optionally contain There is unit price-contact with the carbon containing carbonizing matter of bivalence alkaline inorganic compound (such as solid char produce thing or reclaim at catalyst The carbonizing matter of dilution afterwards, supra), and regulate pH (seeing US4113615).Aromatic hydrocarbons can also be such as removing of getting off: with organic Solvent extraction, processes waste water (seeing US3972693, US4025423 and US4162902) subsequently in stripper.

Process vapor

Steam feed circuit can be provided to supply by process vapor streams (such as 25/40 various produced by energy recovery With 43).

This process vapor stream can be such as generation of getting off: use one or more heat recovery units such as first and the 3rd heat to hand over Exchange unit (400) and (403), make water/vapour source (such as (39a) and (39b)) and the heat energy reclaimed from various process operations Contact.

Any suitable heat recovery units known in the art can be used.Such as can use steam boiler or any its His suitable steam generator (such as shell/pipe in pipe), it can utilize the heat energy of recovery to produce steam.This heat exchange Device can also serve as the superheater ((400a) as in Fig. 2) for steam stream, thus can use the one-level by the method Or multistage recuperation of heat is by steam superheated to desired temperature and pressure, thus eliminates and single fuel is heated The needs of superheater.

Although any water source may be used to produce steam, but carries out water conventionally used in known steam generator system Purify and deionization (about 0.3-1.0 S/cm), with the corrosion process that slows down.

In a kind of embodiment of the inventive method, hydrogenation methanation reaction will have steam demand (temperature, pressure with Volume), and process vapor and process recuperation of heat be enough to provide at least about 97wt% or the biggest of this total steam demand About 98wt% or at least about 99wt% or at least about 100%.If it is required, remaining about 3wt% or lower or about 2wt% or lower or about 1wt% or lower can be provided by supplementary steam stream, and supplementing steam stream can be as steam stream (12) or as in one part input system.In the steady-state operation of described method, process vapor should be to be sufficient for adding The amount of the temperature and pressure of the steam demand of hydrogen methanation reaction.

It is possible if desired to use suitable steam boiler or steam generator to provide supplementary steam stream.Such pot Stove can be e.g. by using any carbonaceous material, such as fine coal, biomass etc., provides energy, and include but do not limit Underproof carbonaceous material (such as fines, supra) in feed preparation manipulation.In one embodiment, such additionally Steam boiler/generator can exist, but be not used in steady state operation.

In an alternate embodiment, process vapor stream provides for being hydrogenated with the whole total of methanation reaction Steam demand, wherein in steady state operation, is substantially absent from supplementary steam stream.

In another embodiment, the process vapor of excess is created.The steam of this excess may be used for such as via steaming Steam turbine generates electricity, and/or in fluid bed driers, this carbon containing feed is dried to desired water capacity, as described below.

Generating

A part of methane product stream (99) may be used for burning (980) and producing steam (982), as a part of any The hydrogen (85) reclaimed is such.As it appears from the above, the recycled vapour of excess can be provided to one or more power generator (984), in burning or steam turbine, producing electric energy, it may be used in factory or on electrical network (power grid) Sell.

Prepare carbon containing feed

Carbonaceous material processing (100)

Microgranule carbonaceous material such as biomass can be such as preparation of getting off with abiotic matter: via respectively or together with pressure Broken and/or grind, produce one or more according to any method such as impact grinding known in the art and wet or dry grinding Carbonaceous particles.Depending on the method for crushing and/or grind this carbonaceous material source, the carbonaceous particles formed can be sieved (that is, according to apart) provides carbon containing feed (32), and it forms hydrogenation methane in catalyst loading process (350) The carbon containing feed (31+32) of the catalysis used by change reactor (200).

Any method well known by persons skilled in the art can be used in sieving this microgranule.Such as screening can by screening or Microgranule passes through a most sieve of sieve carry out.Screening plant can include diagrid, bar screen and wire mesh screens.Sieve can To be static or to be combined with the mechanism for shaking or vibrate this sieve.Or, it is possible to use classification separates carbonaceous particles. Grading plant can include Ore sorter, gas cyclone, hydrocyclone, rake classifier, rotation trommel or Fluidized classification device.This carbonaceous material can also screening or classification before grinding and/or be broken.

This carbonaceous particles can be from about 25 microns or from about 45 microns as particle mean size, high micro-to about 2500 The fine particles of rice or height to about 500 microns supplies.Those skilled in the art can be readily determined the suitable of carbonaceous particles Granularity.The most when a fluidized bed reactor is used, such carbonaceous particles can have such particle mean size, and it makes to contain Material with carbon element is capable of initial fluidisation when the gas velocity used by fluidized-bed reactor.For being hydrogenated with methanator (200) it is desirable that particle size range be Geldart A and Geldart B scope (including the lamination portion of the two), this takes Certainly in fluidization conditions, typically there is limited amount thin (less than about 25 microns) and thick (more than about 250 microns) material.

It addition, some carbonaceous material (such as corn stalk and switchgrass) and industrial waste (such as sawdust) or be not amenable to Crush or grinding operation, or may be unsuitable for directly using, such as owing to ultra-fine granularity.Such material can be formed The bead of suitable dimension or briquetting, for crushing or being directly used in such as fluidized-bed reactor.Generally, bead can be by compacting Prepared by one or more carbonaceous materials；See for example the US2009/0218424A1 being previously incorporated.In other examples, biological Material and coal can make briquetting, as described in US4249471, US4152119 and US4225457.Such bead or pressure Block can be used interchangeably in the following discussion with aforesaid carbonaceous particles.

According to the quality in carbonaceous material source, other feed procedure of processing may be required.Biomass may comprise High water capacity, such as green plants and grass, may require that dry before breaking.Municipal waste and sewage are likely to comprise height containing wet Amount (it can be such as by using press or roll crusher to reduce) (such as US4436028).Equally, abiotic matter (as High humility coal) crushing before may require that dry.Some binding coals may require that partial oxidation is to simplify operation.Lack ion exchange The abiotic matter feed (such as anthracite or petroleum coke) of position can produce other ion exchange site with pretreatment, to promote Catalyst loads and/or combines.Such pretreatment can be completed by any method known in the art, and its generation can The position of ion exchange and/or the porosity (see for example US4468231 and GB1599932 being previously incorporated) of raising feed. Oxidation pre-treatment can use any oxidant known in the art to complete.

Carbonaceous material ratio in carbonaceous particles and type can technology based on abiotic matter and biomass sources consider, Processing economy, availability and nearness select.Availability and nearness for the source of carbonaceous material can affect feed Price, and therefore affect the integral production cost of catalysis gasification method.Such as biomass and abiotic material can be with about 5:95, about 10:90, about 15:85, about 20:80, about 25:75, about 30:70, about 35:65, about 40:60, greatly About 45:55, about 50:50, about 55:45, about 60:40, about 65:35, about 70:20, about 75:25, about 80: 20, about 85:15, about 90:10, or about 95:5 weight ratio mixes, and based on weight in wet base or dry weight, this depends on processing bar Part.

Importantly, carbonaceous material source and this carbonaceous particles such as biomass microgranule and the single component of abiotic matter microgranule Ratio may be used for controlling the other materials characteristic of this carbonaceous particles.Abiotic material (such as coal) and some biological material (such as rice husk) typically comprises substantial amounts of inorganic substances, and it includes calcium, aluminium oxide and silicon dioxide, and it is shape in catalytic gasification device Become inorganic oxide (that is, ash).At the temperature higher than about 500 DEG C-about 600 DEG C, potassium and otheralkali metal meeting and ash In aluminium oxide and silicon dioxde reaction, form insoluble alkali metal aluminosilicate.In this form, alkali metal is substantially Water-insoluble, and be sluggish as catalyst.In order to prevent residue in hydrogenation methanator (200) Accumulation, the customary solid cleaning materials (58) (with (58a)) taking out by-product carbonizing matter, it comprises ash, unreacted carbon containing material Material and other compounds various (both such as alkali metal compound, water solublity and water-insoluble).

In the preparation of carbonaceous particles, the content of ashes of different carbonaceous materials can be chosen as the most about 20wt% or Less, or about 15wt% or less, or about 10wt% or less, or about 5wt% or less, this such as depends on various containing Initial ash in the ratio of material with carbon element and/or various carbonaceous material.In other embodiments, this carbonaceous particles formed Can comprise from about 5wt% or from about 10wt%, arrive about 20wt% or the content of ashes to about 15wt%, micro-based on carbon containing The weight of grain.In other embodiments, the content of ashes of this carbonaceous particles can comprise less than about 20wt%, or less than big About 15wt%, or less than about 10wt%, or less than about 8wt%, or the aluminium oxide less than about 6wt%, weight based on ash. In certain embodiments, this carbonaceous particles can comprise the content of ashes less than about 20wt%, based on the feed processed Weight, wherein the content of ashes of this carbonaceous particles comprises the aluminium oxide less than about 20wt%, or the oxidation less than about 15wt% Aluminum, weight based on ash.

Oxidation aluminum values the lowest in carbonaceous particles finally can reduce in the hydrogenation methanation portion of described method Catalyst loss, particularly base metal catalysts loss.As it appears from the above, aluminium oxide can react with alkaline source, produce insoluble Carbonizing matter, it comprises such as alkali metal aluminate or aluminosilicate.Such insoluble carbonizing matter can cause catalyst recovery yield Reduction (that is, the increase of catalyst loss), and in whole method, thus require supplementation with the other cost of catalyst.

Additionally, the carbonaceous particles formed can have the carbon of considerably higher percentage ratio, and the most higher btu/lb Value and the carbonaceous particles of the every unit weight of methane production.In certain embodiments, the carbon content of the carbonaceous particles formed can Being from about 75wt%, or from about 80wt%, or from about 85wt%, or from about 90wt%, until about 95wt%, based on Abiotic matter and the gross weight of biomass.

In one example, abiotic matter and/or biomass wet lapping (are such as arrived about 25-about 2500 with screening The particle size distribution of m), it is then discharged out its free water (that is, dehydration) uniformly wet cake.For wet lapping, sieve and be dehydrated Suitably the example of method is well known by persons skilled in the art；For example, see the US2009/0048476A1 being previously incorporated.Logical Cross abiotic matter that the wet lapping of a kind of embodiment according to the present invention formed and/or biomass microgranule filter cake containing wet Amount can be about 40%-about 60%, or about 40%-about 55%, or less than 50%.The most permissible Understanding, the water capacity of the wet lapping carbonaceous material of dehydration depends on carbonaceous material particular type, particle size distribution and used concrete Dehydration device.Such filter cake can carry out heat treatment as described herein, and the carbon containing producing one or more reduction humidity in next life is micro- Grain.

Each in one or more carbonaceous particles described can have the composition of uniqueness, as mentioned above.The most permissible Using two kinds of carbonaceous particles, wherein the first carbonaceous particles comprises one or more biological materials and the second carbonaceous particles comprises one Plant or multiple abiotic material.Selectively, single carbonaceous particles comprises one or more carbonaceous materials used.

Load for being hydrogenated with the catalyst of methanation (350)

Hydrogenation methanation catalyst is lateral reactivity for being catalyzed at least the above reaction (I), (II) and (III).So Catalyst well known to a person skilled in the art in general sense, and can include such as alkali metal, alkaline-earth metal and Transition metal and its compound and complex.Typically, this hydrogenation methanation catalyst comprises at least alkali metal, as being disclosed in In the list of references that many is previously incorporated.

For hydrogenation methanation reaction, these one or more carbonaceous particles are typically processed further, with at least one Plant hydrogenation methanation catalyst (typically comprising at least one alkali metal source) to combine, produce the carbon containing feed (31+ of catalysis 32).If using liquid carbon-containing material, then this hydrogenation methanation catalyst can the most closely be mixed in liquid carbon-containing material.

This carbonaceous particles being supplied to catalyst loading can process the carbon containing feed (31+32) forming catalysis, its quilt Deliver to be hydrogenated with in methanator (200), it is also possible to be divided into one or more processing stream, this processing stream of at least one of which with Hydrogenation methanation catalyst combines the feedstock flow forming at least one catalyst treatment.Remaining processing stream can such as process and Its second component combines.Combine additionally, the feedstock flow of this catalyst treatment can process for the second time with second component.Second Component can the e.g. second hydrogenation methanation catalyst, a kind of promoter, or other additives.

In one example, main hydrogenation methanation catalyst (alkali metal compound) can be supplied to single carbonaceous particles (such as potassium and/or sodium source), processes the most respectively and provides one or more promoters and additive (such as calcium source) to same One single carbonaceous particles, produces the carbon containing feed (31+32) of catalysis.For example, see the US2009/0217590A1 being previously incorporated And US2009/0217586A1.

Hydrogenation methanation catalyst and second component can also be supplied to single the as mixture in single process Two carbonaceous particles, produce the carbon containing feed (31+32) of catalysis.

When providing one or more carbonaceous particles to load for catalyst, then at least one this carbonaceous particles and hydrogenation first Alkanizing catalyst combines the feedstock flow forming at least one catalyst treatment.Additionally, any carbonaceous particles can be as above Describe in detail, be divided into one or more processing stream, combine for the component with second or other.The stream formed can be to appoint What combination mixes, and provides the carbon containing feed (31+32) of catalysis, and condition is the feedstock flow quilt of at least one catalyst treatment For forming the feedstock flow of catalysis.

In one embodiment, by least one carbonaceous particles and hydrogenation methanation catalyst and optionally second component In conjunction with.In an alternate embodiment, each carbonaceous particles with hydrogenation methanation catalyst and optionally second component be combined.

Can use any method well known by persons skilled in the art by one or more hydrogenation methanation catalysts with This any carbonaceous particles and/or processing stream combine.Such method includes but not limited to mix with solid catalyst source, and will Catalyst is impregnated on the carbonaceous material of processing.Several dipping method well known by persons skilled in the art may be used for being mixed into hydrogenation Methanation catalyst.These methods include but not limited to incipient wetness impregnation, vapo(u)rability dipping, vacuum impregnation, dip-coating dipping, from Son exchange and the combination of these methods.

In one embodiment, alkali metal hydrogenation methanation catalyst can be by using the molten of catalyst in packing groove Liquid (such as aqueous solution) slurrying, and be impregnated in one or more carbonaceous particles and/or processing stream.When with catalyst and/or During the solution slurrying of promoter, the slurry formed can be dehydrated the feedstock flow providing catalyst treatment to cross, equally typical case Ground is as wet cake.This catalyst solution can be prepared by any catalyst source in the method for the invention, including new or The catalyst supplemented and the catalyst of recirculation or catalyst solution.For slurry dehydration is provided that catalyst treatment crosses to The method of the wet cake of stream includes filtering (gravity or vacuum), centrifugation and fluid compacting.

In another embodiment, as disclosed in the US2010/0168495A1 being previously incorporated, by this carbonaceous particles with Aqueous catalyst solution combines, and produces the wet cake of substantially not draining, mixes the most under the high temperature conditions, and be finally dried to fit When containing wet level.

A kind of be suitable to be combined coal microgranule and/or the processing stream that comprises coal with hydrogenation methanation catalyst provide catalyst The concrete grammar of the feedstock flow processed is via in US2009/0048476A1 and US2010/0168494A1 being such as previously incorporated Described ion exchange.The catalyst managed by ion exchanger is loaded can be based on the adsorption isotherm developed exclusively for coal And maximize, as described in introduced list of references.Such loading provides the feed of the catalyst treatment as wet cake Stream.The other catalyst (including the catalyst being in hole) being retained in the microgranule wet cake of ion exchange can be controlled, with Make it possible to obtain total catalyst desired value in a controlled manner.The catalyst total amount loaded can be by controlling in solution The concentration of catalytic component and time of contact, temperature and method control, as disclosed in the list of references of aforementioned introducing, And as feature as based on initial coal in those skilled in the art can easily determine.

In another example, one of this carbonaceous particles and/or processing stream can process with hydrogenation methanation catalyst, and the Two processing streams can process with second component (seeing the US2007/0000177A1 being previously incorporated).

Carbonaceous particles, processing stream and/or the feedstock flow by aforementioned formed catalyst treatment can be in any combination Mixing, to provide the second carbon containing feed of catalysis, condition is that the feedstock flow that at least one catalyst treatment is crossed is used to form The carbon containing feed (31+32) of catalysis.Finally, deliver to be hydrogenated with methanator (200) by the carbon containing feed (31+32) of catalysis.

Generally, each catalyst load units comprises at least one packing groove, by carbonaceous particles and/or processing stream Solution that is one or more and that comprise at least one hydrogenation methanation catalyst contacts, and forms one or more catalyst treatment mistake Feedstock flow.Selectively, catalyst component can be mixed into one or more carbonaceous particles and/or processing stream as solid particle In, to form the feedstock flow of one or more catalyst treatment.

Typically, it is only or during substantially alkali metal that it is at the carbon containing feed of catalysis when being hydrogenated with methanation catalyst In exist with such amount, this amount be enough to provide the alkali metal atom ratio with the carbon atom in the carbon containing feed of catalysis for from greatly About 0.01, or from about 0.02, or from about 0.03, or from about 0.04, to about 0.10, or to about 0.08, or to big About 0.07, or to about 0.06.

For some feeds, alkaline components can also provide in the carbon containing feed of catalysis, realizes containing than catalysis The total ash content of the combination of the carbonaceous material in carbon feed the is big alkali metal content of about 3-about 10 times, based on quality.

Suitably alkali metal is lithium, sodium, potassium, rubidium, caesium and mixture thereof.It is especially useful that potassium source.Suitably alkali metal Compound includes alkali carbonate, bicarbonate, formates, oxalates, amide, hydroxide, acetate or similar change Compound.Such as this catalyst can comprise following one or more: sodium carbonate, potassium carbonate, rubidium carbonate, lithium carbonate, cesium carbonate, Sodium hydroxide, potassium hydroxide, rubidium hydroxide or Cesium hydrate., and particularly potassium carbonate and/or potassium hydroxide.

Optional promoter or other catalyst additives, such as institute in above introduced list of references can be used Those disclosed.

The feedstock flow (a combination thereof is to form the carbon containing feed of catalysis) that one or more catalyst treatment are crossed typically comprises The carbon containing feed (31+32) with catalysis more than about 50%, more than about 70% or more than about 85% or more than about 90% In conjunction with the catalyst total amount of loading.Percent of total (its feedstock flow phase crossed with various catalyst treatment of the catalyst loaded Close) can determine according to method known to those skilled in the art.

Feedstock flow and processing stream that carbonaceous particles respectively, catalyst treatment are crossed can suitably mix, and control the most total Other qualities of the carbon containing feed (31+32) that catalyst loads or is catalyzed, as previously mentioned.The adequate rate of the various streams of combination will Depend on the quality of carbonaceous material, comprise each and desired performance of the carbon containing feed (31+32) of catalysis.Such as biomass The abiotic matter microgranule stream of microgranule stream and catalysis can produce have urging of predetermined content of ashes with such ratio combine The carbon containing feed (31+32) changed, as previously mentioned.

Feedstock flow, processing stream and the feedstock flow of processing that any Above-mentioned catalytic agent processed, as one or more are dried micro- Grain and/or one or more wet cakes, can combine by any method known to those skilled in the art, and it includes but does not limits In kneading, and horizontal or vertical mixer instance such as single screw rod or twin screw, spiral or barrel mixer.Containing of the catalysis formed Carbon feed (31+32) can store until after with or transfer to one or more feed operation in, be used for being incorporated into hydrogenation first In alkylation reactors.The carbon containing feed of catalysis can be sent to storage according to any method well known by persons skilled in the art or supply Material operation, such as feed screw or pneumatic transfer.

According to the present invention, this carbon containing feed comprises following high water capacity when input hydrogenation methanator: be more than 10wt%, or about 12wt% or bigger, or about 15wt% or bigger, to about 25wt% or less, or to about 20wt% or more Few (gross weight based on carbon containing feed), to such degree, i.e. this carbon containing feed is the most free-pouring.

As used herein, term " substantially flow freely " represent carbon containing feed microgranule under feeding conditions not because Water capacity and reunite.It is desirable that the water capacity of this carbon containing feed microgranule substantially includes, so that the most few (or Do not have) surface moisture.

The carbon containing feed (31+32) of a kind of suitably the most free-pouring catalysis can be according to being previously incorporated The disclosure of US2010/0168494A1 and US2010/0168495A1 produces, wherein mentioned in those are open heat Process step (after catalyst applies) and (or it could even be possible to eliminating) can be minimized.

The dampness of excess can be removed to required degree from the carbon containing feed (31+32) of catalysis.Such as this catalysis Carbon containing feed (31+32) can be dried (that is, process with superheated steam and evaporate liquid) with liquid bed slurry drying machine, or very Empty lower thermal evaporation or removing solution are dried, or flow down dry at noble gas, provide and have required residual water capacity The carbon containing feed of catalysis.

Catalyst reclaims (300)

The reaction under the described conditions of the carbon containing feed (31+32) of catalysis is the commonly provided from hydrogenation methanator (200) crude product stream (52) of lean fines methane rich and solid char thing by-product (58) (with (58a)).Solid char thing is secondary Product (58) typically comprises a certain amount of unreacted carbon, inorganic ash content and the catalyst carried secretly.Solid char thing by-product (58) can remove from hydrogenation methanator (200), be used for sampling, purify and/or urging via carbonizing matter outlet recovery Agent.

As used herein, term " catalyst carried secretly " represents chemical compound, and it comprises hydrogenation methanation catalyst Alkali metal compound present in the catalytical active part of agent, such as carbonizing matter by-product.Such as " catalyst carried secretly " is permissible Include but not limited to soluble alkali metal compound (such as alkali carbonate, alkali metal hydroxide and alkali metal oxide) And/or insoluble alkali cpd (such as alkali metal aluminosilicate).The character of the catalytic component relevant with the carbonizing matter extracted At US2007/0277437A1, US2009/0165383A1, US2009/0165382A1, US2009/ of being such as previously incorporated 0169449A1 and US2009/0169448A1 is discussed.

Solid char thing by-product is continuously or periodically to be exported by carbonizing matter from hydrogenation methanator (200) Taking out, it can e.g. lock hopper system, although additive method is also well known by persons skilled in the art.Removing solid is burnt The method of compound product is to well known to a person skilled in the art.The one that such as EP-A-0102828 can be used to be instructed is this kind of Method.

Carbonizing matter by-product (58) from hydrogenation methanator (200) can be delivered to be catalyzed recovery unit (300), As described below.Such carbonizing matter by-product (58) can also be divided into multiple stream, and one of them can be delivered to catalyst and reclaim single Unit (300), its another stream can serve as such as methanation catalyst (institute in the US2010/0121125A1 being such as previously incorporated State), and do not process for catalyst recovery.

In certain embodiments, when being hydrogenated with methanation catalyst and being alkali metal, in solid char thing by-product (58) Alkali metal can reclaim and produce catalyst recirculation flow (57), and any unrecovered catalyst can pass through catalyst Supplement stream (57) and compensate (see for example the US2009/0165384A1 being previously incorporated).Aluminium oxide in feed adds titanium dioxide Silicon is the most, it is thus achieved that the higher alkali metal response rate is the most expensive.

In one embodiment, solid char thing by-product (58) from hydrogenation methanator (200) is permissible With recirculation gas and water quencher, extract the catalyst that a part is carried secretly.The catalyst (57) reclaimed can import catalyst In filling unit (350), reusing for base metal catalysts.The carbonizing matter (59) of dilution can such as import to any One or more feed preparation manipulations (100) in, be reused for preparation catalysis feed (via pipeline (59a)), burning Drive one or more steam generator (as disclosed in the US2009/0165376A1 being previously incorporated)), or be so used for In multiple application, it is used for example as absorbent (as disclosed in the US2009/0217582A1 being previously incorporated).

Other useful especially recovery and method for recycling are described in US4459138, and the US2007/ being previously incorporated 0277437A1, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/ In 0169448A1.About further method details, it is referred to those documents.

Catalyst can be recycled to one or a combination set of catalyst loading process.Whole catalyst recycle can To input a catalyst loading process, and another process is just with supplementary catalyst.In catalyst loading process, can To control the recirculation level to supplementary catalyst based on single.

In addition to catalyst reclaims, by-product carbonizing matter (58) can also process for reclaiming other by-products, example Such as vanadium, as disclosed in the US patent application 13/094438 being previously incorporated.

Multi-stage process

In the process of the present invention, each process can be carried out in one or more machining cells.Such as can be in the future Load from one or more catalyst and/or the carbon containing feed of feedstock preparation unit operation inputs one or more hydrogenation methanations Reactor.Similarly, can be distinguished by the crude product stream of methane rich produced by one or more hydrogenation methanators Processing or purify or process via them in the combination of different point downstream or purify, this depends on concrete system structure, Such as US2009/0324458A1, US2009/0324459A1, US2009/0324460A1, US2009/ of being previously incorporated Discussed in 0324461A1 and US2009/0324462A1.

In certain embodiments, described method uses two or more hydrogenation methanators (such as 24 hydrogenation Methanator).In such embodiments, the method can comprise and dissipates processing before hydrogenation methanator Unit (that is, less than the sum of hydrogenation methanator), provides multiple hydrogenation first for the carbon containing feed being catalyzed the most at last In alkylation reactors, and/or convergence machining cell can be comprised after hydrogenation methanator (that is, less than hydrogenation methane Change the sum of reactor), for processing by the crude product stream of multiple methane rich produced by multiple hydrogenation methanators.

When described system comprises convergence machining cell, each convergence machining cell can select have acceptance more than meeting The ability of total feed streams 1/n part of poly-machining cell, n is the number assembling machining cell here.Similarly, comprise when system When dissipating machining cell, each machining cell that dissipates can select have the total confession accepted more than being supplied to assemble machining cell The ability of the 1/m part of stream, m is the number dissipating machining cell here.

The embodiment of specific embodiments

A kind of specific embodiments of described method is such scheme, and wherein the method is continuation method, walks wherein Suddenly (a), (b) and (c) is to run in a continuous manner.

Another kind of specific embodiment is such scheme, wherein when being incorporated into fluid bed bottom or before mixed Vapours stream and the stream of oxygen rich air.

Another kind of specific embodiment is such scheme, wherein the gas stream (14) of oxygen rich air is inputted hydrogenation continuously In methanator (200), and the amount of the oxygen provided changes as process control, such as to control hydrogenation The desired running temperature of methanation reaction.When oxygen input hydrogenation methanator, the oxidation/combustion reaction formed (such as with the reaction of the carbon in by-product carbonizing matter and fines) create heat energy (and the most same amount of carbon monoxide and Hydrogen).The amount of oxygen that can increase or reduce input hydrogenation methanator improves or reduces burning/oxidation and thus Amount at the heat energy that hydrogenation methanator situ produces.

Another kind of specific embodiment is such scheme, the crude product stream of methane rich is wherein incorporated into the first heat and hands over Exchange unit reclaims heat energy and produces the crude product stream of the methane rich cooled down.

Another kind of specific embodiment is such scheme, the heat energy that wherein will reclaim in the first heat exchanger unit For producing the first process vapor stream, with this first process vapor stream of superheated, that comes as all or a portion is overheated Steam stream, is incorporated in hydrogenation methanator.

Another kind of specific embodiment is such scheme, at least in the crude product stream of the methane rich wherein cooled down Part carbon monoxide is changed to produce the crude product stream of heat energy and hydrogen rich gas by steam.

Another kind of specific embodiment is such scheme, wherein reclaims heat energy from steam conversion, and will at least The heat energy that a part reclaims, for superheated boiler water supply, is used for producing process vapor.

Another kind of specific embodiment is such scheme, is wherein fully dehydrated the crude product stream of hydrogen rich gas to produce The crude product stream of the hydrogen rich gas of dehydration.

Another kind of specific embodiment is such scheme, wherein by most carbon dioxide and most sulfuration Hydrogen removes from the crude product stream of the hydrogen rich gas of dehydration, to be produced the gas of depriving hydrogen sulphide by the crude product stream of the hydrogen rich gas of this dehydration Body stream, it comprises most hydrogen, carbon monoxide (if present in the crude product stream of the hydrogen rich gas of dehydration) and first Alkane.

Another kind of specific embodiment is such scheme, wherein separates a part of hydrogen from the gas stream of depriving hydrogen sulphide To produce the gas stream of the depriving hydrogen sulphide of hydrogen gas product stream and hydrogen-depleted gas, (it comprises methane, hydrogen and an optionally oxidation to gas Carbon).

Another kind of specific embodiment is such scheme, and (or hydrogen-depleted gas is de-wherein to make the gas stream of depriving hydrogen sulphide The gas stream of hydrogen sulfide, if present) in the presence of carbon monoxide and hydrogen in the presence of methanation catalyst, urging Change in methanator and react to produce the gas stream of the depriving hydrogen sulphide of heat energy and methane rich.

Another kind of specific embodiment is such scheme, wherein reclaims heat energy from catalytic production of methane, and near The heat energy that a few part reclaims is for producing and superheated the second process vapor stream.

Another kind of specific embodiment is such scheme, and wherein this flow of superheated steam basically comprises (or optional Ground only comprises) from the first process vapor stream and the steam of the second process vapor stream.

Another kind of specific embodiment is such scheme, and wherein the method is steam neutrality or steam positivity.

Another kind of specific embodiment is such scheme, wherein in the steady-state operation of the method, does not use fuel The superheater of heating carrys out the steam of superheated input hydrogenation methanator, and this steam comes only by the process heat reclaimed Superheated.

Another kind of specific embodiment is such scheme, and wherein the gas stream of the depriving hydrogen sulphide of this methane rich is conduct Methane product stream reclaims.

Another kind of specific embodiment is such scheme, and wherein this methane product stream is the natural gas of pipeline quality.

Another kind of specific embodiment is such scheme, the wherein target of this hydrogenation methanation reaction (step (b)) Running temperature is at least about 1000 °F (about 538 DEG C)-about 1500 °F (about 816 DEG C), as mentioned above.

Another kind of specific embodiment is such scheme, wherein this flow of superheated steam input temp is of about 500 ° The hydrogenation methanator of F (about 260 DEG C)-about 950 °F (about 510 DEG C), as mentioned above.

Another kind of specific embodiment is such scheme, is wherein combined by the stream of flow of superheated steam and oxygen rich air, defeated Enter the lower area to the fluid bed being hydrogenated with methanator, and the temperature of this combination stream is about 500 °F (about 260 DEG C)-about 900 °F (about 482 DEG C), as mentioned above.

Another kind of specific embodiment is such scheme, and wherein the synthesis gas (step (c)) by producing in situ comes Substantially meet (or meeting) synthesis gas demand；So, there is no that (or not having) synthesis gas joins this hydrogenation methanation In reactor (in addition in the carbon containing feed that may be inherently present in defeated time hydrogenation methanator or fines stream).

Another kind of specific embodiment is such scheme, wherein by being recycled back in hydrogenation methanator Flow of superheated steam, the gas stream of oxygen rich air and fines stream in steam and the steam that produced in situ by carbon containing feed come basic Upper satisfied (or meeting) steam demand.

Another kind of specific embodiment is such scheme, is wherein providing the whole of hydrogenation methanator Primary flow (steam stream, the gas stream of oxygen rich air, carbon containing feed/hydrogenation methanation catalyst and fines recirculation flow) is less than adding When the temperature of the object run temperature of hydrogen methanator introduces, come the fullest by the heat (step (c)) produced in situ Foot (or meeting) heat demand.

Another kind of specific embodiment is such scheme, is wherein supplied to carbon containing feed in feed position be hydrogenated with first In alkanisation, carbonizing matter by-product is to be produced by the reaction of step (b) and (c), and carbonizing matter by-product is higher than containing Carbon feed, on the off-take point of shots, continuously or periodically takes out from hydrogenation methanator.Another kind of embodiment party In case, carbonizing matter by-product is periodically or continuously from fluid bed top to take out.

Another kind of specific embodiment is such scheme, is wherein carried by the by-product carbonizing matter taken out at least partially It is fed in catalyst reclaimer operation.Reclaim catalyst then recirculation and is combined with supplementary catalyst meet be hydrogenated with methanation The demand of reaction.

Claims

1. the method being produced the crude product gas stream of methane rich by on-gaseous carbonaceous material, the method comprising the steps of:

A () supplies in hydrogenation methanator

(2) hydrogenation methanation catalyst,

(3) flow of superheated steam, and

(4) the gas stream of oxygen rich air,

Wherein said hydrogenation methanator comprises fluid bed, and described fluid bed has the top higher than bottom, and wherein will The gas stream of described flow of superheated steam and described oxygen rich air is incorporated into the described bottom of described fluid bed；

(b) at a temperature of object run, in the presence of hydrogenation methanation catalyst, carbon monoxide, hydrogen and steam, make described in add Carbon containing feed reaction described in a part in hydrogen methanator, to produce crude product gas stream and the solid by-product of methane rich Thing carbonizing matter, the crude product gas stream of wherein said methane rich comprise methane, carbon monoxide, hydrogen, carbon dioxide, hydrogen sulfide, Steam, heat energy and the fines carried secretly；With

Wherein:

I the reaction of () step (b) accounts for leading on fluid bed top；

(ii) reaction of step (c) accounts for leading in fluid bed bottom；With

(iii) gross weight based on described carbon containing feed, described carbon containing feed comprises when being supplied to and being hydrogenated with methanator From the high water capacity more than 12wt% to 25wt%, it reaches such degree, i.e. making described carbon containing feed is substantially certainly By flow.

2. the method for claim 1, is characterised by that described carbon containing feed comprises 15wt% when input hydrogenation methanator Or bigger high water capacity.

3. the method for claim 1, is characterised by that described carbon containing feed comprises 20wt% when input hydrogenation methanator Or lower high water capacity.

4. the method for claim 2, is characterised by that described carbon containing feed comprises 20wt% when input hydrogenation methanator Or lower high water capacity.

5. the method for claim 1, is characterised by that the reaction of step (b) has synthesis gas demand and heat demand, and described heat needs Summation synthesis gas demand is that the reaction by step (c) substantially meets；Reaction with step (b) has steam demand, And described steam demand is by the steaming in the input flow of superheated steam of fluid bed bottom, the gas stream of oxygen rich air and fines stream Vapour and substantially met by steam produced by carbon containing feed.

6. the method for claim 1, is characterised by described flow of superheated steam, the gas stream of oxygen rich air, carbon containing feed and hydrogenation Methanation catalyst is incorporated in hydrogenation methanator in the temperature of the object run temperature of the reaction less than step (b).

7. the method for claim 1, is characterised by that described object run temperature is 1000 °F-1500 °F.

8. the method for claim 1, is characterised by the methane in crude product gas stream based on methane rich, carbon dioxide, an oxygen Changing carbon and the molal quantity of hydrogen, the crude product gas stream of described methane rich comprises methane and at least 50mol% of at least 15mol% Methane plus carbon dioxide.

9. the method for claim 1, is characterised by the crude product gas stream of described methane rich is incorporated into the first heat exchanger list Unit reclaims heat energy and produces the crude product gas stream of the methane rich cooled down；Crude product gas stream by the methane rich of described cooling In at least some of carbon monoxide carry out steam conversion to produce heat energy and the crude product stream of hydrogen rich gas；By described hydrogen rich gas Crude product stream is fully dehydrated the crude product stream of the hydrogen rich gas to produce dehydration；Remove from the crude product stream of the hydrogen rich gas of described dehydration Remove most carbon dioxide and most hydrogen sulfide, produce depriving hydrogen sulphide with the crude product stream of the hydrogen rich gas by described dehydration Gas stream, its comprise most hydrogen, if present in dehydration hydrogen rich gas crude product stream in carbon monoxide and first Alkane；With carbon monoxide and hydrogen will be made present in the gas stream of described depriving hydrogen sulphide in catalytic methane converter in methanation React in the presence of catalyst, to produce the gas stream of the depriving hydrogen sulphide of heat energy and methane rich.

10. the method for any one of claim 1-8, is characterised by the crude product gas stream of described methane rich is incorporated into the first heat Exchanger unit reclaims heat energy and produces the crude product gas stream of the methane rich cooled down；With will be in the first heat exchanger unit The heat energy reclaimed for producing the first process vapor stream, and the first process vapor stream described in superheated, come as whole or The flow of superheated steam of a part is incorporated in hydrogenation methanator；By in the crude product gas stream of the methane rich of described cooling At least some of carbon monoxide carry out steam conversion to produce heat energy and the crude product stream of hydrogen rich gas；Come from the conversion of described steam Reclaim heat energy, and the heat energy reclaimed at least partially is used for superheated boiler water supply, be used for producing process vapor；By institute The crude product stream stating hydrogen rich gas is fully dehydrated the crude product stream of the hydrogen rich gas to produce dehydration；Thick from the hydrogen rich gas of described dehydration Product stream removes most carbon dioxide and most hydrogen sulfide, miscarries with the crude product of the hydrogen rich gas by described dehydration The gas stream of raw depriving hydrogen sulphide, it comprises most hydrogen, if present in the crude product stream of the hydrogen rich gas of dehydration Carbonoxide and methane；To make present in the gas stream of described depriving hydrogen sulphide carbon monoxide and hydrogen in catalytic methane converter React in the presence of methanation catalyst, to produce the gas stream of the depriving hydrogen sulphide of heat energy and methane rich；And from described catalysis Methanation is reclaimed heat energy, and is used for the heat energy reclaimed at least partially producing and superheated the second process vapor stream.

The method of 11. claim 10, is characterised by that flow of superheated steam mainly comprises and comes from the first process vapor stream and second The steam of process vapor stream.