CN103842476A

CN103842476A - Gasification of a carbonaceous material

Info

Publication number: CN103842476A
Application number: CN201180070638.7A
Authority: CN
Inventors: 丹尼尔·斯蒂尔; 罗伯特·B·威尔逊; 瑞普达曼·马尔霍特拉; 布莱恩·阿代尔
Original assignee: SRI International Inc
Current assignee: SRI International Inc
Priority date: 2011-03-03
Filing date: 2011-03-03
Publication date: 2014-06-04
Also published as: EP2681292A4; WO2012118511A1; EP2681292A1

Abstract

The invention provides methods and apparatus ultimately for converting a carbonaceous material to liquid hydrocarbons suitable for use, for example, as transportation fuels. In a first step the carbonaceous material is converted to a syngas product, and in subsequent steps the syngas product is converted to the desired liquid hydrocarbons. In one embodiment, coal and methane are converted to syngas, and the syngas product is converted to hydrocarbons through a methanol intermediate. An example use for the methods and apparatus of the invention is in the preparation of aviation fuels.

Description

The gasification of carbonaceous material

Background technology

The coal reserves of the U.S. is enough to meet can predict expection transport fuel demand in the future.But, increase and potential safety hazard although be accompanied by the cost of dependence on import oil, also do not have a company to build up a United States plants coal production transport fuel.

Method of liquefying coal, also becomes the method for coal liquefaction (CTL), refers to the process that is changed into hydrocarbon liquids by coal.Hydrocarbon products is typically used as transport fuel, comprises diesel oil fuel and rocket engine fuel.Concerning some CTL methods, coal gasification is companion's process, plays important initial action by coal being converted to synthetic gas, and synthetic gas is H ₂mixture with CO.Under normal circumstances, liquidation of coal is to carry out in gasifying reactor, and coal is blown into system by gas or water slurry injects wherein.Gas is blown into system and conventionally uses air coal to be blown to the hot-zone of vapourizing furnace.Mixed gas product for example, is transformed into transport fuel according to many factors by the one in several method (using Fischer-Te Luopuxifa).

Current CTL method can be discharged a large amount of CO ₂, consume a large amount of water.With respect to for example JP-8(H/C～1.9 of transport fuel, the Average molecular formula of supposing for the sake of simplicity JP-8 is C ₁₁h ₂₁), hydrogen richness (H/C～0.4-0.8) deficiency of coal, this just means anyly wants the process that all coal the inside or most carbon is transformed into the carbon of JP-8 all to need an extra hydrogen source.In order to manufacture transport fuel, present CTL factory utilizes water-gas shift (WGS) method to consume water and CO in the device after gasification conventionally, produces H ₂and CO ₂produce extra hydrogen.When factory utilizes Fischer-Tropsch synthetic (FTS) by H ₂be transformed into CO with CO ₂during with hydro carbons, CO ₂discharge meeting further increase, this can produce a hydro carbons extensively distributing, and needs extra investment make the cut outside diesel range be transformed into diesel oil.

Current CTL technology is not low-carbon type.By a traditional indirect method FTS, coal is transformed into transport fuel, in coal, 2/3 carbon is with CO ₂form discharge (factory of a 100000BPD can produce the CO of 13,600 ten thousand pounds for one day ₂).Due to these expensive production equipments, current CTL factory needs the capital of every barrel/day about 80,000 U.S. dollars.

Still need a competitive price, and can produce little or there is no CO ₂discharge consumes the method that consumes on a small quantity or not water simultaneously, on a large scale coal is transformed into liquid (for example average daily more than 100,000 barrels).Preferred method is the output level that can utilize various carbonaceous inputs and can expand to easily any expectation.

Invention summary

Method disclosed by the invention is in order to solve one or more above-mentioned shortcomings in current CTL method, and meets one or more above-mentioned demands.

In some specific embodiments, a kind of method for a kind of carbonaceous material that liquefies is provided, comprising: (a) carbonaceous material and methane, water are mixed, in gasifying reactor, reaction generates H ₂and CO; (b) by the H producing in (a) ₂with CO and catalyst mix, in methanol reactor, react methanol; (c), by the alcohol and the catalyst mix that produce in (b), in reactor, reaction forms hydro carbons and water; (d) in circulation (c), generate water enter gasifying reactor and extra carbonaceous material and methyl alcohol reaction.

In some specific embodiments of aforesaid method, carbonaceous material is coal.

In some specific embodiments of aforesaid method, gasifying reactor is to provide heat energy with electric heater unit.

In some specific embodiments of aforesaid method, hydro carbons comprises propylene, wherein this method also further comprises separation of propylene and makes the combination in reactor of propylene and catalyzer form hydro carbons, and the molecular weight of this hydro carbons is within the scope of the change of molecular weight of transport fuel.

In some specific embodiments of aforesaid method, the molecular weight of hydro carbons is within the scope of the change of molecular weight of transport fuel.

In some specific embodiments of aforesaid method, the ratio of coal/methane is greatly between 1.75～20.

In some specific embodiments of aforesaid method, in gasifying reactor, have at least 75% methane and at least 75% coal to change into CO or CO ₂and water.

In some specific embodiments of aforesaid method, having the water in a part (a) at least is the form with steam, and steam wherein adds gasifier at the temperature higher than 500 DEG C.

In some specific embodiments of aforesaid method, the product H in (a) ₂with CO than ratio CO/H ₂between 0.35/1 to 2.5/1 scope.

In some specific embodiments of aforesaid method, what this process was used is (namely neither consume water and also do not produce water) of water neutrality.

In some specific embodiments of aforesaid method, the medial temperature of gasifying reactor inside at least will maintain more than 1200 DEG C.

In some specific embodiments of aforesaid method, oxide catalyst can further add in gasifying reactor, and its oxide catalyst reacts and produces heat with a part of methane or coal in gasifying reactor.

In some specific embodiments of aforesaid method, methane is to provide with the form of air-flow, and coal is just entrained in methanol stream.

In addition, in some specific embodiments, the invention provides a kind of method that carbonaceous material is transformed into transport fuel, the method comprises: at high temperature, the combination in gasifying reactor of carbonaceous material, methane and water produces CO and H ₂, CO/H ₂ratio is 0.35/1～2.5/1, one or more carbonaceous materials in reactor, and methane and water are the device heating of electricity consumption heat production, and product C O and the H in gasifying reactor wherein ₂there is adjustable ratio, to be used for preparing transport fuel.

In some specific embodiments, the product C O in above-mentioned reaction and H ₂in methanol reactor, reaction changes into methyl alcohol.In addition,, in some specific embodiments, be present in the CO in vapour stream ₂be transformed into methyl alcohol, so whole process is to consume CO ₂.These CO ₂can from the source of any appropriate, obtain, comprise the CO in environment ₂with the CO producing in above-mentioned other reaction process ₂(for example, the conversion from methyl alcohol and carbonaceous material to synthetic gas).

In addition, in some specific embodiments, the invention provides a gasifying reactor and make carbonaceous material change into synthetic gas, comprising: (a) reaction chamber; (b) to the device of reaction chamber supply carbonaceous material; (c) to reaction chamber supply methane device; (d) to the device of reaction chamber supply water; (e) heat energy that provides electric power to produce to carbonaceous material, methane, water or their mixture.

In some specific embodiments of aforesaid method and equipment, carbonaceous material is coal.

In some specific embodiments of aforesaid method and equipment, the volume of the reaction chamber of gasifying reactor has 1.0m at least ³.

In some specific embodiments of aforesaid method and equipment, the method also further comprises device from a kind of oxide catalyst to reaction chamber that supply, and the suitable oxidizing of methylene of this oxide catalyst also produces heat.

In some specific embodiments of aforesaid method and equipment, water is to supply with the form of the vapour stream of high temperature and high pressure.

In some specific embodiments of aforesaid method and equipment, provide the device of water to be configured to obtain water and the water from methyl alcohol the propylene reactor from producing propylene.

In addition, in some specific embodiments, the invention provides a kind of liquefaction system that carbonaceous material is changed into hydrocarbon fuel, this liquefaction system comprises: (a) reactor; (b) be used for receiving the refining plant of product in gasifying reactor; (c) be used for receiving the methanol reactor of product in refining plant; (d) be used for receiving the propylene reactor of product in methanol reactor; (e) be used for receiving the fuel reactor of the product in propylene reactor, wherein gasifying reactor has a reception carrying the entrance of methane gas stream of carbonaceous material and one secretly to receive the entrance of steam.

In some specific embodiments of aforesaid method and equipment, gasifying reactor is used for receiving electric energy, and comprises the device that electric energy conversion is become to heat energy.

Other aspects of the present invention, can below provide obvious description, comprise claim and embodiment.

Brief Description Of Drawings

In Fig. 1, provide a skeleton diagram for showing one embodiment of the invention.Coal/steam and methane enter gasifier, and change into synthetic gas output, go downstream and change into a kind of transport fuel.

In Fig. 2, prepare transport fuel according to the present invention from coal and methane, skeleton diagram provides a more detailed description to method.

In Fig. 3, according to the material balance that the invention provides a schematic diagram and equation and illustrate coal converting system, chart has also demonstrated for various types of coal reaction heat and O simultaneously ₂funtcional relationship between the ratio of/coal.Therefore, Fig. 3 a provides the input of coal converting system and the schematic diagram of output.Fig. 3 b provides a chart that shows mud coal, brown coal, bituminous coal and anthracitic reaction heat.Fig. 3 c provides an equation to show the input of coal converting system and the material balance of output in Fig. 3 a.

Detailed Description Of The Invention

Should be understood that: the object of term used herein is just used for describing specific embodiment, and do not mean that restriction.

The term " conventionally " of using in whole specification sheets refers to common practices of the present invention.This term shows that this class gives an example to disclosing of materials and methods of the present invention, not necessarily (unless otherwise indicated).Therefore, here term " conventionally " should be understood to " usually, but not necessarily ".Similarly, term " selectively ", for example, be selectively to exist at a kind of raw material and composition, shows that the present invention had both comprised the example that those have occurred raw material and composition, also comprised the example that those do not occur raw material and composition.

In some specific embodiments, the invention provides the method and apparatus of producing hydrocarbon liquid with carbonaceous material.In some specific embodiments, this hydrocarbon liquid is exactly transport fuel.

In some specific embodiments, the invention provides the method and apparatus of producing synthetic gas with carbonaceous material.In preferred embodiments, the CO/H of product synthetic gas ₂ratio makes synthetic gas be suitable for the production of methyl alcohol.

In some specific embodiments, the invention provides the method and apparatus that carrys out methanol with carbonaceous material via intermediate synthetic gas.

In some specific embodiments, the invention provides the method and apparatus of producing propylene with carbonaceous material.

In some specific embodiments, the invention provides the method and apparatus with carbonaceous material production and transport fuel.These methods are proceeded by intermediate synthetic gas, may further comprise intermediate methyl alcohol, also may further comprise intermediate propylene.In some specific embodiments, in method and apparatus of the present invention, use be all water neutrality or produce water.In some specific embodiments, the invention provides with a kind of carbonaceous material production and transport fuel but do not consume the method and apparatus of water.In some specific embodiments, the invention provides with a kind of carbonaceous material production and transport fuel process and equipment, in these methods, CO ₂be neutral or consume CO ₂.In these specific embodiments, all CO ₂all change in synthetic gas process and produce at carbonaceous material, and in methanol conversion subsequently, consume (for example, the CO in product synthetic gas ₂change into methyl alcohol in downstream).In some specific embodiments, the invention provides with a kind of carbonaceous material production and transport fuel process and equipment, in these methods, do not produce CO ₂.In some specific embodiments, the invention provides with a kind of carbonaceous material production and transport fuel process and equipment, in these methods, water and CO ₂be all neutral, or produce water and consume CO ₂.

In some specific embodiments, the invention provides the method and apparatus for operating coal gasification reactor, the heat energy that this coal gasification reactor produces with electricity is supplied with.

In some specific embodiments, the invention provides with a kind of carbonaceous material production and transport fuel process and equipment, in these methods, final process produces and seldom or not produces CO ₂.

In whole the application, coal is suitable for the method and apparatus in the present invention as a kind of carbonaceous material of example, but this use do not mean that restriction.Except as otherwise noted or from below apparent, present patent application specification sheets is not only applicable to coal, be to be also applicable to other carbonaceous materials, its embodiment below provides.

Equipment

Method and apparatus of the present invention comprises the reaction coal in gasifier.Gasifying reactor (at this also referred to as " vapourizing furnace ") comprises inlet mouth and air outlet, discharges to allow reactant to enter with product.Gasifying reactor also comprises the reactor that allows reactant reaction.Gasifying reactor can further comprise other elements, for example lagging material, sensor, pollution control measures etc.

In some embodiments, vapourizing furnace comprises: a reaction chamber; To the device of reaction chamber supply coal; To the device of reaction chamber supply methyl alcohol; To the method for reaction chamber supply water; With the device to coal, methyl alcohol, water or their mixture supply heat energy.For example, the device of supplying above-mentioned any one composition can comprise one or more pipelines and be connected to the source of the material of supply.This source can be an original raw material storehouse, or can be also the lower procedure of one of reactant as output (output is collected and is recycled to vapourizing furnace).Here, term " reactant " refers to one or more materials that can be fed to vapourizing furnace (such as coal, methane, water etc.).

Vapourizing furnace further comprises that the device of one or more extracts reaction product from vapourizing furnace conventionally.Conventionally, these devices comprise one or more relief outlets that communicate with pipeline.In some embodiments, the discharge line of vapourizing furnace and relief outlet comprise the device (such as strainer, washer etc.) that purifies output gas flow.

In some embodiments, the space that the reaction chamber of gasifying reactor has, is greater than 0.5m ³, or be greater than 1.0m ³, or be greater than 5.0m ³, or be greater than 10m ³, or be greater than 20m ³.In some embodiments, the size of the reaction chamber of gasifying reactor will be applicable to commercial-scale coal gasification.Refer to that with " commercial size " reactor is enough large, to hold the turnout of the gasification product that is suitable for commercially producing.Therefore, this reaction chamber is larger than laboratory scale reaction chamber, and laboratory scale reaction chamber is less than 1.0m conventionally ³.

In some embodiments, in the input of gasifying reactor, comprise a solid phase and a non-solid phase.Solid phase comprises coal, can further comprise a selectable catalyzer.Under normal circumstances, solid phase is to exist with particulate form as described below.Non-solid phase comprises liquid and/or gas, and in some embodiments, non-solid phase is for carrying solid phase or making solid phase fluidised.In some embodiments, non-solid phase is gaseous state completely.Under normal circumstances, non-solid phase comprises a hydrogen source and an oxygenant, below can introduce in detail.Although solid phase and non-solid phase can separately be supplied in certain embodiments, they had just mixed conventionally before entering gasifying reactor.

In some embodiments of the invention, the input of vapourizing furnace be through one or more pipeline supplies to vapourizing furnace, this pipeline is connected with one or more entrances of vapourizing furnace.In some embodiments, each pipeline is only connected with an entrance, and in other embodiment, pipeline may be applicable to for shunting, makes so one or more compositions enter vapourizing furnace through more than one entrance.

Just as mentioned in this article, in some embodiments, solid phase comprises coal.Conventionally coal is supplied to vapourizing furnace with the form of particle.These particles are to prepare in any suitable method with the coal of exploitation, as pulverizing conventional in Coal dressing and grinding equipment.In some embodiments, the mean diameter that joins the coal particle in vapourizing furnace at about 10 μ m between about 100mm, or at 0.1mm between about 5cm, or at 1mm between 5cm, or at 1cm between 4cm.For example, mean diameter can be greater than 10 μ m, or is greater than 0.1mm, or is greater than 1mm, or is greater than 10mm, or is greater than 1.5cm, or is greater than 2cm, or is greater than 3cm, or is greater than 5cm.Again for example, on average directly may be less than 10cm, or be less than 5cm, or be less than 4cm, or be less than 3cm, or be less than 2cm, or be less than 1cm, or be less than 0.5cm, or be less than 1mm, or be less than 0.1mm.Term " mean diameter " refers to the widest size of particle.When coal is while existing with the form of the particle of polymerization, " mean diameter " refers to the widest polymeric size.

Conventionally, solid phase is entrained in non-solid phase, that is to say that solid phase enters and passes through gas reactor in gas and/or liquid stream.But the present invention is also applicable to the embodiment that those solid phases are liquefied by non-solid phase (that is to say gas/liquid flow enough carry out separately solid phase particles, therefore, they are equivalent to a kind of fluid, but seldom or almost do not have solid phase stream to pass through reactor).The present invention equally also remains on the embodiment of fixed bed (that is to say that solid phase keeps motionless in reaction chamber) to solid phase.In stream operated, solid phase is supplied in vapourizing furnace together with non-solid phase being, but in fluidisation and fixed bed operation, solid phase and non-solid phase may be to be also fed to respectively in reactor.

In some specific embodiments, solid phase is supplied to vapourizing furnace with the about 15wt% of mass content to the scope internal load of about 50wt%, or is approximately 25wt% to about 40wt%, and these per-cents are with respect to non-Solid-phase Assay.For example, solid phase load may be greater than approximately 15%, or is greater than approximately 20%, or is greater than approximately 25%, or is greater than approximately 30%, or is greater than approximately 35%, or is greater than approximately 40%, or is greater than approximately 45%.In addition, it is about 50% that solid phase load can be less than, or be less than approximately 45%, or be less than approximately 40%, or be less than approximately 35%, or be less than approximately 30%, or be less than approximately 25%, or be less than approximately 20%.

As above-mentioned, the non-solid phase of putting in vapourizing furnace generally includes a hydrogen source and an oxygenant.In some specific embodiments, hydrogen source is hydro carbons.The example of suitable hydrocarbon polymer is all lower hydrocarbon, and especially those are the hydrocarbon of gaseous state, for example methane, ethane, propane, butane etc. under the reaction conditions of vapourizing furnace.In preferred embodiments, hydrogen source is methane.In addition, in preferred embodiments, hydrogen source is not H ₂.For example, hydrogen source is not water gas shift reaction (namely CO+H ₂o → CO ₂+ H ₂) in H ₂.Therefore, in preferred embodiments, H ₂be not from hydrogen source, to obtain individually and join in reactant.But, because initial hydrocarbon uses as hydrogen source, in hydrocarbon, contain a small amount of H ₂also be understandable.For example, the methane obtaining from natural-gas field may contain H ₂, this brings adverse influence can't to method of the present invention.In some specific embodiments, although there will be in gasifying reactor, water (as oxygenant, sees below), water is not hydrogen source.Therefore,, in total reaction, the hydrogen atom in water does not change into H ₂.

The non-solid phase of putting in vapourizing furnace also comprises a kind of oxygenant.In some specific embodiments, oxygenant is water, particularly with the form of steam.In preferred embodiments, oxygenant is not O ₂or contain a large amount of O ₂gas mixture (for example air).But, being understandable that, water contains a small amount of O as oxygenant ₂.Conventionally so little amount need to not separated from the current of input, and this is very little or almost do not have to the method disadvantageous effect in the present invention.

In some specific embodiments, in the input of gasifying reactor, further comprise a kind of catalyzer.For example, can in inlet flow, add a kind of oxide catalyst to make methyl alcohol or carbonaceous material partial oxidation.This oxidation can be vapourizing furnace heat supply.In some specific embodiments, this oxidation is also used for making methyl alcohol or coal reactant thoroughly to change into more CO and CO ₂.For example, suitable catalyzer comprises powerful catalyst, as in chemical process industry, mixed metal oxide and and transition-metal catalyst be used for selective oxidation (for example ammonia oxidation).In addition, the strong oxide catalyst that is applied to emission control industry also can use, and comprises picture two effect catalyzer and other this class catalyzer.Other catalyzer comprise alkali metal compound, for example alkali metal hydroxide.Oxide catalyst can be bought from commercial source (for example the Claes Johanson horse base of a fruit or BASF) conventionally, but also can select inner synthetic.The specific example of catalyzer comprises vanadium phosphorus oxide (VPO), γ-FeOOH, and Bi ₂moO ₆.

Coal at high temperature reacts in vapourizing furnace with a hydrogen source and an oxygenant.In some specific embodiments, hydrogen source is methane, and oxygenant is steam.In addition,, in some specific embodiments, unique oxygenant that enters vapourizing furnace is steam (namely not adding other oxygenants, for example oxygen, air and so on etc.).At this, will the embodiment of these and other be described in more detail.In the time operating under the pattern of vapourizing furnace in entrained flow, coal particle enters vapourizing furnace from the bottom of vapourizing furnace conventionally, is then transported to top by moving phase.Those will appreciate that those skilled in the art, and in a preferred working method, coal particle can react in up flowing by reaction chamber.Adjust the speed of coal particle reaction and the size of coal particle, make coal particle complete reaction (and therefore disappearing) before reaching the top of vapourizing furnace or outlet.In such a equipment, the inlet flow of vapourizing furnace includes the non-solid phase (for example gas phase) of the slurry of coal particle, and the output stream of vapourizing furnace only contains gas.In the time that vapourizing furnace operates under the pattern of thermopnore or fixed bed, coal particle adds vapourizing furnace conventionally near the bottom of reactor; May there is to add separately (namely by an independent port) in this addition manner from the interpolation of non-solid phase.

In some specific embodiments, the mixture of the gas of gasifying reactor output, comprises CO and H ₂, it is commonly referred to as synthetic gas.By the product further describing hereinafter in vapourizing furnace.

In some specific embodiments, method and apparatus of the present invention further comprises a purification phase.Purification phase communicates with vapourizing furnace in fluid and/or gas.The gas stream of exporting in purification phase receiver gases reactor, these outputs are mixtures of gas or gas and solid particulate and/or liquid completely.

The synthetic gas of vapourizing furnace output may comprise one or more impurity in starting point concentration.The example of this impurity comprises slag, mercury, ammonia, sulphur, sulfocompound (for example H ₂s and COS) and ash content.According to kind and the source of the coal using, also may there is other impurity.In the time that the amount of the impurity occurring can have a negative impact to downstream process, the gasifier of vapourizing furnace output may be sent in a purification devices.

Cleansing phase generally includes washer, catalyzer, sorbent material or other purifying methods, or their combination.This purifying method is normally known in the art, can certainly adopt purification process present or that later develop.

In some specific embodiments, purification phase comprises a reaction chamber, and a kind of or more purifying method (for example previously mentioned method) can be carried out on vapourizing furnace output stream therein.In other embodiment, purification phase does not comprise independent reaction chamber, but comprises one or the purification process of more connecting with pipeline, so that the output stream in vapourizing furnace is transported in next step processing or storing device from vapourizing furnace.

The gaseous product stream of normally a kind of impurity that contains one or more ultimate densities of the output in purification phase, the ultimate density of this kind of or plurality of impurities, compared with initial concentration, significantly reduces.For example, in identical embodiment, the output of purification phase is a kind of synthetic gas, comprise one or more impurity (example is mercury, ashes etc. as previously mentioned), the concentration of these impurity is less than 10 times, or be less than 20 times, or be less than 50 times, or be less than 100 times, or be greater than 100 times and be less than the concentration (the namely input of purification phase) of this impurity in vapourizing furnace output.In the time that purification phase responds chamber, the impurity level of purification phase output stream can be surveyed in the outlet of reaction chamber, and this is understandable.Or in the time that purification phase does not have reactor, the input ingress in the next stage that the impurity level of purification phase output stream can be in this process is measured.

In some specific embodiments, method and apparatus of the present invention also further comprises methanol reactor.Methanol reactor is the output stream (in the time having purification phase) for receiving purification phase or is directly used for receiving the output stream (in the time there is no purification phase) in vapourizing furnace.Therefore no matter, be directly or by purification phase, methanol reactor is all connected with gasifying reactor with liquid/gaseous state.In some specific embodiments, methanol reactor is all connected with gasifying reactor with liquid/gaseous state, make like this liquid state/gaseous product (for example synthetic gas) in gasifying reactor pass in methanol reactor, or the liquid state/gaseous product (for example isolated methane) in methanol reactor can be passed in gasifying reactor.In some specific embodiments, two individually conduit connecting methanol reactor and gasifying reactor, make like this liquid/gas can transmitted in both directions.

Conventionally, the fluid that enters methanol reactor comprises synthetic gas, and synthetic gas changes into methyl alcohol in methanol reactor.In the art, the whole bag of tricks that synthetic gas is changed into methyl alcohol is known, and these methods can be with the present invention in conjunction with application.According to the method difference of selecting, the physical property of methanol reactor (for example type of size, quantity and entrance etc.) and operational condition (for example temperature and pressure etc.) also can be different, and this is understandable.For example, a kind ofly used a kind of catalyzer (for example mixture of a kind of copper, zinc oxide and aluminum oxide), high temperature (for example 250 DEG C), and high pressure (for example 5-10MPa) by the method that synthetic gas is prepared methyl alcohol.In some embodiment and industrial environment, vapourizing furnace operates under sufficiently high air pressure, makes not need extra pressure to meet the requirement that methanol reactor operation is pressed.The productive rate of methyl alcohol is conditional on thermodynamics, so before remaining synthetic gas is recycled to methanol reactor, product must move on in a high-pressure separator.

In the output of methanol reactor, comprise methyl alcohol.Methyl alcohol is hunted down and transfers in the next step in process, and this step is a propylene reactor in some specific embodiments, and will be described in more detail below.Methyl alcohol also can be hunted down and in other processes, use with being intended to.

In some specific embodiments, in the output of methanol reactor, also comprise residual methane.In some specific embodiments, the residual methane in methanol reactor follower is separated from main product logistics, and can be circulated back in vapourizing furnace.Therefore, in these embodiments, methanol reactor comprises a kind of method that methyl alcohol in reactor output and methane are separated, and has the connection of a liquid/gas that methane can be transmitted to get back to vapourizing furnace.In some embodiments, this circulation passage may comprise a compressor and/or well heater and make to increase before entering vapourizing furnace pressure and/or the temperature of methane.Recycle methane stream can add in vapourizing furnace with initial methane blended, also can by one individually entrance join in vapourizing furnace.

In the output of methanol reactor, may further include hydrogen, and one or more supplementary components of different amounts, for example carbon monoxide, carbonic acid gas, water/steam, rare gas element etc.These compositions can be removed by required ordinary method from output stream.In some specific embodiments, hydrogen and methane can be opened from methanol reactor output stream and separating methanol.Hydrogen and methane cycle are got back in vapourizing furnace.In some specific embodiments, only have methane to separate and be circulated back in vapourizing furnace from the output stream of methanol reactor.

In some specific embodiments, the inlet flow of methanol reactor (the namely output stream of vapourizing furnace or purification phase) also comprises carbonic acid gas in addition.In these embodiments, also can further contain water in the output of methanol reactor, and if need, output water can be hunted down and be circulated back in vapourizing furnace.

In preferred embodiments, the syngas product of vapourizing furnace has the ratio that is suitable for directly changing into methyl alcohol.That is to say, need not add extra hydrogen, otherwise will before product synthetic gas enters methanol reactor, adjust CO/H in product synthetic gas ₂ratio.Therefore,, in some specific embodiments, do not need the H producing by water-gas shift reaction ₂carry out methanol.Just as previously described, CO/H in product synthetic gas ₂ratio be adjustable, for example, adjust CO/H in product synthetic gas by adjusting the ratio of methane and coal in raw material ₂ratio.

In some specific embodiments, method and apparatus of the present invention further comprises propylene reactor.Propylene reactor is for receiving output stream in methanol reactor.Therefore, propylene reactor is connected with methanol reactor with liquid/gaseous state.

Under normal circumstances, the fluid that enters propylene reactor comprises methyl alcohol, also can further comprise water.Propylene reactor becomes propylene methanol conversion.The known a variety of methods that become propylene from methanol conversion now, these methods can be used in conjunction with the present invention.The preparing propylene from methanol of Lu Qi limited-liability company exploitation (

) technology is exactly example.According to the method difference of selecting, the physical property of propylene reactor (for example type of size, quantity and entrance etc.) also can be different, and this is understandable.

In some specific embodiments, then methyl alcohol self condensation is eliminated water and is generated propylene.In the output stream of propylene reactor, comprise flow of propylene.General method can produce by product, and by product comprises low-carbon alkanes, ethene, butylene and a small amount of fuel gas.The output stream of propylene reactor also comprises water.After reactor, need to there is a water distilling apparatus to remove the water in hydro carbons.In some embodiments of method of the present invention, the water of removal is back in slurrying device and vapourizing furnace.

In some specific embodiments, the output of propylene reactor further comprises water.It normally exists with the form of steam.In these embodiments, water vapour can be separated and be circulated back in gasifying reactor from output stream.

In some specific embodiments, method and apparatus of the present invention also further comprises hydrocarbon reaction device (being also known as in this article " diesel oil reactor ").In these embodiments, hydrocarbon reaction device is output stream for receiving propylene reactor.In these embodiments, hydrocarbon reaction device is connected with propylene reactor with liquid/gaseous state.Under normal circumstances, the fluid that enters hydrocarbon reaction device comprises propylene, and propylene is changed into heavier hydro carbons by hydrocarbon reaction device.Particularly, in some specific embodiments, hydrocarbon reaction device has changed into propylene the hydrocarbon mixture that is suitable as transport fuel, such as JP-8, kerosene, motor spirit etc.Can in hydrocarbon reaction device, add extra composition if needed.The known a variety of methods that propylene changed into higher hydrocarbons now, these methods can be used jointly with the present invention.In some specific embodiments, the output of hydrocarbon reaction device is JP-8.In some specific embodiments, the output of hydrocarbon reaction device is suitable as automobile-used produce oil.Under normal circumstances, hydrocarbon product will experience the material (for example JP-8 or other transport fuels) that a last rectifying obtains wanting.In the method for the invention, the remaining hydrocarbon of purifying can be circulated back to vapourizing furnace and resolve into synthetic gas, also can be used as fuel and sells.

Or the output of methanol reactor can directly be added in hydrocarbon reaction device and (be also in other words, do not have propylene reactor).In these reaction embodiments, methyl alcohol is directly changed into hydrocarbon fuel by hydrocarbon reaction device.It is known that methanol conversion is become to the method for hydrocarbon fuel, and these methods can be used as required.For example, utilize zeolite catalysis methanol conversion to become hydrocarbon fuel, for example Fuel Petroleum.

Material and input

The input of using in process of the present invention and material comprise a kind of carbonaceous material, hydrogen source, a kind of oxygenant, the energy existing taking heat as form and a kind of selectable catalyzer.Each of these compositions all will provide more detailed description hereinafter.

Method of the present invention comprises the conversion of carbonaceous material to hydrocarbon fuel.Suitable carbonaceous material comprises coal (brown coal, sub-bituminous coal, bituminous coal and hard coal), oil and residual oil (for example, refining resistates), resinous shale, coke, mud coal, pitch or their combination.In some preferred embodiments, carbonaceous material is grizzle, for example brown coal or sub-bituminous coal.As previously mentioned, in the application process of whole patent, coal is that the carbonaceous material of being used as example uses, and is only used to be convenient to describe, and does not mean that restriction but use like this.

In some embodiments of the present invention, the composition of product synthetic gas is controlled by add hydrogen source in vapourizing furnace.Because the source of many carbonaceous materials is to be all rich in carbon but to lack hydrogen, hydrogen source can increase the H of output synthetic gas ₂the ratio of/CO.In some specific embodiments, hydrogen source is hydro carbons.In some specific embodiments, hydrogen source is methane.These methane can obtain from any suitable source.For example, these can be that the methane of coal gas layer (that is to say, can from the settling of coal, extract methane), or methane can be from natural-gas field, or methane can (for example obtain from the solid refuse of landfill or animal cultivation field, from the methane of ruminating animal plant, such as ox belch methane).As described herein, methane can be also reclaim the methane of downstream production and loop back vapourizing furnace.The methane in other sources and the source of above-mentioned arbitrary combination can be used.As previously mentioned, as a part for method and apparatus of the present invention, methanol reactor can change into methyl alcohol synthetic gas, and the output of methanol reactor comprises the mixed gas of methyl alcohol and methane conventionally.The methane here may come with separating methanol, and therefore, in some specific embodiments, the methyl alcohol of supplying with gasification also comprises from the output stream of methanol reactor and to reclaim and the methane of recycle.

In some specific embodiments, the hydrogen source in process of the present invention is another kind of hydrocarbon (such as ethane, propane etc.), and they are rich in hydrogen with respect to coal.In some specific embodiments, hydrogen source is the mixture of multiple compounds, for example Sweet natural gas or biogas.In some specific embodiments, hydrogen source is the comprehensive of one or more sources of mentioning before, for example methane and biogas.

Correspondingly.In some specific embodiments, method disclosed herein is that application methane is used as hydrogen source coal is changed into transport fuel.Many factors makes methane have advantage, comprising: (i) methane has high H/C ratio; (ii) methane provides more energy than other traditional hydrogen sources such as water to process; (iii) methane in coal bed methane and other sources can be utilized; (iv) if coal bed methane is hunted down and utilizes (instead of being discharged in atmosphere) in coal mining process, be positive to the entire effect of environment.Utilize methane as hydrogen source, whole process will have following material balance, and total process is to produce water, instead of consumes water:

The method is flexibly, because according to the difference of the hydrogen richness of coal (X), methane feed speed may be changeable.

In some specific embodiments, hydrogen is added in vapourizing furnace as hydrogen source.Hydrogen may be unique hydrogen source, and in situation, it can strengthen other hydrogen sources but more, as methane.Hydrogen can obtain from any suitable source, for example a water-gas shift (WGS) device.In some specific embodiments, comprise hydrogen (except methane) from the recirculation flow of methanol reactor, it is added in gasifier.In some specific embodiments, the cubic capacity being fed in the gas of vapourizing furnace is hydrogen up to 50%, for example, although quantity still less is also fine (up to 40%, up to 30%, 20% or 10%).

Because carbonaceous material and hydrogen source all lack enough oxygen conventionally, under suitable ratio, change into CO and H ₂so, in vapourizing furnace, provide an oxygenant.

In some specific embodiments, being supplied to the oxygenant in gasifying reactor is water.Such as, although bag adds the situation (oxide catalyst, oxygen etc.) that contains extra or alternative oxygenant in process of the present invention, in some preferred embodiments, water is the unique oxygenant adding in vapourizing furnace.In preferred embodiments, water is to exist with the form of flow of steam at high temperature.For example, add the temperature of steam of gasifying reactor to higher than 400 DEG C, or higher than 500 DEG C, or higher than 600 DEG C, or higher than 700 DEG C, or higher than 800 DEG C, or higher than 900 DEG C, or higher than 1000 DEG C, or higher than 1100 DEG C, or higher than 1200 DEG C, or higher than 1300 DEG C, or higher than 1400 DEG C.Or steam can be characterized as being high pressure.For example, pressure is (or larger) between 200psia and 1500psia, or between 400psia and 1000psia, be all suitable.For example, the pressure of steam may be greater than 200psia, or is greater than 400psia, or is greater than 600psia, or is greater than 800psia, or is greater than 1000psia, or is greater than 1500psia.Again for example, pressure may be less than 1500psia, or is less than 1000psia, or is less than 500psia.

Oxygenant water can obtain from any suitable source.In preferred embodiments, add all or part of water (namely re-using) reclaiming that comprises of water of gasifying reactor to from propylene reactor.Therefore, the output of propylene reactor comprises water and hydro carbons, and it is separated into each composition, and the water producing is got back in gasifying reactor.Generally speaking, in some specific embodiments, the system that is applicable to coal to change into transport fuel in the present invention is water neutrality substantially, this means all reactions are all taken into account, and water is unclean consumption or increase almost.In some specific embodiments, system of the present invention is water positive number, and this just means all takes all reactions into account, and water is clean generation.But, even the whole process of the present invention be water neutrality or water positive number, due to all factors, all likely one or more reaction process needs water outside supplementary quota (for example, due to incomplete recovery dehydration, low effective circulation utilization, leak etc.).Because water is recycled to vaporizer from downstream process, so may need to add water in initial start-up vapourizing furnace.But, under normal circumstances, in the time that the whole process of the product from gasification to transport fuel is all taken into account, the consumption of water is less than about 10mol%(and that is to say the coal of every conversion 1mol with respect to the consumption of coal, the water consuming is less than 0.1mol), or be less than about 5mol%, or be less than about 1mol%.In addition, in some specific embodiments, this process is that water is positive number, and aquatic products amount is greater than about 1mol%(and that is to say the coal of every conversion 1mol with respect to the consumption of coal, just produces the water of 0.01mol), or be greater than about 2mol%, or be greater than about 5mol%, or be greater than about 10mol%, or be greater than about 20mol%, or be greater than about 25mol%, or be greater than about 40mol%.

In some specific embodiments, in order to promote methane and/or burning of coal in vapourizing furnace, need to use oxygenant, for example, in the time that vapourizing furnace needs extra heat (referring to below).Being used for the oxygenant of combustion of methane and/or coal may be selected from steam, oxygen, catalytic oxidant and their combination.Use catalytic oxidant should be can regenerate with reusable.

In some specific embodiments, heat energy is provided for vapourizing furnace and/or is added to the one or more of reactants in vapourizing furnace.In some specific embodiments, heat energy is that the method for generating heat by electricity provides, and its example comprises screen well heater, plasma welding torch etc.Although think that in some specific embodiments renewable energy source is preferred, electric heating method of the present invention can be that the electricity that any suitable method produces provides.The example of renewable energy source comprises wind energy, sun power, Geothermal energy, water power and morning and evening tides.Although be not preferred, other energy also may be used to provide electric energy to equipment of the present invention as coal or oil as biomass combustion or traditional non-renewable energy.In addition, other sources of their combination and electric energy all may be used.

As an alternative or supplement, heat energy also may be provided in vapourizing furnace by the oxidation of carbonaceous material.For example, in vapourizing furnace, biogas or methane are used for producing heat by the energy of oxidation of oxide catalyst.

In some specific embodiments, heat energy is to add one or more reactants in vapourizing furnace to for heating.These reactants can be heated in the time of the entrance through vapourizing furnace, or before arriving entrance, or after entering gasification reactor chamber, or their arbitrary combination.For example, in some specific embodiments, the entrance of vapourizing furnace can configure a screen well heater, plasma welding torch, and one or more of like this reactants are supplied to vapourizing furnace after by well heater.As an alternative or supplement, the device generating heat by electricity carrys out heating and gasifying reaction chamber.Resistor is installed on the whole or top that the example of this embodiment is included in reaction chamber wall.

Electric energy also can be used for heating the water being provided in vapourizing furnace.In some specific embodiments, water is to be provided in vapourizing furnace with the form of steam, and electric heating device increases the temperature of steam as previously mentioned.In some specific embodiments, the water that adds vapourizing furnace to is to exist with the form of liquid, and electric heating device increases the temperature (and in some specific embodiments, water can change into steam) of water.

In some specific embodiments, electric energy is used for heating the methane being fed in vapourizing furnace.Methane can be heated before or after mixing with coal particle.In some specific embodiments, electric energy is used for heating the coal particle being fed in vapourizing furnace.Coal can be with methane blended before heated, may be also heated after mixing, and can be to enter before gasification reactor chamber or afterwards.In some specific embodiments, electric energy is used for heating the methane and the coal particle that are fed in vapourizing furnace.

In some specific embodiments, it is desirable or necessary carrying out heat production by the oxidation of methane or coal.Before such oxidation can occur in and enter vapourizing furnace or in vapourizing furnace.In the time that oxidation occurs in vapourizing furnace, can further need in vapourizing furnace, add extra oxygenant.The oxygenant that is applicable to these methods was being described before.In some specific embodiments, any CO that in vapourizing furnace, methane and/or burning of coal produce ₂all be retained (instead of separated and discharge), and can in downstream process, be consumed as described herein, so do not produce CO in the whole process of liquidation of coal ₂.

Output and product

The main output of gasifying reactor is product synthetic gas, and in downstream process, product synthetic gas is converted to by product, for example transport fuel.In this conversion process, just as described herein, various intermediate products (for example methyl alcohol, propylene, hydro carbons) are prepared.These intermediates can also be considered to product and/or the starting material of other processes of not mentioning here.

In some specific embodiments, as mentioning at this paper elsewhere, the output of gasifying reactor is to comprise CO and H ₂mixed gas, be conventionally also called synthetic gas.The accurate composition of the synthetic gas of output depends on the reactant that is supplied to vapourizing furnace, is understandable so can control by suitably changing the input thing of vapourizing furnace the composition of synthetic gas.For example, can increase H in synthetic gas with respect to the concentration of coal by increasing methane ₂with respect to the amount of CO.Also can increase H in synthetic gas by the source that changes coal ₂with respect to the amount of CO, namely use a kind of grizzle that is rich in hydrogen.Conventionally, method and apparatus of the present invention does not need to add the synthesis gas composition of hydrogen to obtain wanting in vapourizing furnace.In addition, conventionally, method and apparatus of the present invention does not need to add the synthesis gas composition (although water may with the form of steam exist and play oxygenant, just as described in detail herein) of water to obtain wanting to becoming a mandarin of vapourizing furnace.

Usually, according to the present invention, the CO/H that the output synthetic gas of vapourizing furnace comprises ₂mol ratio between 0.35/1～2.5/1.In some specific embodiments, CO/H ₂ratio be greater than 0.35/1, or be greater than 0.5/1, or be greater than 1/1, or be greater than 1.5/1, or be greater than 1.8/1.In some specific embodiments, CO/H ₂ratio be less than 2.5/1, or be less than 2.3/1, or be less than 2/1, or be less than 1.5/1, or be less than 1/1.In the embodiment of hydrocarbon fuel produced according to the invention, the CO/H that the output synthetic gas of vapourizing furnace comprises conventionally according to the present invention ₂mol ratio between 1.5/1～2.5/1, or between 1.7/1～2.3/1, or between 1.9/1～2.1/1.For example, the output synthetic gas of vapourizing furnace may comprise CO/H ₂ratio be approximately 1.9/1, or be approximately 2.0/1, or be approximately 2.1/1.In some preferred embodiments, the CO/H that output synthetic gas comprises ₂ratio be adapted at forming in methanol reactor methyl alcohol.As previously mentioned, can input the ratio of thing and/or the one-tenth of raw material by change and assign to change the content of synthetic gas (for example, use relatively many methane, or relatively rudimentary coal etc.).This is useful especially, for example, because the different target product (, aviation fuel, automobile fuel etc.) in downstream can need the synthetic gas of heterogeneity to realize the conversion of maximum efficiency.

Except CO and H ₂outside (with previously described various impurity), the synthetic gas of vapourizing furnace output may also comprise one or more of compositions, such as CO ₂and water.Water and CO ₂conventionally be transported in methanol reactor by device, they are consumed there or recirculation is got back in vapourizing furnace.

In some specific embodiments, according to the present invention, in the output synthetic gas of vapourizing furnace, do not basically contain nitrogen." do not basically contain " and refer to that the content of nitrogen is less than 5mol% with respect to CO, or be less than 3mol%, or be less than 1mol%, or be less than 0.5mol%.In the time that the per-cent of all output gases with vapourizing furnace is weighed, the content of nitrogen is preferably less than 10mol%, or is less than 5mol%, or is less than 3mol%, or is less than 1mol%.

In some specific embodiments, according to the present invention, in the output synthetic gas of vapourizing furnace, do not basically contain oxygen.Again, " not basically containing " refers to that the content of oxygen is less than 5mol% with respect to CO, or is less than 3mol%, or is less than 1mol%, or is less than 0.5mol%.In the time that the per-cent of all output gases with vapourizing furnace is weighed, the content of oxygen is preferably less than 10mol%, or is less than 5mol%, or is less than 3mol%, or is less than 1mol%.

The output of methanol reactor and propylene reactor had been described above.As mentioned before, these products can be used as the intermediate of production and transport fuel, as generating the intermediate that produces other products, or directly regard the finished product without further conversion.Utilize as far as possible equipment of the present invention to recycle callable component.The product in a stage was separated and gets back in the previously suitable stage.For example, as mentioned before, the product methyl alcohol of methanol reactor contains remaining methane conventionally, and process of the present invention comprises separation of methanol from remaining methane, and circulates remaining methane in gasifying reactor, and it is reacted with extra carbonaceous material.

According to method disclosed herein, product synthetic gas may change into transport fuel by methyl alcohol intermediate.Preferred transport fuel comprises rocket engine fuel (for example, JP-8, Jet-A, JP-5, kerosene etc.), automobile fuel (diesel oil, gasoline etc.), marine fuel etc.Here the molecular formula of said rocket engine fuel JP-8 is C ₁₁h ₂₁, this is an approximation or Average molecular formula.In the present invention, being used for the method for production and transport fuel may further be revised and/or be prepared together with the additive of wanting.

Operation and operational condition

In some specific embodiments, method and apparatus of the present invention provides the gasification that is blown into vapourizing furnace for coal at methane, and being blown into steam in vapourizing furnace at methane is to use as main oxygenant." methane is blown into " refers to that coal particle is transported to vapourizing furnace by methane gas stream.In preferred embodiments, vapourizing furnace is not that air is blown into and neither be blown into by oxygen.

The inlet flow of the vapourizing furnace of mentioning here refers to the methane stream that is entrained with a large amount of coal particles.Under normal circumstances, to add inlet flow be before inlet flow enters gasification reactor chamber to steam.Or, inlet flow in the time entering gasification reactor chamber can with vapor mixing.

In some specific embodiments, according in vapourizing furnace operation of the present invention, in the reaction chamber of vapourizing furnace, comprise and be less than 5mol%, or be less than 3mol%, or be less than the nitrogen of 1mol%, and/or be less than 5mol%, or be less than 3mol%, or be less than the oxygen of 1mol%.In some specific embodiments, in the operating process of vapourizing furnace, reaction chamber is substantially devoid of nitrogen, oxygen, or they both.

As described herein, in order to make coal change into synthetic gas completely, vapourizing furnace has added a hydrogen source.In addition,, in the time that hydrogen source is a kind of hydrocarbon, a part of carbon in hydrocarbon changes into CO in vapourizing furnace.In some specific embodiments, almost do not have the hydrogen source of carbonaceous material and hydrocarbonaceous to burn in vapourizing furnace.For example, in some specific embodiments, when methane is during as hydrogen source, the methane that enters gasifier there is no in vapourizing furnace and burns.In some specific embodiments, the methane burning in gasification reactor chamber is less than 25%, or is less than 20%, or is less than 15%, or is less than 10%, or is less than 5%, or is less than 3%, or is less than 1%.Similarly, in some specific embodiments, the coal that enters gasifier there is no in vapourizing furnace and burns.In some specific embodiments, the coal burning in gasification reactor chamber is less than 25%, or is less than 20%, or is less than 15%, or is less than 10%, or is less than 5%, or is less than 3%, or is less than 1%.In some specific embodiments, observe charcoal particulate catalytic methane conversion and become synthetic gas, therefore, the degree of conversion depends on the density of coal in reaction zone.

In some specific embodiments, the component of the input thing of vapourizing furnace is heated before entering reaction chamber.For example, preferably utilize described herein electrically heated come two of heating steam, methane or they.

In some specific embodiments, in operating process, the internal temperature of vapourizing furnace should remain on more than 500 DEG C, or more than 600 DEG C, or more than 700 DEG C, or more than 800 DEG C, or more than 900 DEG C, or more than 1000 DEG C, or more than 1100 DEG C, or more than 1200 DEG C, or more than 1300 DEG C, or more than 1400 DEG C, or more than 1500 DEG C.The meaning of term " internal temperature of vapourizing furnace " is in gasification reactor chamber, to measure the medial temperature of the various gaseous constituents in temperature place.Conventionally, in the bottom of vapourizing furnace or approach place that reactant enters vapourizing furnace and measure the internal temperature of vapourizing furnace.In some specific embodiments, the temperature needing can be measured and maintain to the inlet flow temperature of vapourizing furnace, instead of monitor the temperature of vapourizing furnace inside.For example, in some specific embodiments, the temperature of steam and/or methane stream maintains more than 500 DEG C individually, or more than 600 DEG C, or more than 700 DEG C, or more than 800 DEG C, or more than 900 DEG C, or more than 1000 DEG C, or more than 1100 DEG C, or more than 1200 DEG C, or more than 1300 DEG C, or more than 1400 DEG C, or more than 1500 DEG C.Its temperature is measured after can entering reaction chamber before air-flow enters gasification reactor chamber or just.As described above, the amount that is applied to the electric heat production of native system by adjustment obtains and keeps this temperature is understandable.

In some specific embodiments, when vapourizing furnace operation, the pressure of vapourizing furnace inside is greater than 1atm.For example, pressure when vapourizing furnace operation in vapourizing furnace is at 1atm～100atm(or larger) between, just as the pressure about the steam for vapourizing furnace of discussing before.Term " pressure of vapourizing furnace inside " refers to the average pressure of measuring the various gaseous constituents in pressure place in gasification reactor chamber.

Total reaction heat can calculate according to the calorific value of coal and the reaction heat information of various reactant and product of report.Calculation result is as shown in table 1.

The methane that table 1 consumes and water and JP-8(are according to C ₁₁h ₂₁) relative content and the reaction heat of inhomogeneity moulded coal

?	Mud coal	Brown coal	Bituminous coal	Hard coal
					Coal (CH _xO _y)	1	1	1	1
CH ₄	0.781	0.751	0.652	0.735
					H ₂O	0.439	0.230	0.085	0.027
C ₁₁H ₂₁	0.162	0.159	0.150	0.158
					ΔH _rxn	-60.0	-39.2	-27.8	-13.0

In all cases, the Δ H of whole simplification process _rxnnegative value (heat release).This shows, in perfect hot integrated situation, whole process is heat release; That is to say and do not need extra energy.For example, but although whole process is heat release, vapourizing furnace still needs extra energy to make at high temperature to occur the transformationreation (generation of synthetic gas) of heat absorption.Can in all sorts of ways and add extra energy to system, the heat energy that preferably uses herein electricity consumption in greater detail to produce.

Be blown in some embodiments of coal gasification stove with methane and steam according to the present invention, coal gasification and steam methane recombining reaction carry out simultaneously.According to described herein, in coal gasifier, steam methane recombining reaction makes hydrocarbon for example, at the lower hydrogen that produces of High Temperature High Pressure (, 800+ DEG C and 20+bar).In addition, the transformation efficiency of the higher methane of temperature is higher.

Just as previously mentioned, it is a thermo-negative reaction that coal changes into synthetic gas.Provide energy to have multiple choices to vapourizing furnace, wherein a kind of (electric energy) discussed before.Conventionally options comprises: (A) methane incomplete combustion in air forms CO and H ₂; (B) methane perfect combustion in air forms CO ₂and H ₂o; (C) biomass are at combustion synthesis in air; (D) pass through CO ₂neutral energy provides electric power; (E) provide electric power by source powered by conventional energy.The options (D) of before discussing is preference.But need only suitable or need, any other option can be used for providing energy to vapourizing furnace.For example, in some specific embodiments, be such as provided to energy in vapourizing furnace and be, for example, by the combination results of the renewable energy resources (water power, hydro-thermal energy, sun power, wind energy etc.) and non-regeneration energy (, oil, coal etc.).The Pros and Cons of these options will be discussed in detail below.

The power generation that option A utilizes, in the aerial incomplete combustion of methane, is used to form CO and H ₂, CO and H ₂be used for methanol.This reaction is heat release, and it provides essential energy to maintain the High Operating Temperature of vapourizing furnace.Make required vapourizing furnace be blown into vapourizing furnace than oxygen for the use of every barrel of JP-8 air large.In addition, the scavenging process of synthetic gas and methanol reactor are essential greater, to process a large amount of nitrogen gas stream.After methanol reactor, separation of nitrogen and unreacted methane.Nitrogen discharge is in atmosphere, and methane cycle is got back to vapourizing furnace.Option B utilizes the perfect combustion of a small amount of methane stream that required energy is provided.This can produce the discharge of a small amount of CO2, but this strong exothermal reaction (802kJ/mol CH ₄) required methane compares few 25 times than option A, based on the identical energy discharging.Option C utilizes the perfect combustion of biomass that required energy is provided.As option B, also there is CO ₂discharge, but this situation it is generally acknowledged, most CO ₂all pass through the growth recirculation of newborn substance.Preferred biomass source can change into energy most effectively, and environment is produced to minimum impact.Option D utilizes electric energy to regard the source of energy, does not produce CO ₂.Alternative sun power, Geothermal energy, water power energy, tidal energy and wind energy of comprising.Electric power energy heating and gasifying stove, for example, utilizes resistive heating.Each selects to need methane or other selective energy of different amounts.The estimation of these input thing quantity is summarized as follows table.

The estimated value of the required various chargings of the various heating and gasifying stove of table 2 method

The factor that needs of device operation of the present invention are considered is exactly cigarette ash, and this is a subject matter that affects commercialization methane reforming feasibility.According to the present invention, under the service temperature of vapourizing furnace, methane decomposition becomes cigarette ash.In other words, methyl alcohol has produced carbon granule in the thermolysis in reaction zone, this further catalysis reaction, cause reactor plugs rapidly.This cigarette ash is also by setting up a steam at guiding methane before entering reactor and/or hydrogen stream is avoided (that is to say, methane first mixed with steam or hydrogen before heat).In addition, high density of hydrogen is proved to be the formation that can suppress cigarette ash.

In some specific embodiments, carbonaceous material is coal, and hydrogen source is methane, method of the present invention provide in vapourizing furnace methane conversion higher than 75%, and coal changes into CO and/or CO ₂transformation efficiency higher than 75%.For example, methane can reach the transformation efficiency that is greater than 80%, or is greater than 85% transformation efficiency, is greater than 90% transformation efficiency, is greater than 95% transformation efficiency.Again for example, coal can reach the transformation efficiency that is greater than 80%, or is greater than 85% transformation efficiency, is greater than 90% transformation efficiency, is greater than 95% transformation efficiency.

Skeleton diagram 1 is the explanation of a specific embodiment of the present invention.In figure, what be supplied to vapourizing furnace has coal, water and methane.The output of vapourizing furnace is fed into cleansing phase at (comprising synthetic gas and impurity), and the impurity such as slag, ammonium, sulphur and mercury are removed at cleansing phase.The synthetic gas product introduction methanol reactor purifying, the output of methanol reactor comprises methyl alcohol and methane.Methane is separated, and is fed into compressor before being added to vapourizing furnace.Methyl alcohol is sent in propylene reactor, propylene reactor output water and propylene.The water of output is cycled back in vapourizing furnace, and the propylene of output is fed in diesel oil reactor, and changes into rocket engine fuel (JP-8).

Fig. 2 has shown the more detailed skeleton diagram of the process of of the present invention.

As previously mentioned, in the method for the invention, oxygen can be used as oxygenant.Fig. 3 has provided such embodiment, wherein (a) and (c) provide respectively a skeleton diagram and a reaction equation to show input and output.Input during the course coal, methane and oxygen, output water and JP-8.In (b), with the O of inhomogeneity moulded coal ₂the function of the ratio of/coal shows reaction heat.Work as O ₂ratio one timing of/coal, rudimentary coal reaction can discharge more heat.

Method and apparatus according to the invention provides the method for a new production synthetic gas, and the method is better than the method for former production synthetic gas.And the synthetic gas of generation is applicable to for production hydrocarbon fuel very much.Here some that mention change into normally known (for example, synthetic gas is to the conversion of methyl alcohol, and methyl alcohol is to the conversion of propylene, and propylene is to the conversion of hydrocarbon fuel) of process of transport fuel about synthetic gas.The present invention for example, by utilizing byproduct and selecting most suitable process known process is used uniquely and (become one, select the method for transformation of methyl alcohol to propylene, its by product is water, and recycle water is water neutrality thereby make method of the present invention).The operational condition of every one-phase of the whole process of the present invention is all optimized, to guarantee that each stage works together.This makes the whole process of formulating that the output of the maximum feature of environmental protection, energy utilization rate and desired product can be provided.

Therefore, in some specific embodiments, by one indirectly route coal is changed into the transport fuel such as JP-8, wherein methyl alcohol is intermediate.Be a kind of cleaning procedure from methanol production hydrocarbon, this process produces water byproduct, and the steam that water is recycled to again a coal and the common charging of methane is blown in vapourizing furnace.This method is useful, because: (1), owing to having avoided the cost of air separation equipment, steam is blown into the less fund input of vapourizing furnace requirement; (2) the common charging of methane makes to contain appropriate hydrogen in product synthetic gas, does not therefore need water-gas to transform (WGS) unit, and this has further reduced cost, CO ₂generation and the consumption of water.Owing to not utilizing coal to produce hydrogen by WGS, the method has also increased the output of coal to carbon in JP-8 conversion process, thereby has reduced the size of gasification unit.In addition, the method is also that carbon is efficient because almost in coal all carbon all changed into the part of fuel Products, and in product nearly 60% carbon from coal (basic condition).

In addition, the benefit of method disclosed herein comprises: the operating restraint of having improved vapourizing furnace operation in having reduced cost; For transport fuel provides clean synthetic gas as JP-8 synthetic (needing advanced gas purification technique avoid poisoning of catalyst and avoid introducing unacceptable environmental pollutant in the finished product before it); Eliminated air gas separation unit (AUS), or a large amount of minimizings its size; By eliminate or Separation and Recovery synthetic gas in a large amount of nitrogen can reduce the size (coal being blown in vapourizing furnace to avoid dilution with methane) of downstream unit.And methane can obtain by capstan, the needs of compression unstripped gas have even been eliminated in this restriction.In addition the elimination of extra oxygen, (or reducing in a large number) makes to have reduced in large quantities CO ₂formation, the CO of generation ₂finally need in downstream process, be converted.Methyl alcohol described herein for example, comprises to the advantage (comparing with FT synthetic route) of the route of diesel engine: strengthened the control of product, do not produced by product CO ₂.In fact, utilize methyl alcohol route can make all CO that produce in vapourizing furnace ₂in methanol reactor, consume methanol and water.

Material, method and apparatus described in the invention are all exemplary, but in their explanation, there is no need to limit with language.For example, in more above-described embodiments, in the output of methanol reactor, contain methane, the methyl alcohol in the output of methanol reactor handlebar reactor described herein and the device of methane separation.But it is also understandable completing separation in propylene reactor importation.Based on the description of this specification sheets, the such or such variation of the present invention is obviously apparent for a person skilled in the art.

All patents mentioned in this article, patent specification and publication entirety are incorporated herein by reference.But, patent, patent description say or publication in the clear and definite definition that comprises be introduced into as a reference, patent, patent specification or publication that these clear and definite definition should be understood to be applicable to merge, instead of the remainder of the application's text, particularly in the application's claim.

Should be understood that, although the present invention is described in conjunction with its preferred specific embodiment, description above and ensuing example are all not mean that the restriction to scope of the present invention for explanation.It will be understood by those of skill in the art that various changes and equal substituting do not exceed in scope of the present invention, in addition, in the scope allowing in the present invention other aspect, advantage and amendment will be apparent to those skilled in the art.

Embodiment

Embodiment 1

The optimization that carbon transforms

It is the principal element of determining vapourizing furnace size that carbon transforms, and vapourizing furnace is the most expensive project in coal liquefaction (CTL) process.The preferred method of CTL can reduce cost production and transport fuel effectively, and the transformation efficiency of the coal of for example, supplying with while producing JP-8 should reach 90%.

Experimental data shows that the transformation efficiency of coal increases along with the increase of temperature.At the relatively gentle temperature of 1200 DEG C, the transformation efficiency of coal approaches 80%, and in the time of 1500 DEG C, the transformation efficiency of coal is up to 93%.In addition, we have studied H in the time of 1300 DEG C ₂: the potential restraining effect of the mixture that CO is 3:1, and observed all coal transformation efficiencys higher than 85% situation, clearly prove that restraining effect is negligible.And in the time that the ratio of steam and carbon is 3:1, in the time of 1400 DEG C, transformation efficiency just can be higher than 90%.

In the experiment of carrying out, also studied CO or the H of high density at 1200 DEG C ₂restraining effect in steam gasification, the conclusion drawing is the H in high density ₂existence under there is faint restraining effect, but restraining effect not obvious (10% transformation efficiency) and is easy to by operating and overcome at higher temperature.

In a word: according in the entrained flow vapourizing furnace of short residence time(SRT) of the present invention, can realize high carbon and transform.

Embodiment 2

Methane under high temperature blows the operation of vapourizing furnace

At 1200 DEG C, utilize the hydrogen of different concns can complete gasification experiment, and the amount of observing the amount of hydrogen and the cigarette ash of formation is negative correlation.Work as H ₂concentration while being 30%, cigarette ash can reduce to acceptable level, this level draws through our a series of experiment.In the time of hydrogen dense, can play slight restraining effect to the conversion of coal, but these inhibition degree can overcome by the operation at higher temperature.

In addition, in series of experiments, the loading capacity of coal is increased to 9.1% from 3.1%.If the loading capacity of coal will reach 30%, need a larger coal feed system.

In a word, these experimental results show that gas blows coal injection system and can at high temperature stably move.

Embodiment 3

The impact that coal/methane loads

Analog calculation shows, when equilibrium state, at 1400 DEG C, operates, and transformation efficiency should reach 90%.In experiment, when service temperature is 1400 DEG C, H ₂the ratio that is 30% steam and coal is 2.0 o'clock, and on-catalytic steam methane transformation efficiency has reached 40%.In carbon catalyzed reaction, speed of reaction is transported to the control of the speed of carbon catalytic surface at least partly, and can expect if the loading of coal is higher, and the transformation efficiency of methane is just higher.But the steam reforming of coal not only produces CO under reaction conditions, also produces a large amount of methane, effectively reduce the clean transformation efficiency of methane.In the test of coal loading the highest (9.1%), the clean impact of observing is the generation of methane, instead of consumes.

Other two factors that affect methane conversion are determined to be: (i) the ratio of steam and carbon; (ii) the amount of hydrogen.Increase steam: the ratio of carbon is just equivalent to the amount of oxygenant in increase system, and this is conducive to the conversion of methane.For stoping methane to be polluted the amount that increases hydrogen by cigarette ash, can increase coal methanogenic amount, and suppress the regenerating of methane of steam catalysis simultaneously.

In a word, the front reactor that the steam methane that the design of reactor of the present invention is considered forms again.In some cases, this makes methane and coal in single reactor assembly have high transformation efficiency simultaneously.The output of front reactor is the input of the vaporized main reactor of coal.

Embodiment 4

Reactor design

In laboratory scale test, gas feed system brings gas preheating is a little provided by being looped around the indirect heating of intake ducting.The well heater of three 144W is for gas transport pipeline, one individually power supply be used for heating steam generating portion and make it to reach 290 DEG C.But thermosteresis surface-area very high and hot transmission is very little.

Gas pre-heating stage comprises the thing that two need complete: (1) is being no more than the material temperature further enthalpy of increase system of restriction in the situation that; (2) it allows to utilize theoretical cycle steam to test hot integrated concept.

An important consideration is exactly the conductor using in heating zone; For useful, it must be conductive, is chemically inert to the gas of supply, at the temperature of needs, is heat-staple, and air-flow is had to minimum resistance.In order to meet all conditions, a kind of select be with diameter be 1/32 "-1/16 " and quartzy pearl.In order to prevent from carrying secretly the system of entering, can a series of screen be installed at arbitrary end of reaction bed.

Embodiment 5

System optimization

The optimizing of reaction conditions and the improvement of process may be a kind of repetitive processes.Under the equilibrium conditions of modeling software estimation, obtain the moiety of specifying.If need to find the maximum value of the vapourizing furnace residence time under pressure, temperature, component productive rate and full range, use the condition of batch reactor to confirm.Laboratory vapourizing furnace provides the initial dynamics data of a small amount of relevant residence time and potential initial yield result.The result of laboratory vapourizing furnace is the input data of modeling software, is used for predicting the residence time and the product output of the vapourizing furnace under full range.Also having a benefit is that software can be simulated various vapourizing furnaces, comprises entrained flow, transport, fixed bed and fluidized-bed gasification furnace.The result of software model can be in process model.

Vapourizing furnace experiment.Radiation coal flow reactor system is used for Study on Coal and cracking, burning and the steam gasification (see Figure 12) of other solid fuels in the time that pressure is 40atm.In this system, be under the typical concentration of vapourizing furnace equipment under full range and pressure by steam injection to (gas volume can reach 25% or more when the 40atm) in gas-entrained stream.The major advantage of this entrained flow equipment is that all products can be hunted down and analyze, thereby makes to reach approximate material balance in effective tolerance.Revise this equipment and be used for studying method of the present invention, if methane and steam combination are by as gas-entrained use.

Claims

1. a method for liquefaction of carbonaceous material, comprises the steps:

(a) carbonaceous material, methane and water react and generate H in gasifying reactor ₂and CO;

(b) in methanol reactor, the H producing in step (a) ₂with CO methanol under the effect of catalyzer;

(c) (methyl alcohol producing in step b) and catalyzer react and generate hydrocarbon and water in reactor;

(d) water forming in step (c) is recycled in gasifying reactor and other carbonaceous material and methane reaction.

2. according to the method for claim 1, it is characterized in that, described carbonaceous material is coal.

3. according to the method for claim 1, it is characterized in that, described gasifying reactor is that the mode of electricity consumption heat production is to heat energy is provided.

4. according to the method for claim 1, it is characterized in that, described hydro carbons comprises propylene, described method also further comprise separation of propylene and make propylene and catalyzer in reactor in conjunction with forming hydro carbons, described hydro carbons is within the scope of the change of molecular weight of transport fuel.

5. according to the method for claim 1, it is characterized in that, the molecular weight of hydro carbons is all within the scope of the change of molecular weight of transport fuel.

6. according to the method for claim 2, it is characterized in that, the ratio of coal/methane is greatly between 1.75～20.

7. according to the method for claim 2, it is characterized in that, in gasifying reactor, having at least 75% methane and at least 75% coal to change into CO or CO ₂.

8. according to the method for claim 1, it is characterized in that, having the water in a part (a) at least is at the temperature higher than 500 DEG C, to add gasifier with the form of steam.

9. according to the method for claim 1, it is characterized in that the product H in step (a) ₂with the ratio of CO be CO/H ₂between 0.35/1～2.5/1 scope.

10. according to the method for claim 1, it is characterized in that, what this process was used is water neutrality.

11. according to the method for claim 1, it is characterized in that, the medial temperature in gasifying reactor at least will maintain more than 1200 DEG C.

12. according to the method for claim 1, it is characterized in that, further in gasifying reactor, adds oxide catalyst, makes it in gasifying reactor, to react and produce heat with a part of methane or coal.

13. according to the method for claim 2, it is characterized in that, methane is to provide with the form of air-flow, and coal is just entrained in methanol stream.

14. according to the method for claim 1, it is characterized in that, whole process is CO ₂neutral, or whole process consumes CO ₂.

15. according to the method for claim 1, it is characterized in that the CO generating in step (a) ₂all be converted into the methyl alcohol in step (b).

16. 1 kinds are transformed into carbonaceous material the method for transport fuel, comprise: at high temperature, the combination in gasifying reactor of carbonaceous material, methane and water produces CO and H ₂, CO/H ₂ratio is between 0.35/1～2.5/1, carbonaceous material in reactor, and methane and water are the method heating of electricity consumption heat production, the product C O in gasifying reactor and H ₂there is adjustable ratio, to be used for preparing transport fuel.

17. 1 kinds change into carbonaceous material the gasifying reactor of synthetic gas, comprising:

(a) reaction chamber;

(b) to the device of reaction chamber supply carbonaceous material;

(c) to the device of reaction chamber supply methane;

(d) to the device of reaction chamber supply water;

(e) device of heat energy that provides electric power to produce to carbonaceous material, methane, water or their mixture.

18. according to the gasifying reactor of claim 17, it is characterized in that, described carbonaceous material is coal.

19. according to the gasifying reactor of claim 17, it is characterized in that, the volume of reaction chamber has 1.0m at least ³.

20. according to the gasifying reactor of claim 17, it is characterized in that, also further supplies containing oriented reaction chamber the device that a kind of applicable oxide catalyst carrys out oxidizing of methylene and produces heat.

21. according to the gasifying reactor of claim 17, it is characterized in that, water is the device with the form supply of the vapour stream of high temperature and high pressure.

22. according to the gasifying reactor of claim 17, it is characterized in that, provides the method for water to be configured to from the water in a propylene reactor that produces propylene with from the water of methyl alcohol.

23. 1 kinds change into carbonaceous material the liquefaction system of hydrocarbon fuel, and described liquefaction system comprises:

(a) gasifying reactor;

(b) refining plant configuring for the product receiving in gasifying reactor;

(c) methanol reactor configuring for receiving the product of refining plant;

(d) the propylene reactor configuring for the product receiving in methanol reactor; With

(e) fuel reactor configuring for the product receiving in propylene reactor,

Wherein said gasifying reactor has the entrance that receives the methane gas stream of carrying carbonaceous material secretly and the entrance that receives steam.

24. according to the liquefaction system of claim 23, and wherein said gasifying reactor is furnished with reception electric energy, and comprises the device that electric energy conversion is become to heat energy.