CN103249815A

CN103249815A - Hydromethanation of a carbonaceous feedstock

Info

Publication number: CN103249815A
Application number: CN201180052570XA
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: 2013-08-14
Anticipated expiration: 2031-10-28
Also published as: JP2013541622A; KR20130109173A; EP2635660A1; CA2814201A1; CN103249815B; WO2012061238A1; AU2011323648A1; US20120102837A1

Abstract

The present invention relates to processes for hydromethanating a carbonaceous feedstock to a methane-enriched synthesis gas, where an oxygen-rich gas stream and the carbonaceous feedstock are fed into a fluidized-bed hydromethanation reactor, and where the carbonaceous feedstock as fed into the hydromethanation reactor has an elevated moisture content in order, for example, to assist in heat management within the hydromethanation reactor.

Description

The hydrogenation methanation of carbon containing feed

Invention field

The present invention relates to carbon containing feed hydrogenation methane is changed into the method for the synthetic gas of methane rich, wherein by the gas stream of oxygen rich air and carbon containing feed input fluidized-bed hydrogenation methanator, and wherein when this hydrogenation methanator of input, this carbon containing feed has high water capacity, and purpose is the heat management for example contributed in this hydrogenation methanator.

Background of invention

Due to factors higher energy prices and environmental concern for example, the carbon containing feed (for example refinery coke, Residual oil, bituminous matter, coal and biomass) be worth by low fuel is produced value-added product (for example pipeline quality substitute natural gas, hydrogen, methyl alcohol, higher hydrocarbon, ammonia and electric energy) and has again been received concern.

Such low fuel is worth can gasify under high temperature and high pressure next life production of synthetic gas of carbon containing feed and flows, and it can change into such value-added product subsequently.

A kind of favourable gasification process is the hydrogenation methanation, wherein by the carbon containing feed in the fluidized-bed hydrogenation methanator, synthetic air-flow (middle BTU the synthesizes air-flow) crude product of the production methane rich that directly is converted under the catalyst source in suitable high temperature and high pressure and steam exist.This obviously is different from conventional gasification process, those method (hot gas based on carbon source partial combustion/oxidation under high temperature and high pressure for example, be typically non-catalytic), wherein synthetic gas (carbon monoxide+hydrogen) is primary product (seldom or not directly producing methane), then it can further process to produce perhaps many other higher hydrocarbon products of methane (via catalytic production of methane, referring to following reaction (III)).

The synthetic air-flow of the formed methane rich of hydrogenation methanation method and conversion/utilize is produced value-added product and is disclosed in for example 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, in US2011/0217602A1 and GB1599932.Can also be referring to people such as Chiaramonte, " Upgrade Coke by Gasification ", Hydrocarbon Processing, September nineteen eighty-two the 255-257 page; With the people such as Kalina, " Exxon Catalytic Coal Gasification Process Predevelopment Program, Final Report ", Exxon Research and Engineering Co., Baytown, TX, FE236924, in December, 1978.

The hydrogenation methanation of carbon source typically comprises four reactions that separate in theory:

Steam carbon: C+H ₂o → CO+H ₂(I)

Water-gas shift: CO+H ₂o → H ₂+ CO ₂(II)

CO methanation: CO+3H ₂→ CH ₄+ H ₂o (III)

Hydrogasification: 2H ₂+ C → CH ₄(IV)

In this hydrogenation methanation reaction, the W-response below three reactions in front (I-III) have mainly caused:

2C +2H ₂O → CH ₄ + CO ₂ (V)。

This integral body hydrogenation methanation reaction is basically thermally equilibrated; But, for example, owing to process thermosteresis and other energy requirements (evaporating the required energy of moisture that enters into reactor with feed), must add some heat to keep thermal equilibrium.

This reaction is also (produces and consume synthetic gas) of synthetic gas (hydrogen and carbon monoxide) balance basically; So, when carbon monoxide, when hydrogen takes out together with product gas, must as required carbon monoxide and hydrogen be joined in reaction to avoid occurring deficiency.

For the net heat that keeps reaction approaches neutral (only marginally heat release or heat absorption) as far as possible, and keep the synthetic gas balance, often by this hydrogenation methanator of the overheated gas of steam, carbon monoxide and hydrogen stream input.Often, carbon monoxide is the recirculation flow separated from product gas with hydrogen stream, and/or provides by the product methane of a reformation/partial oxidation part.Referring to the US4094650 for example introduced previously, US6955595 and US2007/083072A1.

In a kind of variant of this hydrogenation methanation method, required carbon monoxide, hydrogen and heat energy also can come original position at least in part to produce by oxygen being inputted in the hydrogenation methanator.Referring to the US2010/0076235A1 for example introduced previously and US2010/0287835A1 and US patent application 13/211476 (the attorney docket FN-0063 US NP1 that owns together, title is Hydromethanation of a Carbonaceous Feedstock), its applying date is on August 17th, 2011; With the US provisional application 13/228821 of owning together (attorney docket FN-0064 US NP1, title is Hydromethanation of a Carbonaceous Feedstock), it is application on September 9th, 2011.

Result is that the crude product gas stream of " directly " methane rich also contains a large amount of hydrogen, carbon monoxide and carbonic acid gas, it can be for example directly as the middle BTU energy, maybe can process to produce multiple high value products stream, as substitute natural gas, high-purity hydrogen, methyl alcohol, ammonia, higher hydrocarbon, carbonic acid gas (for oil recovery rate and the industrial use improved) and the electric energy of pipeline quality.

In the variant of above-mentioned hydrogenation methanation method, wherein will produce required carbon monoxide, hydrogen and heat energy in the oxygen input reactor for this hydrogenation methanation reaction, main focus is to form focus, and controls and distribute the heat energy produced by oxidizing reaction.The heat management of the difference in the hydrogenation methanator for example can cause too early (being sometimes catastrophic) failure of apparatus, and the caking of carbonaceous material.

Therefore, the problem that solves heat management in the hydrogenation methanator is true(-)running and a key issue optimizing hydrogenation methanation method, the invention provides a kind of solution for this heat management problems.

Summary of the invention

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

(a) in the hydrogenation methanator, supply with

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

(2) hydrogenation methanation catalyst,

(3) flow of superheated steam, and

(4) gas stream of oxygen rich air,

Wherein this hydrogenation methanator comprises fluidized-bed, and described fluidized-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 to this bottom of this fluidized-bed;

(b) at the object run temperature, under hydrogenation methanation catalyst, carbon monoxide, hydrogen and steam exist, make this carbon containing feed reaction of a part in this hydrogenation methanator, to produce thick gas and the solid by-product carbonizing matter of methane rich, the fines that wherein the thick gas of this methane rich comprises methane, carbon monoxide, hydrogen, carbonic acid gas, hydrogen sulfide, steam, heat energy and carries secretly; With

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

Wherein:

(i) reaction of step (b) accounts for leading on fluidized-bed top;

(ii) reaction of step (c) accounts for leading in the fluidized-bed bottom; With

(iii) this carbon containing feed comprises from being greater than the high water capacity of 10wt% to about 25wt% (gross weight based on this carbon containing feed) when being supplied to the hydrogenation methanator, it reaches such degree, that is it is basically free-pouring, making this carbon containing feed.

Method of the present invention can be for for example coming production high value products and by product by various carbonaceous materials.

Except heat management problems, ability in the methanation of the carbon containing feed of higher water capacity input hydrogenation has been improved to the whole efficiency of described method, this is owing to for example having reduced necessary drying in the feed preparation, will further discussing in detail as following.

These and other embodiments of the present invention, feature and advantage will become and be easier to understand to those skilled in the art by reading following detailed description.

Brief Description Of Drawings

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

Fig. 2 produces one or more value-added product for the further crude product stream of processing methane rich, as hydrogen, substitute natural gas and/or electric energy, a kind of embodiment.

Describe in detail

The present invention relates to for the on-gaseous carbonaceous material finally being changed into to the method for one or more increment gaseous products.Further details below is provided.

In the context of the present specification, if there is no not outer pointing out, mentioned herein and whole open source literatures, patent application, patent and other reference all be incorporated to this paper by the totality of introducing with them clearly, for all purposes just as illustrating fully.

Unless otherwise prescribed, otherwise whole scientific and technical terminology used herein has common the understood identical implication with the application those skilled in the art.In the situation of contradiction, with the application's application documents (comprising definition), be as the criterion.

Unless clearly dated, otherwise trade mark means with capitalization.

Except as otherwise noted, otherwise whole percentage, umber, ratio etc. all be by weight.

Except as otherwise noted, otherwise the pressure provided with psi unit is gauge pressure, with the pressure of kPa unit representation, is absolute value.

When a certain amount, concentration or other values or parameter are while providing with scope, or one when listing limit value and lower value and providing, this is understood to clearly disclose any a pair of whole scope formed by any upper and lower bound, and no matter whether disclose respectively described scope.Quoted the numerical value part of certain limit here, unless otherwise directed, otherwise described scope is intended to comprise its end points, and whole integers and mark in this scope.When the range of definition, its purpose not plan limits the scope of the invention to described occurrence.

When term " approximately ", when meaning the end points of value or scope, the present invention should be understood to comprise described occurrence or end points.

As used herein, term " comprises ", " comprising ", " comprising ", " comprising ", " having ", " having " or its any other variation are intended to cover non-exclusive inclusion.For example, a kind of processing, method, goods or the equipment that comprises a row key element needn't only be confined to those key elements, but can comprise key element or the intrinsic key element of these processing, method, goods or equipment that other is not clearly listed.

In addition, unless the contrary is expressly indicated otherwise, otherwise "or" and " and/or " refer to a kind of inclusive or, and nonexcludability.For example, condition A or B, or A and/or B meet following any one: A is that genuine (or existence) and B are false (or non-existent), A is that false (or non-existent) and B are genuine (or existence), and A and B the two be all genuine (or existence).

Being used for describing the various key elements of this paper and " " or " a kind of " of component is only for convenient, and provides on general sense open.This description should be read as comprise a kind of or at least one, unless and its implication clearly, otherwise this odd number equally also comprises plural number.

As used herein, unless definition separately arranged here, otherwise term " basically " means to be greater than about 90% mentioned material, is preferably greater than about 95% mentioned material, and more preferably greater than about 97% mentioned material.If regulation not, per-cent for example, is based on mole when mentioning molecule (methane, carbonic acid gas, carbon monoxide and hydrogen sulfide), otherwise is based on (for example, for the fines of carrying secretly) of weight.

As used herein, unless definition is separately arranged here, term " major portion " means to be greater than 50% mentioned material.If regulation not, per-cent for example, is based on mole when mentioning molecule (hydrogen, methane, carbonic acid gas, carbon monoxide and hydrogen sulfide), otherwise is based on (for example fines to carrying secretly) of weight.

Term " poor " with from initial amount decline synonym.For example from fluid, remove the stream that most a kind of material will produce poor material, it is poor described material basically.Contrary, term " richness " be greater than initial amount synonym.

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

As used herein, term " carbonaceous material " is the material that contains the organic hydrocarbon composition.According to the definition here, carbonaceous material can be divided into biomass or abiotic material.

As used herein, term " biomass " refers to and derives from the organic carbonaceous material that (for example passing by 100 years in) lives recently, comprises plant base biomass and animal based biomass.For the sake of clarity, biomass do not comprise for example coal of fossil base carbonaceous material.For example, referring to the US2009/0217575A1 introduced previously, US2009/0229182A1 and US2009/0217587A1.

As used herein, term " plant base biomass " means to derive from following material: green plants, farm crop, algae and tree, and for example, such as but not limited to sweet sorghum, bagasse, sugarcane, bamboo, little black poplar, hybridization willow, acacia (albizia tree), eucalyptus, clover, clover, oil palm, switchgrass, arabian cron (sudangrass), millet, manioca (jatropha) and Chinese silvergrass (miscanthus) (the huge awns of triploid (miscanthus xgiganteus)).Biomass further comprise the refuse from agricultural planting, processing and/or degraded, for example corn ear and skin, cornstalk, straw, nutshell, vegetables oil, Canola oil (canola oil), rapeseed oil, biofuel, bark, wood chip, sawdust and plant waste.

As used herein, term " animal based biomass " means the refuse produced by animal cultivation and/or utilization.Biological example matter for example includes but not limited to, from the refuse of livestock culturing and processing for example animal manure, birds droppings, poultry garbage, animal tallow and municipal solid waste (effluent sewerage).

As used herein, term " abiotic matter " means to be not included in those carbonaceous materials within defined term " biomass " herein.For example abiotic matter includes but not limited to hard coal, bituminous coal, sub-bituminous coal, brown coal, refinery coke, bituminous matter, liquid petroleum residue or its mixture.For example, referring to US2009/0166588A1, US2009/0165379A1, US2009/0165380A1, US2009/0165361A1, US2009/0217590A1 and US2009/0217586A1.

" liquid heavy hydrocarbonaceous material " is viscous liquid or semisolid material, and it can flow or can produce under hot conditions and flow under envrionment conditions.These materials are residues of typically processing from hydrocarbon material (as crude oil).For example in crude oil refining, first step normally distills with the hydrocarbon mixture by complicated and is separated into different volatile cuts.Typically first step distillation needs under atmospheric pressure heating evaporation hydrocarbon composition as much as possible and is no more than the actual temperature of about 650 °F, because higher temperature can cause thermolysis.Under atmospheric pressure do not have the fraction of distillation to be commonly referred to as " atmosphere petroleum residues ".This fraction can further be distilled under vacuum, and the actual temperature of the highest so about 650 °F can be evaporated more material.Remaining not pot liquor be known as " vacuum petroleum residues ".The two all is considered to the liquid heavy hydrocarbonaceous material in the present invention atmosphere petroleum residues and vacuum petroleum residues.

The indefiniteness example of liquid heavy hydrocarbonaceous material comprises vacuum resid; The atmosphere Residual oil; The petroleum crude oil of heavy and reduction; Pitch, pitch and pitch (naturally occurring and formed by the petroleum refining method); Tar sand oils; Shale oil; The residue of catalyst cracking method; The gelatin liquefaction residue; With other hydrocarbon feed streams that contain a large amount of heavys or cohesive material, as the petroleum wax fraction.

As used herein, term " bituminous matter " is the aromatics carbonaceous solids when room temperature, and can be derived from for example crude oil and the processing of crude oil Tar sands.Bituminous matter also can be considered to liquid heavy hydrocarbon feed.

This liquid heavy hydrocarbonaceous material can comprise a small amount of solid carbon-containing material inherently, for example refinery coke and/or solid bituminite, and it is dispersed in liquid heavy hydrocarbon matrix usually, and remains solid under the hot conditions of the feed condition as the inventive method.

As used herein, term " refinery coke " comprises the solid thermal degradation production (heavy Can Liu Wu – " Residual oil refinery coke ") of the high boiling hydrocarbon fraction that (i) obtains in refining of petroleum; (ii) the solid thermal degradation production of prepared tar sand (tar sand or You Sha – " Tar sands refinery coke ") the two.Such carbonized product comprises for example unprocessed, calcining, needle-like and fluidized-bed refinery coke.

The Residual oil refinery coke also can be derived from crude oil, for example by for example, coking method for the residual crude oil of upgrading heavy-gravity (liquid petroleum residue), derive, this refinery coke comprises ash content as minor component, about 1.0wt% or less typically, about 0.5wt% or less more typically, the weight based on coke.Typically, the ash content in so low ash content coke mainly comprises metal, as nickel and vanadium.

The Tar sands refinery coke can, derived from oil-sand, for example derive by the coking method for the upgrading oil-sand.The Tar sands refinery coke comprises ash content as less component, is typically the about 12wt% of about 2wt%-, and the more typically about about 12wt% of 4wt%-, the gross weight based on the Tar sands refinery coke.Typically, in so high ash content coke, ash content mainly comprises material for example silicon-dioxide and/or aluminum oxide.

Refinery coke can comprise at least approximately 70wt% carbon, at least approximately 80wt% carbon, or at least about 90wt% carbon, the gross weight based on refinery coke.Typically, refinery coke comprises the mineral compound that is less than about 20wt%, the weight based on refinery coke.

As used herein, term " coal " means mud coal, brown coal, sub-bituminous coal, bituminous coal, hard coal or its mixture.In certain embodiments, it is about 85% that the carbon content of this coal is less than, or be less than approximately 80%, or is less than approximately 75%, or is less than approximately 70%, or is less than approximately 65%, or is less than approximately 60%, or is less than approximately 55%, or is less than about 50% weight, the coal weight based on total.In other embodiments, the carbon content of this coal is high 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.Hard coal, bituminous coal, sub-bituminous coal and brown coal can comprise respectively about 10wt%, about about 7wt% of 5-, the approximately about 8wt% of 4-and the approximately ash content of the about 11wt% of 9-, the gross dry weight based on coal.But the ash oontent in any concrete coal source will depend on grade and the source of coal, this is well known to those skilled in the art.Referring to 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.

The ash content that coal combustion produces typically comprise flying dust and bottom ash the two, this is well known to those skilled in the art.Flying dust from bituminous coal can comprise the silicon-dioxide of the about 60wt% of about 20-and the aluminum oxide of about about 35wt% of 5-, the gross weight based on flying dust.Flying dust from sub-bituminous coal can comprise the silicon-dioxide of the about 60wt% of about 40-and the aluminum oxide of about about 30wt% of 20-, based on the flying dust gross weight.Flying dust from brown coal can comprise the silicon-dioxide of the about 45wt% of about 15-and the aluminum oxide of about about 25wt% of 20-, the gross weight based on flying dust.Referring to such as the people such as Meyers " 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 the about 60wt% of about 40-and the aluminum oxide of about about 30wt% of 20-, the gross weight based on bottom ash.Bottom ash from sub-bituminous coal can comprise the silicon-dioxide of the about 50wt% of about 40-and the aluminum oxide of about about 25wt% of 15-, the gross weight based on bottom ash.Bottom ash from brown coal can comprise the silicon-dioxide of the about 80wt% of about 30-and the aluminum oxide of about about 20wt% of 10-, the gross weight based on bottom ash.Referring to 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 (as methane) can be biomass or abiotic matter.

" on-gaseous " material is liquid, semisolid, solid or mixture basically under envrionment conditions.For example coal, refinery coke, bituminous matter and liquid petroleum residue are non-gaseous material, and methane and Sweet natural gas are gaseous materials.

Term " unit " refers to unit operation.When having described, exist while being greater than one " unit ", unless otherwise directed, those unit move in a parallel manner.But single " unit " can comprise series connection or the parallel units that is greater than, this depends on context.For example, sour gas is removed unit can comprise the hydrogen sulfide removal unit, is in series with subsequently the co 2 removal unit.As another example, the pollutant removal unit can comprise for first of first pollution thing removes unit, is in series with subsequently for second of the second pollutent and removes unit.As another example, compressor can comprise the first compressor by fluid compression to the first pressure, be in series with subsequently the second compressor, come further by fluid compression to the 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 all or part of other components derived from this carbon containing feed (for example carbon monoxide, hydrogen and methane).For example " a part of carbon containing feed " comprises the carbon component in the fines that may be present in by product carbonizing matter and recirculation, and this carbonizing matter is fundamentally derived from initial carbon containing feed.

In the context of the invention, term " superheated vapour " refers to incoagulable vapour stream under condition used.

The hydrogenation methanator that term " synthetic gas demand " refers in the reaction for step (b) keeps the synthetic gas balance.As mentioned above, in the desirable stable state hydrogenation methanation reaction in integral body (referring to top equation (I), (II) and (III)), hydrogen and carbon monoxide are that relative equilibrium ground produces and consumes.Because the two is all to take out as the part of gaseous product for hydrogen and carbon monoxide, therefore at least to need basically to keep the amount of this molecular balance, join and/or produce (as described below, via the burning/oxidizing reaction of the oxygen with supplied with) hydrogen and carbon monoxide at hydrogenation methanator situ.In the present invention, must join and/or original position results from hydrogen in hydrogenation methanation reaction (step (b)) and the amount of carbon monoxide is " synthetic gas demand ".

Term " steam demand " refers to the amount that must join the steam in the hydrogenation methanator.Consume steam in the hydrogenation methanation reaction, therefore must in this hydrogenation methanator, add some steam.Carbon for every 2mol in feed produces 1mol methane and 1mol carbonic acid gas, and the theory consumption of steam is 2mol (referring to waiting formula V).In actual practice, steam consumption is not optimum efficiency, and steam is taken out together with product gas; So, need the steam that will be greater than theoretical amount to join in the hydrogenation methanator, this add-on is " steam demand ".Steam can be for example adds via the gas stream of flow of superheated steam and oxygen rich air.Steam add-on (and source) further discusses in detail below.The steam produced by carbon containing feed original position (for example come from the evaporation of any moisture of carbon containing feed, or come from the carbon containing feed in exist or the oxidizing reaction of the hydrogen, methane and/or other hydrocarbon that produce) can help to meet steam demand; But, should be noted that at the temperature lower than hydrogenation methanation reaction temperature original position results from or input " heat demand " that any steam in the hydrogenation methanator will affect the hydrogenation methanation reaction.

Term " heat demand " refer to must join hydrogenation methanator and original position produce (for example via step (c) reaction) by the reaction of step (b) remain on basically thermally equilibrated thermal energy its, as discussed above with discussed in further detail below like that.

Can, for practice of the present invention or test, at this, suitable method and material have been described although be similar to or be equivalent to those methods described herein and material.Therefore material, method and embodiment herein is only exemplary, and except clear is arranged, otherwise right and wrong are determinate.

general machining information

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

According to a kind of embodiment of the present invention, on-gaseous carbonaceous material (10) is prepared to processing in unit (100) at feed, to produce carbon containing feed (32), by its enter catalyst applying unit (350), apply the carbon containing feed (31+32) that the hydrogenation methanation catalyst produces catalysis here.This hydrogenation methanation catalyst typically comprises from the catalyst recycle of recycle catalyst stream (57) with from the make-up catalyst of make-up catalyst stream (56).Further details provides below.

By the carbon containing feed (31+32) of this catalysis and the gas stream (14) of flow of superheated steam (12), oxygen rich air with optionally cross together with hot synthesis gas feed streams (16) and input in hydrogenation methanator (200).This flow of superheated steam (12) and optional hot synthesis gas feed streams (16) excessively can be that (it comprises steam and heat energy to single feed streams, and optionally hydrogen and carbon monoxide) or a plurality of feed streams (itself and the gas stream (14) of oxygen rich air and heat energy, synthetic gas and the steam combination that original position produces, comprise steam and heat energy, and optionally hydrogen and carbon monoxide), come as required at least basically to meet or at least meet synthetic gas, steam and the heat demand of the hydrogenation methanation reaction carried out in hydrogenation methanator (200).

In one embodiment, as the US patent application 13/211476 of owning together (attorney docket FN-0063 US NP1, title is Hydromethanation of a Carbonaceous Feedstock, the applying date is on August 17th, 2011) disclosed, do not have optional hot synthesis gas feed streams (16) excessively, and the gas stream (14) of the carbon containing feed (31+32) of catalysis, flow of superheated steam (12) and oxygen rich air is all inputted in hydrogenation methanator (200) at the temperature of the object run temperature lower than the hydrogenation methanation reaction.

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

This hydrogenation methanator (200) comprises fluidized-bed (202), and this fluidized-bed has top (202b) and bottom (202c), carries out therein the reaction of step (b) and step (c).Be not limited to any concrete theory, the reaction of step (b) (hydrogenation methanation reaction) on top (202b) account for leading, and the reaction (oxidizing reaction) of step (c) in bottom, (202c) accounts for leading.It is believed that the boundary that does not have clear between two parts, but the consumption (and generation of heat energy and synthetic gas) in bottom (202c) along with oxygen exists transition.Also it is believed that under the condition existed, oxygen depletion is very fast in hydrogenation methanator (200); So the major portion of fluidized-bed (202) will be top (202b).

The gas stream (14) of this flow of superheated steam (12) and oxygen rich air can be inputted respectively in hydrogenation methanator (200), but in the bottom (202c) of input fluidized-bed (202), merges before typically.In one embodiment, when the lower region that is incorporated into fluidized-bed (202) (202c), the temperature of two kinds of fluids (individually and in combination) will be lower than the object run temperature of the reaction of step (b).

This carbon containing feed of at least a portion in fluidized-bed (202) bottom (202c) will produce heat energy with the oxygen reaction of gas stream (14) from oxygen rich air, and hydrogen and carbon monoxide (synthetic gas), present in an amount at least sufficient to ideally to meet the heat of hydrogenation methanation reaction of step (b) and synthetic gas demand (do not use ideally independent cross hot synthesis gas feed streams (16)) in the steady-state operation of the method.This comprises the solid carbon of the feed (as carbonizing matter and recirculation fines) that comes from unreacted (fresh) feed, partial reaction, and the reaction of the gas (carbon monoxide, hydrogen, methane and higher hydrocarbon) in the bottom (202c) that can produce from or be carried by feed and recirculation fines.Usually can produce some water (steam), and other by products carbonic acid gas for example, this depends on the degree of burning/oxidation.

In hydrogenation methanator (200) (mainly in the top of fluidized-bed (202) (202b)), the reaction under the hydrogenation methanation catalyst exists of carbon containing feed, steam, hydrogen and carbon monoxide, produce the crude product of methane rich, its crude product stream (50) that finally is used as methane rich is taken out from hydrogenation methanator (200).

The reaction of carbon containing feed in fluidized-bed (202) also produced the by product carbonizing matter, and it comprises unreacted carbon and the non-carbon component that comes from carbon containing feed (comprising the hydrogenation methanation catalyst), as will be described in further detail below such.In order to prevent residue gathering in hydrogenation methanator (200), via carbonizing matter, take out pipeline (58) by the purge of solids of by product carbonizing matter (solid purge) is customary takes out (periodically or continuously).

In one embodiment of the present invention, as the US provisional application of owning together and introducing in front _ _/_ _ _, (the attorney docket FN-0065 US PRV of _ _ _, title is Hydromethanation of a Carbonaceous Feedstock, application simultaneously) disclosed, carbon containing feed (32) (or carbon containing feed (31+32) of catalysis) also is input to the bottom (202c) of fluidized-bed (202).Because the carbon containing feed (31+32) of catalysis is introduced in the bottom (202c) of fluidized-bed (202), therefore carbonizing matter taking-up pipeline (58) will be positioned at a bit, so that one or more on the feed position of the carbon containing feed (31+32) higher than catalysis of by product carbonizing matter take out from fluidized-bed (202), from the top (202b) of fluidized-bed (202), take out typically.

In this embodiment, enter the lower feed point of hydrogenation methanator (200) owing to the carbon containing feed (31+32) of catalysis, with by product carbonizing matter higher point of draw from hydrogenation methanator (200), hydrogenation methanator (200) will be as discussed below upwards flowage structure.

Hydrogenation methanator (200) also typically comprises the zone (206) be positioned under fluidized-bed (202), and these two zones typically separate by turbogrid plates (208) or spacer.Too large and can not be in fluidized bed region (202) the particle of fluidisation, for example macroparticle by product carbonizing matter and coacervate that can not be mobile are collected in the bottom (202c) of fluidized-bed (202) usually, and in regional (206).Such particle typically comprises carbon component (and ash content and catalyst component), and can take out pipeline (58) and (58a) regularly remove from hydrogenation methanator (200) via the carbonizing matter for catalyst recovery as described below.

Typically, before taking out from hydrogenation methanator (200), sent fluidized bed region (202) above initially-separate district (204) crude product of this methane rich.Disengaging zone (204) is optional for example comprises one or more inner cyclonic separators and/or other carry separate particles mechanism secretly.The fines that the crude product gas of " taking-up " (seeing following discussion) methane rich stream (50) typically comprises at least methane, carbon monoxide, carbonic acid gas, hydrogen, hydrogen sulfide, steam, heat energy and carries secretly.

At first the crude product gas stream (50) of this methane rich processed and removed the most fines of carrying secretly, typically for example, by cyclone separator component (360) (one or more inside and/or external cyclone), undertaken, if necessary, can take over the other processing of choosing after it, as Venturi scrubber, as discussed in greater detail.Crude product gas stream (50) that should " taking-up " methane rich therefore is considered to the crude product of fines before separating, and no matter be to carry out the fines separation in inside and/or the outside of hydrogenation methanator (200).

As shown in Fig. 1 is clear and definite, the crude product stream of methane rich (50) is delivered to cyclone separator component (360) from hydrogenation methanator (200) and separate the particle of carrying secretly.Although for the sake of simplicity, in Fig. 1, cyclone separator component (360) is expressed as to single external cyclone, but cyclone separator component as above (360) can be inside and/or external cyclone, and can be also a series of a plurality of inside and/or external cyclone.

The crude product gas of this methane rich stream (50) is processed to the crude product gas stream (52) that produces poor fines methane rich and the fines stream (362) reclaimed in cyclone separator component (360).

The fines stream (362) reclaimed can defeated time hydrogenation methanator (202) in, for example, via defeated time fluidized-bed of fines recirculation line (364) (202) top (202b), and/or via defeated time fluidized-bed of fines recirculation line (366) (202) bottom (202c) (as the US provisional application 13/228821 of owning together (attorney docket FN-0064 US NP1, title is Hydromethanation of a Carbonaceous Feedstock, September 9 2011 applying date) disclosed).In the situation of not defeated time fluidized-bed (202), the fines of recovery stream (362) for example recirculation is got back to feed and is prepared in unit (100) and/or catalyst recovery unit (300).

The crude product gas stream (52) of poor fines methane rich typically comprises at least methane, carbon monoxide, carbonic acid gas, hydrogen, hydrogen sulfide, steam, ammonia and heat energy and a small amount of pollutent, as the remaining residual fines of carrying secretly, and other may be present in volatilization and/or the material that carry (for example mercury) in the carbon containing feed.Typically in the crude product gas stream (52) of poor fines methane rich, there is hardly (total amount typically is less than about 50ppm) coagulable (under envrionment conditions) hydrocarbon.

The crude product gas stream (52) of this poor fines methane rich can be processed in one or more Downstream processing steps, to reclaim heat energy, purification and conversion, produce one or more increment products, for example substitute natural gas (pipeline quality), hydrogen, carbon monoxide, synthetic gas, ammonia, methyl alcohol, other syngas-derived products and electric energy, as disclosed as many documents mentioned in " hydrogenation methanation " part below, and as discussed in greater detail.

Other details and embodiment below is provided.

the hydrogenation methanation

Catalytic gasification/hydrogenation methanation and/or crude product method for transformation and condition are disclosed in for example US3828474 usually, 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 the US2007/0000177A1 owned together, US2007/0083072A1, 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, US2010/0076235A1, 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, title is Hydromethanation of a Carbonaceous Feedstock with Vanadium Recovery), its applying date is on April 26th, 2011, US patent application 13/211476 (attorney docket FN-0063 US NP1, title is Hydromethanation of a Carbonaceous Feedstock, August 17 2011 applying date), in US patent application 13/228821 (attorney docket FN-0064 US NP1, title is Hydromethanation of a Carbonaceous Feedstock, September 9 2011 applying date).

In the of the present invention a kind of embodiment shown in Fig. 1, the carbon containing feed (31+32) of catalysis, flow of superheated steam (12) and the optional hot synthesis gas feed streams (16) of crossing are incorporated in hydrogenation methanator (200).In addition, also the gas stream of a certain amount of oxygen rich air (14) is incorporated in the hydrogenation methanator, produce heat energy and synthetic gas for original position, as top institute is briefly discussed like that in many reference of being introduced with front disclosed such (referring to the US2010/0076235A1 for example introduced previously, US2010/0287835A1, US2011/0062721A1 and US patent application 13/211476).

The gas stream (14) of flow of superheated steam (12), oxygen rich air and mistake hot synthesis gas feed streams (16) (if existence) preferably are incorporated in the hydrogenation methanator at the temperature of the object run temperature lower than the hydrogenation methanation reaction.Although under those conditions, this can produce adverse influence (before the reaction of step (c)) to the heat demand of hydrogenation methanation reaction, but in fact this make the method steam/heat integration fully, and not using the superheater (in the steady-state operation of the method) of fuel heating, it uses a part of product from described method that fuel is provided typically.Typically, will there do not is hot synthesis gas feed streams (16).

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

Hydrogenation methanator (200) is fluidized-bed reactor.Hydrogenation methanator (200) can be for example " flowing downward " reverse flow configuration, wherein the carbon containing feed (31+32) of this catalysis is introduced at higher point, so that particle flows down fluidized-bed (202) towards fluidized-bed (202) bottom (202c), and gas flows and removes at the point higher than fluidized-bed (202) on the direction made progress.

Perhaps, hydrogenation methanator (200) has the also stream structure of " upwards flowing ", wherein the carbon containing feed (31+32) of this catalysis is inputted at lower point (bottom (202c) of fluidized-bed (202)), so that flowing upward to the carbonizing matter by product in fluidized-bed (202) together with gas, particle removes district, for example approach or the top in fluidized-bed (202) top (202b), flow to the top of fluidized-bed (202).In one embodiment, the feed point of carbon containing feed (the carbon containing feed (31+32) of for example catalysis) should produce to the greatest extent rationally and be incorporated in fluidized-bed (200) close to oxygen (gas stream (14) that comes from oxygen rich air) introducing point possibly.Referring to the US patent application of for example owning together with introduce previously _ _/_ _ _, _ _ _ (attorney docket FN-0065 US NP1, title is Hydromethanation of a Carbonaceous Feedstock, simultaneously the application).

Hydrogenation methanator (200) is typically in high pressure and the hot operation of moderate, efflux of solids (the carbon containing feed (31+32) of for example catalysis and recirculation fines (if existence)) need to be incorporated in the reaction chamber of reactor, keep the required temperature of fluid, pressure and flow velocity simultaneously.Those skilled in the art know for the solid input being had to the feed inlet of the reaction chamber of high pressure and/or hot environment, comprise star formula loader, screw feeder, rotory piston and lock hopper.Should be appreciated that feed inlet can comprise two or more pressure compensation elements, lock hopper for example, it will be used alternatingly.In some cases, can prepare at the pressure condition higher than the reactor operating pressure by this carbon containing feed, and therefore microparticle compositions directly can be sent in reactor, without further pressurization.Gas for pressurization can be for example nitrogen of rare gas element, or is more typically carbon-dioxide flow, its carbon-dioxide flow that for example recirculation produces by acid gas removal unit certainly.

Preferably, hydrogenation methanator (200) moves in moderate temperature (comparing with conventional gasification process), and the object run temperature is at least about 1000 °F (about 538 ℃), or at least about 1100 °F (about 593 ℃) to about 1500 °F (about 816 ℃), or to about 1400 °F (about 760 ℃), or to about 1300 °F (704 ℃); Pressure is about 250psig (about 1825 kPa, absolute pressure), or about 400psig (approximately 2860kPa), or about 450psig (about 3204 kPa), to about 800psig (about 5617 kPa), or to about 700psig (about 4928 kPa), or to about 600psig (about 4238 kPa), or to about 500psig (about 3549 kPa).

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

When the gas stream (14) of oxygen rich air is inputted hydrogenation methanator (200), part carbon containing feed (carbon of fines that preferably comes from feed, by product carbonizing matter and the recirculation of partial reaction) will consume in oxidation/combustion reactions, produce heat energy and the typically carbon monoxide of certain tittle and hydrogen (with other gases typically for example carbonic acid gas and steam).The variation of the amount of the oxygen of input hydrogenation methanator (200) provides favourable machining control, finally to keep synthetic gas and thermal equilibrium.The amount that improves oxygen will improve oxidation/burning, and therefore increase the original position thermogenesis.On the contrary, the reduction of amount of oxygen will reduce the original position thermogenesis.The amount of the synthetic gas produced depends on the consumption of oxygen the most at last, and the oxygen of higher amount can cause burn more completely/be oxidized to carbonic acid gas and water, rather than partial combustion becomes carbon monoxide and hydrogen more.

The necessary carbon containing feed that enough burning/oxidation is enough of amount of oxygen in input hydrogenation methanator (200), produce enough heat energy and synthetic gas, with heat and the synthetic gas demand that meets stable state hydrogenation methanation reaction.

In one embodiment, the amount (being included in the gas stream (14) of oxygen rich air) that is provided to the molecular oxygen of hydrogenation methanator (200) 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 to about 0.35 pound of O ₂/ every pound of carbon containing feed.

This hydrogenation methanation and oxidation/combustion reactions will occur simultaneously.The structure that depends on hydrogenation methanator (200), described two steps account for leading in minute other zone, the hydrogenation methanation is on the top of fluidized-bed (202) (202b), and oxidation/burning is in the bottom of fluidized-bed (202) (202c).The gas stream of this oxygen rich air (14) typically mixes with flow of superheated steam (12), and this mixture is located or introduced close to its part in the bottom of fluidized-bed (202) bottom (202c), to avoid forming focus in reactor, with the gaseous product burning of avoiding (minimizing) to obtain mutually.According to the present invention, input has the carbon containing feed (31+32) of the catalysis of high water capacity, particularly is input to fluidized-bed (202) bottom (202c), also contributes to heat dissipation and avoid forming focus in reactor (200).

If there is overheated synthetic gas feed streams (16), this stream will typically be introduced as the mixture with vapour stream (12), and the gas stream of oxygen rich air (14) is introduced separately into fluidized-bed (202) bottom (202c), preferentially not consume synthesis gas components.

The gas stream of oxygen rich air (14) can, by any suitable means input hydrogenation methanators (200), for example be directly injected into the oxygen of purification, oxygen-air mixture, oxygen-vapour mixture or oxygen-noble gas mixtures in reactor.Referring to people such as US4315753 and Chiaramonte, Hydrocarbon Processing, September nineteen eighty-two, 255-257 page.

The gas stream of oxygen rich air (14) produces via conventional air-separating technology typically, and will supply with vapor mixing, with higher than about 250 °F (about 121 ℃), introduce to about 400 °F (about 204 ℃) or under the pressure of about 350 °F (about 177 ℃) or the pressure that exists to the temperature of about 300 °F (about 149 ℃) with at least a little higher than hydrogenation methanator (200).It should be incoagulable that steam in the gas stream of oxygen rich air (14) is transferred in the process of hydrogenation methanator (200) at the stream (14) of oxygen rich air, the stream of oxygen rich air (14) can, in lower pressure transmission, then be pressurizeed before (compression) in being about to be incorporated into hydrogenation methanator (200) like this.

As mentioned above, this hydrogenation methanation reaction has steam demand, heat demand and synthetic gas demand.The combination of these conditions is important factors of determining the operational conditions of the rest part of hydrogenation methanation reaction and the method.

For example, to need the mol ratio of steam and carbon (in feed) be at least about 1 to the steam demand of hydrogenation methanation reaction.But typically, this mol ratio be 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).Steam in the moisture that the water capacity of the carbon containing feed (31+32) of catalysis, the carbon containing feed in hydrogenation methanator (200) produce and the gas stream (14) that is included in flow of superheated steam (12), oxygen rich air and recirculation fines stream (with optional hot synthesis gas feed streams (16) excessively) should be enough at least basically meet the steam demand of (or at least satisfied) hydrogenation methanation reaction.

As mentioned above, this hydrogenation methanation reaction (step (b)) is basically thermally equilibrated, but for example, due to process thermosteresis and other energy requirements (evaporation of moisture on feed), must in the hydrogenation methanation reaction, produce some heat, to keep thermal equilibrium (heat demand).Carbon the gas stream from oxygen rich air (14) be incorporated into the partial combustion/oxidation under existing of oxygen hydrogenation methanator (200) should be enough at least basically to meet the heat of (or at least satisfied) hydrogenation methanation reaction and synthetic gas demand the two.

The gas stream (14) that the pressurization of the feed of the carbon containing for catalysis (31+32) used in hydrogenation methanator (200) and the gas of reaction comprise flow of superheated steam (12) and oxygen rich air (with optional hot synthesis gas feed streams (16) excessively) and optional other nitrogen, air or rare gas element (as argon gas), it can input hydrogenation methanator (200) according to method known to those skilled in the art.As a result, the gas stream (14) of this flow of superheated steam (12) and oxygen rich air must provide with higher pressure, and this pressure makes them can enter into hydrogenation methanator (200).

Ideally, whole fluids all should be input in hydrogenation methanator (200) with the temperature of the object run temperature lower than the hydrogenation methanator, for example is disclosed in the US provisional application 13/211476 of introducing previously.

Flow of superheated steam (12) can, in being low to moderate the temperature of the saturation point under feed pressure, be supplied with but be desirable in the temperature higher than this, to avoid occurring any possibility of condensing.The typical feed temperature of flow of superheated steam (12) is from about 500 °F (about 260 ℃) or from about 600 °F (about 316 ℃) or from about 700 °F (about 371 ℃), to about 950 °F (about 510 ℃) or to about 900 °F (about 482 ℃).The temperature of flow of superheated steam (12) will finally depend on the level of the heat reclaimed from described method, as discussed below.In any case, should not carry out the described vapour stream of superheated (12) with the superheater of fuel heating in the steady-state operation of described method.

When the lower region (202c) of fluidized-bed (202) is inputted in stream (14) combination of superheated vapour stream (12) and oxygen rich air, the temperature of this mix flow will be typically from about 500 °F (about 260 ℃) or from about 600 °F (about 316 ℃) or from about 700 °F (about 371 ℃), to about 900 °F (about 482 ℃) or to about 850 °F (about 454 ℃).

Temperature in hydrogenation methanator (200) can for example be controlled by amount and the temperature of controlling flow of superheated steam (12) and the amount of inputting the oxygen of hydrogenation methanator (200).

Advantageously, steam for this hydrogenation methanation reaction produces and (for example produces waste heat boiler by the process hot trapping from other process operation, so-called " process steam " or " steam that process produces "), and be that the steam produced as process separately provides in some embodiments.The process vapour stream for example produced by heat exchanger unit or waste heat boiler can be used as the flow of superheated steam (12) of part, in input hydrogenation methanator (200), in the US2010/0287835A1 for example introduced previously as be disclosed in and US patent application 13/211476, and such as discussed below.

In certain embodiments, whole processing described herein is at least (the steam neutral) of steam neutrality basically, so that can be via heat exchange for the steam demand (pressure and amount) of hydrogenation methanation reaction, use the process heat in different steps wherein to meet, or (the steam positive) of steam positivity, produce so unnecessary steam, and can be for example for generating.Ideally, the steam that process produces accounts for being greater than about 95wt% or being greater than about 97wt% or being greater than about 99wt% or about 100wt% or higher of hydrogenation methanation reaction steam demand.

The result of hydrogenation methanation reaction is a kind of crude product of methane rich, and the crude product stream using it as methane rich (50) is taken out from hydrogenation methanator (200), and the crude product stream of this methane rich (50) typically comprises CH ₄, CO ₂, H ₂, CO, H ₂s, unreacted steam and other pollutents (as fines of carrying secretly, NH optionally ₃, COS, HCN and/or elemental mercury from vapor), this depends on the character for the carbonaceous material of hydrogenation methanation.

If the hydrogenation methanation reaction moves with the synthetic gas balance, the crude product stream of this methane rich (50), by leaving hydrogenation methanator (200), at least approximately 15mol% or at least approximately 18mol% or at least approximately methane of 20mol%, the mole number of methane, carbonic acid gas, carbon monoxide and hydrogen in the crude product stream based on this methane rich (50) will typically be comprised.In addition, the crude product stream of this methane rich (50) will typically comprise at least the approximately methane of 50mol% and add carbonic acid gas, the mole number of methane, carbonic acid gas, carbon monoxide and hydrogen in the crude product stream based on this methane rich (50).

If the hydrogenation methanation reaction moves so that synthetic gas is excessive, for example comprise higher than or exceeded excessive carbon monoxide and/or the hydrogen (for example the amount due to the gas stream (14) of inputting the oxygen rich air in hydrogenation methanator (200) has produced excessive carbon monoxide and/or hydrogen) of synthetic gas demand, can produce some dilution effect to the molar percentage of the methane and carbon dioxide in the crude product stream (50) of methane rich.

In these methods, available on-gaseous carbonaceous material (10) for example comprises various biomass and abiotic material widely.Carbon containing feed (32) is derived from one or more on-gaseous carbonaceous materials (10), and it is processing in feed preparation zone (100), as described below.

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

Be provided to hydrogenation methanator (200) before, carbon containing feed (32) and hydrogenation methanation catalyst (31) are typically closely mixed (that is, so that the carbon containing feed (31+32) of catalysis to be provided).

further gas processing

Fines is removed

The hot gas effluent that leaves the reaction chamber of hydrogenation methanator (200) can pass through fines remover unit (for example cyclone separator component (360)), this unit is incorporated among hydrogenation methanator (200) and/or outside it, has served as disengaging zone.Particle (that is, fines) overweight and that can not be left the gas entrainment of hydrogenation methanator (200) is turned back to hydrogenation methanator (200), for example turn back to reaction chamber (for example fluidized-bed (202)).

The residual fines of carrying secretly is removed by any suitable device basically, and for example inside and/or external cyclone separator, optionally follow by Venturi scrubber.As mentioned above, via recirculation line (366), these fineves of at least a portion are turned back to fluidized-bed (202) lower region (202c).A part also can turn back to fluidized-bed (202) top (202b) via recirculation line (364).The fines of any remaining recovery can process to reclaim base metal catalysts, or directly the feed preparation is returned in recirculation, as described in the US2009/0217589A1 introduced previously.

Remove " major part " fines and mean to remove a certain amount of fines from formed gas stream, so that Downstream processing is not adversely affected; Therefore, at least should remove most fines.The super-fine material of some lower level can remain to such degree in formed gas stream, that is, Downstream processing is not subject to the impact of significant adverse.Typically, at least approximately 90wt% or at least approximately 95wt% or at least approximately the granularity of 98wt% be greater than about 20 μ m or the fines that is greater than about 10 μ m or is greater than about 5 μ m is removed.

Heat exchange

Depend on hydrogenation methanation condition, the crude product stream of poor fines methane rich (52) can be in about 1000 °F of temperature (about 538 ℃)-about 1500 °F (about 816 ℃), more typically about 1100 °F (about 593 ℃)-about 1400 °F (about 760 ℃), the about 50psig of pressure (about 446 kPa)-about 800psig (about 5617 kPa), more typically approximately 400psig (approximately 2860kPa)-approximately 600psig (about 4238 kPa) and about 0.5 ft/s of speed (approximately 0.15m/s)-approximately 2.0ft/s (about 0.61m/s), more typically approximately 1.0ft/s (0.30m/s)-about 1.5 ft/s (approximately 0.46m/s) generation of getting off.

The crude product stream of poor fines methane rich (52) can for example be provided to heat recovery units, for example the first heat exchanger unit (400) shown in Fig. 2.The first heat exchanger unit (400) has been removed the heat energy of at least a portion from the crude product stream (52) of poor fines methane rich, and the temperature that reduces the crude product stream (52) of poor fines methane rich produces the crude product stream (70) of temperature lower than the cooling methane rich of the crude product stream (52) of poor fines methane rich.The heat energy reclaimed by the second heat exchanger unit (400) can be for generation of the first process vapour stream (40), therein the first process vapour stream (40) of at least a portion defeated getting back in hydrogenation methanator (200) for example.

In one embodiment, as shown in Figure 2, the first heat exchanger unit (400) have steam boiler zone (400b) and the superheat region before it (400a) the two.Boiler water supply stream (39a) can produce the first process vapour stream (40) through steam boiler zone (400b), then it pass through the superheating process vapour stream (25) that vapor superheater (400a) produces suitable temperature and pressure, in hydrogenation methanator (200).Vapor superheater (400a) also can be for example, for other recycled vapour streams (the second process vapour stream (43)) of superheated to the required degree of input hydrogenation methanator (200).

The crude product stream (70) of formed cooling methane rich will be typically in about 450 °F of temperature (about 232 ℃)-about 1100 °F (about 593 ℃), more typically about 550 °F (about 288 ℃)-about 950 °F (about 510 ℃), the about 50psig of pressure (about 446 kPa)-about 800psig (about 5617 kPa), about 400psig (approximately 2860kPa)-approximately 600psig (about 4238 kPa) more typically, with about 0.5 ft/s of speed (approximately 0.15m/s)-approximately 2.0ft/s (approximately 0.61m/s), more typically approximately under 1.0ft/s (0.30m/s)-about 1.5 ft/s (approximately 0.46m/s), leave the second heat exchanger unit (400).

Gas sweetening

Product purifies and can comprise that for example water-gas shift method (700), dehydration (450) and sour gas are removed (800), and optional contaminant trace species is removed (500) and (600) are removed and reclaimed to optional ammonia.

Contaminant trace species is removed (500)

As well known to the skilled person, gas stream for example the pollutant level of the crude product stream of cooling methane rich (70) will depend on the character for the preparation of the carbonaceous material of carbon containing feed.For example some coal (as Illinois #6) can have high sulphur content, and this has caused higher COS to pollute; Other coals for example Powder River Basin coal may comprise the mercury of higher amount, and it can volatilize in hydrogenation methanator (200).

COS can for example remove the crude product stream of cooling methane rich (70) as follows from gas stream: by COS, be hydrolyzed (referring to US3966875, US4011066, US4100256, US4482529 and US4524050), make gas stream through particulate Wingdale (referring to US4173465), acidic buffer CuSO ₄solution (referring to US4298584), the alkanolamine absorption agent that contains tetramethylene sulfone (tetramethylene sulfone) (as methyldiethanolamine, trolamine, dipropanolamine or diisopropanolamine (DIPA)) (referring to US3989811); Or with freezing liquid CO ₂adverse current is cleaned this second cooling gas stream (referring to US4270937 and US4609388).

HCN can be from gas stream for example the crude product stream of cooling methane rich (70) as get off to remove: by with ammonium sulfide or ammonium polysulfide reaction response, producing CO ₂, H ₂s and NH ₃(referring to US4497784, US4505881 and US4508693), or use formaldehyde, clean (referring to US4572826) by the two-stage of ammonium polysulfide or sodium polysulphide subsequently, water absorbs (referring to US4189307), and/or by the MoO for example of the hydrolyst through alumina load ₃, TiO ₂and/or ZrO ₂and decompose (referring to US4810475, US5660807 and US5968465).

Element mercury can for example for example remove the crude product stream of cooling methane rich (70) as follows from gas stream: the absorption of the carbon activated by sulfuric acid (referring to US3876393), the absorption of the carbon of filling by sulphur (referring to US4491609), by containing H ₂the absorption of the amine solvent of S (referring to US4044098), the absorption (referring to US4892567) of the zeolite of filling by silver or gold, become HgO (referring to US5670122), at SO with methanol oxidation with hydrogen peroxide ₂exist lower to the compound oxidation (referring to US6878358) containing bromine or iodine, with the plasma oxidation (referring to US6969494) containing H, Cl and O, and/or for example, with chloride oxidizing gas oxidation (ClO, referring to US7118720).

When with the aqueous solution, removing any or all of COS, HCN and/or Hg, during the waste water produced in contaminant trace species removal unit can import to the treatment unit for waste water (not shown).

When existing, the contaminant trace species of concrete contaminant trace species is removed and should for example, from handled gas stream (crude product stream of cooling methane rich (70)), be removed at least most of (or basically whole) contaminant trace species, typically remove in or lower than the level of the product stream regulation boundary of expectation.Typically, contaminant trace species is removed should remove at least 90% or at least 95% or at least 98% COS, HCN and/or mercury from the first cooling gas stream, the weight based on pollutent before processing.

(600) are removed and reclaimed to ammonia

As well-known to those skilled in the art, the gasification of biomass, some coal, some refinery coke and/or the ammonia that utilizes air can obviously measure in the product stream generation as the source of oxygen for hydrogenation methanator (200).Optionally, gas stream for example the crude product stream of cooling methane rich (70) can one or more ammonia remove and recovery unit (600) in wash with water and remove and reclaim ammonia.

The ammonia recycling can for example be carried out on the crude product stream (70) of the cooling methane rich that directly comes from heat exchanger (400), or below one or two carries out after processing: (i) one or more contaminant trace species is removed unit (500), and (ii) one or more sour converting units (700).

After washing, this gas stream for example crude product stream of cooling methane rich (70) will typically comprise at least H ₂s, CO ₂, CO, H ₂and CH ₄.When the crude product stream (70) of this cooling methane rich, in advance through peracid converting unit (700),, after washing, this gas stream will typically comprise at least H ₂s, CO ₂, H ₂and CH ₄.

Ammonia can reclaim according to method known to those skilled in the art from washer water, can typically for example, as the aqueous solution (61) (20wt%), reclaim.Scrubber waste can forward the treatment unit for waste water (not shown) to.

When existing, ammonia is removed process should for example, remove at least ammonia of most of (with basically whole) from the stream (crude product stream of cooling methane rich (70)) of washing.At ammonia, remove in context, " major part " removed and meaned the component of removing sufficiently high per-cent, in order to can produce the final product of expectation.Typically, ammonia is removed the ammonia composition that process will be removed the first gas stream of at least about 95% or at least about 97% washing, the weight of the ammonia based in described stream before processing.

Water-gas shift (700)

For example, by the crude product stream of the methane rich of part or all (crude product stream of cooling methane rich (70)) input water-gas shift reactor (as sour conversion reactor (700)).

In sour conversion reactor (700), gas for example, experiences sour conversion reaction (also referred to as water-gas shift reaction) under the existence of water-bearing media (steam), so that (or most or basically whole) CO of major general's major portion changes into CO ₂and raising H ₂mark.The generation of the hydrogen content improved is used to for example Optimization of Hydrogen production, or is used to the downstream methanation to optimize H ₂/ CO ratio.

Water-gas shift is processed and can be carried out on the crude product stream (70) of directly carrying out the cooling methane rich of automatic heat-exchanger (400), or carries out on the crude product stream (70) of the cooling methane rich of through contaminant trace species, removing unit (500) and/or ammonia removal unit (600).

A kind of sour conversion method for example is described in detail in US7074373.The method comprises and adds water, or uses the water comprised in gas, and by the adiabatic reaction on steam reforming catalyst of formed water-gas mixture.Typically steam reforming catalyst is included in one or more VIII family metals on heat-resistant carriers.

For method and reactor containing carrying out the acid gas conversion reaction on the gas stream of CO, be well known to a person skilled in the art.Suitable reaction conditions and suitable reactor can be according to must the amount of the CO of dilution changing from gas stream.In some embodiments, the conversion of this acid gas can be from about 100 ℃ or from about 150 ℃ or from about 200 ℃, to about 250 ℃ or to about 300 ℃ or place an order and grade carry out to the temperature of about 350 ℃.In these embodiments, conversion reaction can carry out catalysis by any suitable catalyzer well known by persons skilled in the art.Such catalyzer includes but not limited to Fe ₂o ₃catalyst based (as Fe ₂o ₃-Cr ₂o ₃catalyzer), and other transition metal bases and transition metal oxide catalyst based.In other embodiments, the acid gas conversion can be carried out in multistage.In a kind of specific embodiment, this acid gas conversion is carried out in two-stage.This two-stage approach is used high temperature sequence (sequence), follows by the low temperature sequence.Gas temperature for the high temperature shift reaction is about 350 ℃-about 1050 ℃.Typically high temperature catalyst includes but not limited to ferric oxide, optionally is combined with the chromic oxide of less amount.Gas temperature for the low temperature conversion is about 150 ℃-about 300 ℃, or about 200 ℃-about 250 ℃.Low-temperature shift catalyst includes but not limited to copper oxide, and it can load on zinc oxide or aluminum oxide.Appropriate method for sour switching process is described in the US2009/0246120A1 introduced previously.

This acid conversion reaction is heat release, thus its through heat exchanger commonly used for example the second heat exchanger unit (401) carry out, effectively utilize heat energy.The conversion reactor that adopts these features is well known to a person skilled in the art.In the US7074373 that an example of suitable conversion reactor is introduced in front, be illustrated, although other designs well known by persons skilled in the art are also effective.

After the acid gas conversion routine, the crude product stream of formed hydrogen rich gas (72) comprises CH usually ₄, CO ₂, H ₂, H ₂s, steam, optional CO and optional a small amount of other pollutents.

As mentioned above, the crude product stream of hydrogen rich gas (72) can be provided to for example the second heat exchanger unit (401) of heat recovery units.And the second heat exchanger unit (401) is expressed as independent unit in Fig. 2, it can exist like this and/or be incorporated in sour conversion reactor (700), thus can cooling this acid conversion reactor (700) and remove the heat energy of at least a portion from the crude product stream (72) of hydrogen rich gas, reduce temperature and produce cooling stream.

The heat energy of this recovery of at least a portion can be used for producing the second process vapour stream by water/vapour source.

In the specific embodiment shown in Fig. 2, the crude product stream of hydrogen rich gas (72) is introduced in superheater (401a) after leaving sour conversion reactor (700), follows by boiler water supply preheater (401b).Can use superheater (401a) to carry out the stream of superheated for example (42a) (it can be the part of the crude product stream (70) of cooling methane rich), to produce superheat flow (42b), then it reconsolidate into the crude product stream (70) of cooling methane rich.Perhaps, the product stream of whole cooling methane rich can preheating in superheater (401a), as superheat flow (42b), inputs in sour conversion reactor (700) subsequently.Boiler water supply preheater (401b) can produce the feedwater feed streams (39) of preheating for for example preboiler water supply (46), be used for the one or more of the first heat exchanger unit (400) and the 3rd heat exchanger unit (403), and other steam generations operations.

If expectation is some carbon monoxide contents that keep the crude product stream (50) of methane rich, the gas bypassing loop (71) communicated with the first heating recovery unit (400) can be provided, can walk around sour conversion reactor (700) and the second heat exchanger unit (401) once so that some leave the crude product stream (70) of the cooling methane rich of the first heat exchanger unit (400), and remove unit (800) some points before above and crude product stream (72) combination of hydrogen rich gas at dewatering unit (450) and/or sour gas.When expectation is that while reclaiming independent methane production, this is useful especially, because as described below kept carbon monoxide can be subsequently by methanation.

Dehydration (450)

Remove unit (800) before afterwards and at sour gas at sour conversion reactor (700) and the second heat exchanger unit (401), typically the crude product stream of this hydrogen rich gas (72) is processed to reduce water-content via knockout drum (knock-out drum) or similar water separation device (450).Formed wastewater streams (47) (it will be acidic aqueous stream) can be sent to the treatment unit for waste water (not shown), for further processing.The crude product stream of the hydrogen rich gas of formed dehydration (72a) is delivered to sour gas as described below and is removed unit (800).

Sour gas is removed (800)

Use sour gas removal unit (800) subsequently to remove most H from the crude product stream (72a) of the hydrogen rich gas of dehydration ₂s and most CO ₂and the gas stream (80) of generation depriving hydrogen sulphide.

Sour gas removal method typically comprises makes gas stream contact with solvent (as monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, amino acid whose sodium salt solution, methyl alcohol, hot salt of wormwood etc.), produces and is full of CO ₂and/or H ₂the absorption agent of S.A kind of method can comprise uses Selexol (UOP LLC, Des Plaines, IL USA) or Rectisol (Lurgi AG, Frankfurt am Main, Germany) solvent, it has two series; Each series contains H ₂s absorption agent and CO ₂absorption agent.

A kind ofly be described in front for the method for removing sour gas and be incorporated into US2009/0220406A1.

At least most (for example basically whole) CO ₂and/or H ₂s (with other remaining contaminant trace species) should remove via sour gas removal process.At sour gas, remove in context, " basically " removes and means to have removed enough components of high per-cent, in order to can produce the final product of expectation.Actual removal amount therefore may be different between component and component.For " pipeline quality Sweet natural gas ", only can there is the H of trace (at most) ₂s, although may allow the CO of higher (still few) amount ₂.

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

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

The gas stream of formed depriving hydrogen sulphide (80) will comprise CH usually ₄, H ₂with optional CO (for the downstream methanation), and a small amount of CO typically ₂and H ₂o.

Remove the H of any recovery of (with other processes sour water stripping (SWS) for example) from sour gas ₂s (78) can (comprise the Claus method) by any method known to those skilled in the art and change into elementary sulfur.The liquid that sulphur can be used as melting reclaims.

The CO of any recovery of removing from sour gas ₂(79) can be compressed at CO ₂transmission, industrial application and/or detain storage or other processes (as the recovery of oil strengthened) in pipeline.

The gas stream of formed depriving hydrogen sulphide (80) can be for example directly as medium/high BTU fuel source, or the feed of the battery that acts as a fuel, for example be disclosed in the US2011/0207002A1 and US2011/0217602A1 introduced previously, or further processing as described below.

Hydrogen separation unit (850)

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

In one embodiment, the PSA device is used for to Hydrogen Separation.PSA technique for the gaseous mixture separating hydrogen gas from containing methane (with optional carbon monoxide) normally well known to a person skilled in the art, is disclosed in for example US6379645 (with other citing documents of wherein mentioning).The PSA device is normally commercially available, for example, based on available from Air Products and Chemicals Inc. (Allentown, PA), and the technique of UOP LLC (Des Plaines, IL) etc.

In another embodiment, can use the hydrogen membrane separator, follow by the 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.

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

Hydrogen gas product stream (85) can be as for example energy and/or reactant.For example hydrogen can be as the energy of hydrogen base fuel battery, for generation of power and/or produce steam (referring to 980 in Fig. 2,982 and 984) and/or for hydrogenation methanation method subsequently.Hydrogen also can be used as the reactant in different method for hydrogenation, for example method for hydrogenation in chemistry and oil-refinery industry.

The gas stream of the depriving hydrogen sulphide of hydrogen-depleted gas (82) will mainly comprise methane, and have optional a small amount of carbon monoxide (depending primarily on degree and the bypass of sour conversion reaction), carbonic acid gas (depending primarily on the efficiency of sour gas removal method) and hydrogen (depending primarily on degree and the efficiency of Hydrogen Separation technique).The gas stream of the depriving hydrogen sulphide of hydrogen-depleted gas (82) can directly be used, and/or can as described belowly further process/use.

Methanation (950)

The gas stream (82) of the depriving hydrogen sulphide of the gas stream of all or part of depriving hydrogen sulphide (80) or hydrogen-depleted gas can directly be used as methane product stream (99), or all or part of those streams can further process/purify to produce methane product stream (99).

In one embodiment, the input of the gas stream (82) of the depriving hydrogen sulphide of the gas stream of depriving hydrogen sulphide (80) or hydrogen-depleted gas is supplemented in (trim) methanator (950), produce other methane with carbon monoxide and the hydrogen that may exist in those streams, produce the product stream (97) of methane rich.

If there is hydrogen separation unit (850), the gas stream of a part of depriving hydrogen sulphide (80) can be walked around hydrogen separation unit (850) via by-pass line (86), with the hydrogen content of the gas stream (82) of the depriving hydrogen sulphide of adjusting hydrogen-depleted gas, optimize the H for methanation ₂/ CO ratio.

This methanation reaction can carry out in any suitable reactor, for example single-stage methanator or the staged reactor of single-stage methanator, series connection.Methanator includes but not limited to fixed bed, moving-bed or fluidized-bed reactor.Referring to for example US3958957, US4252771, US3996014 and US4235044.Methanator and catalyzer are normally commercially available.For the catalyzer of methanation and methanation condition, normally various equivalent modifications is known, and will depend on temperature, pressure, flow velocity and the composition of the gas stream of for example introducing.

Because methanation reaction is high heat release, therefore, in different embodiments, the product gas stream of methane rich (97) can for example further be provided to heat recovery units, for example the 3rd heat exchanger unit (403).Although the 3rd heat exchanger unit (403) is to mean as the unit separated, but it can exist like this and/or be incorporated in methanator (950), therefore can cooling methanator unit and remove the heat energy of at least a portion from the gas stream of methane rich, with the temperature of the gas stream that reduces this methane rich.The heat energy reclaimed can be for producing the second process vapour stream (43) by water and/or vapour source (39b).Although do not mean like this in Fig. 2, the 3rd heat exchanger unit (403) can comprise superheat region, follows by the boiler zone, as described for the first heat exchanger unit (400) as front.Because the high exothermicity of methanation reaction, it is further overheated that the second process flow (43) will typically not need, and all or part of can with all or part of superheating process vapour stream (25) combination, as flow of superheated steam (12).But if necessary, superheater (990) can, for the temperature to expectation by flow of superheated steam (12) superheated, be inputted hydrogenation methanator (200).

The product gas stream of methane rich (97) can be used as methane product stream (99), or it can further be processed when needed, by any suitable gas separating method well known by persons skilled in the art, separates and reclaims CH ₄, include but not limited to low-temperature distillation and use molecular sieve or gas delivery (for example pottery) film.Other method for gas purification comprises and for example produces methane hydrate, as disclosed in the US2009/0260287A1, the US2009/0259080A1 that introduce previously and US2009/0246120A1.

Pipeline quality Sweet natural gas

In certain embodiments, the invention provides the method and system that can be produced by the hydrogenation methanation of on-gaseous carbonaceous material " pipeline quality Sweet natural gas " (or " pipeline quality substitute natural gas ")." pipeline quality Sweet natural gas " typically refers to the stream containing methane, its: (1) the calorific value of pure methane ± (methane is 1010btu/ft at the calorific value under standard atmosphere conditions in 5% ³), (2) are substantially free of water (typically dew point is approximately-40 ℃ or lower), and (3) are substantially free of toxicity or corrosive contaminants.In some embodiments of the present invention, the methane product stream described in top method (99) meets such requirement.

wastewater treatment

By contaminant trace species remove, acid conversion, ammonia are removed, sour gas is removed and/or the catalyst recovery process in any one or more formed waste water in residual pollutent can in treatment unit for waste water, remove so that the water can recirculation reclaimed in factory and/or process the water from factory process according to any method well known by persons skilled in the art.Depend on feed and reaction conditions, such residual contaminants can comprise for example aromatic hydrocarbons, CO, CO ₂, H ₂s, COS, HCN, ammonia and mercury.H for example ₂s and HCN can remove as got off: waste water is acidified to pH about 3, uses inert gas treatment acid waste water in stripping tower, and pH is elevated to about 10, and come except deammoniation (referring to US5236557) with this waste water of inert gas treatment for the second time.H ₂s can remove as follows: under residual coke particle exists with this waste water of oxidizer treatment, with by H ₂s changes into the insoluble sulfur hydrochlorate, and it can or remove by filter by flotation (referring to US4478425).Aromatic hydrocarbons can be removed as follows: by waste water with optionally contain unit price-contact with the carbon containing carbonizing matter of the divalence alkaline inorganic compound (carbonizing matter of solid carbonizing matter product or dilution after catalyst recovery for example, and regulate pH (referring to US4113615) supra).Aromatic hydrocarbons also can be removed as got off: use organic solvent extraction, process subsequently waste water (referring to US3972693, US4025423 and US4162902) in stripping tower.

process steam

The various process vapour streams that can provide steam feed loop to supply with to be produced by energy recovery (for example 25/40 and 43).

This process vapour stream can be as the generation of getting off: use for example the first and the 3rd heat exchanger unit (400) and (403) of one or more heat recovery units, water/vapour source (for example (39a) and (39b)) is contacted with the heat energy reclaimed from various process operations.

Can use any suitable heat recovery units known in the art.For example can use steam boiler or any other suitable vapour generator (for example shell/pipe in pipe), it can utilize the heat energy of recovery to produce steam.This heat exchanger also can serve as the superheater (as (400a) of Fig. 2) for vapour stream, thus can with one or more levels the recovery of heat by the method by the steam superheated temperature and pressure to expectation, thereby eliminated the needs to the superheater of independent fuel heating.

Although any water source may be used to produce steam, common water used in known boiler systems is purified and deionization (approximately 0.3-1.0 μ S/cm), with the corrosion process that slows down.

In a kind of embodiment of the inventive method, the hydrogenation methanation reaction will have steam demand (temperature, pressure and volume), and process steam and process recovery of heat are enough to provide at least approximately 97wt% or at least approximately 98wt% or at least approximately 99wt% or at least about 100% of this total steam demand.If necessary, remaining about 3wt% or lower or approximately 2wt% or lower or approximately 1wt% or lower can being provided by supplementary vapour stream, supplementary vapour stream can be used as vapour stream (12) or as in its a part of input system.In the steady-state operation of described method, process steam should be the amount of temperature and pressure that is enough to meet the steam demand of hydrogenation methanation reaction.

If necessary, can provide supplementary vapour stream with suitable steam boiler or vapour generator.Such boiler can be for example by using any carbonaceous material, as fine coal, biomass etc., energy is provided, and includes but not limited to underproof carbonaceous material in the feed preparation manipulation (for example fines, supra).In one embodiment, so other steam boiler/producer can exist, but is not used in steady state operation.

In another embodiment, the process vapour stream provides at least whole total steam demand for the hydrogenation methanation reaction, wherein, in steady state operation, does not basically have supplementary vapour stream.

In another embodiment, produced excessive process steam.This excessive steam can be for for example via steam turbine generating, and/or this carbon containing feed is dried to the water capacity of expectation in the liquid bed drying machine, as described below.

Generating

Part methane product stream (99) can be for burning (980) and generation steam (982), as the hydrogen (85) of any recovery of a part.As implied above, excessive recycled vapour can be provided to one or more power generators (984), in burning or steam turbine, next life the electrogenesis energy, it can be sold for factory or electrical network (power grid) is upper.

prepare the carbon containing feed

Carbonaceous material processing (100)

Particulate carbonaceous material biological example matter and abiotic matter can be as the preparations of getting off: via minute other or together with crushing and/or grinding, according to any method known in the art, for example impact grinding and wet or dry grinding produce one or more carbonaceous particles.Depend on for broken and/or grind the method in this carbonaceous material source, (formed carbonaceous particles can sieve, according to apart) carbon containing feed (32) is provided, it forms the carbon containing feed (31+32) of hydrogenation methanator (200) catalysis used for catalyst loading process (350).

Any method well known by persons skilled in the art all can be used for sieving this particulate.For example the screening can by the screening or by particulate sent a sieve perhaps many sieves carry out.Screening plant can comprise diagrid, bar screen and wire mesh screens.Sieve can be static or be combined with for shaking or vibrate the mechanism of this sieve.Perhaps, can separate carbonaceous particles with classification.Sorting equipment can comprise ore sorter, gas cyclone, hydrocyclone, rake classifier, rotation trommel or fluidized classification device.This carbonaceous material also can screening or classification before grinding and/or fragmentation.

This carbonaceous particles can be used as mean particle size for from about 25 microns or from about 45 microns, highly to about 2500 microns or height, to the fine particles of about 500 microns, supplies with.Those skilled in the art can easily determine the suitable granularity of carbonaceous particles.For example, when using fluidized-bed reactor, such carbonaceous particles can have such mean particle size, when it makes the carbonaceous material gas velocity used at fluidized-bed reactor, can realize initial fluidisation.The size range of making us expectation for hydrogenation methanator (200) is Geldart A and Geldart B scope (the superimposed part that comprises the two), this depends on fluidization conditions, typically has limited amount thin (lower than about 25 microns) and thick (being greater than about 250 microns) material.

In addition, some carbonaceous material (for example cornstalk and switchgrass) and industrial waste (for example sawdust) or can not stand fragmentation or grinding operation, or may be unsuitable for direct use, for example, owing to ultra-fine granularity.Such material can form bead or the briquetting of suitable dimension, for broken or be directly used in for example fluidized-bed reactor.Usually, can prepare by one or more carbonaceous materials of compacting by bead; Referring to the US2009/0218424A1 for example introduced previously.In other examples, biological material and coal can be made briquetting, described in US4249471, US4152119 and US4225457.Such bead or briquetting can use in the following discussion interchangeably with aforesaid carbonaceous particles.

According to the quality in carbonaceous material source, other feed procedure of processing may be essential.Biomass may comprise high water capacity, and for example green plants and grass can need drying before fragmentation.Municipal waste and sewage also may comprise high water capacity (its can for example by reducing with press or roll crusher) (for example US4436028).Equally, abiotic matter (as the high humidity coal) can need drying before crushing.Some caking coals can need partial oxidation to simplify the operation.The abiotic matter feed (as hard coal or refinery coke) that lacks ion exchange site can pre-treatment produce other ion exchange site, to promote catalyst loading and/or combination.Such pre-treatment can complete by any method known in the art, the position that its generation can ion-exchange and/or improve the porosity (referring to the US4468231 for example introduced previously and GB1599932) of feed.Oxidation pre-treatment can complete with any oxygenant known in the art.

Ratio and the type of carbonaceous material in carbonaceous particles can technology consideration, processing economy, operability and the degree of approach based on abiotic matter and biomass sources be selected.For the operability in the source of carbonaceous material and the price that the degree of approach can affect feed, and therefore affect the integral production cost of catalysis gasification method.Biological example matter and abiotic material can be with about 5:95, about 10:90, approximately 15:85, approximately 20:80, about 25:75, approximately 30:70, approximately 35:65, approximately 40:60, about 45:55, approximately 50:50, approximately 55:45, approximately 60:40, about 65:35, approximately 70:20, approximately 75:25, about 80:20, approximately 85:15, approximately 90:10, or approximately 95:5 weight is recently mixed, based on weight in wet base or dry weight, this depends on processing conditions.

Importantly, the ratio of the single component of carbonaceous material source and this carbonaceous particles biological example matter particulate and abiotic matter particulate can be for controlling the other materials characteristic of this carbonaceous particles.Abiotic material (as coal) and some biological material (as rice husk) typically comprise a large amount of inorganic substance, and it comprises calcium, aluminum oxide and silicon-dioxide, and it forms inorganic oxide (that is, ash content) in the catalytic gasification device.In the temperature higher than about 500 ℃-about 600 ℃, potassium and other alkali metal can with ash content in aluminum oxide and silicon dioxde reaction, form insoluble alkali metal aluminosilicate.In this form, basic metal is basically water-insoluble, and is sluggish as catalyzer.In order to prevent residue gathering in hydrogenation methanator (200), customary solid cleaning materials (58) (with (58a)) of taking out the by product carbonizing matter, it comprises ash content, unreacted carbonaceous material and various other compounds (alkali metal compound for example, water-soluble and water-insoluble the two).

In the preparation of carbonaceous particles, the ash oontent of different carbonaceous materials for example can be chosen as approximately 20wt% or still less, or about 15wt% or still less, or about 10wt% or still less, or about 5wt% or still less, this for example depends on the ratio of various carbonaceous materials and/or the initial ash content in various carbonaceous material.In other embodiments, formed this carbonaceous particles can comprise from about 5wt% or from about 10wt%, to about 20wt% or to the ash oontent of about 15wt%, the weight based on carbonaceous particles.In other embodiments, the ash oontent of this carbonaceous particles can comprise and is less than about 20wt%, or is less than about 15wt%, or is less than about 10wt%, or is less than about 8wt%, or is less than the aluminum oxide of about 6wt%, the weight based on ash content.In certain embodiments, this carbonaceous particles can comprise the ash oontent that is less than about 20wt%, the weight of the feed based on processed, and wherein the ash oontent of this carbonaceous particles comprises the aluminum oxide that is less than about 20wt%, or be less than the aluminum oxide of about 15wt%, the weight based on ash content.

In carbonaceous particles, low like this aluminum oxide value finally can be reduced in the catalyst loss in the hydrogenation methanation part of described method, particularly base metal catalysts loss.As implied above, aluminum oxide can react with alkaline source, produces insoluble carbonizing matter, and it comprises for example alkali metal aluminate or aluminosilicate.Insoluble carbonizing matter like this can cause the reduction (that is, the increase of catalyst loss) of catalyst recovery yield, and needs thus the other cost of make-up catalyst in whole method.

In addition, formed carbonaceous particles can have the carbon of obviously higher per-cent, and therefore higher btu/lb value and the carbonaceous particles of the every unit weight of methane production.In certain embodiments, the carbon content of formed carbonaceous particles can be from about 75wt%, or from about 80wt%, or from about 85wt%, or from about 90wt%, until about 95wt%, the gross weight based on abiotic matter and biomass.

In an example, for example, by abiotic matter and/or biomass wet lapping and screening (arriving the size-grade distribution of the about 2500 μ m of about 25-), the free-water (that is, dehydration) of then discharging it becomes uniformly wet cake.The example that is used for the suitable method of wet lapping, screening and dehydration is well known by persons skilled in the art; For example, referring to the US2009/0048476A1 introduced previously.The water capacity of the filter cake by the formed abiotic matter of the wet lapping according to a kind of embodiment of the present invention and/or biomass particulate can be that about 40%-is about 60%, or approximately 40%-is about 55%, or lower than 50%.The water capacity that is appreciated that for a person skilled in the art the wet lapping carbonaceous material of dehydration depends on carbonaceous material particular type, size-grade distribution and concrete dewatering unit used.Such filter cake can be heat-treated as described herein, and one or more reduce the carbonaceous particles of humidity to produce next life.

Each in described one or more carbonaceous particles can have unique composition, as mentioned above.For example can use two kinds of carbonaceous particles, wherein the first carbonaceous particles comprises one or more biological materials and the second carbonaceous particles comprises one or more abiotic materials.Selectively, single carbonaceous particles comprises one or more carbonaceous materials used.

Catalyst loading for hydrogenation methanation (350)

The hydrogenation methanation catalyst is at least above-mentioned reaction of catalysis (I), (II) and (III) lateral reactivity.Such catalyzer well known to a person skilled in the art in general sense, and for example can comprise basic metal, alkaline-earth metal and transition metal with and compound and complex compound.Typically, this hydrogenation methanation catalyst comprises at least basic metal, as is disclosed in many reference of introducing previously.

For the hydrogenation methanation reaction, these one or more carbonaceous particles are further processing typically, with at least one hydrogenation methanation catalyst (typically comprising at least one alkali metal source), combines, and produces the carbon containing feed (31+32) of catalysis.If use the liquid carbon-containing material, this hydrogenation methanation catalyst can for example closely be sneaked in the liquid carbon-containing material.

This carbonaceous particles that offers catalyst loading can process to form the carbon containing feed (31+32) of catalysis, it is sent in hydrogenation methanator (200), also can be divided into one or more processing stream, wherein at least one this processing stream is combined the feed that forms at least one catalyst treatment and is flowed with the hydrogenation methanation catalyst.All the other processing streams can for example be processed to be combined with its second component.In addition, the feed stream of this catalyst treatment can be processed to combine with second component for the second time.Second component can be for example the second hydrogenation methanation catalyst, a kind of promotor, or other additives.

In an example, main hydrogenation methanation catalyst (alkali metal compound) can offer single carbonaceous particles (for example potassium and/or sodium source), process respectively subsequently and provide one or more promotors and additive (for example calcium source) to same single carbonaceous particles, produce the carbon containing feed (31+32) of catalysis.For example, referring to the US2009/0217590A1 introduced previously and US2009/0217586A1.

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

When one or more carbonaceous particles are provided for catalyst loading, at least one this carbonaceous particles is combined to form the feed stream of at least one catalyst treatment with the hydrogenation methanation catalyst.In addition, any carbonaceous particles can be described in detail as top, is divided into one or more processing stream, for second or other combination of components.Formed stream can be mixed with any combination, and the carbon containing feed (31+32) of catalysis is provided, and condition is the feed stream that the feed stream of at least one catalyst treatment is used to form catalysis.

In one embodiment, by least one carbonaceous particles and hydrogenation methanation catalyst and optionally second component be combined.In another embodiment, each carbonaceous particles and hydrogenation methanation catalyst and optionally second component be combined.

Can be by any method well known by persons skilled in the art by one or more hydrogenation methanation catalysts and any this carbonaceous particles and/or the combination of processing stream.Such method includes but not limited to mix with the solid catalyst source, and by catalyst soakage to processing carbonaceous material on.Several dipping method well known by persons skilled in the art can be for sneaking into the hydrogenation methanation catalyst.These methods include but not limited to the combination of incipient wetness impregnation, vapo(u)rability dipping, vacuum impregnation, dip-coating dipping, ion-exchange and these methods.

In one embodiment, basic metal hydrogenation methanation catalyst can pass through to use in packing groove solution (for example aqueous solution) slurrying of catalyzer, and is impregnated in one or more carbonaceous particles and/or processing stream.When the solution slurrying with catalyzer and/or promotor, the feed stream that provides catalyst treatment to cross can be provided formed slurry, equally typically as wet cake.Can be prepared by any catalyst source in the method for the invention by this catalyst solution, comprise catalyzer or the catalyst solution of new or supplementary catalyzer and recirculation.Comprise that for the method for the wet cake that slurry dewatered to provide the feed stream that catalyst treatment crosses filtrations (gravity or vacuum), centrifugation and fluid suppress.

In another embodiment, as disclosed as the US2010/0168495A1 introduced previously, this carbonaceous particles is combined with aqueous catalyst solution, produce the wet cake of not draining basically, then under hot conditions, mix, and finally be dried to the suitable wet level that contains.

A kind of being suitable for is combined to provide the concrete grammar of feed stream of catalyst treatment for via the US2009/0048476A1 as introduced previously and the ion-exchange described in US2010/0168494A1 coal particulate and/or the processing stream that comprises coal with the hydrogenation methanation catalyst.Catalyst loading by ion-exchange mechanism can maximize by the adsorption isothermal line based on developing for coal specially, described in the reference of being introduced.Such loading provides the feed stream as the catalyst treatment of wet cake.Can control the other catalyzer (comprising the catalyzer in hole) on the wet cake of the particulate that is retained in ion-exchange, so that can obtain in a controlled manner total catalyzer target value.The catalyzer total amount of loading can be controlled by concentration and duration of contact, temperature and the method for controlling catalyst component in solution, disclosed in reference as aforementioned introducing, and as the feature of those skilled in the art based on initial coal can easily be determined.

In another example, one of this carbonaceous particles and/or processing stream can be processed with the hydrogenation methanation catalyst, and the second processing stream can be processed with second component (referring to the US2007/0000177A1 introduced previously).

Carbonaceous particles, processing stream and/or can be mixed combining arbitrarily by the feed stream of aforementioned formed catalyst treatment, so that the second carbon containing feed of catalysis to be provided, condition is the carbon containing feed (31+32) that feed stream that at least one catalyst treatment is crossed is used to form catalysis.Finally, the carbon containing feed (31+32) of catalysis is delivered to hydrogenation methanator (200).

Usually, each catalyst loading unit comprises at least one packing groove, and one or more in carbonaceous particles and/or processing stream are contacted with the solution that comprises at least one hydrogenation methanation catalyst, forms the feed that one or more catalyst treatment cross and flows.Selectively, catalyst component can be used as solia particle and is blended in one or more carbonaceous particles and/or processing stream, to form the feed stream of one or more catalyst treatment.

Typically, when the hydrogenation methanation catalyst is only or basically be basic metal, it exists with such amount in the carbon containing feed of catalysis, and the ratio that this amount is enough to provide the carbon atom in the carbon containing feed of alkali metal atom and catalysis is for from 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 about 0.07, or to about 0.06.

For some feeds, alkaline components also can be provided in the carbon containing feed of catalysis, realize than the total ash content of the combination of the carbonaceous material in the carbon containing feed of catalysis large the alkali metal content of about 10 times of about 3-, based on quality.

Suitable basic metal is lithium, sodium, potassium, rubidium, caesium and composition thereof.Useful especially is the potassium source.Suitable alkali metal compound comprises alkaline carbonate, supercarbonate, formate, oxalate, acid amides, oxyhydroxide, acetate or similar compound.For example this catalyzer can comprise following one or more: sodium carbonate, salt of wormwood, rubidium carbonate, Quilonum Retard, cesium carbonate, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide, and particularly salt of wormwood and/or potassium hydroxide.

Can use optional promotor or other catalyst additives, for example, in the reference that introduce front disclosed those.

Feed that one or more catalyst treatment are crossed stream (it combines to form the carbon containing feed of catalysis) typically comprise be greater than about 50%, be greater than about 70% or be greater than about 85% or be greater than the catalyzer total amount of the loading of carbon containing feed about 90% and catalysis (31+32) combination.The percent of total of the catalyzer loaded (its feed stream of crossing to various catalyst treatment is relevant) can be determined according to method known to those skilled in the art.

Divide feed stream and the processing stream that other carbonaceous particles, catalyst treatment are crossed suitably to mix, carry out control example other qualities as the carbon containing feed (31+32) of total catalyst loading or catalysis, as previously mentioned.The adequate rate of the various streams of combination will depend on the quality of carbonaceous material, the performance of each of the carbon containing feed (31+32) that comprises catalysis and expectation.The abiotic matter particulate stream of biological example matter particulate stream and catalysis can, with such ratio combination, produce the carbon containing feed (31+32) of the catalysis with predetermined ash oontent, as previously mentioned.

The feed stream of the feed stream that any aforementioned catalyst treatment is crossed, processing stream and processing, as one or more dry particles and/or one or more wet cakes, can carry out by any method known to those skilled in the art combination, it includes but not limited to mediate, and horizontal or vertical mixer instance is as single screw rod or twin screw, spiral or drum tumbler.The carbon containing feed (31+32) of formed catalysis can store until after with or transfer in the operation of one or more feed, in the hydrogenation methanator.The carbon containing feed of catalysis can be sent to storage or feed operation, for example feed screw or pneumatic transfer according to any method well known by persons skilled in the art.

According to the present invention, high water capacity below this carbon containing feed comprises when input hydrogenation methanator: be greater than 10wt%, or about 12wt% or larger, or about 15wt% or larger, to about 25wt% or still less, or to about 20wt% or still less (gross weight based on the carbon containing feed), to such degree, that is, this carbon containing feed is basically free-pouring.

As used herein, term " unrestricted flow basically " expression carbon containing feed particulate is not reunited because of water capacity under the feed condition.Ideally, the water capacity of this carbon containing feed particulate includes basically, so that only have few (or not having) surface moisture.

A kind of carbon containing feed (31+32) of suitable free-pouring catalysis basically can produce according to the disclosure of the US2010/0168494A1 introduced previously and US2010/0168495A1, and wherein in those are open, mentioned heat treatment step (after catalyzer applies) can minimize (or even likely eliminating).

Can from the carbon containing feed (31+32) of catalysis, remove excessive moisture to required degree.For example the carbon containing feed (31+32) of this catalysis can be dry (with liquid bed slurry drying machine, process vaporised liquid with superheated vapour), or thermal evaporation or to remove solution dry under vacuum, or flow down drying at rare gas element, the carbon containing feed of the catalysis with required residual water capacity is provided.

Catalyst recovery (300)

Carbon containing feed (31+32) reaction under the described conditions of catalysis provides usually from the crude product stream (52) of the poor fines methane rich of hydrogenation methanator (200) and solid carbonizing matter by product (58) (with (58a)).The catalyzer that solid carbonizing matter by product (58) typically comprises a certain amount of unreacted carbon, inorganic ash content and carries secretly.Solid carbonizing matter by product (58) can be removed from hydrogenation methanator (200), for sampling, purify and/or reclaiming catalyzer via the carbonizing matter outlet.

As used herein, term " catalyzer of carrying secretly " means chemical compound, the catalytic activity part that it comprises the hydrogenation methanation catalyst, the alkali metal compound for example existed in the carbonizing matter by product.For example " catalyzer of carrying secretly " can include but not limited to soluble alkali metal compound (for example alkaline carbonate, alkali metal hydroxide and alkalimetal oxide) and/or insoluble alkali cpd (for example alkali metal aluminosilicate).The character of the catalyst component relevant with the carbonizing matter extracted has discussion at the US2007/0277437A1 for example introduced previously, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/0169448A1.

Solid carbonizing matter by product is to export taking-up by carbonizing matter continuously or periodically from hydrogenation methanator (200), and it can be for example the lock hopper system, although additive method is also well known by persons skilled in the art.The method of removing solid carbonizing matter product is well known to a person skilled in the art.A kind of these class methods that for example can use EP-A-0102828 to instruct.

Carbonizing matter by product (58) from hydrogenation methanator (200) can be delivered to catalysis recovery unit (300), as described below.Such carbonizing matter by product (58) also can be divided into a plurality of stream, one of them can deliver to catalyst recovery unit (300), its another stream can be used as for example methanation catalyst (described in the US2010/0121125A1 introduced previously), and does not process for catalyst recovery.

In certain embodiments, when the hydrogenation methanation catalyst is basic metal, basic metal in solid carbonizing matter by product (58) can retrieve to produce catalyst recycle stream (57), and any catalyzer do not reclaimed can flow by catalyst make-up (57) and compensates (referring to the US2009/0165384A1 for example introduced previously).Aluminum oxide in feed adds that silicon-dioxide is more, obtains the higher basic metal rate of recovery more expensive.

In one embodiment, from the solid carbonizing matter by product (58) of hydrogenation methanator (200), can use recycle gas and water quencher, extract the catalyzer that a part is carried secretly.The catalyzer (57) reclaimed can import in catalyst loading unit (350), for reusing of base metal catalysts.The carbonizing matter of dilution (59) can for example import in any one or more feed preparation manipulations (100), be reused for the feed (via pipeline (59a)) of preparation catalysis, burning drives one or more vapour generators (as disclosed as the US2009/0165376A1 introduced previously)), or like this for multiple application, for example, as absorption agent (as disclosed as the US2009/0217582A1 introduced previously).

Other useful especially recovery and method for recycling are described in US4459138, and in the US2007/0277437A1 introduced previously, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/0169448A1.About further method details, can be with reference to those documents.

Catalyzer can be recycled to catalyst loading process one or a combination set of.For example whole catalyst recycle can be inputted a catalyst loading process, and another process is only utilized make-up catalyst.In the catalyst loading process, can be based on the single level of recirculation to make-up catalyst of controlling.

Except catalyst recovery, by product carbonizing matter (58) also can be processed for reclaiming other by products, vanadium for example, as disclosed as the US patent application 13/094438 of introducing previously.

the multistage method

In process of the present invention, each process can be carried out in one or more machining cells.For example the carbon containing feed for preparing unit operation from one or more catalyst loadings and/or feed can be inputted to one or more hydrogenation methanators.Similarly, the crude product stream of the methane rich produced by one or more hydrogenation methanators can process respectively or purify or process or purify in the combination of different point downstream via them, this depends on concrete System Construction, as what discussed in US2009/0324458A1, the US2009/0324459A1, US2009/0324460A1, US2009/0324461A1 and the US2009/0324462A1 that introduce previously.

In certain embodiments, described method is used two or more hydrogenation methanators (for example 4 hydrogenation methanators of 2 –).In such embodiments, the method can comprise and disperse machining cell (before the hydrogenation methanator, be less than the sum of hydrogenation methanator), be used for the carbon containing feed of catalysis the most at last and be provided to a plurality of hydrogenation methanators, and/or can comprise the convergence machining cell (after the hydrogenation methanator, be less than the sum of hydrogenation methanator), the crude product stream of a plurality of methane rich that produced by a plurality of hydrogenation methanators for processing.

When described system comprises the convergence machining cell, each assembles machining cell can select to have the ability of accepting to be greater than total feed streams 1/n part of assembling machining cell, and n is the number of convergence machining cell here.Similarly, when system comprises while dispersing machining cell, each disperses machining cell can select to have the ability of accepting to be greater than the 1/m part that is supplied to total feed streams of assembling machining cell, and m is the number of dispersing 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, therein step (a), (b) and (c) be to move in a continuous manner.

Another kind of specific embodiment is such scheme, wherein when being incorporated into the fluidized-bed bottom or before mix the stream of flow of superheated steam and oxygen rich air.

Another kind of specific embodiment is such scheme, wherein the gas stream of oxygen rich air (14) is inputted in hydrogenation methanator (200) continuously, and the amount of the oxygen provided changes as process control, for example, with the operating temperature of the expectation of controlling the hydrogenation methanation reaction.When oxygen input hydrogenation methanator, formed oxidation/combustion reactions (for example with carbon in by product carbonizing matter and fines react) has produced heat energy (and typically carbon monoxide and the hydrogen of a tittle).The amount of oxygen that can increase or reduce input hydrogenation methanator improves or reduces burning/oxidation and thus in the amount of the heat energy of hydrogenation methanator situ generation.

Another kind of specific embodiment is such scheme, wherein the crude product stream of methane rich is incorporated in the first heat exchanger unit to the crude product stream that reclaims heat energy and produce cooling methane rich.

Another kind of specific embodiment is such scheme, the heat energy that wherein will reclaim in the first heat exchanger unit is for generation of the first process vapour stream, with this first process vapour stream of superheated, come, as a whole or flow of superheated steam part, to be incorporated in the hydrogenation methanator.

Another kind of specific embodiment is such scheme, and wherein at least a portion carbon monoxide in the crude product stream of cooling methane rich is produced the crude product stream of heat energy and hydrogen rich gas by steam conversion.

Another kind of specific embodiment is such scheme, wherein from steam conversion, reclaims heat energy, and the heat energy that at least a portion is reclaimed is for the superheated boiler water supply, for generation of process steam.

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

Another kind of specific embodiment is such scheme, wherein most carbonic acid gas and most hydrogen sulfide are removed from the crude product stream of the hydrogen rich gas of dehydration, produce the gas stream of depriving hydrogen sulphide with the crude product stream of the hydrogen rich gas by this dehydration, it comprises most hydrogen, carbon monoxide (if being present in the crude product stream of hydrogen rich gas of dehydration) and methane.

Another kind of specific embodiment is such scheme, wherein from the gas stream of depriving hydrogen sulphide, separates a part of hydrogen with the gas stream of the depriving hydrogen sulphide that produces hydrogen gas product stream and hydrogen-depleted gas (it comprises methane, hydrogen and carbon monoxide optionally).

Another kind of specific embodiment is such scheme, wherein make gas stream (or the gas stream of the depriving hydrogen sulphide of hydrogen-depleted gas of depriving hydrogen sulphide, if present), existing carbon monoxide and hydrogen are under methanation catalyst exists, and in the catalytic methane convertor, reaction is with the gas stream of the depriving hydrogen sulphide of generation heat energy and methane rich.

Another kind of specific embodiment is such scheme, wherein from catalytic production of methane, reclaims heat energy, and the heat energy that at least a portion is reclaimed for generation of with superheated the second process vapour stream.

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

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

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

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

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

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

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

Another kind of specific embodiment is such scheme, wherein by the stream combination of flow of superheated steam and oxygen rich air, be input to the lower region of the fluidized-bed of hydrogenation methanator, and this temperature in conjunction with stream is about 500 °F (about 260 ℃)-about 900 °F (about 482 ℃), as mentioned above.

Another kind of specific embodiment is such scheme, and the synthetic gas wherein produced by original position (step (c)) meets (or meeting) synthetic gas demand basically; So, there is no that (or not having) synthetic gas joins in this hydrogenation methanator (in the carbon containing feed that may be present in inherently defeated time hydrogenation methanator or fines stream).

Another kind of specific embodiment is such scheme, wherein by recirculation, gets back to the gas stream of flow of superheated steam in the hydrogenation methanator, oxygen rich air and the steam in fines stream and the steam that produced by carbon containing feed original position meets (or meeting) steam demand basically.

Another kind of specific embodiment is such scheme, wherein be provided to whole primary flow of hydrogenation methanator (gas stream of vapour stream, oxygen rich air, carbon containing feed/hydrogenation methanation catalyst and fines recirculation flow) when the temperature of the object run temperature lower than the hydrogenation methanator is introduced, the heat produced by original position (step (c)) meets (or meeting) heat demand basically.

Another kind of specific embodiment is such scheme, wherein the carbon containing feed is supplied in the hydrogenation methanation in the feed position, the carbonizing matter by product is to produce by step (b) and reaction (c), and the carbonizing matter by product is on the point of draw higher than carbon containing feed feed point, continuously or periodically take out from the hydrogenation methanator.In another embodiment, the carbonizing matter by product is periodically or takes out from fluidized-bed top continuously.

Another kind of specific embodiment is such scheme, and the by product carbonizing matter wherein at least a portion taken out is provided in the catalyst recovery operation.The catalyzer reclaimed and then circulation and be combined to meet the demand of hydrogenation methanation reaction with make-up catalyst.

Claims

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

(a) in the hydrogenation methanator, supply with

(2) hydrogenation methanation catalyst,

(3) flow of superheated steam, and

(4) gas stream of oxygen rich air,

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

(b) at the object run temperature, under hydrogenation methanation catalyst, carbon monoxide, hydrogen and steam exist, make the described carbon containing feed reaction of a part in described hydrogenation methanator, to produce thick gas and the solid by-product carbonizing matter of methane rich, the fines that the thick gas of wherein said methane rich comprises methane, carbon monoxide, hydrogen, carbonic acid gas, hydrogen sulfide, steam, heat energy and carries secretly; With

Wherein:

(i) reaction of step (b) accounts for leading on fluidized-bed top;

(iii) described carbon containing feed comprises from being greater than the high water capacity of 10wt% to about 25wt% (gross weight based on described carbon containing feed) when being supplied to the hydrogenation methanator, it reaches such degree, that is it is basically free-pouring, making described carbon containing feed.

2. the method for claim 1, be characterised in that described carbon containing feed comprises about 12wt% or larger high water capacity when input hydrogenation methanator.

3. the method for claim 1, be characterised in that described carbon containing feed comprises about 15wt% or larger high water capacity when input hydrogenation methanator.

4. the method for claim 1-3 any one, be characterised in that described carbon containing feed comprises about 20wt% or lower high water capacity when input hydrogenation methanator.

5. the method for claim 1-4 any one, be characterised in that the reaction of step (b) has synthetic gas demand and heat demand, and described synthetic gas demand, and described heat demand and synthetic gas demand are that reaction by step (c) meets basically; With the reaction of step (b) has steam demand, and described steam demand is that the gas stream of flow of superheated steam by input fluidized-bed bottom, oxygen rich air and the steam in fines stream and the steam produced by the carbon containing feed meet basically.

6. the method for claim 1-5 any one, be characterised in that the gas stream of described flow of superheated steam, oxygen rich air, carbon containing feed and hydrogenation methanation catalyst in the temperature of the object run temperature of the reaction lower than step (b) is incorporated into the hydrogenation methanator.

7. the method for claim 1-6 any one, be characterised in that described object run temperature is at least about 1000 °F (about 538 ℃)-about 1500 °F (about 816 ℃).

8. the method for claim 1-7 any one, the methane (mole number of the methane in the crude product stream based on methane rich, carbonic acid gas, carbon monoxide and hydrogen) that the crude product stream that is characterised in that described methane rich comprises at least about 15mol% and at least the methane of 50mol% add carbonic acid gas (mole number of the methane in the crude product stream based on methane rich, carbonic acid gas, carbon monoxide and hydrogen).

9. the method for claim 1-8 any one, be characterised in that the crude product stream of described methane rich be incorporated into to the crude product stream that the first heat exchanger unit reclaims heat energy and produces cooling methane rich; With the heat energy that will reclaim in the first heat exchanger unit, for generation of the first process vapour stream, and described the first process vapour stream of superheated, come to be incorporated in the hydrogenation methanator as whole or a flow of superheated steam part; At least a portion carbon monoxide in the crude product stream of described cooling methane rich is carried out to the steam conversion to produce the crude product stream of heat energy and hydrogen rich gas; Reclaim heat energy from described steam conversion, and the heat energy that at least a portion is reclaimed is for the superheated boiler water supply, for generation of process steam; The crude product stream of described hydrogen rich gas is fully dewatered to produce to the crude product stream of the hydrogen rich gas of dehydration; Remove most carbonic acid gas and most hydrogen sulfide from the crude product stream of the hydrogen rich gas of described dehydration, produce the gas stream of depriving hydrogen sulphide with the crude product stream of the hydrogen rich gas by described dehydration, it comprises most hydrogen, carbon monoxide (if being present in the crude product stream of hydrogen rich gas of dehydration) and methane; The reaction under methanation catalyst exists in the catalytic methane convertor by the carbon monoxide that makes to exist in the gas stream of described depriving hydrogen sulphide and hydrogen, with the gas stream of the depriving hydrogen sulphide that produces heat energy and methane rich; And reclaim heat energy from described catalytic production of methane, and the heat energy that at least a portion is reclaimed for generation of with superheated the second process vapour stream.

10. the method for claim 9, be characterised in that flow of superheated steam mainly comprises the steam that comes from the first process vapour stream and the second process vapour stream.