WO2007042562A1 - Method for producing synthesis gas or a hydrocarbon product - Google Patents

Method for producing synthesis gas or a hydrocarbon product Download PDF

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Publication number
WO2007042562A1
WO2007042562A1 PCT/EP2006/067363 EP2006067363W WO2007042562A1 WO 2007042562 A1 WO2007042562 A1 WO 2007042562A1 EP 2006067363 W EP2006067363 W EP 2006067363W WO 2007042562 A1 WO2007042562 A1 WO 2007042562A1
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WIPO (PCT)
Prior art keywords
stream
carbonaceous fuel
gas
process according
methanol
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PCT/EP2006/067363
Other languages
French (fr)
Inventor
Robert Erwin Van Den Berg
Johannes Margaretha Anna Joan Van Montfort
Jacobus Hendrikus Scheerman
Johannes Gerardus Maria Schilder
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Shell Internationale Research Maatschappij B.V.
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Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU2006301238A priority Critical patent/AU2006301238B2/en
Priority to EP06807228.9A priority patent/EP1934311B2/en
Priority to JP2008535036A priority patent/JP5254024B2/en
Priority to PL06807228T priority patent/PL1934311T5/en
Publication of WO2007042562A1 publication Critical patent/WO2007042562A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/48Apparatus; Plants
    • C10J3/485Entrained flow gasifiers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/48Apparatus; Plants
    • C10J3/50Fuel charging devices
    • C10J3/506Fuel charging devices for entrained flow gasifiers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/78High-pressure apparatus
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/82Gas withdrawal means
    • C10J3/84Gas withdrawal means with means for removing dust or tar from the gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/08Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/06Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00Details of gasification apparatus
    • C10J2200/15Details of feeding means
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00Details of gasification apparatus
    • C10J2200/15Details of feeding means
    • C10J2200/156Sluices, e.g. mechanical sluices for preventing escape of gas through the feed inlet
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903Feed preparation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0943Coke
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0969Carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/12Heating the gasifier
    • C10J2300/1223Heating the gasifier by burners
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656Conversion of synthesis gas to chemicals
    • C10J2300/1659Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846Partial oxidation, i.e. injection of air or oxygen only

Definitions

  • the present invention is directed to a process for producing synthesis gas (i.e. CO and H2) or a hydrocarbon product from a carbonaceous fuel. More in particular the invention is directed to a process for producing synthesis gas or a hydrocarbon product from a carbonaceous fuel, the process at least comprising the steps of:
  • N2 is used as a transport gas for transporting the carbonaceous fuel, especially if ammonia is one of the intended products.
  • N2 as a transport gas
  • the N2 although relatively inert, may lead to undesirably reducing the catalytic efficiency of downstream processes. This problem is even more pertinent if the process is especially intended for producing a hydrocarbon not containing N-atoms. In particular, nitrogen has been found to adversely affect a methanol- forming reaction.
  • EP-A-444684 describes a process to prepare methanol from solid waste material.
  • a solid waste is combusted at ambient pressure with oxygen and a stream of carbon dioxide.
  • the combustion takes place in a furnace to which solid waste material is supplied from the top and the oxygen and carbon dioxide streams from the bottom.
  • Carbon dioxide is added because it serves as methanol building block and to suppress the temperature in the furnace.
  • the synthesis gas as prepared in the furnace is used to make methanol. Part of the carbon dioxide present in the synthesis gas is recycled to the furnace.
  • EP-A-444684 A disadvantage of the process of EP-A-444684 is that the furnace is operated at ambient pressure. When desiring a high capacity, especially when starting from a solid coal fuel, large furnaces will then be required.
  • a process, which is operated at higher pressure, is described in US-A-3976442.
  • a solid carbonaceous fuel is transported in a CO2 rich gas to a burner of a pressurized gasification reactor operating at about 50 bar.
  • a flow of coal and carbon dioxide at a weight ratio of CO2 to coal of about 1.0 is supplied to the annular passage of the annular burner at a velocity of 150 ft/sec.
  • Oxygen is passed through the centre passage of the burner at a temperature of 300 °F and a velocity of 250 ft/sec.
  • US-A-3976442 thus provides a process wherein the partial oxidation is performed in a pressurized reactor and wherein the use of nitrogen as transport gas is avoided. Nevertheless the use of carbon dioxide as transport gas was never practiced or seriously considered in the intermediate 30 years. This was probably due to the low efficiency of the process as disclosed by this publication.
  • One or more of the above or other objects are achieved by the present invention by providing a process for producing synthesis gas or a hydrocarbon product from a carbonaceous fuel, the process at least comprising the steps of:
  • step (a) supplying a carbonaceous fuel and an oxygen containing stream to a burner of a gasification reactor, wherein a CO2 containing transport gas is used to transport the solid carbonaceous fuel to the burner; (b) partially oxidising the carbonaceous fuel in the gasification reactor, thereby obtaining a gaseous stream at least comprising CO, CO2, and H2 ; (c) removing the gaseous stream obtained in step (b) from the gasification reactor; wherein the weight ratio of CO2 to the carbonaceous fuel in step (a) is less than
  • hydrocarbon product is intended to include any hydrocarbon product, e.g. alkanes, oxygenated alkanes, and hydroxygenated alkanes such as alcohols, in particular methanol.
  • solid carbonaceous fuel may be any carbonaceous fuel in solid form. Examples of solid carbonaceous fuels are coal, coke from coal, petroleum coke, soot, biomass and particulate solids derived from oil shale, tar sands and pitch. Coal is particularly preferred, and may be of any type, including lignite, sub-bituminous, bituminous and anthracite.
  • the CO2 containing stream supplied in step (a) may be any suitable CO2 containing stream.
  • the stream contains at least 80%, preferably at least 95% CO2 •
  • the CO2 containing stream is preferably obtained from a processing step that is performed on the gaseous stream as removed in step (c) , later on in the process .
  • the CO2 containing stream supplied in step (a) is supplied at a velocity of less than 20 m/s, preferably from 5 to 15 m/s, more preferably from 7 to 12 m/s. Further it is preferred that the CO2 and the carbonaceous fuel are supplied as a single stream, preferably at a density of from 300 to 600 kg/m 3 , preferably from 350 to 500 kg/m 3 , more preferably from
  • the weight ratio in step (a) is in the range from 0.12-0.49, preferably below 0.40, more preferably below 0.30, even more preferably below 0.20 and most preferably between 0.12-0.20 on a dry basis.
  • the gaseous stream obtained in step (c) comprises from 1 to 10 mol% CO2, preferably from 4.5 to
  • step (a) may have been pre- treated, if desired, before being supplied to the gasification reactor.
  • the gaseous stream as obtained in step (c) is further processed.
  • the gaseous stream as obtained in step (c) may be subjected to dry solids removal, wet scrubbing, etc.
  • the gaseous stream as obtained in step (c) is subjected to a hydrocarbon synthesis reactor thereby obtaining a hydrocarbon product, in particular methanol.
  • the process further comprises the step of:
  • step (d) shift converting the gaseous stream as obtained in step (c) by at least partially converting CO into CO2, thereby obtaining a CO depleted stream. Also it is preferred that the process further comprises the step of:
  • step (e) subjecting the CO depleted stream as obtained in step (d) to a CO2 recovery system thereby obtaining a CO2 rich stream and a CO2 poor stream. It is even further preferred that the CO2 poor stream as obtained in step (e) is subjected to a methanol synthesis reaction, thereby obtaining methanol.
  • the CO2 rich stream as obtained in step (e) is at least partially used as the CO2 containing stream as supplied in step (a) .
  • FIG. 1 schematically shows a process block scheme of a coal-to-methanol synthesis system.
  • like reference signs relate to like components .
  • FIG. 1 schematically shows a process block scheme of a coal-to-methanol synthesis system.
  • the coal-to-methanol synthesis system comprises: a carbonaceous fuel supply system (F) ; a gasification system (G) wherein a gasification process takes place to produce a gaseous stream of an intermediate product containing synthesis gas; and a downstream system (D) for further processing of the intermediate product into the final organic substance which comprises methanol in the present case.
  • a process path extends through the fuel supply system F and the downstream system D via the gasification system G.
  • the fuel supply system F comprises a sluicing hopper 2 and a feed hopper 6.
  • the gasification system G comprises a gasification reactor 10.
  • the fuel supply system is arranged to pass the carbonaceous fuel along the process path into the gasification reactor 10.
  • the downstream system D comprises an optional dry-solids removal unit 12, an optional wet scrubber 16, an optional shift conversion reactor 18, a CO2 recovery system 22, and a methanol synthesis reactor 24 wherein a methanol-forming reaction can be driven. Preferred details of these features will be provided hereinafter.
  • the sluicing hopper 2 is provided for sluicing the dry, solid carbonaceous fuel, preferably in the form of fine particulates of coal, from a first pressure under which the fuel is stored, to a second pressure where the pressure is higher than in the first pressure.
  • first pressure is the natural pressure of about 1 atmosphere, while the second pressure will exceed the pressure under which the gasification process takes place .
  • the pressure may be higher than 10 atmosphere.
  • the pressure may be between 10 and 90 atmosphere, preferably between 10 and higher than 70 atmosphere, more preferably 30 and 60 atmosphere.
  • the term fine particulates is intended to include at least pulverized particulates having a particle size distribution so that at least about 90% by weight of the material is less than 90 ⁇ m and moisture content is typically between 2 and 12% by weight, and preferably less than about 5% by weight.
  • the sluicing hopper discharges into the feed hopper 6 via a discharge opening 4, to ensure a continuous feed rate of the fuel to the gasification reactor 10.
  • the discharge opening 4 is preferably provided in a discharge cone, which in the present case is provided with an aeration system 7 for aerating the dry solid content of the sluicing hopper 2.
  • the feed hopper 6 is arranged to discharge the fuel via conveyor line 8 to one or more burners provided in the gasification reactor 10.
  • the gasification reactor 10 will have burners in diametrically opposing positions, but this is not a requirement of the present invention.
  • Line 9 connects the one or more burners to a supply of an oxygen containing stream (e.g. substantially pure O2 or air) .
  • the burner is preferably a co-annular burner with a passage for an oxygen containing gas and a passage for the fuel and the transport gas.
  • the oxygen containing gas preferably comprises at least 90% by volume oxygen. Nitrogen, carbon dioxide and argon being permissible as impurities. Substantially pure oxygen is preferred, such as prepared by an air separation unit (ASU) .
  • ASU air separation unit
  • Steam may be present in the oxygen containing gas as it passes the passage of the burner.
  • the ratio between oxygen and steam is preferably from 0 to 0.3 parts by volume of steam per part by volume of oxygen.
  • a mixture of the fuel and oxygen from the oxygen-containing stream reacts in a reaction zone in the gasification reactor 10.
  • a reaction between the carbonaceous fuel and the oxygen-containing fluid takes place in the gasification reactor 10, producing a gaseous stream of synthesis gas containing at least CO, CO2 and H2.
  • Generation of synthesis gas occurs by partially combusting the carbonaceous fuel at a relatively high temperature somewhere in the range of 1000 0 C to 3000 0 C and at a pressure in a range of from about 1-70 bar.
  • Slag and other solids can be discharged from the gasification reactor via line 5, after which they can be further processed for disposal.
  • the feed hopper 6 preferably has multiple feed hopper discharge outlets, each outlet being in communication with at least one burner associated with the reactor. Typically, the pressure inside the feed hopper 6 exceeds the pressure inside the reactor 9, in order to facilitate injection of the powder coal into the reactor.
  • the gaseous stream of synthesis gas leaves the gasification reactor 10 through line 11 at the top, where it is cooled.
  • a syngas cooler (not shown) may be provided downstream of the gasification reactor 10 to have some or most of the heat recovered for the generation of, for instance, high-pressure steam.
  • the synthesis gas enters the downstream system D in a downstream path section of the process path, wherein the dry-solids removal unit 12 is optionally arranged.
  • the dry-solids removal unit 12 may be of any type, including the cyclone type. In the embodiment of Fig. 1, it is provided in the form of a preferred ceramic candle filter unit as for example described in EP-A-551951.
  • Line 13 is in fluid communication with the ceramic candle filter unit to provide a blow back gas pressure pulse at timed intervals in order to blow dry solid material that has accumulated on the ceramic candles away from the ceramic candles.
  • the dry solid material is discharged from the dry-solids removal unit via line 14 from where it is further processed prior to disposal.
  • the blow back gas for the blow back gas pressure pulse is preheated to a temperature of between 200 0 C and 260 0 C, preferably around 225 0 C, or any temperature close to the prevailing temperature inside the dry-solid removal unit 12.
  • the blow back gas is preferably buffered to dampen supply pressure effects when the blow back system is activated.
  • the CC>2 ⁇ recovery system 22 functions by dividing the gaseous stream into a C ⁇ 2 ⁇ rich stream and a CC>2 poor (but CO- and H2 ⁇ rich) stream and.
  • the C ⁇ 2 ⁇ recovery system 22 has an outlet 21 for discharging the C ⁇ 2 ⁇ rich stream and an outlet 23 for discharging the C ⁇ 2 ⁇ poor stream in the process path.
  • Outlet 23 is in communication with the methanol synthesis reactor 24, where the discharged (CO2 poor but) CO- and H 2 -rich stream can be subjected to the methanol-forming reaction.
  • the synthesis gas 10 discharged from the gasification reactor comprises at least H 2 , CO, and CO2 •
  • the suitability of the synthesis gas composition for the methanol forming reaction is expressed as the stoichiometric number SN of the synthesis gas, whereby expressed in the molar contents [H2], [CO], and [CO2],
  • SN ( [H 2 ] - [CO 2 ] )/( [CO] + [CO 2 ] ). It has been found that the stoichiometric number of the synthesis gas produced by gasification of the carbonaceous feed is lower than the desired ratio of about 2.03 for forming methanol in the methanol synthesis reactor 24.
  • the SN number can be improved.
  • hydrogen separated from the methanol synthesis off gas can be added to the synthesis gas to further increase the SN (not shown in Figure) .
  • C0 2 -recovery Any type of C0 2 -recovery may be employed, but absorption based C0 2 -recovery is preferred, such as physical or chemical washes, because such recovery also removes sulphur-containing components such as H 2 S from the process path.
  • absorption based C0 2 -recovery is preferred, such as physical or chemical washes, because such recovery also removes sulphur-containing components such as H 2 S from the process path.
  • the CO 2 -rich stream becomes available for a variety of uses to assist the process, of which examples will now be discussed.
  • a feedback line 27 is provided to bring a feedback gas from the downstream system D to feedback inlets providing access to one or more other points in the process path that lie upstream of the outlet 21, suitably via one or more of branch lines 7, 29, 30, 31, 32 each being in communication with line 27.
  • Blowback lines may be provided at the outlet of the gasifier and the inlet of the optional syngas cooler. Such blowback lines, although presently not shown in
  • Fig. 1 would serve to supply blow back gas for clearing local deposits.
  • Line 27 is in communication with outlet 21, to achieve that the feedback gas contains CO2 from the C ⁇ 2 ⁇ rich stream. Excess C ⁇ 2 ⁇ rich gas may be removed from the cycle via line 26.
  • a compressor 28 may optionally be provided in line 27 to generally adjust the pressure of the feedback gas. It is also possible to locally adjust the pressure in one or more of the branch lines, as needed, either by pressure reduction or by (further) compression. Another option is to provide two or more parallel feedback lines to be held at mutually different pressures using compression in each of the parallel feedback lines. The most attractive option will depend on the relative consumptions. Herewith a separate source of compressed gas for bringing additional gas into the process path is avoided. Typically in the prior art, nitrogen is used for instance as the carrier gas for bringing the fuel to and into the gasification reactor 10, or as the blow-back gas in the dry solids removal unit 12 or as purge gas or aeration gas in other places. This unnecessarily brings inert components into the process path, which adversely affects the methanol synthesis efficiency. CO2 is available from the gaseous stream anyway, and the invention seeks inter alia to advantageously make use of that.
  • One or more feedback gas inlets are preferably provided in the fuel supply system such that in operation a mixture comprising the carbonaceous fuel and the feedback gas is formed.
  • an entrained flow of the carbonaceous fuel with a carrier gas containing the feedback gas can be formed in conveyor line 8 to feed the gasification reactor 10. Examples can be found in the embodiment of Fig. 1, where branch lines 7 and 29 discharge into the sluicing hopper 2 for pressurising the sluicing hopper 2 and/or aerating its content, branch line 32 discharges into the feed hopper 6 to optionally aerate its content, and branch line 30 feeds the feedback gas into the conveyor line 8.
  • the feedback gas is preferably brought into the process path through one or more sintered metal pads, which can for instance be mounted in the conical section of sluicing hopper 2.
  • the feedback gas may be directly injected.
  • one or more feedback gas inlets can be provided in the dry-solids removal unit 12 where it can be utilized as blow-back gas.
  • one or more feedback gas inlets can be provided in the form of purge stream inlets for injecting a purging portion of the feedback gas into the process path to blow dry solid accumulates such as fly ash back into the gaseous steam.
  • the C ⁇ 2 ⁇ recovery system 22 can alternatively be located downstream of the hydrocarbon synthesis reactor 24, since a significant fraction of the CO2 will generally not be converted into the organic substance to be synthesised.
  • an advantage of an upstream location relative to the methanol synthesis reactor 24 is that the CO- and H2- rich stream forms an improved starting mixture for a subsequent methanol synthesis reaction, because it has an increased stoichiometric ratio - defined as
  • [X] signifies the molar content of molecule X whereby X is H 2 , CO, or CO 2 - closer to the optimal stoichiometric number of 2.03 for the synthesis of methanol.
  • an optional shift conversion reactor 18 is disposed in the process path upstream of the C0 2 -recovery system 22.
  • the shift conversion reactor is arranged to convert CO and Steam into H 2 and CO 2 .
  • Steam can be fed into the shift conversion reactor via line 19.
  • An advantage hereof is that the amount of H 2 in the gaseous mixture is increased so that the stoichiometric ratio is further increased.
  • the CO 2 as formed in this reaction may be advantageously used as transport gas in step (a) .
  • the methanol that is discharged from the methanol synthesis reactor 24 along line 33 may be further processed to meet desired requirements, for instance including purification steps that may include for instance distillation, or even including conversion steps to produce other liquids such as for instance one or more of the group including gasoline, dimethyl ether (DME) , ethylene, propylene, butylenes, isobutene and liquefied petroleum gas (LPG) .
  • purification steps may include for instance distillation, or even including conversion steps to produce other liquids such as for instance one or more of the group including gasoline, dimethyl ether (DME) , ethylene, propylene, butylenes, isobutene and liquefied petroleum gas (LPG) .
  • DME dimethyl ether
  • LPG liquefied petroleum gas
  • the feedback inlets can be connected to an external gas supply, for instance for feeding in CO 2 or N 2 or another suitable gas during a start-up phase of the process.
  • the feedback inlet may then be connected to the outlet arranged to discharge the feedback gas containing CO2 from the internally produced CO 2 -rich stream.
  • nitrogen is used as external gas for start-up of the process. In start-up situations no carbon dioxide will be readily available.
  • the amount of carbon dioxide as recovered from the gaseous stream prepared in step (b) is sufficient the amount of nitrogen can be reduced to zero.
  • Nitrogen is suitably prepared in a so-called air separation unit which unit also prepares the oxygen-containing stream of step (a) .
  • the invention is thus also related to a method to start the process according to a specific embodiment of the invention wherein the carbon dioxide as obtained in step (e) is used in step (a) .
  • nitrogen is used as transport gas in step (a) until the amount of carbon dioxide as obtained in step (e) is sufficient to replace the nitrogen.
  • Table I illustrates, in a line up as shown and described with reference to Fig. 1, the effect of using CO2 from the CC>2-recovery system 22 for coal feeding and blowback purposes, instead of nitrogen, on the synthesis gas composition.
  • the nitrogen content in the synthesis gas is decreased by more than a factor of ten utilizing the invention relative to the reference.
  • the CO 2 content has increased a little relative to the reference, but this is considered to be of minor importance relative to the advantage of lowering the nitrogen content because CO 2 does not burden the methanol synthesis reaction as much as nitrogen.
  • CO 2 will always be part of the synthesis gas composition, especially after performing a water shift reaction.
  • Table II illustrates, in a line up as shown and described with reference to Fig. 1, the effect of using a weight ratio of CO 2 to the solid coal fuel of less than 0.5 (dense phase) according to the invention (T1-T3) , as compared with the weight ratio of about 1.0 (dilute phase) as used in the Example I of US-A-3976442.
  • the oxygen consumption per kg oxygen according to the present invention is significantly lower than the oxygen consumption in case of Example I of US-A-3976442.
  • the weight ratio of CO2 to coal is between 0.12 and 0.20.
  • the invention has here been illustrated in accordance with a coal-to-methanol process and system.
  • the invention is applicable in an analogue way to synthesis of hydroxygenated alkanes in general, including other alcohols, dimethyl ether (DME) , or synthesis of alkanes, oxygenated alkanes, which may be formed by subjecting the gaseous stream of synthesis gas to for instance a Fisher- Tropsch reaction.
  • the invention also provides one or more process advantages in manufacturing of H2.
  • H2 separator for H2 manufacturing the methanol-forming reactor 24 is not necessary, but instead there may be a H2 separator for separating an H2 ⁇ rich gas from the synthesis gas stream. Examples of an H2 separator are a pressure swing adsorber
  • PSA PSA
  • a membrane-separator or a cold box separator or combinations of said processes.
  • An advantage of a PSA is that the separated H2 is readily available at elevated pressure .

Abstract

The present invention relates to a process for producing synthesis gas or a hydrocarbon product from a carbonaceous fuel, the process at least comprising the steps of : (a) supplying a carbonaceous fuel and an oxygen containing stream to a burner of a gasification reactor, wherein a CO2 containing transport gas is used to transport the solid carbonaceous fuel to the burner; (b) partially oxidising the carbonaceous fuel in the gasification reactor, thereby obtaining a gaseous stream at least comprising CO, CO2, and H2 ; (c) removing the gaseous stream obtained in step (b) from the gasification reactor; wherein the weight ratio of CO2 to the carbonaceous fuel in step (a) is less than 0.5 on a dry basis.

Description

METHOD FOR PRODUCING SYNTHESIS GAS OR A HYDROCARBON
PRODUCT
The present invention is directed to a process for producing synthesis gas (i.e. CO and H2) or a hydrocarbon product from a carbonaceous fuel. More in particular the invention is directed to a process for producing synthesis gas or a hydrocarbon product from a carbonaceous fuel, the process at least comprising the steps of:
(a) supplying a carbonaceous fuel and an oxygen containing stream to a burner of a gasification reactor, wherein a CO2 containing transport gas is used to transport the solid carbonaceous fuel to the burner;
(b) partially oxidising the carbonaceous fuel in the gasification reactor, thereby obtaining a gaseous stream at least comprising CO, CO2, and H2 ; Various methods for the production of synthesis gas or a hydrocarbon such as methanol from a carbonaceous fuel are known.
An example of a process for the production of synthesis gas and methanol from coal is described in a paper by M.J. van der Burgt and J. E. Naber, entitled «Development of the Shell Coal Gasification Process» (published in the proceedings of the third BOC Priestley Conference, held in September 1983 in London) . In the described system and process, ground and dried coal is pressurized in a lock-hopper and pneumatically fed to a gasification reactor where it is converted into a gaseous fuel base material by reacting with a blast containing oxygen and steam or air. The gaseous fuel base material is fed to a downstream system including a CO shift convertor, CO2 removal, and a methanol synthesis reactor.
In many known processes, N2 is used as a transport gas for transporting the carbonaceous fuel, especially if ammonia is one of the intended products.
A problem of the use of N2 as a transport gas is that the N2, although relatively inert, may lead to undesirably reducing the catalytic efficiency of downstream processes. This problem is even more pertinent if the process is especially intended for producing a hydrocarbon not containing N-atoms. In particular, nitrogen has been found to adversely affect a methanol- forming reaction.
EP-A-444684 describes a process to prepare methanol from solid waste material. In this process a solid waste is combusted at ambient pressure with oxygen and a stream of carbon dioxide. The combustion takes place in a furnace to which solid waste material is supplied from the top and the oxygen and carbon dioxide streams from the bottom. Carbon dioxide is added because it serves as methanol building block and to suppress the temperature in the furnace. The synthesis gas as prepared in the furnace is used to make methanol. Part of the carbon dioxide present in the synthesis gas is recycled to the furnace.
A disadvantage of the process of EP-A-444684 is that the furnace is operated at ambient pressure. When desiring a high capacity, especially when starting from a solid coal fuel, large furnaces will then be required. A process, which is operated at higher pressure, is described in US-A-3976442. In this publication a solid carbonaceous fuel is transported in a CO2 rich gas to a burner of a pressurized gasification reactor operating at about 50 bar. According to the examples of this publication a flow of coal and carbon dioxide at a weight ratio of CO2 to coal of about 1.0 is supplied to the annular passage of the annular burner at a velocity of 150 ft/sec. Oxygen is passed through the centre passage of the burner at a temperature of 300 °F and a velocity of 250 ft/sec. US-A-3976442 thus provides a process wherein the partial oxidation is performed in a pressurized reactor and wherein the use of nitrogen as transport gas is avoided. Nevertheless the use of carbon dioxide as transport gas was never practiced or seriously considered in the intermediate 30 years. This was probably due to the low efficiency of the process as disclosed by this publication.
It is an object of the present invention to provide a process having a higher efficiency.
It is another object of the present invention to provide an alternative process for producing synthesis gas or a hydrocarbon product, in particular methanol.
One or more of the above or other objects are achieved by the present invention by providing a process for producing synthesis gas or a hydrocarbon product from a carbonaceous fuel, the process at least comprising the steps of:
(a) supplying a carbonaceous fuel and an oxygen containing stream to a burner of a gasification reactor, wherein a CO2 containing transport gas is used to transport the solid carbonaceous fuel to the burner; (b) partially oxidising the carbonaceous fuel in the gasification reactor, thereby obtaining a gaseous stream at least comprising CO, CO2, and H2 ; (c) removing the gaseous stream obtained in step (b) from the gasification reactor; wherein the weight ratio of CO2 to the carbonaceous fuel in step (a) is less than
0.5 on a dry basis. It has been found that according to the present invention - using a dense phase for supplying the carbonaceous fuel - a highly efficient process for producing synthesis gas or a hydrocarbon product can be obtained. A further advantage of the present invention is that, for a given amount of carbonaceous fuel to be partially oxidised in the gasification reactor, a smaller reactor volume can be used, resulting in lower equipment expenses . Also, it has been found that using the relatively low weight ratio of CO2 to the carbonaceous fuel in step (a) less oxygen is consumed during the process.
Further, less CO2 has to be removed from the system afterwards than if dilute phase is used. According to the present invention, the term hydrocarbon product is intended to include any hydrocarbon product, e.g. alkanes, oxygenated alkanes, and hydroxygenated alkanes such as alcohols, in particular methanol. The term solid carbonaceous fuel may be any carbonaceous fuel in solid form. Examples of solid carbonaceous fuels are coal, coke from coal, petroleum coke, soot, biomass and particulate solids derived from oil shale, tar sands and pitch. Coal is particularly preferred, and may be of any type, including lignite, sub-bituminous, bituminous and anthracite. The CO2 containing stream supplied in step (a) may be any suitable CO2 containing stream. Preferably the stream contains at least 80%, preferably at least 95% CO2 • Furthermore, the CO2 containing stream is preferably obtained from a processing step that is performed on the gaseous stream as removed in step (c) , later on in the process .
As the person skilled in the art is familiar with suitable conditions for partially oxidising a carbonaceous fuel thereby obtaining synthesis gas, these conditions are not further discussed here.
Preferably, the CO2 containing stream supplied in step (a) is supplied at a velocity of less than 20 m/s, preferably from 5 to 15 m/s, more preferably from 7 to 12 m/s. Further it is preferred that the CO2 and the carbonaceous fuel are supplied as a single stream, preferably at a density of from 300 to 600 kg/m3, preferably from 350 to 500 kg/m3, more preferably from
375 to 475 kg/m3. According to a preferred embodiment of the process according to the present invention, the weight ratio in step (a) is in the range from 0.12-0.49, preferably below 0.40, more preferably below 0.30, even more preferably below 0.20 and most preferably between 0.12-0.20 on a dry basis.
Preferably the gaseous stream obtained in step (c) comprises from 1 to 10 mol% CO2, preferably from 4.5 to
7.5 mol% CO2 on a dry basis when performing the process according to the present invention. The person skilled in the art will readily understand that the streams supplied in step (a) may have been pre- treated, if desired, before being supplied to the gasification reactor. Also, it is preferred that the gaseous stream as obtained in step (c) is further processed. As an example, the gaseous stream as obtained in step (c) may be subjected to dry solids removal, wet scrubbing, etc. Preferably the gaseous stream as obtained in step (c) is subjected to a hydrocarbon synthesis reactor thereby obtaining a hydrocarbon product, in particular methanol. Further it is preferred that the process further comprises the step of:
(d) shift converting the gaseous stream as obtained in step (c) by at least partially converting CO into CO2, thereby obtaining a CO depleted stream. Also it is preferred that the process further comprises the step of:
(e) subjecting the CO depleted stream as obtained in step (d) to a CO2 recovery system thereby obtaining a CO2 rich stream and a CO2 poor stream. It is even further preferred that the CO2 poor stream as obtained in step (e) is subjected to a methanol synthesis reaction, thereby obtaining methanol.
According to an especially preferred embodiment the CO2 rich stream as obtained in step (e) is at least partially used as the CO2 containing stream as supplied in step (a) .
Hereafter the present invention will be further illustrated by way of example, with reference to the following non-limiting drawings in which: Fig. 1 schematically shows a process block scheme of a coal-to-methanol synthesis system. In the Figures like reference signs relate to like components .
Figure 1 schematically shows a process block scheme of a coal-to-methanol synthesis system. For simplicity, valves and other auxiliary features are not shown. The coal-to-methanol synthesis system comprises: a carbonaceous fuel supply system (F) ; a gasification system (G) wherein a gasification process takes place to produce a gaseous stream of an intermediate product containing synthesis gas; and a downstream system (D) for further processing of the intermediate product into the final organic substance which comprises methanol in the present case. A process path extends through the fuel supply system F and the downstream system D via the gasification system G.
In the described embodiment the fuel supply system F comprises a sluicing hopper 2 and a feed hopper 6. The gasification system G comprises a gasification reactor 10. The fuel supply system is arranged to pass the carbonaceous fuel along the process path into the gasification reactor 10. The downstream system D comprises an optional dry-solids removal unit 12, an optional wet scrubber 16, an optional shift conversion reactor 18, a CO2 recovery system 22, and a methanol synthesis reactor 24 wherein a methanol-forming reaction can be driven. Preferred details of these features will be provided hereinafter.
The sluicing hopper 2 is provided for sluicing the dry, solid carbonaceous fuel, preferably in the form of fine particulates of coal, from a first pressure under which the fuel is stored, to a second pressure where the pressure is higher than in the first pressure. Usually the first pressure is the natural pressure of about 1 atmosphere, while the second pressure will exceed the pressure under which the gasification process takes place .
In a gasification process, the pressure may be higher than 10 atmosphere. In a gasification process in the form of a partial combustion process, the pressure may be between 10 and 90 atmosphere, preferably between 10 and higher than 70 atmosphere, more preferably 30 and 60 atmosphere. The term fine particulates is intended to include at least pulverized particulates having a particle size distribution so that at least about 90% by weight of the material is less than 90 μm and moisture content is typically between 2 and 12% by weight, and preferably less than about 5% by weight.
The sluicing hopper discharges into the feed hopper 6 via a discharge opening 4, to ensure a continuous feed rate of the fuel to the gasification reactor 10. The discharge opening 4 is preferably provided in a discharge cone, which in the present case is provided with an aeration system 7 for aerating the dry solid content of the sluicing hopper 2.
The feed hopper 6 is arranged to discharge the fuel via conveyor line 8 to one or more burners provided in the gasification reactor 10. Typically, the gasification reactor 10 will have burners in diametrically opposing positions, but this is not a requirement of the present invention. Line 9 connects the one or more burners to a supply of an oxygen containing stream (e.g. substantially pure O2 or air) . The burner is preferably a co-annular burner with a passage for an oxygen containing gas and a passage for the fuel and the transport gas. The oxygen containing gas preferably comprises at least 90% by volume oxygen. Nitrogen, carbon dioxide and argon being permissible as impurities. Substantially pure oxygen is preferred, such as prepared by an air separation unit (ASU) . Steam may be present in the oxygen containing gas as it passes the passage of the burner. The ratio between oxygen and steam is preferably from 0 to 0.3 parts by volume of steam per part by volume of oxygen. A mixture of the fuel and oxygen from the oxygen-containing stream reacts in a reaction zone in the gasification reactor 10. A reaction between the carbonaceous fuel and the oxygen-containing fluid takes place in the gasification reactor 10, producing a gaseous stream of synthesis gas containing at least CO, CO2 and H2. Generation of synthesis gas occurs by partially combusting the carbonaceous fuel at a relatively high temperature somewhere in the range of 1000 0C to 3000 0C and at a pressure in a range of from about 1-70 bar. Slag and other solids can be discharged from the gasification reactor via line 5, after which they can be further processed for disposal.
The feed hopper 6 preferably has multiple feed hopper discharge outlets, each outlet being in communication with at least one burner associated with the reactor. Typically, the pressure inside the feed hopper 6 exceeds the pressure inside the reactor 9, in order to facilitate injection of the powder coal into the reactor.
The gaseous stream of synthesis gas leaves the gasification reactor 10 through line 11 at the top, where it is cooled. To this end a syngas cooler (not shown) may be provided downstream of the gasification reactor 10 to have some or most of the heat recovered for the generation of, for instance, high-pressure steam. Finally, the synthesis gas enters the downstream system D in a downstream path section of the process path, wherein the dry-solids removal unit 12 is optionally arranged. The dry-solids removal unit 12 may be of any type, including the cyclone type. In the embodiment of Fig. 1, it is provided in the form of a preferred ceramic candle filter unit as for example described in EP-A-551951. Line 13 is in fluid communication with the ceramic candle filter unit to provide a blow back gas pressure pulse at timed intervals in order to blow dry solid material that has accumulated on the ceramic candles away from the ceramic candles. The dry solid material is discharged from the dry-solids removal unit via line 14 from where it is further processed prior to disposal.
Suitably, the blow back gas for the blow back gas pressure pulse is preheated to a temperature of between 200 0C and 260 0C, preferably around 225 0C, or any temperature close to the prevailing temperature inside the dry-solid removal unit 12. The blow back gas is preferably buffered to dampen supply pressure effects when the blow back system is activated.
The filtered gaseous stream 15, now substantially free from dry solids, progresses along the downstream path section of the process path through the downstream system, and is fed, optionally via wet scrubber 16 and optional shift conversion reactor 18, to the Cθ2~recovery system 22. The CC>2~recovery system 22 functions by dividing the gaseous stream into a Cθ2~rich stream and a CC>2 poor (but CO- and H2~rich) stream and. The Cθ2~ recovery system 22 has an outlet 21 for discharging the Cθ2~rich stream and an outlet 23 for discharging the Cθ2~ poor stream in the process path. Outlet 23 is in communication with the methanol synthesis reactor 24, where the discharged (CO2 poor but) CO- and H2-rich stream can be subjected to the methanol-forming reaction. The synthesis gas 10 discharged from the gasification reactor comprises at least H2, CO, and CO2 • The suitability of the synthesis gas composition for the methanol forming reaction is expressed as the stoichiometric number SN of the synthesis gas, whereby expressed in the molar contents [H2], [CO], and [CO2],
SN = ( [H2] - [CO2] )/( [CO] + [CO2] ). It has been found that the stoichiometric number of the synthesis gas produced by gasification of the carbonaceous feed is lower than the desired ratio of about 2.03 for forming methanol in the methanol synthesis reactor 24. By performing a water shift reaction in shift conversion reactor 18 and separating part of the carbon dioxide in C02-recovery system 22 the SN number can be improved. Preferably hydrogen separated from the methanol synthesis off gas can be added to the synthesis gas to further increase the SN (not shown in Figure) . Any type of C02-recovery may be employed, but absorption based C02-recovery is preferred, such as physical or chemical washes, because such recovery also removes sulphur-containing components such as H2S from the process path. The CO2-rich stream becomes available for a variety of uses to assist the process, of which examples will now be discussed.
A feedback line 27 is provided to bring a feedback gas from the downstream system D to feedback inlets providing access to one or more other points in the process path that lie upstream of the outlet 21, suitably via one or more of branch lines 7, 29, 30, 31, 32 each being in communication with line 27.
Blowback lines may be provided at the outlet of the gasifier and the inlet of the optional syngas cooler. Such blowback lines, although presently not shown in
Fig. 1, would serve to supply blow back gas for clearing local deposits. Line 27 is in communication with outlet 21, to achieve that the feedback gas contains CO2 from the Cθ2~rich stream. Excess Cθ2~rich gas may be removed from the cycle via line 26.
A compressor 28 may optionally be provided in line 27 to generally adjust the pressure of the feedback gas. It is also possible to locally adjust the pressure in one or more of the branch lines, as needed, either by pressure reduction or by (further) compression. Another option is to provide two or more parallel feedback lines to be held at mutually different pressures using compression in each of the parallel feedback lines. The most attractive option will depend on the relative consumptions. Herewith a separate source of compressed gas for bringing additional gas into the process path is avoided. Typically in the prior art, nitrogen is used for instance as the carrier gas for bringing the fuel to and into the gasification reactor 10, or as the blow-back gas in the dry solids removal unit 12 or as purge gas or aeration gas in other places. This unnecessarily brings inert components into the process path, which adversely affects the methanol synthesis efficiency. CO2 is available from the gaseous stream anyway, and the invention seeks inter alia to advantageously make use of that.
One or more feedback gas inlets are preferably provided in the fuel supply system such that in operation a mixture comprising the carbonaceous fuel and the feedback gas is formed. Herewith an entrained flow of the carbonaceous fuel with a carrier gas containing the feedback gas can be formed in conveyor line 8 to feed the gasification reactor 10. Examples can be found in the embodiment of Fig. 1, where branch lines 7 and 29 discharge into the sluicing hopper 2 for pressurising the sluicing hopper 2 and/or aerating its content, branch line 32 discharges into the feed hopper 6 to optionally aerate its content, and branch line 30 feeds the feedback gas into the conveyor line 8.
The feedback gas is preferably brought into the process path through one or more sintered metal pads, which can for instance be mounted in the conical section of sluicing hopper 2. In the case of conveyor line 8, the feedback gas may be directly injected.
In addition or instead, one or more feedback gas inlets can be provided in the dry-solids removal unit 12 where it can be utilized as blow-back gas. Again in addition or instead, one or more feedback gas inlets can be provided in the form of purge stream inlets for injecting a purging portion of the feedback gas into the process path to blow dry solid accumulates such as fly ash back into the gaseous steam. In the broadest definition of the invention, the Cθ2~ recovery system 22 can alternatively be located downstream of the hydrocarbon synthesis reactor 24, since a significant fraction of the CO2 will generally not be converted into the organic substance to be synthesised. However, an advantage of an upstream location relative to the methanol synthesis reactor 24 is that the CO- and H2- rich stream forms an improved starting mixture for a subsequent methanol synthesis reaction, because it has an increased stoichiometric ratio - defined as
([H2] - [CO2]) / ([CO] + [CO2]) wherein [X] signifies the molar content of molecule X whereby X is H2, CO, or CO2 - closer to the optimal stoichiometric number of 2.03 for the synthesis of methanol.
In the embodiment of Fig. 1, an optional shift conversion reactor 18 is disposed in the process path upstream of the C02-recovery system 22. The shift conversion reactor is arranged to convert CO and Steam into H2 and CO2. Steam can be fed into the shift conversion reactor via line 19. An advantage hereof is that the amount of H2 in the gaseous mixture is increased so that the stoichiometric ratio is further increased. The CO2 as formed in this reaction may be advantageously used as transport gas in step (a) .
Naturally, the methanol that is discharged from the methanol synthesis reactor 24 along line 33 may be further processed to meet desired requirements, for instance including purification steps that may include for instance distillation, or even including conversion steps to produce other liquids such as for instance one or more of the group including gasoline, dimethyl ether (DME) , ethylene, propylene, butylenes, isobutene and liquefied petroleum gas (LPG) .
It is remarked that the feedback inlets can be connected to an external gas supply, for instance for feeding in CO2 or N2 or another suitable gas during a start-up phase of the process. When a sufficient amount of syngas - and accordingly a sufficient amount of CO2 - is being produced, the feedback inlet may then be connected to the outlet arranged to discharge the feedback gas containing CO2 from the internally produced CO2-rich stream. Preferably nitrogen is used as external gas for start-up of the process. In start-up situations no carbon dioxide will be readily available. When the amount of carbon dioxide as recovered from the gaseous stream prepared in step (b) is sufficient the amount of nitrogen can be reduced to zero. Nitrogen is suitably prepared in a so-called air separation unit which unit also prepares the oxygen-containing stream of step (a) . The invention is thus also related to a method to start the process according to a specific embodiment of the invention wherein the carbon dioxide as obtained in step (e) is used in step (a) . In this method nitrogen is used as transport gas in step (a) until the amount of carbon dioxide as obtained in step (e) is sufficient to replace the nitrogen. Example 1
The following Table I illustrates, in a line up as shown and described with reference to Fig. 1, the effect of using CO2 from the CC>2-recovery system 22 for coal feeding and blowback purposes, instead of nitrogen, on the synthesis gas composition. The synthesis gas capacity
(CO and H2) was 72600 NM3/hr, but any other capacity will do as well. The middle column gives the composition of the synthesis gas exiting from wet scrubber 16 when CO2- rich feedback gas from the C02-recovery system 22 was utilized for coal feeding into the gasification reactor 10, and blow back of the dry solids removal unit 12. The right hand column gives a reference where N2 was used instead of the feedback gas. Table I : compos ition ( in wt . %
Figure imgf000017_0001
As can be seen, the nitrogen content in the synthesis gas is decreased by more than a factor of ten utilizing the invention relative to the reference. The CO2 content has increased a little relative to the reference, but this is considered to be of minor importance relative to the advantage of lowering the nitrogen content because CO2 does not burden the methanol synthesis reaction as much as nitrogen. Moreover CO2 will always be part of the synthesis gas composition, especially after performing a water shift reaction. Example 2
The following Table II illustrates, in a line up as shown and described with reference to Fig. 1, the effect of using a weight ratio of CO2 to the solid coal fuel of less than 0.5 (dense phase) according to the invention (T1-T3) , as compared with the weight ratio of about 1.0 (dilute phase) as used in the Example I of US-A-3976442. As can be seen from Table II, the oxygen consumption per kg oxygen according to the present invention is significantly lower than the oxygen consumption in case of Example I of US-A-3976442. Preferably the weight ratio of CO2 to coal is between 0.12 and 0.20.
Table II: influence of weight ratio of CO2 to the carbonaceous fuel
Figure imgf000018_0001
The invention has here been illustrated in accordance with a coal-to-methanol process and system. However, the invention is applicable in an analogue way to synthesis of hydroxygenated alkanes in general, including other alcohols, dimethyl ether (DME) , or synthesis of alkanes, oxygenated alkanes, which may be formed by subjecting the gaseous stream of synthesis gas to for instance a Fisher- Tropsch reaction. In particular, the invention also provides one or more process advantages in manufacturing of H2. The person skilled in the art will understand that for H2 manufacturing the methanol-forming reactor 24 is not necessary, but instead there may be a H2 separator for separating an H2~rich gas from the synthesis gas stream. Examples of an H2 separator are a pressure swing adsorber
(PSA) , a membrane-separator or a cold box separator or combinations of said processes. An advantage of a PSA is that the separated H2 is readily available at elevated pressure .

Claims

C L A I M S
1. Process for producing synthesis gas or a hydrocarbon product from a carbonaceous fuel, the process at least comprising the steps of:
(a) supplying a carbonaceous fuel and an oxygen- containing stream to a burner of a gasification reactor, wherein a C02 containing transport gas is used to transport the solid carbonaceous fuel to the burner;
(b) partially oxidising the carbonaceous fuel in the gasification reactor, thereby obtaining a gaseous stream at least comprising CO, CC>2, and H2 ;
(c) removing the gaseous stream obtained in step (b) from the gasification reactor; wherein the weight ratio of CO2 to the carbonaceous fuel in step (a) is less than 0.5 on a dry basis.
2. Process according to claim 1, wherein the CO2 containing stream supplied in step (a) is supplied at a velocity of less than 20 m/s, preferably from 5 to 15 m/s, more preferably from 7 to 12 m/s.
3. Process according to claim 1 or 2, wherein the weight ratio in step (a) is in the range from 0.12-0.49, preferably below 0.40, more preferably below 0.30, most preferably below 0.20 on a dry basis.
4. Process according to claim 3, wherein the weight ratio in step (a) is in the range from 0.12-0.2. 5. Process according to one or more of the preceding claims, wherein the gaseous stream obtained in step (c) comprises from 1 to 10 mol% CO2, preferably from 4.5 to
7.
5 mol% CC>2 on a dry basis.
6. Process according to one or more of the preceding claims, wherein the solid carbonaceous fuel is coal.
7. Process according to one or more of the preceding claims, wherein the gaseous stream as obtained in step (c) is further processed, thereby obtaining a hydrocarbon product, in particular methanol.
8. Process according to claim 7, wherein the process further comprises the step of:
(d) shift converting the gaseous stream as obtained in step (c) by at least partially converting CO into CO2, thereby obtaining a CO depleted stream.
9. Process according to claim 7 or 8, wherein the process further comprises the step of:
(e) subjecting the CO depleted stream as obtained in step (d) to a CO2 recovery system thereby obtaining a CO2 rich stream and a CO2 poor stream.
10. Process according to claim 9, wherein the CO2 poor stream as obtained in step (e) is subjected to a methanol synthesis reaction, thereby obtaining methanol.
11. Process according to claim 9 or 10, wherein the CO2 rich stream as obtained in step (e) is at least partially used as the CO2 containing stream as supplied in step (a) .
12. Method to start the process according to claims 9 and 10 or 9 and 11, wherein nitrogen is used as transport gas in step (a) until the amount of carbon dioxide as obtained in step (e) is sufficient to replace the nitrogen .
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