CN101707864A - Integrated processes for generating carbon monoxide for carbon nanomaterial production - Google Patents

Integrated processes for generating carbon monoxide for carbon nanomaterial production Download PDF

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Publication number
CN101707864A
CN101707864A CN200880019143A CN200880019143A CN101707864A CN 101707864 A CN101707864 A CN 101707864A CN 200880019143 A CN200880019143 A CN 200880019143A CN 200880019143 A CN200880019143 A CN 200880019143A CN 101707864 A CN101707864 A CN 101707864A
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China
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flow
carbon dioxide
air
carbon
hydrogen
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K·麦克凯格
W·蒋
R·克里什纳穆希
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Linde LLC
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Linde Inc
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Priority claimed from US11/974,953 external-priority patent/US20080305029A1/en
Priority claimed from US11/974,952 external-priority patent/US20080305028A1/en
Priority claimed from US11/974,954 external-priority patent/US20080305030A1/en
Application filed by Linde Inc filed Critical Linde Inc
Publication of CN101707864A publication Critical patent/CN101707864A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Abstract

The integrated processes of the dry reforming or partial oxidation upstream of the carbon nanotube-producing reactor are described allowing the carbon monoxide to be produced on an as-needed basis, negating the need to transport carbon monoxide to the production site or store large quantities of carbon monoxide on-site. The apparatuses allowing to carry out such integrated processes are also provided. Carbon dioxide emissions may be eliminated from the carbon nanotube production process. This may be achieved by recycling the carbon dioxide byproduct and mixing it with the feed to the partial oxidation process.

Description

Generation is used for the integrated processes of the carbon monoxide of carbon nanomaterial production
CROSS-REFERENCE TO RELATED APPLICATIONS
The priority that No. the 60/933598th, the U.S. Patent application sequence that the U.S. Patent application sequence that the application requires to submit on June 6th, 2007 according to 35U.S.C. § 119 (e) U.S. Patent application sequence was submitted on June 6th, No. 60/933599 1 was submitted on June 6th, No. 60/933600 1, the full content of these applications is by with reference to being incorporated into this.
Technical field
This disclosure relates generally to make the method for carbon nanomaterial, and more particularly, the partial oxidation that relates to according to common charging produces carbon monoxide and uses the carbon monoxide that so produces to make the integrated processes of carbon nanomaterial.
Background of invention
The various carbon nanomaterials that comprise Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and carbon nano-fiber can use suitable commercial method to react by carbon monoxide production by Boudart.This method can comprise carbon monoxide and the catalyst precarsor gas that keeps below the catalyst precursors decompose temperature are supplied to the mixed zone.Available another kind of method comprises by the metal catalytic particle is contacted under the temperature that is enough to the catalytic production CNT with the carbonaceous gas of effective dose produces CNT.The CNT that obtains comprises the Single Walled Carbon Nanotube of major part, and available metal catalytic particle comprises group VIII metal or VIb family metal.Also can use other to utilize the method for Boudart reaction to produce carbon nanomaterial.
Said method is characterised in that and has some shortcoming and defect.For example, the deposit of high toxicity and inflammability carbon monoxide feed gas and operation produce many safety problems.In addition, these methods cause a large amount of greenhouse gas emissions usually, for example produce carbon nanomaterial per ton and will discharge about four tons of carbon dioxide.
Avoid or alleviate the influence of above-mentioned deficiency, and, need to use better method to produce carbon nanomaterial in order to improve the purpose of group method efficient.
Summary of the invention
In some embodiments, provide the method that obtains carbon nanomaterial.A kind of method comprises that compounding hydrocarbon material flow, carbon dioxide stream and oxygen flow are to form the compounding logistics, in conversion reactor, make hydro carbons in the compounding logistics form the conversion air-flow of the hydro carbons of the oxygen comprise hydrogen, carbon monoxide, carbon dioxide, non-reacted parts and non-reacted parts through conversion process, make reformed gas stream remove the oxygen that transforms non-reacted parts in the air-flow then, produce the deoxidation air-flow that comprises hydrogen, carbon monoxide, carbon dioxide and non-reacted parts hydro carbons through deoxidation.Can in deoxidation equipment, remove the step of non-reacted parts oxygen.
Can for example use single-stage or multistage membrane separator then or utilize transformation (pressure-swing) adsorption process, from deoxidation flow separation hydrogen, form main flow and byproduct stream, wherein, main flow comprises carbon monoxide, carbon dioxide and non-reacted parts hydro carbons, and byproduct stream comprises hydrogen.
Main flow can be directed at the carbon nanomaterial production unit then, preparation carbon nanomaterial, and carbon dioxide, but carbon monoxide recirculation and be directed at conversion reactor.Perhaps, can make main flow remove most of carbon dioxide and non-reacted parts hydro carbons, form the carbon monoxide stream of substantially pure, be directed at the carbon nanomaterial production unit then through further separating.This main flow purifying will help preparing the carbon nanomaterial of some kind, especially Single Walled Carbon Nanotube.
Also can utilize the additive method that separates the deoxidation air-flow, include, but are not limited to deep cooling separating method. in one embodiment, the method for separating this logistics will depend primarily on the carbon monoxide purity of production scale and carbon nanomaterial preparation method requirement.
In one embodiment, the invention provides the equipment of producing carbon nanomaterial, this equipment comprises the conversion reactor that the mixture of hydro carbons, carbon dioxide and oxygen is changed into the conversion air-flow that comprises hydrogen, carbon monoxide, carbon dioxide, non-reacted parts oxygen and non-reacted parts hydro carbons, and the deacidification unit that is communicated with the conversion reactor fluid.Can use the non-reacted parts oxygen in this deacidification unit removal reformed gas, preparation comprises the deoxidation air-flow of hydrogen, carbon monoxide, carbon dioxide and non-reacted parts hydro carbons.
This equipment can further comprise single-stage or the multistage membrane separator that is communicated with the deacidification unit fluid, and described separator is used for from deoxidation flow separation hydrogen, and forms the main flow that comprises carbon monoxide, carbon dioxide and non-reacted parts hydro carbons.
In one embodiment, replace membrane separator, this equipment can further comprise with the deacidification unit fluid and being communicated with, and is used for from deoxidation flow separation hydrogen, and forms the psa unit or the cryogenic separation unit of the main flow that comprises carbon monoxide, carbon dioxide and non-reacted parts hydro carbons.
This equipment can further comprise the carbon nanomaterial production unit that is communicated with the membrane separator fluid, wherein, this carbon nanomaterial production unit prepares carbon nanomaterial and carbon dioxide stream, this equipment also comprise be communicated with carbon nanomaterial production unit fluid, be used for the recirculation carbon monoxide, be used for the device of carbon dioxide conductance to conversion reactor.
Brief Description Of Drawings
Fig. 1 is the equipment schematic diagram according to the preparation carbon nanomaterial of one embodiment of the present invention.
Fig. 2 is the equipment schematic diagram according to the preparation carbon nanomaterial of another embodiment of the present invention.
Fig. 3 is the equipment schematic diagram of the preparation carbon nanomaterial of another embodiment according to the present invention.
Describe in detail
Hereinafter use to give a definition and abridge, unless other description is arranged:
Term " SWCN " is defined as hollow, substantially for columniform pipe, it is by substantially chemical pure carbon manufacturing, diameter is about the 0.4-4 nanometer.
That term " multi-walled carbon nano-tubes " is defined as is arranged in co-axial alignment, close space length, substantially be columniform pipe, and it is by substantially chemical pure carbon manufacturing, and overall diameter is about the 3-100 nanometer.
Term " CNT " expression SWCN and multi-walled carbon nano-tubes.
Term " carbon nano-fiber " is defined as the structure of substantially cylindrical, and its diameter is about the 1-100 nanometer, by with stacked arrangement mode close space length, truncated cone, substantially chemical pure carbon manufacturing.
Term " carbon nanomaterial " is defined as the structure that is made of substantially chemical pure carbon, and the size on its at least one direction is less than 100 nanometers. Carbon nanomaterial comprises: fullerene, SWCN, multi-walled carbon nano-tubes, carbon nanohorn, carbon nano-fiber, individual layer and Multi-layer graphite platelet.
Term " hydro carbons " is defined as a kind of organic compound, and its molecule only is made of carbon and hydrogen.
Term " catalyst " is defined as the speed that changes chemical reaction or productive rate but this does not consume in this process or the indeclinable material of chemical property substantially.
Term " noble metal " expression is different with most of base metals, can highly corrosion-resistant or oxidation and not diffluent metal.Example includes, but are not limited to platinum, palladium, gold, silver, tantalum etc.
Term " base metal " expression is any base metal of oxidation easily.Example includes, but are not limited to nickel, molybdenum, tungsten, cobalt etc.
Term " Boudart reaction " expression following chemical reaction (I):
2CO→C+CO 2 (I)
Term " reformation " expression is by using heat, pressure, making molecular chemistry reorganization (reformation) form the chemical process of different products in the presence of catalyst usually.
The process of a kind of renormalization compound of term " dry weight is whole " expression for example uses the hydro carbons of reforming methane with carbon dioxide and so on to prepare synthesis gas.
The process of a kind of renormalization compound of term " steam reformation " expression for example makes the hydro carbons of water reforming methane and so on prepare synthesis gas.
Term " synthesis gas " is the abbreviation of term " forming gas ", and expression comprises the carbon monoxide of variable quantity and the admixture of gas of hydrogen.
Term " partial oxidation " is the whole type of a kind of dry weight, expression is injected in the combustion chamber by hydro carbons and the oxygen with preheating, hydro carbons and mode less than the oxygen generation oxidation reaction of the required stoichiometry of completing combustion in the combustion chamber, the gas that will comprise hydro carbons changes into the process of the mixture of hydrogen, carbon monoxide and other trace components (for example carbon dioxide, water and other hydro carbons).
Term " catalyzing part oxidation " is illustrated in structural noble metal of suitable carrier (for example platinum, palladium or rhodium) or base metal (for example nickel) and so on catalyst and has the partial oxidation that carries out down.
Term " ice chest " expression comprise heat exchanger and distillation column and so on cryogenic technology equipment, the mixture that comprises carbon monoxide and hydrogen at least can be separated into the device of the independent flow of carbon monoxide and hydrogen.If there is low molecular weight hydrocarbons in the mixture, then also can use this device to separate.
The thin barrier layer of some materials that exists in term " film " the expression permission fluid mixture to pass through greater than the speed of other materials.
Adsorbent at least a material in the fluid-absorbent mixture and discharge a kind of separation process of the adsorbed material of a part under lower pressure at least according to qualifications under elevated pressure is used in term " transformation absorption " expression.
Describe in detail
To reform or partial oxidation process is combined in the upstream of carbon nanomaterial-production reactor, make it possible to prepare as required carbon monoxide, and do not need carbon monoxide is transported to the production place or lays in a large amount of carbon monoxide on the spot.In this integrated processes, can be near the CO2 emission of fully eliminating in the made of carbon nanotubes process.This can mix with the charging of delivering to partial oxidation process by the recycled carbon dioxide accessory substance and with it realizes.This integrated processes may be more suitable for variation scale or distributed production plant, comprises that more a spot of in other cases hydrogen accessory substance makes its purifying and compression sub-economic those factories that become.
Can obtain synthesis gas by the dry weight adjusting method of hydro carbons such as methane.Can use various hydro carbons, it is as known in the art using the dry weight adjusting method of these hydro carbons.A kind of possible dry weight is put in order path (that is partial oxidation) shown in following reaction (II):
2CH 4+CO 2+O 2→3CO+3H 2+H 2O (II)
More particularly, partial oxidation process carries out under temperature (for example about 700-1400 ℃) that raises and elevated pressure (for example the highest about 150 atmospheric pressure) usually shown in the reaction (II).This process can be carried out in the presence of catalyst.Can from various available options as known in the art, select appropriate catalyst.For example, useful catalyst can comprise noble metal (for example platinum, palladium or rhodium) or transition base metal (for example nickel).Metal can embed in the porous carrier (for example aluminium oxide or zeolite).
Can use various conditions to react the partial oxidation process shown in (II). can be to the optimum condition of partial oxidation, be that temperature, pressure, catalyst, hydro carbons/oxygen ratio are selected. for example can use following condition, temperature is greater than about 1000 ℃, for example about 1300 ℃, pressure is up to 150 atmospheric pressure.
Synthesis gas by preparation shown in the reaction scheme (II) can comprise hydrogen, carbon monoxide, remaining unreacted carbon dioxide and remaining unreacted oxygen.Can further process this mixture, by removing the carbon monoxide that every other component (that is, hydrogen, unreacted carbon dioxide and unreacted oxygen) obtains purifying.Purge process can be as described below.
Can thereby the synthesis gas stream deoxidation be removed non-reacted parts oxygen from synthetic air by using partial oxidation process.Can from many known options, select to carry out required appropriate process of deoxidation process and equipment.The result is to form the deoxidation air-flow that comprises hydrogen, carbon monoxide and carbon dioxide.
Can be from deoxidation flow separation hydrogen, formation comprises the main flow of carbon monoxide, carbon dioxide and non-reacted parts hydro carbons and the byproduct stream that comprises hydrogen.Can realize separating by the separation method that uses film with hydrogen and deoxidation synthesis gas.
Can select suitable film.Can use various films, comprise polymer, metal porous carrier etc., described film is as known in the art.Film can comprise the thin layer of silicon dioxide that is deposited on the porous alumina carrier.Bore dia is about the 5-10 nanometer.Can by about 600-650 ℃, in argon gas atmosphere, the chemical vapour deposition (CVD) tetraethyl orthosilicate, on aluminum oxide base material, form silicon dioxide layer, until reaching required hydrogen permeability degree.So from the carbon monoxide flow point from hydrogen do not need to be further purified.On the contrary, can choose recovery and output wantonly as fuel, as discussed below.
After the separation of hydrogen as discussed above, the main flow that comprises carbon monoxide, carbon dioxide and non-reacted parts hydro carbons the carbon nanomaterial production unit be can be directed at, thereby above-mentioned Boudart reaction (I) preparation carbon nanomaterial and carbon dioxide stream utilized.But comprise the carbon dioxide stream recirculation of that part of carbon dioxide that forms as the Boudart reaction result and be used for partial oxidation.Carrying out the Boudart reaction is as known in the art to make the necessary condition of carbon nanomaterial, and those skilled in the art can select optimum condition.
According to concrete kind, size and the purity of required carbon nanomaterial, may need to remove carbon dioxide and non-reacted parts hydro carbons, and the carbon monoxide of substantially pure is supplied to the carbon nanomaterial production unit from main flow.This can realize by the method that comprises following any side of utilization: embrane method, pressure swing adsorption method, absorption process etc.In each situation, can be with the carbon monoxide conductance of purifying to the carbon nanomaterial production unit, and carbon dioxide and hydrocarbon material flow be recycled to reformer unit.
With reference to figure 1, hydro carbons 1 is directed at pretreatment reaction device A.Sulphur can be removed in this hydro carbons pretreatment reaction device unit, makes the various alkene that may exist saturated, and optional pre-reforming hydro carbons 1.Leave after the pretreatment reaction device A, hydro carbons enters among the hydrocarbon conversion reactor B via pipeline 3.This hydrocarbon conversion reactor B can be the catalyzing part oxidation equipment that carries out catalytic partial oxidation process.This hydrocarbon conversion reactor B can also be self-heating cat reformer or non-catalytic partial oxidation equipment, is respectively applied for self-heating catalytic reforming process or the non-catalytic partial oxidation process of carrying out.
The carbon dioxide gas stream 9 of hydrocarbon material flow 3, oxygen flow 2 and recirculation all can be directed at hydrocarbon conversion reactor B, in this reactor, under about 700-1400 ℃ the temperature, be up under 150 atmospheric pressure, choosing wantonly in the presence of suitable catalyst, carry out conversion process.
Product is left this air-flow of hydrocarbon conversion reactor B. via pipeline 4 and can be comprised hydrogen then, carbon monoxide, carbon dioxide, unreacted oxygen, unreacted hydrocarbons (for example methane) and water. after the various heat recycle process, this air-flow 4 is directed at deacidification unit C, to remove trace unreacted oxygen. then with air-flow 5 and recirculation flow 11 compoundings from second level film F, D compresses by compression unit, and be directed at the waste gas stream 10 that first order film unit E. sees through by pipeline 6 and can comprise most of hydrogen, and exportable acting as a fuel. the logistics 7 of the rich carbon monoxide of elevated pressures is directed at second level film unit F, with the more highly purified carbon monoxide stream of preparation, this carbon monoxide stream further is used as the charging 8 of carbon nanomaterial production unit G with the preparation carbon nanomaterial. will flow 9 recirculation from the carbon dioxide by-product of nano-sized carbon production unit G then and get back to hydrocarbon conversion unit B.
This nano-sized carbon production unit G can comprise the plurality of sub unit, comprise nano-sized carbon produce reactor, be used for from effluent stream separating solids nano-sized carbon product separator, be used to separate and the device of recirculation unreacted feed gas and optional being used for from the device of carbon dioxide by-product flow point from unwanted accessory substance.
With reference to figure 2, can be by still not using the process of oxygen to obtain synthesis gas in reformation hydro carbons (for example methane).The whole path of a kind of possible anaerobic dry weight is shown in following reaction (III):
CH 4+CO 2→2CO+2H 2 (III)
More particularly, dry weight shown in the reaction (III) is had suffered Cheng Tongchang and is carried out under temperature (for example about 700-1000 ℃) that raises and elevated pressure (for example the highest about 150 atmospheric pressure).This process can be carried out in the presence of catalyst.Can from various known options, select suitable catalyst.For example, useful catalyst can comprise noble metal (for example platinum, palladium or rhodium) or transition base metal (for example nickel).Metal can embed in the porous carrier (for example aluminium oxide or zeolite).
In fact, for reformer unit being carried out optimum operation and avoid on process equipment, forming coking, can choose the combination of using the whole and steam reformation of dry weight wantonly.A kind of possible steam reformation path is shown in following reaction (IV):
CH 4+H 2O→CO+3H 2 (IV)
If the use steam reformation then can be selected best service condition (that is, temperature, pressure, catalyst).For the preparation carbon nanomaterial, require to make reformer to produce the amount maximum of carbon monoxide, and make the amount minimum that produces hydrogen.Therefore, the charging of delivering to reformer can be included as and avoid forming the needed steam as much as possible of coking.
In aspect of Fig. 2, comprise hydrogen, carbon monoxide, remaining unreacted carbon dioxide and remaining unreacted hydrocarbons by the synthesis gas for preparing shown in the reaction scheme (III).By removing every other component (that is, hydrogen, unreacted carbon dioxide and unreacted hydrocarbons) to required degree, can further process this mixture, obtain the carbon monoxide of purifying.Purge process is as described below.
Can remove hydrogen and unreacted hydrocarbons, stay the main flow that comprises carbon monoxide and carbon dioxide and comprise hydrogen and the byproduct stream of unreacted hydrocarbons.Thisly can finish by using above-mentioned one or more films from synthesis gas separation of hydrogen and unreacted hydrocarbons.These films can be with described identical with reference to figure 1.Perhaps, this separation can be used other appropriate method for example pressure swing adsorption method and/or separation by deep refrigeration are finished.
Use after film separation of hydrogen and the unreacted hydrocarbons, the main flow that comprises carbon monoxide and carbon dioxide can be directed at the carbon nanomaterial production unit, adopt Boudart reaction as discussed above (I) to produce carbon nanomaterial and carbon dioxide stream.Perhaps, the carbon dioxide in the main flow can be removed to required degree, prepare pure substantially carbon monoxide stream, then this logistics is directed at the carbon nanomaterial production unit.But this carbon dioxide stream of recirculation (comprising non-reacted parts carbon dioxide that is present in the main flow and the carbon dioxide that forms as the Boudart reaction result) also is used for the whole and vapour reforming of dry weight dry weight whole or that be used to make up, and is as discussed above.
With reference to figure 2 this is described in more detail.As shown in Figure 2.Hydro carbons 201 can be directed at pretreatment reaction device 2A.Sulphur can be removed in this hydrocarbon pretreatment reaction device unit, makes the various alkene that may exist saturated, and optional pre-reforming hydro carbons 201.The untreated hydrocarbon material flow 202 of part can be to hydrocarbon conversion reactor 2B fuel supplying.
Leave after the pretreatment reaction device 2A, hydro carbons can enter among the hydrocarbon conversion reactor 2B via pipeline 203.As shown in Figure 2, adopt hydrocarbon conversion reactor 2B to carry out dry carbon dioxide reforming process and catalytic steam reforming process.Can select various other hydrocarbon conversion reactors 2B when needing.
The carbon dioxide gas stream 10 of hydrocarbon material flow 203, steam 215 and recirculation can enter hydrocarbon conversion reactor 2B, in this reactor, can under about 700-1000 ℃ the temperature, be up under 150 atmospheric pressure, choose wantonly in the presence of suitable catalyst and carry out conversion process. product can be used as air-flow 204 and leaves hydrocarbon conversion reactor 2B.
In Fig. 2, air-flow 204 comprises for example methane of hydrogen, carbon monoxide, unreacted steam, unreacted carbon dioxide and unreacted hydrocarbons.Air-flow 204 can be directed at heat reclamation device 2C then, this device comprises process heat boiler, various heat exchanger and cooling tower (not shown), air-flow 204 is cooled to the downstream temperature of requirement.Therefore, the chemical composition that air-flow 205 can be identical with air-flow 204, but leave heat reclamation device 2C with the temperature that is lower than air-flow 204.But this process preparation process steam 215 and from the output steam 214 of water 213.
Air-flow 205 can enter first order film unit 2D then, in this unit, from the remainder separating most hydrogen and the carbon dioxide of air-flow, causes forming two kinds of separated stream.These two kinds of logistics are to comprise the main flow 206 of most of carbon monoxide, part unreacted carbon dioxide and part unreacted hydrocarbons and mainly comprise hydrogen and the waste gas that sees through of most of unreacted carbon dioxide stream 216.
The waste gas stream 216 that sees through can be directed at hydrocarbon conversion unit 2B then acts as a fuel.Product from fuel combustion can leave unit 2B by flowing out logistics 217.The rich carbon monoxide main flow 206 of elevated pressures can be directed at second level film unit 2E then, in this unit, further separate carbon monoxide and remaining unreacted carbon dioxide, with more highly purified carbon monoxide stream 207 of preparation and the carbon dioxide enriched logistics 211 that sees through.
Carbon monoxide stream 207 can flow 209 with preparation carbon nanomaterial 208 and useless carbon dioxide further as the charging of carbon nanomaterial production unit 2F.Carbon dioxide enriched can be seen through logistics 211 by compression unit 2G compression, get back among the first order film unit 2D by pipeline 212 recirculation then, be recycled among the hydrocarbon conversion unit 2B by compression unit 2H compression and by logistics 210 from the useless carbon dioxide stream 209 of carbon nanomaterial production unit 2F.
In some cases, carbon nanomaterial production unit 2F can comprise plurality of sub unit (not shown), comprise carbon nanomaterial produce reactor, be used for from effluent stream separating solids carbon nanomaterial product 208 device, be used to separate and the subelement of recirculation unreacted feed gas and possible being used for from the device of carbon dioxide by-product flow point from unwanted accessory substance.
Equipment shown in Figure 2 and method can have many variations.Can produce the heat of reformer needs by burning from the part hydrogen product of reformer.Perhaps, can sell the hydrogen product, provide fuel for reformer with natural gas.In addition, can utilize heat that the exothermic reaction among the carbon nanomaterial reactor unit 2F discharges to delivering to the feeding preheating of reformer, thereby reduce the fuel quantity of this process need.
In one embodiment, can import the carbon dioxide of additional quantity, mix with the charging of delivering to reformer, to realize extra advantage from external source.When the hydro carbons of delivering to reformer is methane, also can via logistics 218 will as many as equimolar amounts outside carbon dioxide deliver to reactor.In these cases, overall process is shown in following overall reaction (V):
CH 4+CO 2→2C+2H 2O (V)
This process provides a kind of means that consume carbon dioxide, thereby prevents from it is released in the atmosphere, it is believed that carbon dioxide is the main actor of global warming.Because overall reaction (V) is heat release, integrated by each unit operations of this process being carried out effective energy, can realize Joint Production CNT and the isolated outside carbon dioxide that produces seldom or do not have under the additional combustion fossil fuel.
In other situations of describing with reference to figure 3, also can have suffered journey and obtain synthesis gas by the dry weight shown in the reaction scheme (III).Dry weight is had suffered journey with similar substantially with reference to figure 2 described contents, comprises the optional steam reformation that utilizes.With identical before, but the recycled carbon dioxide accessory substance mixes it amount of the carbon monoxide that the raising reformer is produced with the charging of delivering to reformer.
But can use some additional features. these additional features can comprise uses ice chest to replace membrane separator, from synthesis gas separation of hydrogen and unreacted hydrocarbons. and these characteristics can be used for the large-scale production producer. and also this method makes preparation hydrogen as valuable common product.
Can be described in more detail this with reference to figure 3.As shown in Figure 3, hydro carbons 301 can be directed at pretreatment reaction device 3A.The same with Fig. 2, hydrocarbon pretreatment reaction device 3A can remove sulphur, makes the various alkene that may exist saturated, and optional pre-reforming hydro carbons 301.Part hydrocarbon material flow 302 can be hydrocarbon conversion reactor 3B fuel supplying.
Leave after the pretreatment reaction device 3A, hydro carbons can enter among the hydrocarbon conversion reactor 3B via pipeline 303.Adopt the hydrocarbon conversion reactor 3B among Fig. 3 to carry out dry carbon dioxide reforming process and catalytic steam reforming process.Can select various other hydrocarbon conversion reactors 3B when needing.
The carbon dioxide gas stream 313 of hydrocarbon material flow 303, steam 316 and recirculation can be in hydrocarbon conversion reactor 3B, react under about 700-1000 ℃ temperature.Product can be left hydrocarbon conversion reactor 3B by pipeline 304.Air-flow 304 can comprise hydrogen, carbon monoxide, carbon dioxide and unreacted hydrocarbons (for example methane).This air-flow 304 can be directed at heat reclamation device 3C then.Heat reclamation device 3C also can comprise process heat boiler, various heat exchanger and cooling tower (not shown), with cooling blast 304.
Then, the air-flow 304 that is cooled to the downstream temperature of requirement can be used as air-flow 305 and enters carbon dioxide and remove unit 3D.The chemical composition of air-flow 305 of leaving heat reclamation device 3C is identical with air-flow 304, but temperature is lower than air-flow 304.But also production process steam 316 and output steam 315 (from water 314) among the heat reclamation device 3C.Remove among the unit 3D at carbon dioxide, can obtain carbon dioxide stream 312 and poor carbon dioxide stream 306 from air-flow 305.
The carbon dioxide 312 that separates can be directed at carbon dioxide compression unit 3H then, be recycled among the hydrocarbon conversion unit 3B as logistics 313 then.Poor carbon dioxide stream 306 can walk to carbon monoxide separative element 3E, preparation product carbon monoxide stream 307 and thick hydrogen stream 309.Available typical carbon monoxide separator can comprise ice chest, film system or psa unit.Can select only carbon monoxide separator.The waste gas that leaves carbon monoxide separative element 3E can be flowed 318 recirculation, as the fuel of hydrocarbon conversion unit 3B.Outflow logistics 319 can comprise the product of the fuel combustion that is supplied to hydrocarbon conversion unit 3B.
The carbon monoxide 307 that produces among the carbon monoxide separative element 3E can be directed at carbon nanomaterial production unit 3F.Useless carbon dioxide stream 311 from carbon nanomaterial production unit 3F carbon dioxide compression unit 3H can be directed at, the logistics of compression hydrocarbon conversion reactor 3B can be directed at then.Logistics 308 comprises the solid nano carbon product, and can for example comprise the solid carbon nano material that is deposited on screen cloth or the filter, perhaps can comprise the logistics of the eluting gas (for example, carbon monoxide, carbon dioxide etc.) that is rich in the carbon nanomaterial product.
Nano-sized carbon production unit 3F can comprise plurality of sub unit (not shown), for example carbon nanomaterial produce reactor, be used for from effluent stream separating solids carbon nanomaterial product device, be used to separate and the device of recirculation unreacted feed gas and possible being used for from the device of carbon dioxide by-product flow point from unwanted accessory substance.
Thick hydrogen stream 309 can enter pressure-swing absorption apparatus 3G, and this device comprises sorbent material usually.Usually this sorbent material is active carbon or zeolite 5A sorbent material.The product of pressure-swing absorption process can be a high pressure hydrogen, and this product leaves unit 3G as logistics 310.The residual gas that exists in this logistics will leave unit 3G via pipeline 317, and can be used as the fuel gas among the hydrocarbon conversion unit 3B.
Can design many versions of said process.For example, can produce the needed heat of reformer from the part hydrogen product of reformer by burning.Perhaps, can sell the hydrogen product, with the fuel of natural gas as reformer.Perhaps, can utilize heat that the exothermic reaction among the carbon nanomaterial reactor unit 3F discharges to delivering to the feeding preheating of reformer, thereby reduce the fuel quantity of this process need.
In one embodiment, can import the carbon dioxide of additional quantity, it be mixed with the charging of delivering to reformer, to realize extra advantage from external source.When the hydro carbons of delivering to reformer is methane, also can via logistics 320 will as many as equimolar amounts outside carbon dioxide deliver to reactor.Under these conditions, overall process can be shown in overall reaction (V).Add the amount that the carbon dioxide of importing has reduced the hydrogen accessory substance of this process generation to reformer.
This method provides a kind of means that consume carbon dioxide, prevents from thus carbon dioxide is released in the atmosphere, it is believed that carbon dioxide is the main actor of global warming.Because overall reaction (V) is heat release, it is integrated to carry out effective energy by each unit operations to this process, can realize Joint Production CNT and the isolated outside carbon dioxide that produces seldom or do not have under the additional combustion fossil fuel.
The scheme for combining of all methods discussed above helps in fact to eliminate CO2 emission in the carbon nanomaterial preparation process.Can also import the part charging of carbon dioxide as process.Therefore, this integrated processes can be as the effective ways that completely cut off carbon dioxide with the form of valuable product (carbon nanomaterial).
Should be appreciated that method and apparatus as herein described only is an example, those skilled in the art can change and revise under the situation of principle that does not depart from this disclosure and scope.All such changes and modifications all are intended to be included within the scope of above-mentioned disclosure.And all representative example that disclosed differ and establish a capital and will select, because each side capable of being combined provides required result.Therefore, this disclosure is limited by following claim only.

Claims (23)

1. method for preparing CNT, this method comprises:
(a) preparation comprises the synthesis gas of carbon monoxide, carbon dioxide, hydrogen and hydro carbons;
(b) from synthesis gas separation of hydrogen and hydro carbons, with preparation carbon monoxide and the product gas flow of carbon dioxide and the accessory substance air-flow of hydrogen and hydro carbons;
(c) use the carbon monoxide in the product gas flow to prepare CNT; And
(d) will be from product air-flow and the carbon dioxide recirculation of producing from CNT.
2. the method for claim 1 is characterized in that, the preparation synthesis gas comprises:
(a) hydrocarbonaceous gas stream and carbon dioxide gas stream compounding are formed the compounding air-flow;
(b) transform the compounding air-flow and form synthesis gas.
3. method as claimed in claim 2 is characterized in that, transforms the compounding air-flow and is included in 700-1000 ℃ temperature and is up to that to carry out dry weight under 150 atmospheric pressure whole.
4. method as claimed in claim 3 is characterized in that, transforms the compounding air-flow and further comprises steam reformation.
5. method as claimed in claim 3 is characterized in that described reformation is carried out in the presence of platinum, palladium, rhodium or Raney nickel.
6. method as claimed in claim 2 is characterized in that, this method comprises that further preliminary treatment hydro carbons air-flow is to remove impurity.
7. method as claimed in claim 2 is characterized in that hydro carbons is a methane.
8. the method for claim 1 is characterized in that, the preparation synthesis gas comprises:
(a) compounding hydrocarbonaceous gas stream, carbon dioxide gas stream and Oxygen Flow form the compounding air-flow;
(b) transform the compounding air-flow and form the conversion air-flow that comprises carbon monoxide, carbon dioxide, hydrogen, unreacted hydrocarbons and unreacted oxygen; And
(c) make the deoxidation of conversion air-flow, to remove unreacted oxygen and to form synthesis gas.
9. method as claimed in claim 8 is characterized in that, transforms under the temperature that the compounding air-flow is included in 700-1400 ℃, is up under 150 atmospheric pressure, in the presence of platinum, palladium, rhodium or Raney nickel, hydro carbons is carried out catalytic reforming.
10. method as claimed in claim 8 is characterized in that, this method comprises that further preliminary treatment hydro carbons air-flow is to remove impurity.
11. method as claimed in claim 8 is characterized in that, hydro carbons is a methane.
12. the method for claim 1 is characterized in that, this method further comprises and product gas flow is separated into carbon monoxide stream and carbon dioxide flows.
13. the method for claim 1 is characterized in that, this method further comprises carries out purifying and reclaims pure hydrogen the hydrogen in the accessory substance air-flow.
14. an equipment for preparing CNT, this equipment comprises:
(a) synthesis gas production unit, preparation comprises the synthesis gas of carbon monoxide, carbon dioxide, hydrogen and hydro carbons;
(b) separative element is used for from synthesis gas separation of hydrogen and hydro carbons, to obtain carbon monoxide and the product gas flow of carbon dioxide and the accessory substance air-flow of hydrogen and hydro carbons;
(c) made of carbon nanotubes unit is used for using the carbon monoxide of product gas flow to prepare CNT; And
(d) carbon dioxide recirculator is used for the carbon dioxide from the CNT production unit is recycled to the synthesis gas production unit.
15. equipment as claimed in claim 14, it is characterized in that the synthesis gas production unit comprises carbon dioxide source, hydrocarbon gas source, compounding becomes the compounding device of compounding air-flow and transforms the conversion reactor that the compounding air-flow forms synthesis gas with hydrocarbon gas with carbon dioxide.
16. equipment as claimed in claim 15 is characterized in that, conversion reactor is the combination of doing reformer unit or dried reformer unit and steam reformer unit.
17. equipment as claimed in claim 15 is characterized in that, hydro carbons is a methane.
18. equipment as claimed in claim 14, it is characterized in that, the synthesis gas production unit comprises the carbon dioxide source, the hydrocarbon gas source, the oxygen source, compounding becomes the compounding device of compounding air-flow with oxygen with carbon dioxide, hydrocarbon gas, makes the compounding air-flow transform the conversion reactor that forms the conversion air-flow that comprises carbon monoxide, carbon dioxide, hydrogen, unreacted hydrocarbons and unreacted oxygen, and removes unreacted oxygen and form the deacidification unit of synthesis gas from the reformed gas diffluence.
19. equipment as claimed in claim 18 is characterized in that, conversion reactor is the cat reformer unit with platinum, palladium, rhodium or Raney nickel.
20. equipment as claimed in claim 18 is characterized in that, hydro carbons is a methane.
21. equipment as claimed in claim 14 is characterized in that, separative element is membrane separator, psa unit or cryogenic separator.
22. equipment as claimed in claim 14 is characterized in that, this equipment further comprises the purification unit that product gas flow is separated into carbon monoxide air-flow and carbon dioxide gas stream, and wherein this purification unit is membrane separator, psa unit or cryogenic separator.
23. equipment as claimed in claim 14 is characterized in that, this equipment further comprises from the refinery unit of accessory substance gas stream purification and recovery hydrogen.
CN200880019143A 2007-06-06 2008-06-04 Integrated processes for generating carbon monoxide for carbon nanomaterial production Pending CN101707864A (en)

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US11/974,953 US20080305029A1 (en) 2007-06-06 2007-10-17 Integrated processes for generating carbon monoxide for carbon nanomaterial production
US11/974,952 US20080305028A1 (en) 2007-06-06 2007-10-17 Integrated processes for generating carbon monoxide for carbon nanomaterial production
US11/974,954 US20080305030A1 (en) 2007-06-06 2007-10-17 Integrated processes for generating carbon monoxide for carbon nanomaterial production
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