CN107075388A

CN107075388A - Pass through the system and method for the catalysis mild temperature pyrolysis manufacture hydrocarbon and modification coal of coal

Info

Publication number: CN107075388A
Application number: CN201580033375.0A
Authority: CN
Inventors: W·拉塔; M·塔吉特; H·加达拿; W·威廉斯; J·阿斯曼; R·贝林豪森; L·姆莱奇科
Original assignee: Amina LLC LP
Current assignee: Amina LLC LP
Priority date: 2014-05-23
Filing date: 2015-05-22
Publication date: 2017-08-18
Also published as: RU2016149452A; PL420377A1; US20170198221A1; PH12016502332A1; RU2016149452A3; CA2950138A1; WO2015179806A1; AU2015263935A1

Abstract

A kind of method for modifying of solid carbonaceous material, including solid carbonaceous material is heated in the presence of a catalyst and under the conditions of partial thermal decomposition, and obtain the solid carbonaceous product of modification, gaseous product and dead catalyst.

Description

Pass through the system and method for the catalysis mild temperature pyrolysis manufacture hydrocarbon and modification coal of coal

The cross reference of related application

During the application is the world (PCT) the patent application serial numbers PCT/US 2015/032252 submitted on May 22nd, 2015 State's thenational phase application, the PCT application requires the U.S. Provisional Patent Application Serial No. 62/002 submitted on May 23rd, 2014, 674 rights and interests and priority.Aforementioned application is hereby incorporated by by quoting with its full text.

Technical field

Present techniques relate generally to a kind of system and method, its can be used for by solid carbonaceous material be converted into one group it is useful Product.More specifically, this technology is related to a kind of system and method, solid carbonaceous material is changed into gas by it using catalyst Product, product liquid, and/or modification solid product (for example, modifying solid carbonaceous product).

Background technology

In view of the distribution on global of crude oil reserve is uneven and the limited property of the crude oil reserve of public attention, to based on can replace For raw material (for example：Coal, biomass etc.) constantly increase to develop the demand of replacement production technology.In past many decades, coal Liquefaction (CTL) technology has been achieved for some progress.The approach of the production hydrocarbon liquid technically most preferably determined includes gasification, one As include the steam and the co-feeding generation synthesis gas of oxygen of higher temperature.It is being further converted to methanol intermediate or is being closed for direct Into before, it is necessary to significantly cleaned to gained synthesis gas, and therefore generally include a kind of base of integrated multi-step approach In the equipment of gasification, it typically builds and operated costliness.Another approach that hydrocarbon liquid is produced from coal is so-called direct Coal liquefaction (DCL) approach, it is included by the way that coal solid and pure hydrogen are carried out into HIGH PRESSURE TREATMENT by its direct liquefaction.Even if should DCL methods can typically utilize catalyst, but the selectivity of the required hydrocarbon product stream come out from catalytic reactor is low and needs Further to handle.In other words, the DCL methods can not be conditioned to produce specific hydrocarbon products, and particularly produce relatively low point The hydrocarbon of son amount.Therefore, the DCL product streams need significant other chemical modification step, this structure for causing facility and operation Need to spend great amount of cost.Another conventional route that hydrocarbon liquid is produced from coal is gasified or is pyrolyzed by mild temperature.Pass through The liquid product stream that conventional pyrolysis is obtained includes relatively high concentration of molecular weight tar, and it needs significantly to modify, allusion quotation Carried out by catalytic hydrogenation type.Relative to the C containing non-heteroatom₁-C₁₂The selectivity of the total pyro lysis temperature product of hydrocarbon products is relatively It is low.

The content of the invention

There is provided a kind of method for modifying of solid carbonaceous material in one aspect.This method include in the presence of a catalyst, Solid carbonaceous material is heated under the conditions of partial thermal decomposition, and obtains the solid carbonaceous product of modification, gaseous product and dead catalyst.Gu A kind of non-limiting examples of body carbonaceous material are coals, therefore, and a kind of example for modifying solid carbonaceous product is modification coal product.

There is provided the solid carbonaceous material in ore-sorting system is converted into the side that modifies solid carbonaceous product on the other hand Method.This method includes solid carbonaceous material and catalyst being introduced into pyrolysis reactor, produces gaseous product flow and solid product Stream, wherein the solid product stream include modifying solid carbonaceous product.This method also includes：Gas production is reclaimed from the reactor Logistics, and reclaim from the reactor solid product stream.A kind of non-limiting examples of solid carbonaceous material are coals, because This, a kind of example for modifying solid carbonaceous product is modification coal product.

There is provided the method that the biomass in ore-sorting system is converted into modification solid product on the other hand.This method Including biomass and catalyst are introduced into pyrolysis reactor, gaseous product flow and modification solid product are produced, wherein solid is produced Logistics includes dead catalyst and the modification solid product.This method also includes：The modification solid product and dead catalyst are separated, with And the dead catalyst of the separation is transferred to regenerator, the regenerator removes at least one of any not hot in dead catalyst Coal, coke and the other carbonaceous materials of solution.The weight of ash content in modification solid product is retained in be incorporated into pyrolysis reactor In biomass Ash weight at least 60%.This method also includes：Gaseous product flow is transferred to separator, it produces liquid Body product and gaseous product.

Pyrolysis reactor can be operated at about 300 DEG C to about 1100 DEG C.In some embodiments, this can be included about 350 DEG C to about 850 DEG C or about 400 DEG C to about 700 DEG C.When carbonaceous material can have the stop of about 0.01 second to about 5 hours Between.In some embodiments, the residence time is about 0.1 second to about 1 minute.The catalyst useful load of pyrolysis reactor can be From about 0 (zero) to about 100g catalyst/g carbonaceous feed materials.In some embodiments, catalyst useful load can be from about 0.05g catalyst/g feed materials are to about 10g catalyst/g feed materials.The rate of heat addition of carbonaceous material can be in reactor About 0.1 DEG C/sec to about 1000 DEG C/sec.

In at least one embodiment, starting carbonaceous material is directly entered pyrolysis reactor.In other embodiments, Into before the pyrolysis reactor, can by such as pulverizer, drier, and/or it is any be discussed below other are suitable pre- Processor and preprocess method are pre-processed to carbonaceous material.

In at least one embodiment, starting carbonaceous material and catalyst are concomitantly introduced into pyrolysis reactor, it is described Catalyst can be mixed with carbonaceous material before entering the reactor or in reactor.Leaving the efflux of solids of reactor includes Dead catalyst and modification solid product.Then efflux of solids is separated into the first efflux of solids for mainly containing modification solid product, its Further processing can be sent to as modification solid fuel or is burnt, and mainly contains the second efflux of solids of dead catalyst, its Regeneration reactor can be delivered to, pyrolysis reactor is then recycled back into.For example, the granularity of modification carbonaceous material and catalyst Distribution can be intentionally different, and this allows to be separated according to the difference of granularity, weight and/or density by appropriate classification technique Two kinds of solids.Other technologies can substitute clasfficiator or are used in combination with clasfficiator, and it includes but is not limited to other clasfficiators Technology, electrostatic separation, electronic separation, the electrically separated and/or Magneto separate of friction.The system of the application can use high gradient magnetic point From device, it attracts weak paramagnetic particle or very thin ferromagnetic particle using high magnetic gradient.System as described herein can make Open gradient magnetic separation is used, it separates the particle fallen according to its magnetic characteristic in the stream that falls.System as described herein Electric separator can be used, wherein feed particles are powered from Ions Bombardment and are fixed on going barrel.At this electronic point From in device, the particle with high electrical conductivity tends to quickly lose its electric charge, and those particles with smaller electric conductivity (particle more insulated) tends to keep attachment, causes the separation of particle.Friction electric separator makes particle charge by friction, so Particle is set to be deflected by electric field with symbol and size according to its electric charge afterwards.

According to another embodiment, solid (such as catalyst and carbonaceous material) can keep dividing in pyrolysis reactor From.One embodiment is：Catalyst is fixed in the reactor, and for example wherein catalyst is fixed on the wall of reactor by plating On, and carbonaceous material enters and leaves pyrolysis reactor.In such a system, it need not will substantially be urged outside reactor Agent carries out solid-solid with modification solid product and separated, because these solids keep separation in reactor.

According to another embodiment, solid is mixed, then separated in reactor.One such embodiment is： Reactor be fluid bed form, wherein by catalyst and starting carbonaceous material inside reactor (or enter reactor it Before) mixed (for example, doping).After carbonaceous material and catalyst closely interaction, the solid product circulation of mixing The solid-solid separator (such as internal classification device) positioned inside reactor is crossed with separating catalyst and carbonaceous material.At this In the system of sample, substantially catalyst need not be subjected to solid-solid separation from solid product outside reactor, because They are separated in reactor.

Gaseous product flow can be transferred to one or more separative elements, for example, condensed fluid product stream and separate product Into required cut.One such embodiment of separative element is：Sour gas removes system, wherein by sulfur-bearing chemicals and Most of carbon dioxide is removed, and is each become high-purity and (is for example concentrated) stream.Other separators can be used, and can be removed Other compounds, such as hydrogen cyanide (HCN) or ammonia (NH₃).Can capture highly concentrated carbon dioxide stream be used for chelate or For in equipment or pipeline is used with outside, such as improving oil recovery.Highly concentrated sulfur-containing compound Stream can be treated for landfill, to produce available solid sulfur, or produce available sulfur-containing compound, such as sulfuric acid.

Gaseous product flow can include：One or more non-condensable gas or chemicals, such as methane, ethane, ethene, Carbon monoxide, carbon dioxide and/or hydrogen.Can not condensate flow can also be processed further with produce be used for produce other chemistry The synthesis gas of product (such as, but not limited to methanol, mixed alcohol and/or Fischer-Tropsch (Fischer Tropsch) product).It is this can not Condensate flow may be used as during fuel, for example, process or equipment other operating units provide heat.For example, will Gaseous product (such as methane, ethene, ethane, hydrogen) can have by flowing through pyrolysis apparatus as recyclegas or second Benefit.Recycling gaseous product can provide other hot and/or hydrogen (because the usual hydrogen content of coal is low) into reactor.Liquid Stream can be captured as synthetic crude, or be separated further available hydrocarbon chemicals being extracted into two or more chemistry Product stream.

In addition, it is probably favourable that fuel gas is introduced into pyrolysis apparatus from external source.For example, can be added from external source Natural gas and/or natural gas liquids (such as propane, propylene, butane, butylene, iso-butane, isobutene).The fuel of these additions Gas is by for providing fluidizing gas and the dual purpose of the yield of increase usable fuel.If facility (for example, equipment) is close So-called " idle gas " is laid in, wherein such component is generally handled by torch, this will be particularly advantageous.It is this natural The mixture of gas, natural gas liquids and other condensable hydrocarbons is commonly known as " moisture ".For the purpose of this patent, " moisture " will It is understood to the mixture of natural gas, natural gas liquids and other condensable hydrocarbons.

This common production can advantageously provide synergistic benefits.In the method, the free radical present in coal and higher hydrocarbon The pyrolysis of these fuel gas will be catalyzed, effectively carries out gas-liquids conversion simultaneously with coal separation.This especially has to methane pyrolysis Profit, methane pyrolysis is extremely difficult in the presence of no free radical to be carried out.Free radical is warm by the one way from methane to high-rank fuel Solve conversion ratio from<1% increases to about 10%.

Another embodiment is directed to use with the system and method that catalyst converts carbonaceous material to a variety of useable products. Carbonaceous material can include coal (for example, rudimentary coal), biomass, waste, pitch or any two or more and plant carbonaceous material Combination.Before pyrolysis reactor is entered, carbon raw material can be pre-processed, such as by crushing to adjust (for example, grinding Mill, reduction etc.) granular size of raw material carbonaceous material and/or be dried contains with reducing the moisture in raw material carbonaceous material Amount.

Pyrolysis reactor is configurable to moving bed, entrainment thermopnore, fluid bed or any suitable reactor, wherein institute There is solid material (such as carbonaceous material, catalyst) to be moved through these reactors.Alternately, pyrolysis reactor can match somebody with somebody It is set to fixed bed or any suitable system, wherein catalyst is being reacted with entering and leaving the carbonaceous material of reactor Period remains stationary.

Except immobilized catalyst reactor (the single efflux of solids of wherein only modification solid product stream leaves reactor) Outside, the solid material of pyrolysis reactor, including modification solid product and dead catalyst are left, at least two efflux of solids are separated into (i.e. solid-solid is separated), it includes predominantly modifying first-class and predominantly dead catalyst the second (example of solid product Such as, catalyst stream).The solid-solid separation of solid material can be carried out in pyrolysis reactor internal in-situ partially or completely And/or carried out after reactor is left.In other words, leave pyrolysis reactor solid material can in inside reactor or External discrete.The solid-solid separation of first and second streams can use clasfficiator or similar techniques to carry out, such as according to grain Degree, quality and/or Density Separation solid, electrostatic separation technique or magnetic separation technique.

Catalyst stream including dead catalyst can be sent to regenerator (for example, regenerating unit), and wherein dead catalyst leads to Cross any remaining (for example, retaining or remaining etc.) carbonaceous material that burns be reproduced with the main catalyst for producing regeneration and The grey residue of the carbonaceous material of burning.A part of dead catalyst can be sent back to reactor without regeneration, or can be lost Abandon.The gas (such as air) for carrying oxygen can be introduced into regeneration reactor with regeneration of spent catalyst and in regeneration reactor Burn remaining carbonaceous material.The air-flow left from regenerator can include resulting flue gas.Leave the part of regenerator Or whole flue gases can be used for directly or indirectly providing heat to other elements of pyrolysis reactor, drier and/or system Amount.Some or all gases for leaving regenerator can be used for the catalyst transport of regeneration to pyrolysis reactor.

The non-solid product flowed out from pyrolysis reactor can be separated at least two streams (for example, gaseous product flow and liquid Body product stream).Liquid product stream by the chemical modification of separation process can be used as further processing, or collection is used as and closed Into crude product stream, it can be refined into chemical composition (such as C₅-C₁₂) or hydrocarbon, including aromatic hydrocarbons.Gaseous product flow can pass through Separating treatment is further handled into multiple available technique streams (including can not condensate flow) to carry out chemical modification, or gas is produced Logistics is used in equipment, such as is collected as gaseous fuel or as another product stream.

Some or all of non-condensable gas product streams can burn for calorific value.The heat can be used for carbon raw material Pretreatment, in pyrolysis reactor or in equipment elsewhere.

Some or all of gaseous product flows can be introduced into sour gas removal system, wherein carrying the compound of sulphur And/or nitrogen-containing compound (such as ammonia and hydrogen cyanide) and/or carbon dioxide are separated.Sulfur-containing compound can be handled further simultaneously It is used as available sulfur-containing compound (such as, but not limited to elementary sulfur and/or sulfuric acid) sale.Carbon dioxide stream can be isolated, or As useable products, such as, but not limited to for improving oil recovery.

There is provided the ore-sorting system for converting coal into modification coal product at least one embodiment, and institute Stating ore-sorting system includes pyrolysis reactor, the first separator, regenerator and the second separator.Pyrolysis reactor has one and entered Mouthful, the entrance receives coal and catalyst.Pyrolysis reactor produces gaseous product flow and modification coal product stream (its from coal and catalyst Include dead catalyst and modification coal product).First separator separation modification coal product and dead catalyst.Regenerator has one and entered Mouthful, the entrance receives the dead catalyst separated from the first separator.Regenerator removes at least one of in dead catalyst Coal, coke and the other carbonaceous materials of He Wei pyrolysis.Second separator has an entrance, and the entrance, which is received, comes from pyrolytic reaction The gaseous product flow of device, and the second separator produces product liquid and gaseous product from gaseous product flow.It is retained in modification Grey weight in coal product can be at least the 60% of the grey weight being introduced into the coal in pyrolysis reactor.

Brief description of the drawings

Fig. 1 is an illustrative reality of the system and method flow for converting carbonaceous materials to one or more useable products Apply the schematic diagram of example.

Fig. 2 be the system and method flow that converts carbonaceous materials to one or more useable products another is illustrative The schematic diagram of embodiment.

Fig. 3 be the system and method flow that converts carbonaceous materials to one or more useable products another is illustrative The schematic diagram of embodiment.

Fig. 4 be the system and method flow that converts carbonaceous materials to one or more useable products another is illustrative The schematic diagram of embodiment.

Fig. 5 is a chart, is compared by the various products that are produced respectively using the experimental system of catalyst and sand Yield.

Fig. 6 is another chart, compares the various products by being produced respectively using the experimental system of catalyst and sand Yield.

Fig. 7 is another chart, compares the various products by being produced respectively using the experimental system of catalyst and sand Yield.

Fig. 8 is arranged to provide the cross-sectional view of an exemplary embodiment of the pyrolysis reactor of solid-solid separation.

Fig. 9 is the perspective view of a part for Fig. 8 pyrolysis reactor.

Figure 10 is another perspective view of a part for Fig. 8 pyrolysis reactor.

Figure 11 is arranged to provide the local horizontal of another exemplary embodiment of the pyrolysis reactor of solid-solid separation Section/perspective view.

Figure 12 is arranged to provide the signal of another exemplary embodiment of the pyrolysis reactor of solid-solid separation Figure.

Embodiment

For clarity, before various embodiments disclosed herein are discussed, it will define and discuss in detail this Some terms used in application.Term " solid carbonaceous material " is (for example：SCM, carbonaceous material or CM) be in normal temperature and (25 DEG C, 1 bar absolute pressure) is the material of solid under pressure, and it includes and/or produced carbon and/or hydrocarbon.Solid carbonaceous material Non-limiting examples include coal, peat, lignite, biomass, coke, semi-coke, petroleum coke, tar or pitch.Unless otherwise Illustrate, term " carbonaceous material " refers to " solid carbonaceous material ".Term " volatile materials ", " moisture " of solid carbonaceous material (such as water), " fixed carbon " and " content of ashes " should mean as in the standard of American Society Testing and Materials 3172 (ASTM 3172) The value that the approximate analysis of definition is determined.Term " the solid carbonaceous product of modification " (for example, modification solid carbonaceous material) refers to relative There are one or more any materials in following nine kinds of characteristics in starting carbonaceous material.First, according to ASTM D5865 sides The higher calorific value that method (by basic pattern is received, such as including moisture, ash content and other non-combustible materials) is determined (contracts in this application It is written as " HHV ").Second, determined according to ASTM D5865 methods (butt, wherein moisture are determined by the methods of ASTM 3172) Higher calorific value.3rd, according to ASTM D5865 methods, (drying, ash free basis, wherein moisture and ash content pass through the sides of ASTM 3172 Method determine) determine higher calorific value.4th, the relatively low volatility materials determined according to ASTM D3172 methods.5th, according to The relatively low total sulfur content that ASTM D4239 methods are determined.6th, the relatively low organic sulfur determined according to ASTM D2492 methods Content.7th, the relatively low sulphates content determined according to ASTM D2492 methods.8th, it is true according to ASTM D2492 methods Fixed relatively low pyritic sulfur content.9th, the relatively low moisture determined according to ASTM D3172 methods.In addition, with any spy Determining the term " modification " that material (for example, coal, biomass etc.) is used together will also define as described above.It should be appreciated that unless It is otherwise noted, otherwise term " modification carbonaceous product " is referred to " the solid carbonaceous product of modification ".

When referring to " reservation " and other suitable terms (for example, retaining and keeping here), it should be noted that as in the application Disclosed method, raw material (including solid carbonaceous material) is fundamentally converted into solid carbonaceous product by it.Therefore, lead to Consider every kind of component in solid carbonaceous feedstock is retained in how much productions more solid carbonaceous than consideration in solid carbonaceous product for often The absolute weight fraction of component is more accurate in thing.Therefore, term " reservation " represents a part for given component, the given component In the solid carbonaceous feedstock in comprising modification carbonaceous product.For example, component X reservation, can be herein (for example, in table In) begged for as the kg components X included in modification carbonaceous product divided by the 100kg components X included in solid carbonaceous feedstock By.Therefore, it is considered unconverted weight fraction.If for example, coals of the 100kg containing 3% sulphur by weight turned The modification coal that 60kg contains 3% sulphur by weight is turned to, then sulphur is left 60kg/100kg sulfur feedstocks, because coal raw material contains 3kg sulphur, and modify coal product and contain 1.8kg sulphur.Term " deliming machine " refers to reduce the content of ashes in solid carbonaceous material Any device.

One purpose of solid carbonaceous material pyrolysis is the fuel and organic chemicals to form higher value.Therefore, it is desirable to The conversion ratio of the organic component in raw material solid carbonaceous material is set to maximize to required end-state.However, in fact, almost All naturally occurring (for example, biomass-based and fossil base) solid carbonaceous feedstocks contain the ash being attached in solid carbonaceous material Point-inorganic material.This ash content is highly stable, and solid carbonaceous material most of chemical conversions (for example burning, Gasification, pyrolysis) in, when solid carbonaceous material is converted, ash content is discharged from solid carbonaceous material.For example, in fire coal steaming In vapour power station, this ash content can show as clinker or flying dust accessory substance.

The ash content (such as " free ash ") of this release is particularly problematic in catalyzed conversion.The usual height of catalysis material Designed for specific and/or controlled selectivity and activity.This be by design catalyst surface chemistry and form including its Porosity and structure are realized.Ash content disturbs all these key features.Inorganic ions in ash content can manipulate active sites The surface chemistry of point, and grey fine powder generally block pores and can change form.This causes many adverse effects, wherein it is several It is described herein.First, the activity reduction caused due to the reduction of the activity and/or useable surface area of catalyst can cause anti- Answering the productivity ratio of device reduces the yield reduction with product.Second, it may occur however that poisoning, it is necessary to the regeneration of frequent catalyst, or Even more seriously, the irreversible inactivation of dead catalyst needs to be supplemented with raw catelyst person, and this causes excessive waste and not Economic method.3rd, the selectivity to required product may be reduced.For example, to required light hydrocarbon and BTEX, (following article is fixed Justice) selectivity determined by the shape and surface-active of catalyst.The change in aperture will reduce the selectivity to these materials, lead Cause uncontrolled thermal cracking.4th, it is not necessary to accessory substance may increase.In the absence of a catalyst, not by The thermal cracking of control causes to produce many unwanted materials, for example tar and (such as phenol, its is right containing heteroatomic organic matter People is poisonous, and is also poisonous substance in many downstream purification operations).

Various tarry distillates are known.For example, these include ammoniacal liquor (about 100 DEG C of boiling range), light oil (boiling spread 100 DEG C to about 170 DEG C) and may be containing materials such as benzene, toluene and dimethylbenzene, middle oil (170 DEG C to about 230 DEG C of boiling range and can It can contain relatively low naphthalene cut, heavy oil (boiling spread be 230 DEG C to about 270 DEG C) and higher naphthalene cut may be contained, it is green Oil (boiling spread be 270 DEG C to about 360 DEG C) and any cut may be contained, and residue of the boiling point higher than 360 DEG C or " pitch ".

Similarly, Gourde(G) graceful (Goodman) et al. is in its nineteen fifty-three entitled " coal cryogenic carbon in accurate laboratory equipment Change experiment (Low Temperature Carbonization Assay of Coal in a Precision Laboratory Apparatus in report) ", for the products collection efficiency of charcoal, tar, water, light oil and gas component, Fischer is used (Fischer) assay method determines the major pyrolytic product of various types of coals.Light oil constituents is described as comprising not same amount Benzene,toluene,xylene and aromatic naphthas and a small amount of carbon disulfide, naphthalene, unsaturated hydrocarbons and paraffinic hydrocarbonses.Base In Fischer analysis method, tar contains the hydrocarbon component higher than light oil, and higher hydrocarbon is mainly by being greater than about C₁₀Carbon atom, boiling range it is high Constituted in about 270 DEG C of hydrocarbon molecules.For the purpose of the application, " tar " or " tar product " is interpreted as by the bibliography Definition (i.e. the hydrocarbon containing more than 10 carbon atoms, and " non-tar light oil " or " non-tar light oil product " or referred to as " light oil ", " light oil product " is understood to refer to any hydrocarbon containing 10 or less carbon.Typical uncatalyzed pyrolysis of coal method is tended to Light oil product obtains relatively low products weight ratio with tar product, and it is much smaller than 1 in the range of about 0.08-0.25；And The present processes tend to light oil product and obtain relatively high products weight ratio with tar product, and it is much larger than 1, in about 5- In 1000 or bigger scope.In addition, in the present processes, the phenol for producing reduced levels is (and other containing heteroatomic Organic matter).The constraint by any particular theory or explanation is not intended to, the presence of active catalyst seems to reduce the phenol of generation Amount.For example, in the figure 7, it will be seen that compared with using catalyst, when (little or no to be lived using catalysis using sand Property) when, phenol higher level.It can be even advantageous that (there is little or no catalytic activity with working as to use when a catalyst is used Sand when compare), the toluene level of generation increase so that the toluene of generation is more than phenol (that is, the generation produced by weight Phenol is less than the toluene produced by weight).In addition, in table 2 (hereafter), it will be seen that not any exemplary Phenol or any other hetero atom are observed in embodiment.In a word, it is undesirable to fettered by any theoretical or explanation, it is believed that Two principal elements contribute to this superior performance：1) there is active catalyst, and it is 2) any in modification carbonaceous material product The chelating (for example absorb and/or adsorb) of the tar of middle generation, generally modification carbonaceous material product is harmless consequently as fuel Change burning.

Explain that the presence of active catalyst is important for the excellent properties of this method according to our work.Enter one Step is believed, compared with former method, and the present processes have excellent operability and selectivity to required product, because Compared with method before, the ash content much less of release.The reduction of ash content release is considered as partially due to limiting raw material intentionally The level of conversion of solid carbonaceous material is so that most of ash content in product carbonaceous material is retained.Therefore, catalyst exposes In " free ash " than prior method much less.The conversion of limitation solid carbonaceous feedstock is a unique aspect intentionally (and some violate intuition).Although the economy and productivity ratio that convert solid carbonaceous feedstock as much as possible are probably the note that induces one Purpose, it is believed that control conversion ratio make it that producing conversion of the free ash minimized than maximizing solid carbonaceous feedstock has Bigger benefit.

Term " not condensable (fuel) gas " refer to it is any can not at 40 DEG C by pressurize into liquid (i.e. with less than The gas of 40 DEG C of critical-temperature) and the material of condensation.In addition, discharging the not condensable of heat when being reacted with air or oxygen Gas is referred to herein as " can not condensed fuel gas ".

Term " condensable fuel ", for example：Liquefied petroleum gas (LPG), be when being reacted with air or oxygen discharge heat, And at 40 DEG C by pressurize it is condensable but without more than 7 carbon atoms and be not aromatics gas.

Term " light hydrocarbon " be it is any as herein defined can not condensed fuel gas or the condensable fuel of lightweight.

Term " BTEX " represents benzene, toluene, ethylbenzene, meta-xylene, paraxylene or ortho-xylene.

Term " containing heteroatomic organic matter " is any organic molecule with sulphur, oxygen and/or nitrogen.

Term " higher hydrocarbon " be it is any as herein defined be not light hydrocarbon or BTEX hydrocarbon.

Term " weight hourly space velocity " (WHSV) represents the feed rate (weight/hour) of substrate divided by included in reactor In catalyst weight.Weight hourly space velocity has unit hr-1.As used herein, weight hourly space velocity will be based on dry weight The weight of contained catalyst in the charging per hour of the coal of meter and reactor.The weight of catalyst will be come one of in two ways It is determined that.For without the reactor (such as batch (-type) or fixed bed reactors) for removing or adding catalyst, catalyst weight will It is the initial weight of the catalyst added in reactor.For some reactors, (some of which or all catalyst are continuous Ground elutriation), catalyst weight by be catalyst reactor stable state weight, wherein stable state by by input be equal to the amount of leaving (by weight) fresh catalyst is defined.This is commonly known as catalyst " delay ", and by fluid bed or can carry The known correlation of riser reactors is measured or estimated.

Term " catalyst activity " represents the volatile materials converted within the time of specified rate by every catalyst weight Weight.Catalyst activity can be calculated by the way that WHSV to be multiplied by the fraction conversion ratio of volatile materials in reactor, Huo Zhetong Calculated after equally WHSV* (reservation of 1- volatile materials).

Term " fresh catalyst " represents to be never exposed to the catalyst of reactant at reaction conditions, such as from supplier Locate the raw catelyst obtained.

Term " dead catalyst " is represented in identical reaction condition (for example：Temperature, pressure, inlet flow rate) under, compared to It is initially exposed to any catalyst with more low activity during this method.This is probably the catalysis because many reasons are caused The several non-limiting examples for the reason for agent is inactivated are：Coking or carbonaceous material absorption or gather, metal (and ash content) absorption or Accumulation, abrasion, metamorphosis (including varying aperture, cation or anion substitution), and/or chemistry or composition change.

Term " regenerated catalyst " represents that entering to be about to its activity by the catalyst failed as defined above increases to Higher than its method as the level of dead catalyst, as described above.This potentially includes reversal for example as described above or removing The possible cause that pollutant is reduced as activity.The catalyst of regeneration can have the activity more than or equal to fresh catalyst, But typically, regenerated catalyst has the activity between dead catalyst and fresh catalyst.

Term " HERB " is to represent mixing, elutriation, the acronym of lift bed.With two kinds of solids, (both are consolidated Body has different densities or granularity) any reactor operate in this way：By one of solid substantially from reactor Elutriation (that is, most of particle entrainment in a fluid and with riser pattern carry out) and another solid be substantially fluidisation, But in the reactor not by elutriation, such as in the non-limiting examples of bubbling bed reactor.Fig. 9-13 is HERB pyrolytic reactions The non-limiting example of device.

Term " pyrolysis " refers to the thermalization credit of organic substance in the case of in the absence of oxygen, at elevated temperatures Solution.Generally, the pyrolysis of organic substance produces gas (and product liquid when gaseous product temperature is reduced), and leaves rich in carbon The solid residue of content：Charcoal.Pyrolysis be different from other high-temperature technologies, such as burn and hydrolyze because it be not related to generally with oxygen, The reaction of water or any other reagent.As used herein, pyrolysis should further provide for excluding having for high pressure (more than 4 bars) steam (commonly referred to as " reforming ") is added in destination, and the purposefully addition of high pressure (more than 4 bars) hydrogen (commonly referred to as " is hydrogenated with Processing "), but these technologies can be used for the rear pyrolysis of thermal decomposition product further to modify.In addition, as it is used herein, pyrolysis It should not exclude：The water or hydrogen added at low pressures together with reagent, or it is used as the water with a part for the mixture of reagent Or hydrogen (includes but is not limited to the water that is added in gas fluidized medium or absorption is carried on solid carbonaceous material or catalyst Water into pyrolytic reaction).

The so-called approximate analysis of coal be to by it is a series of regulation or standard method of test come the moisture determined, ash content, wave Volatile material and fixed Carbon analysis.It is to determine the letter of the distribution of the product obtained when coal sample is heated under given conditions Folk prescription method.According to definition, product is divided into four groups by proximate coal analysis, and it is (1) moisture；(2) volatile materials, it is by heat Gas and the steam composition driven away during solution；(3) non-volatile component of fixed carbon --- coal；(4) ash content --- remained after burning Remaining inorganic residue.Standard method of test (ASTM D-3172) for approximate analysis covers approximate point with coal and coke The analysis method of phase separation association, and the combination of the determination of each and the 4th kind of the calculating of actually three kinds property.Water Divide, volatile materials and ash content are all determined by making coal be subjected to defined temperature levels in predetermined time interval.According to Regulation, weight loss is due to moisture loss (1 hour at about 107 DEG C) and volatile materials loss (7 points at about 950 DEG C Clock).Rear remaining residue referred to as ash content is lighted at the final temperature.After fixed carbon is 100 summations for subtracting these three values Difference.In low volatility material (such as coke and anthracite), fixed carbon value is approximately equal to the elemental carbon content of sample.Although this A little programs are developed for coal, but identical ASTM method is widely used for biomass and other organic substances. In the application, it is any be mentioned on receive or synthesize the volatile materials on any solid carbonaceous material, fixed carbon, ash content and Moisture will be understood as measuring by this method.

Because that the method for testing of volatile materials design in this way, be included in essentially driving off All volatile materials in parent material, this method can be described as complete pyrolysis；And partial thermal decomposition is characterised by waving Volatile material part release, and partial thermal decomposition by by pyrolytical condition adjust to milder condition (for example,<950 DEG C Relatively low pyrolysis temperature and/or<The relatively low pyrolysis time of 7 minutes) realize.

The volatile values of coal are for selecting certain types of coal combustion equipment and optimal between the coal that equipment is used together It is critically important for matching.These values in terms of setting up and keeping appropriate burn rate are valuable for fuel engineering teacher. As overview, low volatility anthracite burns soon unlike high volatile bituminous coal, therefore, and both fuel types exist It is not necessarily interchangeable in given boiler configuration.Therefore, the amount of the volatile materials retained in pyrolyzing coal be important quality because Element, is included in and determines in its adaptability as boiler oil.If for example, it is that semi-coke or coke shape are produced that product coal, which crosses pyrolysis, Thing, then this may limit its as boiler oil outflow select, even if it can be used for metallurgical application, for example, make steel.

Solid carbonaceous material can be pre-processed before catalysis pyrolysis apparatus is entered.Pre-treatment step can be to improve The mode of the gross mass for the product that beginning carbonaceous material is produced in the reactivity and/or raising catalysis pyrolysis apparatus in catalysis pyrolysis apparatus Purpose carry out.Embodiment is pre-processed as one can include crushing (for example, grinding) and classification starting carbonaceous material To strengthen the thermal characteristics and mass transfer characteristic of starting carbonaceous material.Other embodiments can include：Remove in starting carbonaceous material Moisture (such as dry) and/or ash content and mineral component (for example washing), to promote the carbonaceous material of pretreatment in catalytic thermal Solve the high response in device (for example, the release of volatile materials and reactivity in enhancing catalysis pyrolysis apparatus).

When the catalyst being related in reactor, term " fixation " (such as " immobilization ") refers to prevent catalyst from leaving Reactor, is not necessarily catalyst remains stationary or fixation in reactor.The fixation of catalyst can be real by many methods Show, including but not limited to following methods：First, catalyst can be fixed on filling out for reactor by depositing, electroplating or adhere to On material, material all in one piece or wall.Second, extrudate can be used or larger catalyst granules or crystal grain so that catalyst can not be by Air-flow is fluidized or carried secretly.3rd, size or quality exclusion can be used, wherein catalyst can be fluidized, but be not fluidized Gas is carried or carried secretly, but carbonaceous reactant is carried (i.e. " elutriation ") by fluidizing gas.4th, size exclusion passes through sieve aperture Size (allow the carbonaceous reactant of reduced size by but do not allow catalyst to pass through) prevents catalyst from leaving reactor.It is right In third and fourth kind of method, catalyst does not have fixed position, and can be moved in reactor, but it is limited in reaction Moved in device.

When being related to modification solid product or catalyst, such as in the predominantly stream of modification solid product/catalyst, art Language " main " refers to be more than 50%.Therefore, the stream of predominantly modification coal product includes the modification coal product more than 50%.

Abbreviation HC is used to refer to hydro carbons, is generally used for defining any molecule containing hydrogen and carbon atom.We also generally pass through Included in molecule with C_xThe carbon number that form is represented represents hydrocarbon, and wherein x is contained carbon number in hydrocarbon.For example, C₁、 C₂And C₃Will be understood as representing respectively containing 1, any hydrocarbon of 2 or 3 carbon.

When referring to solid, liquid, gas or its any combination of separation, term " separation " is not necessarily mean that generation 100% separation.Even if when pure separation is probably preferable, it will be appreciated that 100% separation generally can not be obtained, thus it is real Term " separation " means the separation as close possible to 100% on border.

Usually refer to the attached drawing, discloses integrated thermal cracking and the system and method for catalyzed conversion of coal, to obtain essence Coal separation product stream, its moisture, sulphur, mercury, nitrogen and oxygen content are significantly reduced, and acquisition there is no molecular weight tar and containing miscellaneous The hydrocarbon-rich product stream of atomic compound.This method operates one group of unit (including catalysis pyrolysis reactor, catalyst regeneration units Separated with least part product) combined with gas, liquid and solid product stream.Include solid-solid in the method and separate step Suddenly, modification (for example, selected) coal product is separated with dead catalyst.This method can also include gas separator, for example Acid gas removal plants (AGR) system, it removes or separated undesirable compound and/or element in gaseous product flow.Acid Property gas removal plants can be used for removing or separate such as carbon dioxide (CO₂) (without calorific value), hydrogen sulfide (H₂S), ammonia (NH₃), hydrogen cyanide (HCN) and any other pollution and/or any one or combination of the compound for carrying sulphur.Pass through gas Body separation (for example, acid gas removal plants) can include come the product separated：Sulfur-containing compound stream and/or high concentration CO₂ Stream, it can be used for improving oil recovery, CO₂Seal up for safekeeping or other suitable purposes.

System and method as disclosed herein can (such as rudimentary coal, biomass, pitch, solid give up by carbonaceous material Thing or any suitable material for carrying carbon) it is converted into one group of available product, including modification carbonaceous product and gas and liquid Body product.When being heated to pyrolysis temperature, carbon raw material release volatile materials.More inappropriate carbonaceous material will be included such as Coke, its is substantially used up its volatile content.Catalysis pyrolysis reactor partly or entirely will convert volatile materials For gaseous product, and some parts volatile materials can also be converted into solid carbon or coke residue.With starting carbonaceous material Material is compared, remaining solid material be with higher thermal value (higher energy density) and relatively low pollution element (such as sulphur, mercury and/or Nitrogen) modification efflux of solids.Some light hydrocarbon compounds (such as C₁To C₃) pyrolysis apparatus can be co-fed to and/or from hydrocarbon product stream Reclaim and be recycled back into pyrolysis apparatus.

System and method as disclosed herein can be utilized such as pyrolysis reactor (for example, system, unit), catalysis Any combinations of agent regeneration reactor (for example, system, unit etc.) and/or solid-solid piece-rate system (for example, unit).Can To be produced in system and method using catalyst so that solid carbonaceous material is converted into available gaseous product, available liquid Thing, available solid product or its any combinations.

Pyrolysis reactor as disclosed herein can using relatively mild temperature and duration short method, by This promotes part catalytic thermal solution, opposite with the volatile materials for removing solid carbonaceous material completely.Mild temperature pyrolysis reactor It can be operated at about 300 DEG C about 1100 DEG C.In some embodiments, pyrolysis reactor can be at about 350 DEG C to about 850 DEG C Lower operation.In other embodiments, pyrolysis reactor can be operated at about 400 DEG C to about 700 DEG C.With other technology phases Than, many advantages are provided using the pyrolysis reactor of mild temperature condition and partial thermal decomposition method, it is described herein wherein Several advantages.First, the energy intensity of relatively mild operating condition (for example, temperature) is relatively low.Second, the gaseous product flow of recovery Contain less tar.For example, the amount for the light oil (for example, non-tar, it can include LPG) that the present processes are produced is more than The amount of the tar of generation.According to some embodiments, produced in the weight and method of the light oil produced in (the application's) method The ratio of the weight of raw tar is more than 0.3.According to other embodiment, the ratio is more than 1.As disclosed herein, it is pyrolyzed Reactor can produce the products weight ratio of relatively high light oil product and tar product, its be far longer than 1 (such as 5-1000, Or bigger).The tar generation run into other pyrolysis of coal methods is handled and/or eliminated this simplifies product.3rd, these System can produce three out of phase useable products, wherein each can be used for various purposes (to include but is not limited to fuel or change Learn precursor).For example, these systems can produce available solid product (such as efflux of solids), available product liquid (such as liquid Body stream), available gaseous product (such as gas stream) or its any combinations.It is solid carbonaceous that efflux of solids contains that quality significantly improves Material, it may be used as fuel or is processed further, such as being gasified totally.The physical state of the material of fluid stream can be Liquid or gas, this depends on the temperature and pressure specifically flowed.Fluid stream can include sub-fraction high value alkene and aromatic hydrocarbons, it Can be separated as synthetic crude to be processed in existing oil plant or batch sell.Fluid stream can also include a variety of chemistry Product, it can be used as fuel in equipment, or can be separated into vendible fuel (such as hydrogen, carbon monoxide, LPG, liquid Change natural gas (NGL) etc.), it is used as monomer and/or the intermediate of subsequent chemistry method.4th, by gentle temperature conditionss Lower operation pyrolysis reactor, some volatile materials will be discharged from initial solid carbonaceous material, remainder Modification solid product will be retained in for example to modify in solid coal product so that modification solid coal product is more suitable for fired downstream behaviour Make.

Illustrated embodiment of Fig. 1 configuration illustrateds into the system 100 using solid carbonaceous material (such as rudimentary coal).Such as Shown in figure, the system includes pulverizer 101, drier 102, for the component that is pyrolyzed (for example：Pyrolysis reactor 103, heat Solve device etc.), separator is (for example：Condenser 104, clasfficiator 105, product separative element 106 etc.) and regenerator 107 (for example, again Raw component, regenerator unit, regeneration reactor).Coal is introduced in pulverizer by pipe 111 (for example, conveyer, pipeline etc.) Pre-processed in 101, the size of coal be reduced to the particle of suitable dimension, then sent it in drier 102, For example pass through pipe 112.Pulverizer 101 may include entrance 113, and it is configured to introduce air (for example, air of relatively dry) Into pulverizer to help the moisture-free coal during crushing, and outlet 114, it is configured to remove sky relatively wet in pulverizer 101 Gas.In drier 102, coal particle is subjected to dry gas (such as air) to reduce the moisture in coal particle.Drier 102, which include entrance 121 air of relatively dry (be used for introduce) and entrance 122, (is configured to flow out from drier 102 relatively wet Air).Then dry coal is sent to pyrolysis reactor 103 from drier 102, such as by inlet tube 123 (for example, One entrance), the outlet of drier 102 is fluidly connected to the entrance of pyrolysis reactor 103 by inlet tube 123.

In pyrolysis reactor 103, coal and catalyst contact.Catalyst can be introduced by second entrance.According to one Non-limiting example, reactor 103 includes second entrance 132 and (is configured to introduce fresh catalyst (for example, previously unreacted Catalyst)) and the 3rd entrance 133 (being configured to regenerated catalyst introducing reactor 103).Catalyst can be acid catalysis Agent, fluid cracking catalyst, hydrocracking catalyst etc..Can be simultaneously using one or more catalyst types.This catalysis Agent and carrier can include but is not limited to：Metal such as Mo, Zn, Ga, Pt, W, Ni, V, Co, Mn or Cu；Metal oxide；Carbon substrate Material；With any of the above mixture of two or more.The illustrative examples of such catalyst and catalyst carrier can include But it is not limited to：Molybdenum, palladium, ruthenium, osmium, nickel, cobalt, rhenium, molybdenum, zinc, gallium, tungsten, vanadium, manganese, copper or any two or more plant such gold The mixture or alloy of category, natural zeolite, synthetic zeolite, CNT, graphene, graphite, aluminum oxide and silica.One In a little embodiments, catalyst can be micropore (aperture is up to 2 nanometers).In other embodiments, catalyst can be with It is (aperture is more than 50 nanometers) of mesoporous (aperture is 2 to 50 nanometers) or macropore.And in other embodiments, catalyst Material can be any combination of mixing of micropore, mesopore and macroporous structure.

Although being not necessarily whole, some zeolites can have formula M x/n [(AlO₂)x(SiO₂)y]·mH₂O, wherein M is alkali metal or alkaline-earth metal, and x and y are the tetrahedron sums of per unit structure cell, wherein for alumina base zeolite, y/x ratio Value is about 1 to about 5, for silicone zeolite, and y/x is about 10 to about 100.M is alkali metal or alkaline-earth metal, and n is 1 or 2.Si/ in formula Al ratio can be 12:1 to 1000:In the range of 1.In some embodiments, Si/Al ratio is 14 in formula:1 to 500:1.In some embodiments, Si/Al ratio is 15 in formula:1 to 250:1.In formula, m is the hydrone of crystallization Number.Other synthetic zeolites are commonly known and can also use.Exemplary zeolite includes but is not limited to：With AEL, BEA, CHA, EUO, FAO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, LEV, OFF, TON, MWW, MCM and MFII topology The zeolite of structure.Zeolite may also include such as, but not limited to：ZSM-5、PSH-3、ITQ-2、ZSM-12、MCM-22、MCM-36、 MCM-49, MCM-56, MCM-58, MCM-68, H- β, HY, H-USY, H-MOR and HZSM-5.The illustrative structure cell composition bag of zeolite Include but be not limited to：Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·27H₂O；Na₆[(AlO₂)₆(SiO₂)₁₀]·12H₂O；(Na,TPA)₃ [(AlO₂)₃(SiO₂)₉₃]·16H₂O；Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆]·264H₂O；Na₅₆[(AlO₂)₅₆(SiO₂)₁₃₆]· 250H₂O；And Na₈[(AlO₂)₈(SiO₂)₄₀]·24H₂O, wherein TPA are tetrapropyl ammoniums.It can also use by framework type code (FTC) other frameworks of description.

Although being not necessarily whole, some zeolites have formula | M_x/n(H₂O)_y|[Al_xSi_(t-x)O_2t]-IZA, wherein visitor Body species is listed between braces (" | ... | "), and main body frame is listed between braces (" [...] ").M represents charge balance Cation, x is the number of structure cell middle skeleton aluminium atom, and n is cationic charge, and y is the number of the hydrone of absorption, and t is structure cell The sum (Al+Si) of middle skeleton Tetrahedral atoms, IZA is by the structure committee of International Zeolite Association (Structure Commission of the International Zeolite Association) the framework type code specified.

As disclosed herein, it can be post-processed (such as by dealuminzation or logical for the zeolite in system and method Cross ion exchange (na form is for example converted into H- forms (for example, H- β, H-Y, H-USY, H-MOR and HZSM-5))).So Dealuminated zeolite can be used for for example help promote ethylene oligomerization.In addition, for example, zeolite granular can be densified (for example, rear place Manage to increase the bulk density of particle).

Catalyst can have large-scale aperture (for example, average pore size).For example, catalyst can have about 0.26 to about 0.74nm aperture.This is included with about 0.26 to about 0.57nm, about 0.28 to about 0.48nm, about 0.31 to about 0.45nm, with And about 0.51 to about 0.55nm, about 0.53 to about 0.56nm, and about 0.65 to about 0.70nm aperture catalyst.For example, A Zeolite (for example, with LTA structure) can have about 0.41nm aperture.In addition, for example, P zeolites are (for example, with GIS knots Structure) there can be about 0.31 × 0.45nm aperture.In addition, for example, ZSM-5 zeolite (for example, with MFI structure) can have About 0.53 × 0.56nm aperture.In addition, for example, ZSM-5 zeolite (for example, with MFI structure) can have about 0.53 × 0.56nm or about 0.51 × 0.55nm aperture.In addition, for example, X zeolites (for example, with FAU structures) can have about 0.74nm aperture.In addition, for example, Y zeolites (for example, with FAU structures) can have about 0.74nm aperture.In addition, example Such as, modenite (for example, with MOR structures) can have about 0.65 × 0.70nm or about 0.26 × 0.57nm aperture. Aperture provided herein is example, and is not substantially restricted.

Pyrolysis reactor can be operated at about 300 DEG C to about 1100 DEG C.Carbonaceous material can have 0.01 second to about 5 small When residence time.In some embodiments, the residence time is about 0.1 second to about 1 minute.The catalyst dress of pyrolysis reactor Carrying capacity can be about 0.01g catalyst/g carbonaceous feeds to about 100g catalyst/g carbonaceous feeds.In some embodiments, urge Agent load capacity is that about 0.05g catalyst/g is fed to about 20g catalyst/g chargings.In other embodiment again, catalyst Useful load is that about 0.1g catalyst/g is fed to about 10g catalyst/g chargings.The carbonaceous material being introduced into pyrolysis reactor plus Hot speed can be about 0.1 DEG C/sec to about 1000 DEG C/sec.It should be noted, however, that fast pyrogenation can relate to surpass in reactor Cross 1000 DEG C/sec of the rate of heat addition.

Also shown in FIG. 1, solid exports to clasfficiator 105 by pipe 134 from pyrolysis reactor 103.Pyrolytic reaction Device 103 can include other outlets.For example, gaseous product can pass through pipeline 135 from the second outlet of pyrolysis reactor 103 (for example, pipe) reaches such as condenser 104 and removed, for further handling and (such as separating).Clasfficiator 105 is configured to separation Useless urged by the modification coal product that is reclaimed by the first outlet 151 of clasfficiator and by what the second outlet 171 of clasfficiator was reclaimed Agent.

According to an illustrative embodiments, pyrolysis reactor is fluid bed, wherein coal and catalyst in required reaction Suspend in the gas phase and mix in residence time.Solid can be separated in the reactor mainly contains the first of modification coal to produce Efflux of solids and the second efflux of solids for mainly containing dead catalyst.Modification coal is typically referred to：When burn-up (for example, burning), pass through Rudimentary coal (the example that moisture and/or pollutant are for example removed improve efficiency and/or to reduce coal discharge and change and (such as improve) Such as, ub-bituminous coal, lignite etc.).As one embodiment, the catalysis pyrolysis of coal can enter at a temperature of about 350 DEG C to about 850 DEG C OK, and it can have residence time of 0.1 second to about 1 minute during catalytic process.

The first efflux of solids for modifying coal can be taken out from reactor for further handling or using.For example, in order to Modification coal is transported to other places, modification coal can be granular or block.In addition, for example, modification coal can be used in equipment Make solid fuel.Solid product stream can carry a certain amount of dead catalyst.Can the second efflux of solids containing some modification coals (for example, used catalyst stream) arrives regenerator for example, by pipeline or conveyer transfer (for example, conveying), and it is in a regenerator Mix to remove any coke and/or remaining coal on dead catalyst, urged with regenerating with air or any suitable oxygen-containing gas Agent.

As shown in figure 1, dead catalyst is separated by clasfficiator 105, and feeding regenerator (is for example managed) via pipeline 171 107, to be used to regenerate (such as recovering (rejuvenation)) in the form of dead catalyst stream.Dead catalyst stream can directly come Self-pyrolysis reactor, such as pyrolysis reactor for internally performing solid-solid separation.Oxygen flow can be introduced again Raw device 107, regenerator 107 can be used for being carried to all or almost all of regenerator 107 in burning dead catalyst stream can Combustion things matter (such as coke, coal).Regenerator 107 includes an entrance, and air-flow enters regenerator by the entrance.Gas access Can be identical or different with dead catalyst inflow entrance.For example, gas (for example, air) can be introduced by gas access 172.Again Raw device also includes：Outlet line 174 (for example, pipe), the catalyst stream of regeneration flows out to enter pyrolytic reaction by pipeline 174 Device.In a regenerator, air or another suitable gas for carrying oxygen are introduced into at least one in the dead catalyst that burns Divide coke/coal, with regeneration of spent catalyst.Regenerator 107 can include outlet 173, and regenerator passes through its eluting gas, such as cigarette Road gas leaves regenerator by outlet 173.Optionally, at least a portion regenerator outlet gas can be used for the catalyst of regeneration It is carried to pyrolysis reactor.A small amount of purging of regenerated catalyst can be used for the accumulation for preventing ash content or other impurity.For example, purging Valve 175 can (first outlet of blow down valve 175 be connected to the 3rd of pyrolysis reactor 103 the by it in outlet line 174 and pipeline Entrance 133) between provide in a series arrangement.The second outlet 176 of blow down valve 175 is configured to make the catalyst that has purged from system In pass through.

Once regeneration, catalyst, which may return to pyrolysis reactor 103, is used for the further catalysis pyrolysis of coal.For example, again Raw catalyst can be re-introduced into pyrolysis reactor 103 via the 3rd entrance 133.Pyrolysis reactor 103 can be included in addition Or less entrance and/or outlet.For example, reactor can include the first and second outlets, wherein efflux of solids is configured to Reactor is left by first outlet, and fluid stream is configured to leave reactor by second outlet.

Leaving a part of gas of regenerator can include：A part of catalyst (such as particulate), it can be recovered simultaneously Carry out in conjunction with or be introduced directly into pyrolysis reactor with the holding phase with a part for the regenerated catalyst in regenerated catalyst stream The catalyst of prestige-coal ratio.The ratio of catalyst and coal can be e.g., from about 0.001g catalyst/g carbonaceous feeds to about 100g Catalyst/g carbonaceous feeds.In some embodiments, the ratio of catalyst and coal is about 0.01g catalyst/g carbonaceous feeds to about 100g catalyst/g carbonaceous feeds.In other embodiments, the ratio of catalyst and coal is that about 0.05g catalyst/g carbonaceous is entered Expect to about 20g catalyst/g carbonaceous feeds.In other embodiments, the ratio of catalyst and coal is about 0.1g catalyst/g carbon Matter is fed to about 10g catalyst/g carbonaceous feeds.It can include in catalyst regeneration cycle other reactive or non-reacted Solid is used as thermal source.For example, sand can be recycled together with catalyst, wherein sand absorbs excessive heat in a regenerator.Hot sand It is carried in pyrolysis reactor, the carbonaceous solid material that wherein its heat is entered absorbs.

The fluid product stream come out from pyrolysis reactor, which can be transferred to downstream, to be used to further handle.For example, fluid Product stream can be transferred to the operation of one group of unit, wherein fluid product stream be separated into one or more liquid hydro-carbon products streams, The group of any two or more in one or more gaseous product flows, one or more aqueous flows, and/or the above stream Close.It is configured for use as influenceing the part of gas-liquids separation as shown in figure 1, fluid product stream is sent to from pyrolysis reactor 103 The system (such as condenser 104) of condenser.Condenser 104 can also play a part of Liquid-liquid decanter, due to not mixing Dissolubility, it allows aqueous solution body phase to be separated with hydrocarbon liquid.As illustrated, air-flow is for example, by pipeline 141 (for example, outlet) Product separative element 106 is led to from the outlet of condenser 104, for further processing.It is organic according to illustrative embodiments Liquid is separated by condenser 104 from waterborne liquid, wherein organic liquid via second outlet pipeline 142 (for example, pipe) from Condenser 104 is removed, and waterborne liquid is removed via the 3rd outlet line 143 (for example, pipe).All or part of every kind of water Property liquid flow and/or hydrocarbon liquid stream can be used in the downstream of other systems in such as equipment (such as facility) or method. In one such embodiment, at least a portion aqueous liquid stream and/or a part of hydrocarbon stream can be used for briquetting coal product stream.Liquid Hydrocarbon stream can be packaged as synthetic crude, or be further separated into specific product stream, such as rich in BTEX and/or BTX (examples Such as, the mixture of aromatic hydrocarbon (such as, but not limited to benzene, toluene and three kinds of xylene isomers)) stream.Liquid hydrocarbon streams can also It is further processed by the chemical modification in other chemical reactors, for example the deoxidation for any product for carrying oxygen Purpose.Gaseous product flow can be used as fuel in a device or be separated into a kind of or more than one useable products stream.

As a part for gas and the separative element of product liquid, product stream can be removed at system by sour gas Reason, to capture the compound, nitrogen-containing compound (such as ammonia or hydrogen cyanide) and/or the carbon dioxide that carry sulphur.Rich in carbon dioxide Stream can be isolated, sell and transport, or for improving oil recovery.As shown in figure 1, CO₂Stream can pass through product Separative element 106 is separated and removed via first outlet pipeline 161 (for example, pipe).Sulfur-containing compound can be used as load sulphur It is processed further before product (for example, being used as element solid sulphur, sulfuric acid etc.) packaging, or delivers to landfill yard.Equally such as Fig. 1 institutes Show, sulfur-containing compound can be separated by product separative element 106 and removed via second outlet pipeline 162 (for example, pipe).Acid Property gas to remove system can be that fluid product stream leaves one of first separation method of pyrolysis reactor, or can be in separation It is further downstream in method.Other compound/products can also be recovered.For example, product separative element 106 is configurable to from gas Hydrocarbon is separated in stream, and the hydrocarbon of recovery is passed through via the 3rd outlet line 163 (for example, pipe).

The heat of other processes may be used as input heat into pyrolysis reactor in system, such as heating carbonaceous material Material.For example, the heat from hot regenerated catalyst can be used for providing heat and required temperature kept in pyrolysis reactor.Separately Outside, for example, the flue gas for leaving catalyst regenerator can be used for directly or indirectly carrying to drier and/or pyrolysis reactor Heating load.Combining combustion can be mixed to produce for drier, pyrolysis with some gaseous product flows by leaving the flue gas of regeneration unit The heat of other devices, method or unit in reactor and/or equipment.Flue gas and the mixing of some fuel gas can have Sharp ground further reduces the oxygen content in flue gas.Can not condensing gas stream can with the air in equipment, fresh air and/ Or during air burning with other devices into drier, pyrolysis reactor, regeneration reactor and/or equipment, method Or unit provides heat.The burning gases can be used for producing steam, such as being used in facility.

According to an embodiment, regeneration reactor is burnt dead catalyst or carrying using pure oxygen gas flow or oxygen-enriched stream Wholly or largely combustible in carbonaceous material into regeneration reactor.According to another embodiment, by oxygen deprivation (example Such as, wherein oxygen content be diluted to less than 2%) stream be used together with regenerator.According to other embodiment, using hydrogen, steam, CO₂, CO or its these any combination remove carbon in dead catalyst.In further embodiment, by oxygen and foregoingization Product mix to remove the coke on dead catalyst.In all these embodiments, the air-flow left can be rich in CO₂, and And can separate for chelating, improving oil recovery or other suitable purposes.According to an embodiment, pass through combustion Burn, at least one of steam and reducing gas, remove at least one of any coal not being pyrolyzed in catalyst, coke and Carbonaceous material.

According to an embodiment, the solid in pyrolysis reactor is removed from reactor and ex situ is separated into master The efflux of solids and main dead catalyst stream (for example, stream with more than 50% catalyst) wanted.Because the cost of catalyst is bright Aobvious to be higher than carbonaceous material, it is desirable to catalyst holding as much as possible and circulation.It therefore, it can adjustment solid-solid separation So that the amount of the catalyst mixed with efflux of solids is minimized, in addition using increase the amount of carbonaceous material mixed with dead catalyst stream as Cost.According to illustrative embodiments, during solid-solid is separated, capture percent 80 (80%) by weight or more Many dead catalyst.Preferably, solid-solid separate during capture by weight 90% or more dead catalyst.

The separation of this solid-solid can be carried out by many separation methods, including but not limited to clasfficiator, Magneto separate, Electrostatic separation or any two or more plant the combination of such separation method.For example, the granularity of carbonaceous material and catalyst point Cloth is intentionally different, it is allowed to which appropriate classification technique separates two kinds of solids according to the difference of granularity, weight and/or density. In one such embodiment, the average grain diameter into the carbonaceous material of pyrolysis reactor is about 100 μm to about 300 μm.Another In one such embodiment, carbonaceous material has about 10 μm to about 100 μm of average grain diameter.In one embodiment, enter The average grain diameter of the catalyst of pyrolysis reactor is about 300 μm to about 500 μm.In another such embodiment, catalyst With about 500 μm to about 1000 μm of average grain diameter.Clasfficiator is used to effectively separate modification solid product with catalyst. In another embodiment, before the catalyst stream of regeneration returns to pyrolysis reactor, it can also separate and leave regenerator Efflux of solids, to remove all or some ash content and/or impurity.For example, efflux of solids can be with demineraliting and/or demetalization with except impurity elimination Matter.Wet method, solid-liquid method or any other suitable method can be used for regeneration of spent catalyst.Urged as " fresh " of supplement catalyst Agent can be provided by supplier, and it is by other sources (for example, reuse in method for pyrolysis discussed herein Catalyst or reuse from conventional fluid catalytic cracking (FCC) method) dead catalyst is regenerated and/or de- gold Category.In other words, " fresh " catalyst need not catalyst be constituted only by " fresh " (such as unreacted), and can be " fresh " The mixture of catalyst and regenerated catalyst.

Some or all of air streams can using in system (for example, process of system) or facility elsewhere.Example Such as, the air for leaving pulverizer may be used as the overfire air in boiler to reduce the NO in stove_x(such as one oxidation two Nitrogen, nitric oxide etc.) generation.Similarly, from regenerator flue gas and the light gas product from pyrolysis reactor (CO、H₂, methane, ethane and ethene) can be used in stove, and can be mixed with other chemical substances, to obtain its calorific value It is used to take off-NO with as melt flow again or chemical agent injection_xPurpose.

In any of above embodiment, pyrolysis reactor may be configured such that catalyst and carbonaceous solid material with by The speed (for example, flow velocity, rate travel etc.) of control enters and leaves pyrolysis reactor.In another embodiment, it is pyrolyzed anti- Device is answered to may be configured such that catalyst is fixed in pyrolysis reactor when solid carbonaceous material enters and leaves reactor. In any embodiment, carrier gas can be used for or be not used in may move solid by reactor come pneumatic conveying, and can use In or with the being not used in hydrodynamics mixing and chemical conversion in enhancing reactor.It is catalyzed using the immobilization in reactor Agent, it is not necessary to carry out ex situ solid-solid separation.

Fig. 2 and Fig. 3 illustrate illustrated embodiment, and it is arranged to from raw material (for example, carbon raw material (such as coal)) Efflux of solids can be used, can use liquid flow and/or the system of available gas stream by producing.Except each system configuration is that will recycle gas Outside (it is derived from another process in system) is introduced into pyrolysis apparatus, the system that the system that Fig. 2 and Fig. 3 are shown is similar to Fig. 1.Cause This, uses same reference numbers, to recognize similar elements (for example, part, component etc.) in Fig. 1 to 3.

Fig. 2 system is using gas is recycled, and it is by gas-gas separator (for example, product separative element 106th, acid gas removal plants) separated with other gases.Then by air-flow --- it is (such as cold in gas-liquid separator Condenser) in separated with available liquid --- be divided into two or more available air-flows, and afterwards at least one of one or Multiple available air-flows return to pyrolysis apparatus as gas recovery.As shown in Fig. 2 the air-flow from gas-liquid separator passes through production Thing separative element 106 is separated into three available air-flows, wherein first is CO₂Stream 161, second is the (example of gas stream containing hydrogen sulphide 162 Such as H₂S), and the 3rd is hydrocarbon stream 163.At least a portion of hydrocarbon stream 163 is for example, by pipeline 265 (for example, pipe) conveying To pyrolysis apparatus 203 to use wherein.For example, gas-gas separator can be directed into heat with separation of methane, a portion Device 203 is solved, and remainder is recycled for other places.System 200 can alternatively include valve or other suitable devices, this Such as available air-flow (for example, hydrocarbon stream) is separated into two individually streams by a little devices so that a part is used as recycling gas Body and another be used for elsewhere.System 200 can alternatively include valve, to purge part in product separative element and pyrolysis Recirculated air between device.As shown in Fig. 2 the first valve 264, which is configured to control, passes through hydrocarbon of the pipeline 265 towards pyrolysis apparatus 203 The flowing of air-flow 163 is arranged under pipeline 265 with the flowing of the appropriate hydrocarbon gas of recovery for other purposes, and the second valve 266 Trip, to control the flowing of air-flow that is purged via purging outlet 268 and be followed again via recirculation line 267 (for example, pipe) It is looped back to the flowing of the air-flow of pyrolysis apparatus 203.

See also Fig. 2, and according to an embodiment, the air-flow of pyrolysis reactor 203 is left by gas vent Include uncondensable fuel gas.The air-flow can enter such as acid gas removal plants system, and removing wherein All sulphur compounds and at least most of carbon dioxide.Sulphur compound can be processed and (for example fill) or change into can Product, such as solid state component sulphur or sulfuric acid.CO₂Stream can be further purified or be transferred to is used for other mesh elsewhere , for example improve oil recovery.Then can further treatment and purification air-flow it is (main to reclaim lighter molecules amount gas It is methane, ethane, ethene, hydrogen, CO) and for fluidizing pyrolysis reactor.Lighter molecules amount gas is recycled back into pyrolysis An advantage in device is：These gases have the second interaction in pyrolysis apparatus, and promoting the yield of liquid hydrocarbon fraction increases. Another advantage that these gases are recycled back into pyrolysis apparatus be it need not introduce another raw material (for example for fluidize and It is used as the nitrogen of carrier gas), it reduce operation and equipment cost.The non-condensable gas portion not recycled in pyrolysis reactor Point can also be used for regeneration reactor, drier, pyrolysis reactor or for burning in the boiler be added heat and/or De--NO_xTechnology.Non-condensable gas can also be fractionated into single component (example by low temperature distillation or other suitable modes Such as methane, ethane, ethene, hydrogen, carbon monoxide) and be processed further, recycle or sell.

System shown in Fig. 3 make use of without gas-gas separator (for example, product separative element, acid gas removal Device) separation recycling gas.In other words, at least a portion air-flow --- it is in gas-liquid separator (for example, cold Condenser) in separated with available liquid --- be transmitted directly to (gas-gas separation before) pyrolysis apparatus 303 as recycling gas Body.The remainder of air-flow can downstream send into fractionation unit, such as low temperature distillation or other suitable separators, to enter Air-flow is separated into more than one available gas product stream by one step.As shown in figure 3, leaving the air-flow of condenser 104 via pipe Line 341 (for example, pipe) is by pipeline to valve 364, and valve 364 controls to arrive product separative element via pipeline 366 (for example, pipe) The flowing of 106 air-flow and the flowing via pipeline 365 (for example, pipe) to the air-flow of pyrolysis apparatus 303.Therefore, valve 364 controls many The gas of condenser 104 is left less as recycling gas is assigned to pyrolysis apparatus 303, and how much gas by product separative element 106 in the further processing of downstream distribution.

Referring again to Fig. 3, according to illustrated embodiment, recycling gas before product separative element 106 is entered from First condenser 104 comes out.The major advantage of Recovery and recycle gas is before separative element：The size of separative element can be with It is smaller, because they do not handle recycling gas.Less size reduces equipment size and cost, and reduces separation Energy requirement.As the embodiment in Fig. 2, the light molecular weight gas into pyrolysis reactor promotes the heat of liquid hydrocarbon fraction Solve yield increase.

In other embodiments, pyrolytic reaction is fragmented into more than one reactor assembly.Fig. 4 shows this point The embodiment of section reactor assembly.As illustrated, system includes the first pyrolization modules 403 (for example, the first pyrolysis apparatus, first anti- Answer device etc.), wherein carbon raw material material (such as coal) is pyrolyzed to produce gas pyrolysis product stream and solid product.Gaseous product Flow through by first outlet pipe 435 and to be sent to the second pyrolization modules 408 from the first pyrolization modules 403.Solid product goes out via second Mouth pipe 434 is transferred to clasfficiator 105 from the first pyrolization modules 403.

As shown in figure 4, the pyrolytic reaction in the first pyrolization modules 403 is catalytic reaction.In the first pyrolization modules of catalysis In, catalyst can be fresh (i.e. new) catalyst, regeneration catalyst (such as from regenerator) or its any group Close.The solid product produced by the first pyrolization modules 403 is transported to downstream solid-solid via pipeline 434 (for example, pipe) and separated Device (such as clasfficiator 105), to separate dead catalyst and modification solid product (such as modifying coal).By the first pyrolization modules 403 The gas pyrolysis product stream of generation is transported to second pyrolization modules 408 in downstream (for example, second via pipeline 435 (for example, pipe) Pyrolysis apparatus, second reactor etc.).Similar to Fig. 2 and Fig. 3, Fig. 4 also includes：Join with the digital identical that Fig. 1 is used into Fig. 3 Numeral is examined, it is intended to identify similar or common element (for example, part, component etc.).Therefore, the identical ginseng of not repeated description herein Examine numeral.

As shown in figure 4, the second pyrolization modules 408 include an entrance, it, which is configured to receive, comes from the first pyrolization modules (example Such as by suction line 435) gaseous product flow, and wherein by gaseous product flow catalytic treatment into gaseous product and liquid Product.Second pyrolization modules 408 can include other entrance.For example, the second pyrolization modules 408 can include be configured to via Pipeline 481 (for example, pipe) receives the second entrance of fresh catalyst and is configured to receive regeneration via pipeline 482 (for example, pipe) 3rd entrance of catalyst.Second pyrolization modules 408 can include one or more outlets.For example, the second pyrolization modules 408 can With including：First outlet, by the first outlet, gaseous product is sent to condenser 104 via pipeline 484 (for example, pipe)；The Two outlets, dead catalyst is transferred to regenerator by it via pipeline 483 (for example, pipe).Therefore, dead catalyst can be conveyed To regenerator with regeneration of spent catalyst.Fig. 4 is illustrated：First catalyst regenerator 107, it is configured to regeneration in the first pyrolysis group The dead catalyst used in part 403；With the second catalyst regenerator 409, it is separated with the first catalyst regenerator 107, and It is configured to the dead catalyst that regeneration is used in the second pyrolization modules 408.With two single regenerators in two heat Solve in component using being probably favourable for the system of different catalysts.

Second catalyst regenerator 409 is received via the suction line 483 (for example, pipe) from the second pyrolization modules 408 Dead catalyst.Oxygen flow can introduce regenerator 409 by suction line 492, and can be used for burning from the second heat The all or almost all combustibles carried in the dead catalyst for solving component 408.Regenerator 409 also includes：Outlet line 494 (for example, pipe), the catalyst of regeneration leaves regenerator 409 by outlet line 494.The catalyst of at least a portion regeneration can be with It is sent to the second pyrolization modules 408.Regenerator 409 can include second outlet 491, and regenerator outlet gas such as flue gas is led to Cross second outlet 491 and leave regenerator.Optionally, at least a portion regenerator outlet gas can be used for taking the catalyst of regeneration Take pyrolysis reactor to.A small amount of purging of regenerated catalyst can be used for the accumulation for preventing ash content or other impurity.For example, blow down valve 495 can be with the series system of outlet line 494, so that the catalyst purged in system passes through via pipeline 496.Pipeline 482 It is configurable to the catalyst of regeneration backing into the second pyrolization modules 408.Pipeline 482 can be in the downstream of blow down valve 495.

Although Fig. 4 shows two single regenerators, the system is configurable to single regenerator, for example The situation of identical catalyst is used in two pyrolysis apparatus.Solid product can be sent to the first downstream process, product liquid The second downstream process can be sent to, and gaseous product can be sent to the 3rd downstream process.For example, the system can include Product separative element, such as condenser, the suitable separators of AGR or any other, further to refine the production exported from system Thing.

In pyrolysis reactor/step, the presence of a part of volatile materials of solid carbonaceous feedstock in solid catalyst It is lower to produce.As example, the raw material can be coal (including lignite), biomass or the peat of any rank.In the reactor, the phase Prestige maximizes the contact between catalyst and solid material, farthest to control yield and selectivity as far as possible.From From the point of view of this viewpoint, fluid bed or riser reactor are preferable.The design of this bed maximizes mixing and avoids two kinds The spontaneous separation of solid substrate (catalyst and raw material).It is assumed that the mixing in fluid bed and riser reactor is main by each The fluidization characteristic of solid is determined, and fluidization characteristic is determined by particle size and shape, it is usually desirable to match catalyst and solid The size and dimension of raw material.On the other hand, expect to separate dead catalyst with raw material after pyrolysis step, because dead catalyst Need to regenerate and reuse (for example, due to its cost relatively high compared with raw material), and the residue from carbon raw material Solid needs to be removed and processed as vendible accessory substance (together with pyrolysis gas).Most standard it is industrial obtainable Solid-solid separator often relies on the difference of size, density and shape, and by using size exclusion, fluidisation or divides Level is to realize separation.Therefore, there is intrinsic balance in the combination that the two units are operated.Make the form phase of two kinds of solids Seemingly, so as to be efficiently separated in sacrifice and cause the same of loss of product, catalyst loss or costliness and/or external separation scheme When, good reactivity contact is provided in pyrolysis apparatus；Or make to mix bad in the reactor, the low list of product needed for causing Journey yield and/or low selectivity.Due to these balances, reaction and product point are completed usually using two single unit operations From.

A kind of method for eliminating downstream solid-solid separator (such as clasfficiator) is to use pyrolysis reactor, and it is configured Reactor (such as via entrance and exit) is entered and left for the carbonaceous material using fixed catalyst.Fixation can advantageously be permitted Perhaps carbonaceous reactant is operated in separation out of catalyst without providing other separative element in reactor downstream.However, The need for catalyst regeneration must also be solved, because catalyst coking as the normal outcome for carrying out pyrolytic reaction.

According to an illustrative method, three circulations are used.In first circulation, pyrolysis reactor is equipped with catalyst, its Temperature of reactor can be preheated to.Reactor is heated to required pyrolysis temperature, and coal is drawn together with fluidizing gas Enter.Fluidizing gas can be any non-oxidized gas, including but not limited to nitrogen, helium, neon, argon gas, appropriate hydrocarbon gas, recycling Or fresh fuel gas, recycling or fresh compressed petroleum gas, carbon dioxide or hydrogen.It is anti-that fluidisation provides carbonaceous Answer the mixing between thing and catalyst solid.Reactor can be run with (a) true batch mode, wherein being initially charged into limited amount Carbonaceous reactant and kept for certain time in pyrolysis reactor；Or with (b) semi-batch mode operation, wherein by reactant Pyrolysis reactor is continuously added to, and is continuously removed from pyrolysis reactor together with fluidisation and product gas by carrying secretly.In feelings In condition (a), residence time (residence time), Ran Houzeng are controlled by the residence time (dwell time) of fixed charging Plus solid product pneumatic conveying with entrained solids product and is gone out reactor by fluidization gas velocity, thus make its again with new carbon Qualitative response raw material is again loaded into together.In situation (b), the gas velocity of fluidizing gas must be over solid carbonaceous reactant Entraining velocity, and by controlling the residence time (but should be always greater than solid carbon to aequum gas velocity regulation The entraining velocity of matter raw material).Truly in batches with half point batch mode, catalyst is by final coking.This will be apparent, Because selectivity of product will change.The hydrocarbon products of generation will decline, and generally selecting property will also change.When it happens, stop Only fresh feed (or no longer adding batch of material), and reactor is placed in second circulation.

In second circulation, separation dead catalyst and modification carbonaceous product.If it flows as really running in batches Change speed increase so that modification carbonaceous product is carried over reactor.If it stops carbonaceous material with semi-batch mode operation Raw material is flowed into reactor, and can improve fluidizing velocity (that is, superficial gas velocity).In any case, once modifying Carbonaceous product stream stops or the acceptable part of upgraded product has been moved off reactor, then reactor prepares to follow for the 3rd Ring.

In the 3rd circulates, reactor is then placed in regeneration mode.Reactor fluidizing gas is changed into from non-oxidized gas Oxidizing gas, including but not limited to air, oxygen, nitrous oxide or other nitrogen oxides.Oxidizing gas can be by any Inert gas further dilutes.Then coke is burnt up from dead catalyst in exothermic reaction.This will produce the flue gas of heat, and And reactor may need cooling.This heat and hot flue gases can be captured and for other places in this method, including But it is not limited to：Moisture-free coal, improve steam be used for remove downstream sour gas, preheat for pyrolysis cyclical reactant or directly Flue gas is injected in coal-burning boiler or heat recovery steam generator.

Once catalyst regenerates, then reactor may return to first circulation, and start again at pyrolysis.It should be noted that logical Cross and changed using multiple reactors and valve, this method can be configured in this way, you can with advantageously with continuous or close Continuous mode (in the case where being pyrolyzed in batches) is produced.For example, three reactors can be used with cyclical variations configuration, One in wherein three reactors in each cycle operation all the time (that is, a reactor in first pyrolysis cyclical, A reactor in second separation circulation, and a reactor in the 3rd regeneration cycle).

Fig. 8-12 illustrates the illustrative embodiments of pyrolysis reactor, and it is configured to provide solid in pyrolysis reactor Body-solid separation, and downstream solid-solid separator need not be provided.Pyrolysis reactor is configured to allow for difference (for example, chi Very little, density, shape) catalyst and raw material Maximum Contact, to solve above-mentioned many problems.For example, Fig. 8-12 pyrolytic reaction Device is configured to：Using different sizes, density and shape to maximize contact；Allow independent control solid material and catalyst Reactor residence time, this can be by making catalyst absorb more coke and accessory substance rather than be forced before it is required Leave reactor and significantly reduce the amount that catalyst is recycled；And separation is provided in reactor, it may not be needed independent list Atom operation influence solid/solid separation.Reactor is configurable to transmit valve using flow field, sieve, plate, inclination and/or solid The continuous solid that is contacting and separating.Each reactor can include two kinds of solids with substantially different particle diameter distribution (PSD), institute With appropriately sized sieve most of solid being distributed with greater particle size will not be allowed to pass through, and made most of with compared with small particle point The solid of cloth passes through.Both solids can have substantially different fluidization characteristic so that rise in a kind of solid (larger floating Power solid) and a kind of solid decline (smaller buoyancy solid) when there is gas fluidized speed.Gas flowfield is configurable to promote Smaller buoyancy solid is downward, and larger buoyancy solid is upward.Each reactor can include one or more barriers, described Barrier is configured to promote contact of two kinds of different solids on its respective stroke by reactor.Adverse current feeding can be passed through (that is, smaller buoyancy solid is removed from bottom at top, and larger buoyancy solid is added from bottom reactor and moved from top Go out) further increase contact.There is each reactor the flow field and path of adjustment particle to provide to solid material and catalyst The ability of the independent control of residence time in the reactor.Catalyst can be bigger than solid material and has smaller buoyancy, And it may be desirable to keep catalyst residence times to be substantially greater than residence time of solid material.However, each reactor can To be adjustable, to adapt to a variety of possibilities, include but is not limited to：The solid material longer than catalyst residence times is provided Residence time or the solid material residence time equal with catalyst residence times, and provide and smaller than catalyst buoyancy consolidate Body raw material.

Fig. 8-10 shows pyrolysis reactor 503, and it is configured to provide for the solid-solid separation of raw material and catalyst.Reactor 503 include：Housing 530 with generally elongated tube shape, it limits inside center room 532 and may be logically divided into change flow field Multiple seed cell 532a-532g, mix and depart to be provided in each room.Housing 530 has an arrival end 533, arrival end 533 are configured to the raw material of such as rudimentary fine coal being introduced into housing.Housing 530 has in the end relative with arrival end 533 One outlet 534.Modification raw material for example modifies coal product, passes through entrainment and any gas one that reactor is left via the port of export Rise and leave.Optionally, reactor can include one or more fixed plates in centre chamber.As shown in figure 8, reactor 503 is wrapped The first fixed plate 536 is included, it is arranged between the board component 541 of arrival end 533 and first, and is also included：Second fixed plate 537, it is arranged between the board component 546 of the port of export 534 and the 6th.Each fixed plate 536, fixed plate 537 can be configured to has It is similar with sieve plate discussed below, with the multiple apertures of identical (for example, hole, opening, aperture etc.).

Centre chamber 532 can be divided into seed cell 532a-532g by one or more movable panel components.As shown in figure 8, anti- Device is answered to include six board component 541-546.However, the other embodiment of reactor is configurable to more or less quantity Board component.

Each board component 541-546 can include at least one plate.As shown in Figures 9 and 10, each board component includes solid Plate 548 (for example, plate without aperture, aperture or hole) and sieve plate 549 are (for example, with least one aperture, aperture or hole Plate, and according to illustrative embodiments, the plate with multiple holes), wherein each plate (for example, solid slab, sieve plate) can be relative Flowing between housing 530 (and centre chamber) independently mobile a pair of adjacent seed cells to control reactor 503.For example, each Plate 548, plate 549 may be configured to slide between fully open position and fully closed position, in fully open position, whole Individual plate is located at the outside of centre chamber 532 (for example, in hull outside), and the whole of centre chamber is covered in fully closed position, whole plate Individual cross-sectional area.Multiple centre positions that each plate can be positioned between fully open position and fully closed position.When solid When body plate 548 is in fully closed position, stopped completely by solid panel by the flowing of centre chamber.When sieve plate 549 is in completely During closed position, forbid around plate flowing, but may occur the flowing in one or more holes by sieve plate.In the middle of each Position, project rings flowing (for example, increase flowing, limitation flowing).Sieve plate 549 be configured to prevent catalyst by while can be with Pass through raw material (for example, carbonaceous material (such as rudimentary coal)).Each board component is configurable to the phase homonymy (example from housing Such as, top side) it is mobile so that when plate is least partially open, the gap between the distal end of plate and housing formed with housing 530 On identical opposite side (for example, bottom side).Alternately, the reactor with two or more board components is configurable to tool There is the board component from the different sides movement of housing, to provide gap in the alternate sides of reactor.

The alignment of reactor 503 can be changed, such as relative to vertically and horizontally, to change the relative angle of reactor. For example, the angle of reactor can be adjusted to spend any angle spent to 90 (90) from 0 (zero).Reactor is configurable to lead to The plate and angle of reactor is overregulated to be formed with various sizes of catalyst bed (such as catalyst granules caking).Reactor Angle be used to produce the cross-sectional area of change in each room.This changes effective fluidizing velocity of whole room.It can lead to Change sieve plate and/or solid Board position is crossed further to manipulate speed flowing field.In other words, the size of catalyst bed can pass through The plate and angle of reactor is adjusted to customize.Such an arrangement provides very flexible geometry, it advantageously helps to manipulate Solid and fluidizing agent (be usually gas, but may be liquid), blocking up in efflux of solids is avoided to produce while maximum mixing Plug and bridge joint.Fig. 9 shows a part for housing 530 and centre chamber 532, and it, which has, includes the veneer of sieve plate 549 and solid panel 548 Component, and can be moved relative to housing 530 and independently of one another.As illustrated, sieve plate 549 and solid slab 548 are all in Between position.

Figure 10 shows some features of the geometry (for example, mixing in seed cell 532b) of mixing chamber.Obviously , the significant change in room of available cross-sectional flow area.In order to understand flowing, but not with any particular theory or explanation The understanding to reactor is limited, control is flowed and four aspect/features of mixing are further described.First, pipeline A₁Represent the cross-sectional area that can be used for smaller buoyancy solid to fall into lower room.Second, pipeline A₂Represent to can be used for larger buoyancy solid The cross-sectional area risen with fluidizing agent from lower room.3rd, pipeline A₃Represent the most wide cross section that can be used for conveying in room Product.4th, arrow Q_FluidRepresent the flowing of the fluidizing agent in seed cell.The speed (u) of fluidizing gas or any solid can pass through Carry out rough estimate by its volume flow divided by available for the cross-sectional area of flowing.Therefore, the solid of less buoyancy is in its maximum resistance Flowing downward and will be provided by position 1 at plug point, and following computational methods (1) can be used to calculate.

u₁ ^{Smaller buoyancy solid}=Q_{Smaller buoyancy solid}/A_-

(1)

The importance of this point is that, due to the bridge joint during solid is shifted and is stored, solid may be blocked.However, The upward fluidizing velocity may insure that these solids do not stagnate in seed cell.Fluidizing velocity determines by the cross-sectional area of position 2, And following computational methods (2) can be used to calculate.

Preferably, fluidizing velocity is more than or equal to the critical entraining velocity of larger buoyancy solid.In some embodiments, Fluidizing velocity is more than or equal to the minimum fluidization velocity of smaller buoyancy solid.When solid, which is fluidized medium, to be pushed up, produce The turbulent area of agitation, this prevents solid from blocking because the particle of less buoyancy flowed out from room and by two kinds of turbulent closure scheme not Same solid.

Position 3 in Figure 10 is (for example, pipeline A₃) be available for flowing the maximum cross-section area point.At point 3, fluidisation Speed is minimum, and it can use following computational methods (3) to calculate.This allows substantial amounts of independent tuning to allow to separate and increase Plus time of contact.If necessary to separation degree and good contact, then the speed can be adjusted to the stream less than smaller buoyancy solid Change speed, so as to produce the stagnant zone of the less buoyant particles slightly bubbled, and force and pass through with larger buoyant particles.

One advantage of inclined reactor (for example, relative to vertical inclination) is that inclination is different available for these are adjusted Speed is mixed and separated to maximize.In addition, for the embodiment of pyrolysis, pyrolysis gas is released during reaction, and with fluidisation Gas flows together in the same direction, increases the total amount along the gas stream of reactor length, causes along reactor length Superficial gas velocity increase.This can be by changing inclination or volume (for example, by adjustable plate interval) in each room To solve.The inclination of change can also be realized by tandem reactor or by crooked pipeline.In addition, Fig. 8-10 reactor Configuration allow the residence time for independently controlling larger buoyancy solid and floating body solid because they are by the path of container Different.In the entrainment riser of cocurrent, all solids are roughly the same with the residence time of fluidizing agent and special by fluidisation Property determine.When one of which solid is catalyst and other solid carbonaceous materials are the raw materials of question response, expect Independently control these residence times.Finally, can be by the rank higher than the bottom in the container with multiple stages Larger buoyant material is supplied at section to realize extra coal separation, and more to have an opportunity to depart from from less buoyant material.At this In the case of kind, relatively low stage (injection solid carbonaceous feedstock coal below) is used for oxidizing gas regeneration of spent catalyst.

Reactor 503 can include second outlet 538, and the second outlet 538 is configured to dead catalyst being delivered to regeneration Device.As shown in figure 8, second outlet 538 is arranged near the arrival end 533 of housing 530.For example, second outlet 538 can be set The bottom side of the first seed cell between the first fixed plate and the first board component.Reactor 503 can include second entrance 539, its It is configured to introduce catalyst (for example, combination of raw catelyst, regenerated catalyst, these catalyst).As shown in figure 8, second enters Mouth 539 can be arranged near the port of export 534 of housing 530.For example, second entrance 539 can be arranged on the 7th fixed plate and The top side of the 7th seed cell between 6th board component.This arrangement can be advantageously employed gravity and guide catalyst from second entrance into Second outlet.

Figure 11 shows another illustrated embodiment of pyrolysis reactor 603, and it is configured to provide for raw material and catalysis The solid-solid separation of agent.Reactor 603 includes housing 630, and its tool extends to the second end 632 from first end 631, and greatly It is in elongated tubular shape to cause.According to an embodiment, reactor 603 is essentially perpendicularly aligned, wherein first end 631 in bottom side, Second end 632 is in top side.According to other embodiment, reactor 603 can be tilted, for example with relative to vertical direction into inclination Theta alignment.Reactor 603 can include one or more board components, and it is configured to inside center room 640 being divided into many height Room (for example, seed cell 641-646).

Reactor 603 can include one or more entrances.As shown in figure 11, it is arranged on being arranged to for first end 631 Receive the first entrance 633 of fluidizing gas.Equally, it is second entrance 634 to be arranged near first end 631, its be configured to by Raw material (such as rudimentary coal) is introduced into reactor 603.For example, second entrance 634 is configurable to raw material introducing reactor 603 In second seed cell 642.It is the 3rd entrance 635 to be arranged near the second end 632, and it is configured to catalyst (for example, new catalysis Agent, regenerated catalyst, the combination of these catalyst) it is introduced into reactor 603.For example, the 3rd entrance 635 is configurable to urge Agent is introduced into the 6th seed cell 646.

Reactor 603 can include one or more outlets.As shown in figure 11, reactor 603 includes：First outlet 636, It is configured to remove the dead catalyst in reactor；Second outlet 637, it reclaims modification raw material, example by the second outlet 637 Such as modify coal product.First outlet 636 can be arranged near first end 631.For example, first outlet 636 can be configured to remove The dead catalyst gone in the first seed cell 641.Second outlet 637 can be arranged near the second end 632.For example, second outlet 637 It is configurable to remove modification coal product from the outlet seed cell in the downstream of the 6th seed cell 646 and removes waste gas (for example, thermal decomposition product Gas and/or fluidizing gas).According to another embodiment, waste gas can be discharged via second outlet 637 so that modification is former Material and waste gas leave reactor 603 together.Therefore, waste gas and modification raw material can be in the internal or external separation of reactor 603.

As described above, reactor 603 can include one or more board components, it is configured to reactor being defined to son Room.As shown in figure 11, reactor 603 includes seven board component 651-657, and reactor 603 is divided into seed cell 641-646 by it, even Access port seed cell and outlet seed cell.Each board component includes one or more plates.As illustrated, the first board component 651 and the 7th Board component 657 all includes a veneer, and it is configured to the sieve plate on plate with multiple holes.The size in hole can be customization.Root According to illustrative embodiments, the dimensional configurations in hole are：The particle of raw material is allowed to pass through.But prevent catalyst granules from passing through simultaneously. Therefore, sieve plate can be with separating catalyst and raw material, while raw material is flowed by reactor from seed cell to seed cell.First board component 651 and the 7th the plate of board component 657 fixed relative to housing 630.The board component 656 of second board component 652 to the 6th can be configured It is to include the second plate that sieve plate and neighbouring sieve plate are set, wherein the second plate has the opening being arranged in solid section.Raw material can To pass through the opening in sieve plate and the second plate.According to another embodiment, in the board component 656 of the second board component 652 to the 6th Each include veneer, it has solid section and screen sections, and wherein screen sections are configured to the stream of limiting catalyst Dynamic but permission raw material flows through the hole of screen sections.The screen sections of the board component 656 of second board component 652 to the 6th can be from longitudinal axis Line 658 is offset, for example, with over-over mode as shown in figure 11, wherein phase of the second, the 4th and the 6th sieve plate on longitudinal axis Like side, and the 3rd and the 5th sieve plate is on the similar side relative with the second, the 4th and the 6th sieve plate.This skew of screen sections Arrangement can advantageously induce raw material to be flowed by the alternating of reactor 603, this can make more raw material be exposed to catalyst And add the residence time.

As illustrated, each in seed cell 646 of the second seed cell 642 to the 6th is used as segmentation reaction zone, wherein raw material Modification raw material is formed after catalyst, reaction.First seed cell 641 is used as Disengagement zone so that pass through the second board component 652 Dead catalyst can be recaptured for regeneration by outlet 636.

Reactor 603 is configurable to include one or more transfer valves (for example, by-passing valve, guiding valve, gate valve etc.), and it is matched somebody with somebody It is set to flowing of the control by reactor 603.For example, valve 660 can be provided with control catalyst the adjacent seed cell of each pair it Between flowing.First valve 660 is by the first pipe (extending to valve 660 from the first seed cell 641) and the second pipe (from the second seed cell 642 Extend to valve) fluidly connect the first seed cell 641 and the second seed cell 642.Similarly, second, third, the 4th and 660 points of the 5th valve The second seed cell 642 and the 3rd seed cell 643, the 3rd seed cell 643 and the 4th seed cell 644, the 4th seed cell 644 and the 5th are not fluidly connected Seed cell 645 of seed cell 645 and the 5th and the 6th seed cell 646.Second, third, the 4th and the 5th each in valve 660 include The pipe that each seed cell is connected with valve.Each valve 660 is adjustable to (for example, increase, reduction) by the flow velocity of valve.

Valve can be provided to control each entrance by reactor 603 and/or the flowing of outlet.For example, can provide Valve is to control material flow by first entrance 634 and/or the catalyst by second entrance 635 to flow.In addition, for example, Valve can be provided to control the flowing by the dead catalyst of first outlet 636 and/or the modification raw material by second outlet 637 Flowing.

Figure 11 reactor 603 by controlling larger buoyant particles (particle for including solid carbonaceous material raw material) manually Solid flowing, the switching valve flowed downward using the smaller buoyant particles (including catalyst) of control, and by the way that centre chamber is complete It is divided into the seed cell with board component (including plate) to prevent flowing up for catalyst, to realize many phases disclosed herein Hope effect.In this configuration, solid completely free-flowing open cross-sections region is not allowed, because the stream of catalyst granules It is dynamic to be restricted.As oblique structure fluid bed, the reactor is designed to force larger buoyant particles upwards, and existed using sieve Smaller buoyant particles are captured in each seed cell.

Figure 11 reactors 603 can avoid urging for bottom by the way that reactor is separated into multiple regions (for example, seed cell) Agent is accumulated.These regions can have variable-volume to tackle increased air-flow, because cracked gas escapes during the course of the reaction Go out and with fluidizing gas mixing and together with flow, so along reactor length gas stream total amount increase.By with Mainly solid but include the plate of sieve (a part of plate of sieve is designed to only allow raw material (for example, coal) to pass through), reactor point From solid (such as raw material, catalyst), this advantageously can be being eliminated for carrying out solid-solid point outside reactor 603 From the need for.Preferably, the local velocity that the cross-sectional area of part sieve is produced is higher than the critical entraining velocity of larger buoyant particles. It is highly preferred that the cross-sectional area of part sieve may be designed to minimum fluidisation speed of the local velocity more than smaller buoyant particles produced Degree, so as to force to carry out agitation movement.The position of sieve perforate/sieve aperture can change between sieve, to force raw material to pass through reaction Zigzag path in device.Slide-valve OR gate valve can also be opened once in a while, to allow catalyst to pass downwardly through in the reactor.Frequency It can be determined by coking rate.These catalyst can also be simply discharged into common catalyst collection container.This can also By typical solid metering valve (such as rotary valve or auger) come continuous metering.Advantageously, minimum seed cell is (for example, One seed cell 641) lower section of coal raw material point (for example, entrance 634) is arranged on, to allow any entrainment coal time to depart from.Advantageously, Disengagement zone becomes renewing zone, it is allowed to which hot flue gases enter pyrolysis apparatus.In this case, fluidizing gas can include oxidation group Point, such as oxygen.In addition, oxidizing gas may be preferred that rich in air or oxygen, to avoid system from being overloaded by nitrogen.

Figure 12 shows another illustrated embodiment of pyrolysis reactor 703, and it is configured to provide for solid carbon material Expect the solid-solid reactor of raw material and catalyst.Pyrolysis reactor 703 also provides the solid carbonaceous product of modification and dead catalyst Solid-solid separation.Especially, as described above, reactor 703 is configured with the fluidized catalyst not being entrained (for example The bubbling bed of catalyst).

Reactor 703 includes housing 730, and it has first (for example, bottom) part 731 and second (for example, top) portion Divide 732.Part I 731 has the general tube shape for limiting interior subordinate room, and Part II 732 has on restriction inside The conical shaped shape of room.Conical butt center section can interconnect Part I 731 and Part II 732.Reactor 703 can include one or more than one entrance.First feed pipe 741 is arranged on the end of Part II 732 and fluid connects It is connected to the first dipping tube 751 (it is extended in fluidized state 735).Second feed pipe 742 is arranged on the end of Part II 732 And it is fluidly connected to the second dipping tube 752 (it is extended in fluidized state 735).Raw material can pass through the first feed pipe 741 It is introduced into one of the second feed pipe 742 in the interior room of reactor 703, and catalyst can be by the first and second feed pipes Another is introduced into interior room.As illustrated, reactor 703 includes the 3rd entrance, it is arranged on the end of Part I 731 (for example, end relative with the end of Part II 732), and be configured to receive fluidizing gas from pipe 743.3rd entrance quilt It is configured to that fluidizing gas is incorporated into interior room via fluidizing gas distribution device 745.Reference numeral " 739 " represents fluidized bed level (for example, below dense bed with the adjustable interface above dilute phase solid).

Reactor 703 can include the outlet of one or more than one as shown in figure 12, and first outlet pipe 761 is arranged on the Two parts 732 (for example, its end).First outlet pipe 761 is configured to outflow fluidizing gas, pyrolysis product gas and modification carbonaceous Product.Second outlet pipe 762 is arranged on (for example, its end) place of Part I 731 and is configured to flow out dead catalyst.Example Such as, second outlet pipe 762 can surround the 3rd entrance and pipe 743.Therefore, modification carbonaceous product is left via first outlet 761 Reactor 703, and dead catalyst leaves reactor 703 via second outlet pipe 762.In the experimental study of the reactor, We have demonstrated that reactor can be run so that the solid for leaving reactor by outlet 761 contains to be catalyzed less than 1 parts by weight The weight ratio of the parts by weight carbonaceous product of agent/100.

Now, the comparison of real data will be discussed, including from (it is configured as first as riser with reactor 703 Reactor (i.e. embodiment 1), then second is used as mixing elutriation lift bed (HERB) reactor (i.e. embodiment 2)) it is similar anti- The real data for answering device to reclaim.In first time is run, riser reactor is configured as operation to provide the partially catalyzed of coal Pyrolysis.Reactor configurations are into the pyrolysis reactor with a diameter of 3/4 inch, and it has 8 feet of heated height, and feeds Coal and catalyst mixture.Reactor also has unheated Disengagement zone (being arranged on above heating zone), and it is about 7 feet of high x 3/4 inch diameter.Catalyst and coal enter reactor from bottom.Make in addition, providing nitrogen by the distributor of reactor bottom For fluidizing gas.Gas and solid are taken out from reactor head, they enter cyclone separator there, and wherein solid is gentle Body is separated at a temperature of the outflow of pyrolysis reactor.Then product gas is sampled with gas chromatograph (GC) light to determine Component (for example, less than component of benzene), and heavier component is condensed in liquid trap, GC posts are then injected into quantitatively to be divided Analysis.Dead catalyst and modification coal product is weighed to determine catalyst organic efficiency and coal conversion ratio.In analysis modification coal product Carbon content, volatile materials, ash content and sulphur.In the embodiment described in this application, catalyst is generally described as by we It is bigger than carbonaceous material, finer and close or more constant.This selection is to consider driving by economic rather than technology.Economy urge factor because Have beneficial to catalyst to be configured to larger, finer and close or relatively fixed material, because larger, finer and close or relatively fixed material Tend to less processing and tend to less conveying.Due to the processing of reduction, loss will be minimized, and because catalyst is logical It is often more more expensive than carbonaceous material, generally preferably minimize catalyst loss.However, it can also reverse catalyst and carbonaceous material The effect of material.The material needed it is larger, finer and close or relatively it is fixed do not have on the operability or validity of this method it is influential close Degree, size or mobility difference,.It will thus be appreciated that any specifically related to bigger than carbonaceous material, more constant or finer and close The embodiment of catalyst also impliedly disclose carbonaceous material configuration bigger than catalyst, more constant or finer and close.Accordingly All positions of carbonaceous material and catalyst in ground, process schematic will also be inverted.

During starting, heat is supplied by the thermal regeneration device container (being used as catalyst reservoir) being attached during studying Catalyst carrys out heating response device.Catalyst is recycled between regenerator vessel and pyrolysis reactor, until reaching stable state Temperature.Catalyst stream is controlled by the gate valve between regenerator vessel and pyrolysis reactor.Flow velocity beforehand through gate valve position and Weight-calibration, and verified by the gross weight before and after operation.Once reaching temperature, just drawn with auger in the bottom of pyrolysis reactor Enter coal raw material.The feed rate of coal by auger speed control.Meanwhile, modification coal product and dead catalyst from riser Merging stream be released to product collecting container.The catalyst that progress is run up in regenerator vessel (holder) exhausts.

Process conditions and result, which are included in table 1, (to see below).Although experiment is stable and can control, this Plant configuration identified with some defects.First, as practical problem, because the catalyst consumption is high, it is longer that it is difficult to operation Time.Catalyst occurs together with product, so having to be separated in a further step.Second, it is clear from result See, the optimum contacting time of catalysis pyrolytic reaction is not provided.When with the result in less laboratory installation (Fig. 5-Fig. 7) Compared to when, the conversion ratio of coal is low, and the low yield of all hydrocarbon and fuel Products.

In the configuration of embodiment 1, it is difficult to increase the residence time, because this needs to reduce fluidizing velocity, and fluidisation is reduced Speed can cause entrained catalyst loss.However, determining will successfully modify coal product with urging by adjusting fluidizing velocity Agent is separated, so that the bubbling bed that coal particle elutriation passes through catalyst.In a reservoir, coal and catalysis in lower bubbling bed region Agent is sufficiently mixed, and because the density of coal is smaller and particle mean size is smaller, and coal will be while elutriation comes out from bed Catalyst is waited behind.It is assumed that this thing happens, midrange speed is arrived into fluidizing velocity regulation, i.e., two types (coal and are urged Agent) the respective entraining velocity of particle between speed.This container is considered as mixing reactor, because it completes elutriation As the riser on coal stream and bubbling, the fluid bed on catalyst while separation.Therefore, the reactor is in the application In be described as HERB reactors.

In example 2, using reactor configurations same as Example 1, but reprogramming allows it to conduct The operation of HERB reactors, the partial thermal decomposition to carry out coal.First, fluidized catalyst is filled into 8 feet of heating zones of riser. Then coal is sent into the bottom of pyrolysis apparatus.During running, fresh catalyst is added without.

Although being had differences between embodiment 1 and embodiment 2, embodiment 2 provides many excellent better than embodiment 1 Point.First, compared with Example 1, embodiment 2 can run the much longer time, while using the catalyst of much less.The Two, embodiment 2 can be used for dual purpose, in addition to carrying out catalysis pyrolytic reaction, also separate modification coal product with catalyst. As a result show：Seldom catalyst flees from pyrolysis reactor during running.It is not bound by the limitation discussed or explained, it is believed that implementing The most correlative factor that good selectivity and conversion ratio are realized in example 2 (i.e. HERB pyrolysis reactors configure) is the dense of catalyst in coal Degree is high, to promote to be more beneficial for control selections and the condition of conversion ratio.This obtains the support of the result in table 1, wherein fuel Yield increase to from 8.43% in embodiment 1 in embodiment 2 22.80%, more valuable fuel (such as condensable combustion Expect) as lighter component increases in embodiment 2 as 7.42%, the BTEX components of most worthy from 3.74% in embodiment 1 2.18% risen to from 0.29% in embodiment 1 in embodiment 2.As a result solid carbonaceous feedstock (such as coal) and selection are shown Effective contact of property and active catalyst.

It should be noted that, although on surface foundation, the stop of solid carbonaceous material and catalyst in embodiment 2 is (i.e. Contact) time is longer than embodiment 1 (referring to 14 rows of table 1), if the percent by volume of reactor of the correction with catalyst, The calculating of coal and catalyst effective time of contact is actually relatively low in example 2.For example, carrying out such correct, it is assumed that anti- It is 0.65 second to answer for about the 76% of the body product effective time of contact for being coal in catalyst, embodiment 2, and in embodiment 1 is 3.77 Second.Therefore, although we start increase with the time of contact of reactor to expect to increase the extent of reaction, but in fact we subtract Lack the residence time of coal, but, it is surprising that the degree of reaction substantially increases.This can be partially by Theory Solution Release, in example 2, feed coal and effective residence time that catalyst is effectively contacted are actually longer.

Table 1：The running parameter of above-described embodiment 1 and the reactor of embodiment 2, and according to the recovery of the two embodiments Product.

It should be appreciated that this method can be used for various carbonaceous materials, its can have different amounts of volatile materials, ash content, Fixed carbon, sulphur and calorific value (commonly referred to as grade).However, by testing various coals, it has been found that：Even if the coal of different stage and Carbonaceous material can also be compared by observing conversion ratio and yield based on raw material carbonaceous material.

In order to preferably illustrate this point, based on above-mentioned data, following table includes Production rate and other quality factor.Separately Outside, based on us Heuristics and the estimation range based on simulation (simulation is based on mass balance and energy balance), we All reactors scope that continuously operation is observed is summarized in the following table.It is emphasized that these are for the application The non-limiting scope of the practice of method/system.

Table 2：Process performance quality factor are calculated by the data in table 1.

Table 3：Observed in continuous operation (HERB and riser configuration), and based on laboratory data, continuous fortune The process performance quality factor scope that row and simulation (simulation is based on mass balance and energy balance) are calculated.

These quality factor illustrate the unique ability of this method/system of the application, that is, are carrying out carbonaceous material modification While useful material is provided, and this method has the operability better than existing method.The meaning of line number code is further solved Release as follows：

The weight fraction for the sulphur that row 2 is kept in modification carbonaceous material is measured.It this method reduce modification carbonaceous material Sulphur in material.It is not intended to be fettered by any theoretical or explanation, our result indicate that：Organic sulfur and sulfuric acid in carbonaceous material Salt discharges as hydrogen sulfide, and only remains pyritic sulfur.It is anticipated that pyritic sulfur is attached in ash content, therefore pyrite The sulphur of reservation is similar to the ash content retained in modification carbonaceous material.

The weight fraction for the ash content that row 3 is kept in modification carbonaceous material is measured.This method is unique in that Most of ash content in carbonaceous material is retained in carbonaceous material.This is the key advantage of this method：Arbitrarily adsorb in catalyst The ash content in upper and blocking catalyst hole is considerably less.Ash content accumulation on catalyst is that the known of most of pyrolysis catalysts can not Inverse inactivation, therefore our method will not run into this problem.

The weight fraction for the fixed carbon that row 4 is kept in modification carbonaceous material is measured.It is all (in many situations Under) or most fixed carbon be retained in modification carbonaceous product in.Known fixed carbon is difficult to be pyrolyzed, particularly the temperature in this method Under degree, therefore do not fettered by any particular theory or explanation, it is believed that be not remain in the fixed carbon in modification carbonaceous material The coke on catalyst is aoxidized or becomes by the oxygen in carbonaceous material.In other words, no fixed carbon changes into hydrocarbon products.

The weight fraction for the volatile materials that row 5 is kept in modification carbonaceous material is measured.Not by any specific reason By or the constraint explained, it is believed that volatile materials is the main source of all hydrocarbon discharged in the method, because fixed Carbon is more difficult to pyrolysis.From our Germicidal efficacy to scope can be seen that us and generally retain a part of volatile materials.So And, we select retain some volatile materials in product coal because in these experiments it is desirable that final product be It is capable of the coal of active combustion in the boiler.(coal of active combustion is commonly known as " steam coal " in the boiler).Steam coal needs Some volatile materials so that they can easily be ignited.There is no volatile materials, coal will not active combustion.However, tool The coal for having low volatility materials is typically used as the coking coal used in steel-making.Our method can be in more unfavorable condition (example Such as, higher temperature, more long residence time) under carry out, to convert largely or entirely volatile materials, obtain being suitable for refining The coking coal of steel.

It is expert in 6- rows 10, we are counted again based on the volatile substance in carbonaceous material rather than total carbonaceous material weight Point counting number yield.Non-limiting work theory based on us, it is believed that, because most of hydrocarbon come from volatile materials, because This yield and selectivity based on volatile content are meaningful.We have seen that, this allows us predictably to compare The performance of different grades of carbon raw material.

It is expert in 11- rows 15, we calculate by weight fraction selectivity based on the volatile substance converted in this process. It is the good measure for the volatile materials how this method effectively utilizes conversion to the overall selectivity (row #15) of hydrocarbon.Perfectly Method will be close to 100%.It can be readily seen that with the validity of HERB configuration operation reactors, because the conversion more than 70% Volatile materials produce hydrocarbon.

In row 16, we calculate modification index.The modification Index Definition is the calorific value and raw material carbonaceous of modification carbonaceous product The ratio of the calorific value of material (based on what is received).Many factors determine this index, although we often increase calorific value, but differ Surely it is higher value, because many factors cause the value to be moved toward opposite direction.For example, removing the almost institute in raw material There is moisture.This will increase calorific value and improves the efficiency of boiler.In addition, for example, removing most of volatility thing in raw material Matter.Relative calorific value according to volatile materials relative to remaining component in carbonaceous material, can increase or decrease the calorific value of product. If for example, content of ashes in raw material is high, the non-volatile content in carbonaceous material (fixed carbon+ash content) is relative to waving Volatile material is relatively low, therefore the reduction of volatile materials will reduce calorific value.In addition, for example, removing the major part in raw material Oxygen.This can increase calorific value of the product relative to raw material.Based on above-mentioned factor, it is anticipated that hyperoxia, high-moisture and low-ash Carbon raw material has higher modification index, and vice versa.

In (table 3) row 19 and row 20, it should be noted that CO₂Generation can be according to the type of used carbonaceous material Change.

Now, the illustrative product for describing mild catalytic pyrolysis reactor is constituted.The illustrative result of pyrolysis reactor It is presented in table 4 (seeing below).Product composition to change to being urged at 400 DEG C using zeolite catalyst based on being pyrolyzed the reality of rudimentary coal The analysis of laboratory experiment result.About 45% volatile materials is converted into gas, liquid and modification solid product, for example, modify Coal product.(for example, increase, reduction) level of conversion can be adjusted, such as by increasing or decreasing reaction temperature and/or reactor Residence time.Available product contains valuable alkene and aromatic hydrocarbons.The result of catalysis pyrolysis shows：It is not greater than C₁₂Chemical combination Thing, this shows, if during this catalysis pyrolytic reaction is amplified to bigger Commercial scale and such as tested in small-scale laboratory Accurately implement like that, then tar or other heavy viscous materials seldom or need not be handled.

Table 4：The estimation chemical composition of the product (only hydrocarbon) for the rudimentary coal sample being pyrolyzed with zeolite catalysts.

Now, shown to graphically in Fig. 5-Fig. 7 using the experimental result of experiment test device.Experimental system includes Fluidized-bed reactor.Fig. 5 is compared uses the system of catalyst and sand to include variousization of lower molecular weight hydrocarbon at 400 DEG C The yield of compound.Fig. 6 is compared at 400 DEG C using catalyst, at 400 DEG C using sand and catalyst is used at 600 DEG C System include lower molecular weight hydrocarbon various compounds yield.Fig. 7 is compared at 400 DEG C using catalyst, 400 Yield at DEG C using sand and at 600 DEG C using various compounds in the system of catalyst.

System and process as disclosed herein can be integrated with other commercial Applications.The example of this commercial Application includes But it is not limited to：Coal fired power generation facility (for example, factory), gas-liquids conversion (GTL) facility, coal/coke/gasification of biomass (CCBG) facility, blast furnace (BF) facility, and oil refining and/or steam cracking equipment.Coal fired power generation facility may be used as outlet, be used for For example：Waste heat from system, the excess steam from system, the fuel gas for co-fired boiler, for being segmented NO_xReduction Fuel gas (for example, the rich reducing agent spraying technique etc. flowed as so-called " reburning "), and/or boiler in modification coal. GTL facilities can be used together with system, with by any suitable method, by the fuel gas of lesser value and/or other (particularly light hydrocarbon is (for example, C for hydrocarbon₁-C₄)) it is modified to useful heavier liquid hydrocarbon (such as liquid fortune of other higher values Defeated fuel).For example, GTL equipment can be used together with system is converted into fischer-tropsch liquids to convert a hydrocarbon to synthesis gas and synthesis gas Body, converts synthesis gas to methanol and methanol is converted into gasoline, is used as the oligomeric of light olefin (such as ene-propylene-butene) Thing is converted into gasoline-range hydrocarbon, for the alkylation of isobutene and butane to form isooctane fuel additive, and for it It is converted.CCBG facilities may be used as outlet, outflow：Waste heat from system, the excess steam from system, use in gasification furnace In co-feeding fuel gas, the modification coal as gasification furnace raw material, crude synthesis gas (for example, H₂With CO supply) it is middle as altogether The fuel gas, and/or reforming steam of charging are (to supply other H₂/ CO) in fuel gas and hydrocarbon.BF facilities can make With the modification coal from system is as the substitute of smelter coke raw material or is used as Pulverized coal injecting (PCI) raw material in equipment.Refining Oil and/or steam cracking device may be used as outlet, be used for：Waste heat and/or excess steam from system, and for producing Hydrogen, CO, methane, ethane, ethene, propane, propylene, butane, butylene, pentane, amylene and its all derivatives (including fuel, Solvent, monomer, polymer, specialty chemicals and a large amount of exquisite product) hydrocarbon and fuel gas raw material.

Now, the calculated examples to the process according to an embodiment are described.Implementation below includes：It is whole Close the coal ore dressing plant in pulverized coal friring power plant.For this example, coal Designing Ore-Dressing Plants are the lignite using the North Dakota State, mark Claim 50 ton hour raw coal capacity.Elementary analysis and approximate analysis (the base ＆ Stults (Kitto＆ of North Dakota State lignite Stultz), 2005) it is presented in table 5.

Table 5：The coal analysis (base ＆ Stults (Kitto＆Stultz), 2005) of North Dakota State lignite：

Calculated examples are entered using the system (entering pyrolysis reactor using recycling gas (such as methane)) shown in Fig. 2 Row is calculated.Using rudimentary coal as solid carbonaceous material ore-sorting system is calculated to produce one or more useable products.It is rudimentary Coal enters pulverizer, and granularity is reduced into suitable size distribution wherein.Introduce air into pulverizer with pulverizer Mobile coal simultaneously removes the moisture of some in coal.As an example, about 29% moisture can be had by leaving the fine coal of pulverizer. In order to further reduce the moisture of coal, coal is separated with pulverizer air, then for example, by pipeline to drier, Hot-air moisture-free coal is used there, until its water content is about 3%.Therefore, air can be by drier with moisture-free coal.This is System can be configured to directly or indirectly dries fine coal using the flue gas from catalyst regenerator.The system may be configured to profit With the hot flue gases produced by burning fuel, directly or indirectly to dry fine coal.Coal be transferred to pyrolysis apparatus (for example, It is catalyzed pyrolysis reactor) before, coal can be separated with gas.

Coal enters pyrolysis apparatus, and wherein regenerated catalyst and fresh catalyst is fluidized together with coal, during with enough stops Between be used to be pyrolyzed, to reach the required extent of reaction at about 400 DEG C.In an example, 45% volatile materials turns in coal Formation gas product compositions, similar to the result in above-mentioned EXPERIMENTAL EXAMPLE.In pyrolysis reactor remove coal in it is all or Almost all of residual moisture.All or almost all sulphur in coal are converted to H₂S, COS and SO₂, cause modification coal to have Significantly lower sulfur content.Methane loop can be used for making grain fluidized in pyrolysis reactor and convey solid and gaseous product Go out reactor.Efflux of solids is separated with air-flow first, is then further separated into mainly modifying coal stream and dominant failure (for example loses It is living) catalyst stream.Catalyst inactivation in reactor, mainly by coke laydown on a catalyst.Clasfficiator can be used for will Solid product is separated into modification coal stream and dead catalyst stream.

Usually the modification coal product of powder type can be transported for being processed further, and coal dust is converted into and is easy to The product (such as bead or briquet) of transport.Modification coal can also inject in boiler the purpose for being used for burning and produce steam.By In the quality of modification coal, modification coal is more cleaned and more effective than the original raw coal (for example, rudimentary coal) being incorporated into pulverizer Burn on ground.Modifying coal has higher calorific value, and according to an example, it is about 11,760Btu/lb (with 7,090Btu/lb phases Than), throughput rate is 24.2 ton hours.Coal characteristic (calculating) is presented in table 6.In this embodiment, modification coal keeps it More than the 80% of original calorific value, and most of remaining calorific value is the calorific value in gaseous product and product liquid.

Table 6：Modify the expection coal analysis of coal.

Main dead catalyst stream is transferred to regenerator by entrance, and air introduces regenerator by second entrance.At this In calculated examples, dead catalyst has by weight about 5% carbon from coking.In addition, solid-solid separation causes useless urge Agent stream has the modification coal less than about 3% in dead catalyst.Air burns dead catalyst at about 600 DEG C in a regenerator Coke.Being expected with dead catalyst will burn completely into any modification coal after regenerator, only leave ash content of coal and regeneration Catalyst.Effluent stream from regenerator is the flue gas with about 4% oxygen, and its level promotes to enter all of regenerator Carbonaceous material (being included in the coke on dead catalyst) almost burning completely.Flue gas has about 20 volume % CO₂.Gas and Solid dividually flows out from regeneration reactor.A small amount of catalyst stream (e.g., from about 3% or less) for regenerating or recycling can lead to Cross the blow device purging for being fluidly connected to regenerator outlet.The catalyst stream of purification prevents coal ash in catalyst recirculation circuit In accumulation.The catalyst stream of remaining recycling or regeneration can be transferred to other elements in system, for example, recycle The input of catalyst stream passes through pyrolysis apparatus.

Pyrolysis apparatus may be configured to using fresh catalyst (that is, non-recirculated or regenerated catalyst) keep required The ratio of catalyst and coal.Fresh catalyst is introduced into pyrolysis apparatus by entrance, and can measure or control fresh catalyst Amount to keep the ratio of catalyst and coal in pyrolysis apparatus.

Based on the calculating data presented in Fig. 5, at 400 DEG C, the input of 50 ton hour coals, outflow pyrolysis reactor is with Swim the expected final gaseous product flow and product liquid of separative element：

Another system can include flue gas and be pyrolyzed fluidisation, wherein all or part of flue gas from regeneration reactor can For fluidizing pyrolysis reactor.Preferably, any necessary heat will be provided for pyrolysis reactor using enough flue gas, And help to make the carrier gas of coal and catalyst and gaseous product to flow out pyrolysis reactor.Due to entering the sky of regeneration reactor Gas, flue gas will be main by N₂、H₂O、CO₂, CO and SO₂Combination composition.Any one can be used in the regeneration of catalyst Or a variety of O₂, hydrogen, CO₂, CO and/or steam.Alternately, the flue gas from regenerator can be kept and pyrolysis reactor Separation.

Generally, for example in flue gas, if CO₂Concentration it is too dilute when, for example in the presence of nitrogen and/or in trace oxygen In the presence of, then CO₂Capture and purifying are more difficult.Therefore, CO is worked as₂During by nitrogen and oxygen gas pollution, for CO₂Trapping and purification Required process equipment it is larger.And work as CO₂When concentration is too dilute, many processing systems (such as sour gas recovery system) can not Reclaim CO₂.In system and method as disclosed herein, the substantially nitrogen-free and nothing of high concentration are produced in pyrolysis reactor The CO of oxygen₂.Therefore, it is exclusively used in capturing CO from pyrolysis reactor₂Sour gas remove system by with relatively small equipment, And mixed with the flue gas (coming from regenerator) containing nitrogen and oxygen that regenerator is air burning and gained with pyrolysis gas The situation of conjunction is compared, and the system can be using the selection of more recovery technologies.

Although it should be noted that discussed coal as carbonaceous material and its can be used for system described in this application and side The example of raw material in method, but other suitable materials can be used in the system and method.For example, can be used as in the application The other types of coal of raw material in the system and method for description includes but is not limited to：Lignite or brown coal, subbituminous coal, pitch, Anthracite, mud coal or its any combinations.Liquid derived from coal or oil include but is not limited to：Pyrolysis-derived oils, oiliness coal slurry, coking Derived oils, gasification derived oils, hydrogenation derived oils or its any combinations, can be used as raw material.Tar sands include but is not limited to：Slightly Tar sands, Tar sands derived liquid, pitch, pitch or its any combinations, can be used as raw material.Oil shale includes but not limited In：Raw oil shale, oil shale derived liquid, kerogen or its any combinations, can be used as raw material.Waste oil, including but do not limit In：Cooking oil, machine oil etc. and combinations thereof, can be used as raw material.Urban waste, such as solid waste or waste water Sludge is handled, raw material is can be used as.Waste plastics, such as recycled plastic, can be used as raw material.Biomass includes but not limited In：Lignocellulose biomass is (for example：Various agricultural residues, wheat and straw, maize straw, forestry residue, sawdust, Wood chip and bark etc.), lignocellulose biomass derived oils are (for example：Pyrolysis-derived oils, hydropyrolysis oil, bio-crude oil etc.), The various oil containing lipid are (for example：Plant-derived lipids oil, manioca, palm, lipid oils derived from algae etc.) and its any group Close, can be used as raw material.Oil includes but is not limited to：Various petroleum derived oils, crude oil, oil refining derived oils, pitch, synthesis are former Oil, base oil, oil residues, mink cell focus and its any combinations can be used as raw material.Other suitable materials are also used as original Material.Preferably, when exposed to cracking conditions (for example, being heated to pyrolysis temperature), carbon raw material release volatile materials.Compared with Inappropriate carbonaceous material will include those of substantially used up volatile matter content, for example：Coke.In addition, any of the above described Raw material can be used alone or as co-feeding (for example, co-feeding raw material) and one or more other raw materials (on being derived from State raw material) it is used together.

A kind of method for modifying of solid carbonaceous material of paragraph A., including in the presence of a catalyst and under the conditions of partial thermal decomposition Solid carbonaceous material is heated, and obtains the solid carbonaceous product of modification, gaseous product and dead catalyst.

Methods of the paragraph B. as described in paragraph A, wherein solid carbonaceous material are coals, and modify solid carbonaceous product and be Modify coal product.

Methods of the paragraph C. as described in paragraph A or B, wherein being retained in the fixation carbon weight modified in solid carbonaceous product To fix at least the 50% of carbon weight in solid carbonaceous material.

Methods of the paragraph D. as any one of paragraph A-C, wherein being retained in the ash content modified in solid carbonaceous product Weight is at least 60% of Ash weight in solid carbonaceous material.

Methods of the paragraph E. as any one of paragraph A-D, wherein being retained in the volatilization modified in solid carbonaceous product Property material weight be solid carbonaceous material in volatile materials weight about 10% to about 90%.

Methods of the paragraph F. as any one of paragraph A-E, wherein being retained in the volatile materials in modification coal product Weight be coal in volatile materials weight about 10% to about 90%.

Methods of the paragraph G. as any one of paragraph A-F, in addition to：Heating is carried out under the conditions of partial thermal decomposition Before, the initial solid carbonaceous material is pre-processed using at least one of drier, deliming machine and washer.

Methods of the paragraph H. as any one of paragraph A-G, in addition to：Obtain CO₂, its amount is more than initial solid carbonaceous The about 10wt% of volatile materials in material.

Methods of the paragraph I. as any one of paragraph A-H, in addition to：By gaseous product with modifying solid carbonaceous product Separated.

Methods of the paragraph J. as any one of paragraph I, in addition to：By the gaseous product of separation be condensed into gas stream and Liquid flow.

Methods of the paragraph K. as any one of paragraph A-J, in addition to：Obtain can not condensed fuel gas, its amount is The about 1wt% of volatile materials to about 40wt% in initial solid carbonaceous material.

Methods of the paragraph L. as any one of paragraph A-K, in addition to：Obtain can not condensed fuel gas, its amount is Originate the about 1wt% to about 40wt% of volatile materials in coal.

Methods of the paragraph M. as any one of paragraph A-L, in addition to：LPG is obtained, its amount is initial solid carbonaceous material The about 1wt% of volatile materials to about 40wt% in material.

Methods of the paragraph N. as any one of paragraph A-M, in addition to：BTEX is obtained, its amount is initial solid carbonaceous The about 0.5wt% of volatile materials to about 40wt% in material.

Methods of the paragraph O. as any one of paragraph A-N, in addition to：Higher hydrocarbon is obtained, its amount is initial solid carbon The about 0.3wt% of volatile materials to about 20wt% in material.

Methods of the paragraph P. as any one of paragraph A-O, in addition to：Obtain and contain heteroatomic organic matter, its amount is not More than the 5wt% of volatile materials in initial solid carbonaceous material.

Methods of the paragraph Q. as any one of paragraph A-P, wherein dead catalyst and the solid carbonaceous product conduct of modification Mixture is reclaimed.

Methods of the paragraph R. as any one of paragraph A-Q, wherein dead catalyst and the solid carbonaceous product difference of modification Reclaim.

Methods of the paragraph S. as any one of paragraph A-R, in addition to：By making dead catalyst with containing at least one The admixture of gas of oxidizing gas contacts the regeneration of spent catalyst to form regenerated catalyst.

Methods of the paragraph T. as any one of paragraph S, a part of regenerated catalyst of wherein at least is in other solid Heated in the presence of carbonaceous material in subsequent partial thermal decomposition reaction.

Methods of the paragraph U. as any one of paragraph A-T, in addition to：By using acid solution pickling dead catalyst with Form regenerated catalyst and regeneration of spent catalyst.

Methods of the paragraph V. as any one of paragraph S-U, a part of regenerated catalyst of wherein at least is consolidated in other Heated in the presence of body carbonaceous material in subsequent partial thermal decomposition reaction.

Methods of the paragraph W. as described in paragraph A-V, wherein being retained in the weight for modifying the total sulfur in solid carbonaceous product No more than the 80wt% of total sulfur in initial solid carbonaceous material.

Methods of the paragraph X. as any one of paragraph A-V, wherein being retained in organic in the solid carbonaceous product of modification The weight of sulphur is no more than the 50wt% of organic sulfur in initial solid carbonaceous material.

A kind of solid carbonaceous materials by ore-sorting system of paragraph AA. are converted into the method for modifying solid carbonaceous product, institute The method of stating includes：

Solid carbonaceous material and catalyst are incorporated into pyrolysis reactor to produce gaseous product flow and solid product stream, Wherein the solid product stream includes the solid carbonaceous product of modification；

The gas recovery product stream from reactor；With

Solid product stream is reclaimed from reactor.

Methods of the paragraph AB. as described in paragraph AA, wherein solid carbonaceous material are coals, and modify solid carbonaceous product It is modification coal product.

Methods of the paragraph AC. as any one of paragraph AA-AB, wherein catalyst is fixed in pyrolysis reactor；And And this method also includes：The solid carbonaceous product of separation modification from the catalyst in pyrolysis reactor.

Methods of the paragraph AD. as any one of paragraph AA-AC, in addition to：

The dead catalyst of separation is reclaimed from pyrolysis reactor；

Dead catalyst is transferred to regenerator；With

Dead catalyst regeneration is carried out in a regenerator, wherein removing the coal not being pyrolyzed, coke and the carbonaceous in dead catalyst Material.

Methods of the paragraph AE. as any one of paragraph AA-AD, in addition to：

Gaseous product flow is transferred to separator；With

Condensed gas product stream at least in part, produces refined air-flow, hydrocarbon liquid stream and aqueous solution body phase in the separator Stream.

Methods of the paragraph AF. as any one of paragraph AA-AE, wherein solid product stream also include dead catalyst, should Method also includes：

After pyrolysis reactor reclaims solid product stream, by the solid product flow separation into modify solid carbonaceous product and The dead catalyst of dead catalyst, the wherein separation is included in catalyst and the coal, coke and the carbonaceous material that are not pyrolyzed at least It is a kind of.

Methods of the paragraph AG. as described in paragraph AF, in addition to：

The catalyst of separation is transferred in regenerator, wherein remove catalyst at least one of coal not being pyrolyzed, At least one of coke and carbonaceous material；With

Gaseous product flow is transferred in separator, wherein in the separator that the gaseous product flow is cold at least in part It is solidifying, produce refined air-flow, hydrocarbon liquid stream and aqueous solution body phase stream.

Methods of the paragraph AH. as any one of paragraph AA-AG, wherein by burning, steam and reducing gas At least one, removes at least one of at least one of coal not being pyrolyzed, coke and carbonaceous material in catalyst.

Methods of the paragraph AI. as any one of paragraph AA-AH, wherein pyrolysis reactor be configured to HERB, fluid bed, One kind in moving bed or entrainment thermopnore, and wherein coal and catalyst is moved through pyrolysis reactor.

Methods of the paragraph AJ. as any one of paragraph AA-AI, wherein solid product stream is transferred out of pyrolysis reactor To solid-solid separator, the solid-solid separator is separated to modifying solid carbonaceous product and dead catalyst.

Methods of the paragraph AK. as any one of paragraph AA-AJ, wherein solid-solid separator include clasfficiator, should Clasfficiator will modify solid carbonaceous product and be separated from dead catalyst according to one of granularity, quality or density.

In the size and density of methods of the paragraph AL. as any one of paragraph AA-AK, wherein dead catalyst at least One different from least one in the size and density of the solid carbonaceous product of modification, and wherein solid-solid is separated The clasfficiator of device will modify solid carbonaceous product and dead catalyst is separated according to one of granularity, quality or density.

Methods of the paragraph AM. as any one of paragraph AA-AL, in addition to：

Introduce before pyrolysis reactor, reduce the size of the particle of solid carbonaceous material in pulverizer；With

Solid carbonaceous material is pre-processed in pretreatment unit, the pretreatment unit include it is following at least one： Drier, it, which is configured to utilize, heats coal of the fluid stream drying from pulverizer；Washer, it is configured to washing and comes from pulverizer Coal；And deliming machine, it is configured to remove the ash content in coal, wherein the pretreatment unit is arranged on the pulverizer and institute State between pyrolysis reactor.

Methods of the paragraph AN. as any one of paragraph AM, wherein the fluid stream heated is using carrying oxygen Produced during at least one of any coal not being pyrolyzed, coke and carbonaceous material in gas removing dead catalyst, by regenerator Raw hot flue gases.

Methods of the paragraph AO. as any one of paragraph AE-AN, wherein separator also include sour gas and remove system System, the sour gas removes system and following at least one is separated from gaseous product flow：Carry the compound of sulphur, carry nitrogen Compound and carbon dioxide.

Methods of the paragraph AP. as any one of paragraph AA-AO, wherein introducing the catalyst of pyrolysis reactor includes： Part I, it includes the regenerated catalyst from regenerator receiver；And Part II, it includes unregenerated raw catelyst, And the regenerated catalyst of wherein described Part I has the relative temperature higher than the raw catelyst so that regeneration catalyzing Agent turns into heating medium to heat the coal being incorporated into pyrolysis reactor.

The catalysis of methods of the paragraph AQ. as any one of paragraph AA-AP, wherein solid carbonaceous material is pyrolyzed about Carried out at a temperature of 350 DEG C to about 850 DEG C.

Methods of the paragraph AR. as any one of paragraph AA-AQ, wherein the solid carbon material being introduced into pyrolysis reactor Material is with about 0.2 to about 25kg/hr/kg catalyst weight hourly space velocity.

Methods of the paragraph AS. as any one of paragraph AA-AR, wherein solid carbonaceous material has in catalytic process The residence time of about 0.1 second to about 1 minute.

Methods of the paragraph AT. as any one of paragraph AA-AS, wherein the catalyst being introduced into pyrolysis reactor is with consolidating The weight ratio of body carbonaceous material is about 0 to about 100.

Methods of the paragraph AU. as any one of paragraph AA-AS, in addition to：

Sour gas is provided and removes system, it is configured as the always gaseous product of self-pyrolysis reactor and from regenerator The capture of at least one of gas and separation CO₂, wherein regenerator be configured to regenerate the useless catalysis from pyrolysis reactor Agent；With

Obtain CO₂, its amount is more than the about 4wt% for drying ashless coal.

Methods of the paragraph AV. as any one of paragraph AA-AU, in addition to：Obtain CO₂, its amount is more than initial solid The about 10wt% of volatile materials in carbonaceous material.

Methods of the paragraph AW. as any one of paragraph AA-AV, in addition to：Obtain CO₂, it is ashless that its amount is more than drying The about 4wt% of coal.

Methods of the paragraph AX. as any one of paragraph AA-AW, in addition to：

Regeneration of spent catalyst in a regenerator, wherein regenerator is configured to produce hot flue gases during regenerating；With

At least a portion of the hot flue gases is transferred to pyrolysis reactor so that pyrolysis reactor is fluidized.

Methods of the paragraph AY. as any one of paragraph AX, wherein CO, CO will be included₂, water, in hydrogen and oxygen At least one gaseous fluid is introduced into regenerator, to promote to remove the coal not being pyrolyzed, coke and the carbonaceous material in dead catalyst Material.

Methods of the paragraph AZ. as any one of paragraph AY, in addition to：Collection includes CO₂Hot flue gases for Carbon chelates or improved oil recovery.

Methods of the paragraph BA. as any one of paragraph AX-AZ, in addition to：Make hot flue gases by heat exchanger with Produce the heat for heating the solid carbonaceous material in pyrolysis reactor.

Methods of the paragraph BB. as any one of paragraph AX-BA, wherein regenerator are in addition to using air or replace Air, also using steam to pass through hydrolysis and at least one of steam gasification removes coal, coke and carbonaceous in dead catalyst Material.

Methods of the paragraph BC. as any one of paragraph AX-BB, wherein regenerator are included using hydrogen or at least one Other hydrogeneous chemicals including hydrocarbon, reduction removes coal, coke and carbonaceous material from dead catalyst.

Methods of the paragraph BD. as any one of paragraph AA-BC, wherein gas is co-fed in pyrolysis reactor, Wherein described gas includes at least one light hydrocarbon compounds reclaimed from gaseous product flow.

Methods of the paragraph BE. as any one of paragraph AA-BD, wherein at least one light hydrocarbon compounds are circulated back to Pyrolysis reactor.

Methods of the paragraph BF. as any one of paragraph AA-BE, in addition to：BTEX is obtained, its amount is initial solid carbon The about 0.5wt% of volatile materials to about 80wt% in material.

Methods of the paragraph BG. as any one of paragraph AA-BF, wherein biomass is co-fed into pyrolysis reactor In.

Methods of the paragraph BH. as any one of paragraph AA-BG, wherein by oil shale, coal derived liquid, Tar sands and At least one of oil is co-fed in pyrolysis reactor.

Methods of the paragraph BI. as any one of paragraph AA-BH, wherein by least one of moisture and natural gas altogether It is fed in pyrolysis reactor.

Methods of the paragraph BJ. as any one of paragraph AA-BI, wherein pyrolysis reactor include fixed catalyst, make Obtain solid carbonaceous material and be moved through reactor relative to catalyst, to produce gaseous product flow and solid product stream, this method Also include：

Gaseous product flow is transferred to separator at least a portion gaseous product flow is condensed into liquid at least in part Product and gaseous product；And

Wherein described solid product stream contains less than the parts by weight of 1 part by weight of catalyst/100 modification carbonaceous product.

The method that a kind of biomass by ore-sorting system of paragraph CA. is converted into modification solid product, this method includes：

The biomass and catalyst are introduced into pyrolysis reactor to produce gaseous product flow and modification solid product stream, should Solid product stream includes dead catalyst and modification solid product；

Separation modification solid product and dead catalyst；

The dead catalyst of separation is transferred to regenerator, the regenerator removes at least one of any in dead catalyst Coal, coke and the carbonaceous material not being pyrolyzed；With

Gaseous product flow is transferred to the separator for producing product liquid and gaseous product；

The weight of ash content in modification solid product is wherein retained in be introduced into the biomass of pyrolysis reactor ash content extremely Few 60wt%.

Methods of the paragraph CB. as any one of paragraph CA, wherein by weight, the amount of the phenol of generation, which is less than, to be produced Toluene amount.

Methods of the paragraph CC. as any one of paragraph CA or CB, wherein by weight, the amount of the tar of generation is less than The amount of the light oil of generation.

As it is used herein, term " about ", " about ", " substantially " and similar terms are intended to the master with present disclosure The consistent broad sense of the general and generally acknowledged usage of the those of ordinary skill in the art of topic.Present disclosure is examined It will be understood by those skilled in the art that these terms are intended to illustrate some features, the wherein description and requirement of these features Its scope is not limited in the accurate number range provided.Correspondingly, these terms are interpreted as：Show to being retouched Unsubstantiality the or inessential modification or change for the theme stated and be claimed are considered as belonging to appended claims Described in the scope of the present invention.

As used herein term " coupling ", " connection " etc. mean that two components are either directly or indirectly connected to one another. Such combination can be (for example, detachable or releasable) of static (for example, permanent) or activity.Such knot Conjunction can be by the way that the two components or the two components and any extra intermediate member be formed integrally with each other to be single Unitary body, or by by the two components or the two components and any other intermediate member be attached to one another come Realize.

Position herein to element is (for example：" top ", " bottom ", " top ", " lower section " etc.) reference be only used for retouching State the orientation of various elements in accompanying drawing.It should be noted that：According to other illustrative embodiments, the orientation of various elements can not Together, and these changes are intended to be covered by present disclosure.

The construction and arrangement of the element (for example, ore-sorting system) of system as shown in the illustrated embodiment are only illustrative 's.Although several embodiments of present disclosure are only described in detail, the those skilled in the art for reading present disclosure are readily apparent that, In itself without departing from the novel teachings and advantage of cited theme in the case of, many modifications are all possible (examples Such as, the change in terms of the size of each element, size, structure, shape and ratio, parameter value is installed and arranged, materials'use, face Change in terms of color, orientation etc.).For example, the multiple element being shown as integrally formed can be by some or element structure Into, the position of element can overturn or otherwise change, and can change or change discrete elements or the property of position Matter or quantity.

In addition, word " illustrative " used herein is meant as example, example or example.It is described herein as " saying Any embodiment of bright property " or design are not necessarily to be construed as compared with being preferred or favourable for other embodiment or design (and such term is not meant to that such embodiment is necessarily special or five-star example).On the contrary, word " is said The use of bright property " is intended to that concept is presented in a concrete fashion.Correspondingly, all such modifications are intended to be included in the model of present disclosure Within enclosing.In the case of without departing from scope of the following claims, it can be set preferred and other examples embodiment Other substitutions, modifications, changes and omissions are carried out in meter, operating condition and arrangement.

As used herein " about " will be understood by those of ordinary skill in the art, and the context that will be used according to it And change to a certain extent.If there is the use of the unclear term of those of ordinary skill in the art, it is contemplated that it is used Context, " about " will imply that be up to compared to concrete term 10% positive and negative scope.

In the context of description key element (particularly in the context of appended claims), term "/kind " and The use of "the" and similar referent should be interpreted that including odd number and plural number the two, unless otherwise indicated herein or context It is clearly contradicted.The narration of this paper number ranges is provided merely as individually indicating the shorthand of each independent numerical value fallen into the range of this Method, unless otherwise specified herein, each individually numerical value, which is quoted, to be incorporated in the present specification, and is individually here just as it As narration.All methods described herein can be carried out with any appropriate order, unless otherwise specified herein or in addition with Context is clearly contradicted.Unless otherwise indicated, provided herein is any and all example or exemplary language (for example, " such as ") Use be only intended to that embodiment is better described, be construed as limiting without the scope to claim.Language in specification should not When being interpreted to indicate that any key element being not claimed is required.

Although some embodiments have been shown and described, but it is to be understood that according to the ordinary skill people of this area Member, in the case of without departing from the broad aspect of technology as defined in claims below, can be changed wherein Become and change.

The embodiment of exemplary description herein is in the absence of any one or more key elements not disclosed herein, one It can be appropriately carried out in the case of individual or multiple limitations.Thus, for example, term "comprising", " comprising ", " containing " etc. will be wide Understand generally and unrestrictedly.In addition, term and expression used herein already functions as descriptive term rather than restricted Term, and shown in being not intended to when using these terms and expression to exclude and described, feature or part thereof it is any etc. Thing is imitated, and is to recognize that the various modifications in the range of technology claimed are possible.In addition, phrase is " substantially By ... constitute " those key elements and other key element for specifically stating are will be understood to comprise, these other key elements will not Substantially influence the basic and novel feature of technology claimed.The exclusion of phrase " consist of " is any not to be indicated Key element.

Present disclosure is not limited to embodiment described in this application.In feelings without departing from the spirit and scope of the present invention Under condition, many modifications and variations can be carried out, this will be apparent to the person skilled in the art.More than Illustrate, except enumerated herein in addition to those, the functionally equivalent method and composition in the range of present disclosure is for ability It is obvious for the technical staff in domain.Such modifications and variations are intended to fall under in scope of the following claims.This Disclose only by the have the right four corner of the equivalent of requirement of the clause in appended claims and these claims is limited. It should be appreciated that present disclosure is not limited to specific method, reagent, compound composition or biosystem, they can send out certainly Changing.It is also understood that terms used herein is merely to the purpose illustrated to specific embodiment, not purport Limited.

As it will appreciated by a person of ordinary skill, for any and all purposes, particularly in terms of written description is provided, All ranges disclosed herein also includes：The combination of any and all possible subrange and its subrange.Any model listed Enclosing to be considered as easily：Fully describe and cause same range be broken down at least equal half, 1/3rd, A quarter, 1/5th, ten/first-class.As non-limiting examples, each scope discussed in this article can be easily Resolve into down 1/3rd, in 1/3rd and upper three/first-class.It will further be appreciated by those of ordinary skill in the art that such as " at most ", " at least ", all language such as " being more than ", " being less than ", including the numerical value described, and refer to then resolve into as above institute The scope for the subrange stated.Finally, as it will appreciated by a person of ordinary skill, scope includes each individually member.

All publications, patent application, the patent of issue and the other files quoted in this manual, which are quoted, to be incorporated into This, as each single publication, patent application, the patent of issue or other files are indicated as being definitely and individually Combined by reference.Those definition models contradicted with present disclosure are excluded included in the definition being incorporated by reference into text Enclose.

, can also be to the designs of various illustrated embodiments, operation bar in the case of without departing from the scope of the present invention Part and arrangement carry out other substitutions, modifications, changes and omissions.For example, any key element disclosed in one embodiment can be with It is incorporated to or is used together with any other embodiment disclosed herein.In addition, for example, the order of any process or method and step Or order can be changed or resequence according to alternative embodiment.Any means-plus-function clause, which is intended to, to be covered in The structure of the execution function of this description, and not only covered structure equivalent but also cover equivalent structure.Not inclined , can be in preferred and design, operative configurations of other illustrative embodiments in the case of from scope of the following claims With other substitutions, modifications, changes and omissions are carried out in arrangement.

Claims

1. a kind of method for modifying of solid carbonaceous material, including：

Solid carbonaceous material is heated in the presence of a catalyst and under the conditions of partial thermal decomposition, and

Obtain the solid carbonaceous product of modification, gaseous product and dead catalyst.

2. the method as described in claim 1, wherein the solid carbonaceous material is coal, and the solid carbonaceous product of modification It is modification coal product.

3. the method as described in claim 1, wherein the fixation carbon weight being retained in the solid carbonaceous product of modification is institute State and at least the 50% of carbon weight is fixed in solid carbonaceous material.

4. the method as described in claim 1, wherein the Ash weight being retained in the solid carbonaceous product of modification is described At least the 60% of Ash weight in solid carbonaceous material.

5. method as claimed in claim 2, wherein the Ash weight being retained in the modification coal product is ash content weight in coal At least the 60% of amount.

6. the method as described in claim 1, wherein the weight for the volatile materials being retained in the solid carbonaceous product of modification Measure as about 10% to about 90% of volatile materials weight in the solid carbonaceous material.

7. method as claimed in claim 2, wherein the weight for the volatile materials being retained in the modification coal product is coal About the 10% to about 90% of middle volatile materials weight.

8. the method as described in claim 1, in addition to：Before being heated under the conditions of partial thermal decomposition, using drier, take off At least one of grey machine and washer are pre-processed to initial solid carbonaceous material.

9. the method as described in claim 1, in addition to：Obtain CO₂, its amount is more than volatility thing in initial solid carbonaceous material The about 10wt% of matter.

10. the method as described in claim 1, in addition to：Gaseous product is separated with the solid carbonaceous product of modification.

11. method as claimed in claim 11, in addition to：The gaseous product of separation is condensed into gas stream and liquid flow.

12. method as claimed in claim 11, in addition to：The gaseous product of separation is compressed, gas stream and liquid flow is formed.

13. the method as described in claim 1, in addition to：Obtain can not condensed fuel gas, its amount is initial solid carbonaceous material The about 1wt% of volatile materials to about 40wt% in material.

14. method as claimed in claim 2, in addition to：Obtain can not condensed fuel gas, its amount be starting coal in volatility The about 1wt% of material to about 40wt%.

15. the method as described in claim 1, in addition to：LPG is obtained, its amount is more than volatility in initial solid carbonaceous material The about 1wt% of material to about 40wt%.

16. method as claimed in claim 2, in addition to：LPG is obtained, its amount is more than the pact of volatile materials in starting coal 1wt% to about 40wt%.

17. the method as described in claim 1, in addition to：BTEX is obtained, its amount is volatility thing in initial solid carbonaceous material The about 0.5wt% of matter to about 40wt%.

18. method as claimed in claim 2, in addition to：BTEX is obtained, its amount is the pact for originating volatile materials in coal 0.5wt% to about 40wt%.

19. the method as described in claim 1, in addition to：Higher hydrocarbon is obtained, its amount is volatility in initial solid carbonaceous material The about 0.3wt% of material to about 20wt%.

20. method as claimed in claim 2, in addition to：Higher hydrocarbon is obtained, its amount is the pact for originating volatile materials in coal 0.3wt% to about 20wt%.

21. the method as described in claim 1, in addition to：Obtain and contain heteroatomic organic matter, its amount is not more than initial solid carbon The 5wt% of volatile materials in material.

22. method as claimed in claim 2, in addition to：Obtain and contain heteroatomic organic matter, its amount is not more than initial solid carbon The 5wt% of volatile materials in material.

23. the method as described in claim 1, wherein the dead catalyst and the solid carbonaceous product of the modification are used as mixture Reclaim.

24. method as claimed in claim 2, wherein the dead catalyst and the modification solid coal are reclaimed as mixture.

25. the method as described in claim 1, wherein the dead catalyst and the solid carbonaceous product of the modification are separately recovered.

26. method as claimed in claim 26, in addition to：By making the dead catalyst with containing at least one oxidizing gas Admixture of gas contact regenerate the dead catalyst to form regenerated catalyst.

27. method as claimed in claim 27, a part of regenerated catalyst of wherein at least is in other solid carbon material It is heated in the presence of material in subsequent partial thermal decomposition reaction.

28. method as claimed in claim 26, in addition to：By using dead catalyst described in acid solution pickling to form regeneration Catalyst and regenerate the dead catalyst.

29. method as claimed in claim 29, a part of regenerated catalyst of wherein at least is in other solid carbon material It is heated in the presence of material in subsequent partial thermal decomposition reaction.

30. the method as described in claim 1, wherein the weight for the total sulfur being retained in the solid carbonaceous product of modification does not surpass The 80% of the total sulfur weight crossed in initial solid carbonaceous material.

31. the method as described in claim 1, wherein the weight for the organic sulfur being retained in the solid carbonaceous product of modification is not More than the 50% of the weight of the organic sulfur in initial solid carbonaceous material.

32. the method as described in claim 1, wherein the weight for the sulfate being retained in the solid carbonaceous product of modification is not More than the 50% of the weight of the sulfate in initial solid carbonaceous material.

33. a kind of solid carbonaceous material by ore-sorting system is converted into the method for modifying solid carbonaceous product, methods described bag Include：

The gaseous product flow is reclaimed from the reactor；With

The solid product stream is reclaimed from the reactor.

34. method as claimed in claim 34, wherein the solid carbonaceous material is coal, and the solid carbonaceous production of modification Thing is modification coal product.

35. method as claimed in claim 34, wherein the catalyst is fixed in the pyrolysis reactor；And the side Method also includes：The solid carbonaceous product of modification is separated from the catalyst in the pyrolysis reactor.

36. method as claimed in claim 36, in addition to：

The dead catalyst of separation is reclaimed from the pyrolysis reactor；

The dead catalyst is transferred to regenerator；With

The dead catalyst is regenerated in the regenerator, wherein removing the coal not being pyrolyzed, coke and the carbonaceous in dead catalyst Material.

37. method as claimed in claim 36, in addition to：

The gaseous product flow is transferred to separator；With

Condense the gaseous product flow at least in part in the separator, produce refined air-flow, hydrocarbon liquid stream and aqueous solution Body phase stream.

38. method as claimed in claim 34, wherein the solid product stream also includes dead catalyst, methods described is also wrapped Include：

After the pyrolysis reactor reclaims the solid product stream, by the solid product flow separation into the modification solid Carbonaceous product and the dead catalyst, the wherein dead catalyst of the separation include the catalyst and the coal, the coke that are not pyrolyzed At least one of with carbonaceous material.

39. method as claimed in claim 39, in addition to：

The catalyst of separation is transferred in regenerator, wherein removing at least one of coal not being pyrolyzed, coke in catalyst At least one of with carbonaceous material；With

The gaseous product flow is transferred in separator, wherein in the separator that the gaseous product flow is cold at least in part It is solidifying, produce refined air-flow, hydrocarbon liquid stream and aqueous solution body phase stream.

40. method as claimed in claim 40, wherein by least one of burning, steam and reducing gas, removing is urged At least one of at least one of coal not being pyrolyzed, coke and carbonaceous material in agent.

41. method as claimed in claim 39, wherein the pyrolysis reactor is configured to HERB, fluid bed, moving bed or folder With one kind in thermopnore, and wherein, coal and catalyst are moved through the pyrolysis reactor.

42. method as claimed in claim 39, wherein the solid product stream is transferred out to solid from the pyrolysis reactor Body-solid separator, the solid-solid separator separation solid carbonaceous product of the modification and the dead catalyst.

43. method as claimed in claim 39, wherein the solid-solid separator includes clasfficiator, the clasfficiator according to One of granularity, quality or density, the solid carbonaceous product is separated from the dead catalyst.

44. method as claimed in claim 44, wherein at least one of size and density of the dead catalyst with it is described Modify at least one of the size and density of solid carbonaceous product difference, and point of wherein described solid-solid separator Level device is according at least one of size and density the separation solid carbonaceous product of the modification and the dead catalyst.

45. method as claimed in claim 34, in addition to：

Introduce before pyrolysis reactor, reduce the size of the particle of the solid carbonaceous material in pulverizer；With

The solid carbonaceous material is pre-processed in pretreatment unit, the pretreatment unit includes following at least one： Drier, it, which is configured to utilize, heats coal of the fluid stream drying from pulverizer；Washer, it is configured to washing and comes from pulverizer Coal；Deliming machine, it is configured to remove the ash content in coal, wherein the pretreatment unit is arranged on the pulverizer and the heat Between solution reactor.

46. method as claimed in claim 46, wherein the heating fluid stream is useless using the gas removing for carrying oxygen The hot flue gases produced in catalyst during at least one of any coal not being pyrolyzed, coke and carbonaceous material by regenerator.

47. method as claimed in claim 40, wherein the separator, which also includes sour gas, removes system, the sour gas Removal system separates following at least one from the gaseous product flow：Carry sulphur compound, carry nitrogen compound and Carbon dioxide.

48. method as claimed in claim 34, wherein introducing the catalyst of the pyrolysis reactor includes：First Point, it includes the regenerated catalyst from regenerator receiver, and Part II, and it includes unregenerated raw catelyst, and its Described in Part I regenerated catalyst have the relative temperature higher than the raw catelyst and coal so that the regeneration is urged Agent is heating medium to heat the coal being incorporated into the pyrolysis reactor.

49. method as claimed in claim 34, wherein the catalysis of the solid carbonaceous material is pyrolyzed at about 350 DEG C to about 850 Occur at a temperature of DEG C.

50. method as claimed in claim 50, wherein the solid carbonaceous material being introduced into the pyrolysis reactor has about 0.2 To the weight hourly space velocity of about 25kg/hr/kg catalyst.

51. method as claimed in claim 50, wherein the solid carbonaceous material has about 0.1 second to about in catalytic process The residence time of 1 minute.

52. method as claimed in claim 34, wherein the catalyst and solid carbonaceous material that are introduced into the pyrolysis reactor Weight ratio be about 0 to about 100.

53. method as claimed in claim 34, in addition to：

Sour gas is provided and removes system, it is configured as from the gaseous product from the pyrolysis reactor and from regenerator The capture of at least one of gas and separation CO₂, wherein the regenerator, which is configured to regeneration, comes from the pyrolysis reactor Dead catalyst；With

Obtain CO₂, its amount is more than the about 4wt% for drying ashless coal.

54. method as claimed in claim 34, in addition to：Obtain CO₂, its amount is more than volatility in initial solid carbonaceous material The about 10wt% of material.

55. method as claimed in claim 34, in addition to：Obtain CO₂, its amount is more than the about 4wt% for drying ashless coal.

56. method as claimed in claim 34, in addition to：

Regeneration of spent catalyst in a regenerator, the regenerator is configured to produce hot flue gases during regenerating；With

At least a portion of the hot flue gases is transferred to the pyrolysis reactor so that the pyrolysis reactor is fluidized.

57. method as claimed in claim 57, wherein CO, CO will be included₂, water, the gas of at least one of hydrogen and oxygen Fluid is introduced into the regenerator, to promote to remove the coal not being pyrolyzed, coke and the carbonaceous material in dead catalyst.

58. method as claimed in claim 58, in addition to：Collection includes CO₂The hot flue gases for carbon chelate or carry One kind that high recovery rate method is recovered the oil.

59. method as claimed in claim 58, in addition to：Make the hot flue gases by heat exchanger to produce for heating The heat of solid carbonaceous material in the pyrolysis reactor.

60. method as claimed in claim 57, wherein the regenerator is in addition to using air or replaces air, is also used Steam is to pass through hydrolysis and at least one of steam gasification removes coal, coke and carbonaceous material in dead catalyst.

61. method as claimed in claim 57, wherein the regenerator uses hydrogen or at least one its including hydrocarbon Its hydrogeneous chemicals, reduction removes coal, coke and carbonaceous material from dead catalyst.

62. method as claimed in claim 34, wherein gas is co-fed in the pyrolysis reactor, wherein the gas Including at least one light hydrocarbon compounds reclaimed from the gaseous product flow.

63. the method as described in claim 63, wherein at least one light hydrocarbon compounds are circulated back to the pyrolysis instead Answer device.

64. the method as described in claim 63, in addition to：BTEX is obtained, its amount is volatility in initial solid carbonaceous material The about 0.5wt% of material to about 80wt%.

65. method as claimed in claim 34, wherein biomass is co-fed in the pyrolysis reactor.

66. method as claimed in claim 34, wherein by least one in oil shale, coal derived liquid, Tar sands and oil Plant and be co-fed in the pyrolysis reactor.

67. method as claimed in claim 34, wherein at least one of moisture and natural gas are co-fed into the pyrolysis In reactor.

68. method as claimed in claim 34, wherein the pyrolysis reactor includes fixed catalyst so that the solid carbon Material is moved through reactor relative to catalyst, to produce the gaseous product flow and the solid product stream, the side Method also includes：

The gaseous product flow is transferred to separator to be condensed at least a portion gaseous product flow at least in part Product liquid and gaseous product；And

69. a kind of method that biomass by ore-sorting system is converted into modification solid product, methods described includes：

The biomass and catalyst are introduced into pyrolysis reactor to produce gaseous product flow and modification solid product stream, it is described Solid product stream includes dead catalyst and the modification solid product；

The separation modification coal product and the dead catalyst；

The dead catalyst of separation is transferred to regenerator, the regenerator removes at least one of any in the dead catalyst Coal, coke and the carbonaceous material not being pyrolyzed；With

The gaseous product flow is transferred to the separator for producing product liquid and gaseous product；

The weight for the ash content being wherein retained in the modification solid product is grey to be introduced into the biomass of the pyrolysis reactor At least the 60% of the weight divided.

70. the method as described in claim 1, wherein by weight, the amount of the phenol of generation is less than the amount of the toluene produced.

71. the method as described in claim 1, wherein by weight, the amount of the tar of generation is less than the amount of the light oil produced.