EP2126006A1 - Procédé et dispositif de préparation d'énergie, de carburants ou de matières premières chimiques par mise en uvre de substances biogènes à bilan co2 neutre - Google Patents

Procédé et dispositif de préparation d'énergie, de carburants ou de matières premières chimiques par mise en uvre de substances biogènes à bilan co2 neutre

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Publication number
EP2126006A1
EP2126006A1 EP08701376A EP08701376A EP2126006A1 EP 2126006 A1 EP2126006 A1 EP 2126006A1 EP 08701376 A EP08701376 A EP 08701376A EP 08701376 A EP08701376 A EP 08701376A EP 2126006 A1 EP2126006 A1 EP 2126006A1
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EP
European Patent Office
Prior art keywords
gas
production
biosynthesis
fuel
generation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP08701376A
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German (de)
English (en)
Inventor
Oliver Neumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SPIRIT OF TECHNOLOGY AKTIENGESELLSCHAFT
Original Assignee
Spot Spirit Of Technology AG
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Filing date
Publication date
Application filed by Spot Spirit Of Technology AG filed Critical Spot Spirit Of Technology AG
Publication of EP2126006A1 publication Critical patent/EP2126006A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/026—Dust removal by centrifugal forces
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/18—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1261—Heating the gasifier by pulse burners
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1668—Conversion of synthesis gas to chemicals to urea; to ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • thermal gasification processes has essentially produced three different types of gasifier, the entrained flow gasifier, the fixed bed gasifier and the fluidized bed gasifier.
  • Literature for fluidized-bed gasification which forms part of this application can be found in the following literature: Wolfgang Adlroch, Rheinbraun AG, Hisaaki Sumitomo Heavy Industries, Ltd., Joachim Wolff, Karsten Radtke (Speaker), "High-Temperature Winkler Gasification of Municipal Solid Waste” , Krupp ühde GmbH, Gasification Technology Conference, San Francisco, California, USA; October 8-11, 2000; Conference Proceedings Literature for circulating fluidized bed in the composite system, which is part of this application, can be found in the following literature: "Decentralized electricity and heat generation based on biomass gasification V ⁇ ; R. Rauch, H. Hofbauer; Lecture University of Leipzig 2004.
  • Literature for combination fixed bed (rotary tube) which is part of this application can be found in the following literature: 30 MV Carbo V Biomass Gasifier for Municipal CHP; The CHP Project for the City of Aachen Dr Rudioff; Lecture Paris October 2005.
  • gasification takes place in two stages.
  • the biomass is split at 500 0 C in their volatile and solid components.
  • the result is a tar-containing gas and additionally "charcoal".
  • the gas is burned at temperatures of more than 1200 0 C, with the tars decay into CO2 and H2. With the hot flue gas and the Charcoal is then produced a CO and H2-containing product gas.
  • the fluidized bed gasifiers can be subdivided into two processes, which differ in the heating of the fluidized bed, the circulating fluidized bed gasifier and the stationary fluidized bed gasifier.
  • Literature for desulfurization in a fluidized bed gasification which forms part of this application can be found in the following literature: Gasification of Lignite and Wood in the Lurgi Circulating Fluidized Be Gasifier; Research Project 2656-3; Final Report, August 1988, P.Mehrling, H.Vierrath; LURGI GmbH; for Electric Power Research Institute PaIo Alto Californic: ZWS Pressure Gasification in Combination Block Final Report BMFT FB 03 E 6384-A; P.Mehrling LURGI GmbH; Bewag.
  • the present gasification of the biomass also in a fluidized bed with steam as the reaction and fluidizing medium.
  • this is a stationary fluidized bed with two specially developed pulse burners, which allow an indirect heat input into the fluidized bed located in the reactor.
  • this method is referred to as a SPOT method.
  • the advantage compared to the fixed-bed gasifier and the circulating fluidized bed is the lack of pronounced temperature and reaction zones.
  • the fluidized bed consists of an inert bed material. This ensures a simultaneous sequence of the individual partial reactions and a homogeneous temperature (about 800 ° C.).
  • the process is virtually depressurised (up to a maximum of 0.5 bar) and is therefore technically easy to implement. It is characterized by a high economic efficiency.
  • the acquisition costs are among the aforementioned carburetor types.
  • the starting point for further use as fuel is the medium-calorific gas from the bio-synthesis gas plant (based on renewable raw materials), which after dedusting and scrubbing of condensable hydrocarbons (oil quench) via a turbo compressor to about 20 bar compressed and through the following process steps can be refined:
  • the synthetic gas-based process of the present invention is capable of producing high-quality fuel from 100% biomass 23to.
  • the inventive method and the corresponding devices require a purification of the generated synthesis gas to this in the specially developed Pulse burners (including pilot burner) energetically implement.
  • the system is based on the "in situ removal" of the gaseous pollutants in the reaction space of the
  • the pollutant components to be removed from the product gas are the pollutant components to be removed from the product gas
  • the goal is to remove the sulfur-containing gas components (mainly H2S) with the help of aggregate materials such as limestone, dolomite or similar processed or naturally occurring aggregates.
  • sulfur-containing gas components mainly H2S
  • this method can also be used for the sulfur accompanying substances of the same main group of the periodic table Se (selenium) and Te (Telur). Investigations on these procedures show that in the
  • thermodynamic stability Due to the thermodynamic stability, the pollutants sulfur, telur selenium are deposited with high efficiency directly, whereas the adsorption of chlorine requires once more reactive adsorbents and an adaptation to the reaction temperatures.
  • the gaseous pollutant components forming in the reaction of the starting materials are transported to the solid particles of the adsorbents in the form of a two-phase reaction (gas-solid) by convection and diffusion of the pollutant to the adsorbent particle and react there to form a thermodynamically stable salt. These particles are discharged with the ash or partly separated into the gas purification stages downstream of the gas path, in particular in the multicyclone and the sintered metal fine filters, where they are selectively discharged.
  • the goal is the absorption or removal of chlorine, which is present as a chlorine radical and derived from organic chlorine compounds.
  • Other chlorine compounds are possible.
  • chlorine salts chlorides are less relevant in the context of the method according to the invention.
  • the method can be extended to the group of halogens (Cl, J, Br, F) according to the thermodynamic properties of the individual components.
  • the absorbents or reactants are introduced in terms of process technology at the most suitable site for the respective task.
  • the injection into the external cyclone is expedient, especially to find suitable reaction conditions for the case of chlorine absorption.
  • the control of the metering of additives takes place either via a ratio control with variable ratio between feedstock and additive or via a trim-back control, the reference variable reflecting the pollutant concentration measured in the synthesis gas.
  • deposition of dust as a further step in the synthesis gas makes special demands on the deposition of extremely fine, high-carbon dust.
  • dedusting takes place in a multicyclone and a downstream battery of sintered metal filters.
  • This gas purification stage (dedusting) consists of a multicyclone as pre-treatment stage and downstream one
  • the multi-cyclone consists of a battery of small cyclones, which are mounted in a housing on a support plate.
  • the incoming product gas (containing dust and adsorbent), distributed according to the flow resistance almost equally to the individual elements of the multi-cyclone. In these elements, the separation of a partial flow of the dust takes place (together with the adsorbent).
  • the gas leaves the apparatus, the dust collects together with the likewise deposited adsorbent in the funnel of the apparatus, from where the separated substances are discharged.
  • the second stage of this hot gas cleaning and dedusting consists of fine filters with sintered metal candles.
  • dust and laden Adsorbensan At these forms of the candles of the non-separated in the multicyclone stage dust and laden Adsorbensan turnover a filter cake, which causes in addition to the dust separation in particular in the case of the deposition of chlorine-containing pollutants without significant increase in Schadstoffadsorption.
  • Layer thickness and the low flow rate of the cake are essential parameters.
  • the subject of the present invention is the production of chemical raw materials, fuels and energy from renewable raw materials by means of the SPOT process described in other applications.
  • the SPOT process allows energy, fuels and chemical intermediates to be produced on a large scale from renewable raw materials or biomass, which in turn is the starting material for the entire range of products produced today on the basis of petrochemistry.
  • the proposed process routes shown in the following description are thus exemplary of the possibilities, but are also the " key processes that form the interface between the renewable resources and the other chemical processes on the basis of a closed cycle.
  • Starting materials are all Renewable resources, which, and this is the only theoretical restriction, can be reduced to residual moisture content to preferably below 35% mass - with an energy expenditure that is significantly lower than the substance-bound, chemical energy or the corresponding calorific value.
  • the process is therefore unsuitable for highly aqueous biomass containing only a small percentage by mass of solids (eg manure).
  • the remaining renewable biomasses, power greenies, animal feed, also plant waste, wood of all sorts and species can be converted into an extensively usable intermediate product with this process, the specific adaptations eg of feed preparation and the entry into the gasification reactor and bed management are marginal.
  • carrying out the gasification process as an allothermal gasification process makes it possible to generate a synthesis gas in a highly efficient manner, which otherwise is only available by gasification by means of oxygen.
  • the latter route leads via the technically complex, energetically by the thermodynamic conversion processes low-emission generation of electrical energy and the subsequent production of oxygen.
  • This design thus allows all the energies required for production CO2-neutral, -. as a net CO2 consumer by e.g. Urea synthesis or more modern variants of the Fischer-Tropsch methanol synthesis, which increases the CO2 content of the synthesis gas and converts this proportion of CO2.
  • Gases (essentially methane) as fuel to generate the heat of reaction of the gasification process in the SPOT gasification process, through energy efficiency and high material utilization of the starting materials.
  • the gas engine for generating mechanical energy (propulsion of ships, for example) or generating electricity by means of internal combustion heat engines, including utilization of the residual heat of the flue gases by a downstream steam turbine process;
  • FIG. 1 Figures Ia-Ic show an overview of the different process routes
  • Fig. 2 shows the circuit variant supply of the pulse burner with fuel gas
  • Fig. 3 shows an overview of dedusting, quenching, cooling and compression
  • Fig. 4 shows the syngas configuration, quenching and stripper cooling
  • FIG. 5 shows the gas compression to the pressure level necessary for the down-stream processes
  • Fig. 7 shows a biosynthesis gas crude gas conversion (Crude Gas Shift); 8 shows the gas scrubbing using the example of the Rectisol process for the total purification of the biosynthesis gas before use in catalytic systems;
  • Fig. 9 shows the synthesis of methanol from biosynthesis gases
  • Fig. 11 shows the fish-Tropsch synthesis based on the biosynthesis gas for the production of synthetic fuels and chemical raw materials
  • Fig. 12 shows the production of hydrogen from biosynthesis gas by decomposition by gas scrubbing, pressure swing adsorption or cryogenic decomposition
  • Fig. 13 shows the potential uses of hydrogen as an intermediate for various industrial syntheses
  • Fig. 14 shows the use of hydrogen from biosynthesis gas as fuel for fuel cells
  • Fig. 15 shows the ammonia synthesis with subsequent urea production by the use of hydrogen from biosynthesis gas
  • Fig. 16 shows a possible use of biosynthesis gas as fuel of a gas turbine plant with waste heat utilization and thermal power coupling
  • Fig. 17 shows the use of biosynthesis gas as fuel for large engines for propulsion of ships and for the generation of electricity
  • Fig. 18 shows the use of biosynthesis gas as fuel for large engines for propulsion of ships; 19 shows the use of biosynthesis gas as fuel for
  • FIGS. 1 a to 1 c A description is given of the individual processes of the modular process routes for the production of energy, synthetic fuels, hydrogen and chemical products based on biosynthesis gas, as can be seen from FIGS. 1 a to 1 c.
  • the design of the SPOT gasification plant allows the use of the high-calorie off-gases, which are generated as residual gases or purge gases of circuits in the processes described below, as fuel for the pulsed burner system (US Pat. Impulse burner and integrated pilot burner).
  • the result of this measure is the increase in the overall efficiency of the process steps and the optimal use of the renewable raw material used.
  • the high calorific off-gas is used to generate the necessary heat of reaction.
  • the pulse burners and the integrated pilot burners are equipped for this purpose with several independent supply lines for the different fuel gases and exhaust gases.
  • the processes become an integrated element of the SPOT carburetor, the process steps to a directly unmistakably connected unit. (See Fig. 2 circuit variants supply the pulse burner with fuel gas.
  • the technical equipment allows for starting the
  • the cooling to temperatures between preferably 150 0 C and 200 0 C (design 170 ° C) and the mechanical dedusting in a multicyclone and a downstream battery of sintered metal filters. (see Fig. 3 concept of dedusting the SPOT method).
  • the cooling of the gas can, as shown in FIG. 3, take place in one or more stages before the gas purification, partly before the multicyclone, partly between the multicyclone and the gas filters.
  • Quenching and gas cooling to remove condensable trace amounts in the biosynthetic gas is another approach to optimized use of the system.
  • the gas is cooled in two stages by quench and by direct countercurrent cooling in the scrubbing tower to temperatures preferably below 100 0 C.
  • This two-step process is divided into the evaporative cooling in the quench, which is operated with oil or other suitable non-aqueous media, and the subsequent cooling in the scrubbing tower, wherein the coolant can be carried in countercurrent, DC, or cross flow.
  • Quenches stands for an injection cooling.
  • the gas is introduced into the quench, wherein the flow of the process apparatus can be carried out by the integration vertically from above, from the side or from below.
  • the admission of the gas takes place with the Ouench medium
  • the gas cooling takes place here by evaporative cooling.
  • the gas is further cooled in a column with internal internals and in direct contact with the cooling medium.
  • the injected in the quench and abandoned in the washing and cooling column refrigerant collects in the template, either as an integrated part of the column or as a separate Container is executed. The consumed in the process
  • This medium is passed through a cooling circuit by means of air cooler and water cooler and fed to the wash column.
  • a cooling circuit by means of air cooler and water cooler and fed to the wash column.
  • variants are possible which provide for the separation of quench and scrubber sumps. By series connection of two acted upon with one or with different cooling medium heat exchanger, this process can be adapted to the respective requirements.
  • the medium which is applied to the cooling / washing column, passes into the sump after passing through the internals. From this sump, the quench with cooling medium is also applied.
  • This cooling system allows the cooling of the sump by circulating this stream.
  • the condensable organic fractions present in the gas are cooled in the process described, separated and enriched in the washing / cooling medium.
  • a downstream demister defogger to remove fine spray mist
  • the gas stream of adhering, entrained washing / cooling medium is released. Through this process, the gas has the required temperature level for the subsequent process stages.
  • Concentration requires a partial flow to be expelled from this cycle. This purge stream is returned and converted in the carburetor together with the feedstock to biosynthesis gas.
  • the dust and condensate-free gas is fed to the compression stage. (See Fig. 4 Flow diagram gas conditioning by quench with
  • FIG. 5 shows a flow diagram with a compression stage.
  • the actual compression is used either as an integrated stage of the downstream heat engine (large engine, turbocharger) as an integrated compression stage Gas turbine plants, designed as a separate stage or in a mixed form.
  • flow machines turbines
  • reciprocating compressors preferably Roots compressors
  • Another aspect is the production of input materials for
  • the H2 / CO ratio of the biosynthesis gas is adapted to the requirements of the subsequent process.
  • the technical bio-synthesis gas is after conditioning, compression by reacting a portion of the CO contained in the gas with water to H2 and CO2 (homogeneous water gas reaction) to catalyst systems, such as iron oxide-chromium oxide catalysts or equivalent catalyst systems implemented.
  • This conversion the so-called crude gas conversion (crude gas shift reaction), has the advantage that the water vapor contained in the syngas as Reaction partner is available and a saturation of the
  • the entire synthesis gas stream is treated; to produce methanol or hydrocarbons after the Fischer-Tropsch synthesis, only a partial stream of the biosynthesis gas is converted to adjust a specific CO / H2 fraction.
  • a special characteristic of the process route described here is the possibility of influencing the H2 to CO ratio by adapting the operating parameters of the SPOT process by way of their reaction so that the portion of the gas stream to be converted is minimized.
  • FIG. 7 shows the circuits of the CO shift process / processes, complete shift or partial shift reaction.
  • Gas scrubbing by physical scrubbing (Rectisol) is another process step.
  • the biosynthesis gas as it leaves the conditioning and compression stage of the plant operating according to the SPOT process and the crude shift reaction, requires a gas purification adapted to the requirements of the downstream plants before further processing into H2, fuels or chemical products , In particular, the removal of catalyst poisons and the adjustment of the stoichiometry of the reactions as the basis for the requirements of the feed gas plays the decisive role.
  • the Rectisol process for physical washing is exemplified.
  • the main elements of the process are the absorber (wash tower) and the regenerators.
  • the absorber In the absorber, the interfering gas components are washed out in countercurrent and the washing liquid is loaded with it.
  • the regenerator In the regenerator these substances are separated from the washing liquid. The eluate is recycled and the separated products are processed further.
  • Resin images higher hydrocarbons (naphtha, crude benzene, iron and Metallcarbonyle) and water can be performed in this one process stage.
  • the crude gas at a mean pressure of 5 to 40 bar is at temperatures between
  • Methanol is regenerated by depressurization, evacuation and heating and then reused.
  • the product of this stage is a gas with synthesis unit for downstream processes such as the methanol synthesis, the ammonia synthesis or the hydro-cracking process.
  • by-products include naphtha, pure CO2 (for example, for urea synthesis) and H2S-rich gas.
  • FIG. 8 shows a gas purification process for adjusting the synthesis unit of the biosynthesis gas. Another aspect is the production of methanol as a fuel and raw material for chemical products.
  • the purified biosynthesis gas adjusted to a H2 / CO ratio of 2 and converted to 20 to 25 bar by converting a partial flow, is converted to methanol in the methanol process.
  • a process route here is the world selected low pressure method.
  • Fischer-Tropsch synthesis for the production of hydrocarbons is another alternative.
  • the conditioned and with respect to the CO / H2 and CO2 residual content adjusted to the necessary input conditions of the Fischer-Tropsch synthesis gas is converted to hydrocarbon in the catalytic Fischer-Tropsch synthesis.
  • the information to be the solid catalyst reaction proceeds in the temperature ranges between 200 ° C and 350 0 C and at pressures between 20 and 30 bar above.
  • the product gas of the Fischer-Tropsch process is obtained as a mixture and is usually processed in a hydro-cracker / production diesel with the highest cetane.
  • the Fischer Tropsch process supplies not only diesel (fuel), naphtha (chemical gasoline) LPG but also waxes (oligomeric hydrocarbons).
  • FIG. 11 describes the Fischer Tropsch synthesis from biosynthesis gas as the basis for synthetic fuels and as a chemical raw material with its secondary products. This can be done by generation or direct separation or after complete shift reaction.
  • H2 in pure form can be obtained from biosynthesis gas via the described process steps.
  • the by-product of the shift reaction CO2 is separated in the subsequent gas purification process (eg Rectisol process). Basically, here are three different processes:
  • Fig. 12 shows the generation of hydrogen (H2) from biosynthesis gas by decomposition by gas scrubbing, pressure swing adsorption or cryogenic decomposition.
  • the possible uses of hydrogen based on bio-syngas are manifold. Besides being used in fuel cells for the direct generation of electricity, the hydrogen can be directly added to the synthesis e.g. of ammonia and used as an intermediate for a variety of chemical syntheses.
  • FIG. 12 shows various process routes for hydrogen production from biosynthesis gas
  • FIG. 13 gives a section of the possibilities for using this gas as a reaction partner in chemical syntheses.
  • Another aspect is the use of hydrogen in fuel cells to generate electrical energy.
  • FIG. 14 shows the use of the hydrogen produced from renewable raw materials as fuel in FIG. 14
  • Fuel cells for generating electrical energy are provided.
  • Process heat which arises in the fuel cell process, is used via a water / steam process to generate electricity by means of a steam turbine and generator, whereby the possibility exists, by the extraction of heat from the
  • Another process step may be the use of ammonia based on the biosynthesis gas (hydrogen production) and conversion to ammonia and further processing by addition of CO2 to urea.
  • Hydrogen is converted to ammonia after conversion in a high-pressure catalytic reaction with nitrogen derived from air separation.
  • FIG. 15 shows this process.
  • the ammonia produced can be further processed to urea with the CO2 produced in the gas purification stage.
  • thermodynamic processes using bio-syngas as fuel.
  • electrical energy based on bio-syngas can be generated via the classic thermo-dynamic processes. These classic routes include the generation of steam in a gas boiler, as well as the utilization of the steam generated thereby in the steam turbine and the use of the gas in the gas turbine in the form of a combined process.
  • the electrical energy is generated once directly by the driven by the gas turbine generator and the waste heat of the combustion gases of this turbine used to generate steam. The transformation of the steam thus generated to electrical energy by means of steam turbine and generator.
  • biosynthesis gas as fuel for heat engines with internal combustion offers itself.
  • These machines which are used as two-stroke diesel engines e.g. are used in the field of propulsion of ships, are now state of the art with powers of 100 MW.
  • the technical biosynthesis gas as obtained after conditioning before or after the compression stage, Can be used directly as a fuel gas without further workup.
  • these consumers such as boiler plants or as industrial furnaces (lime rotary kilns), it is also possible to further simplify the conditioning process.
  • Another aspect is the generation of electrical energy by gas turbine or steam turbine process with thermal power coupling.
  • This process path corresponds to the classic GUD process (gas and steam).
  • This type of process is characterized by the use of the efficiency advantage due to the temperature working point of the gas turbine and the use of waste heat, which can be operated by post-firing at its optimum point. (Working temperature gas turbine up to 1500 0 C, steam turbine greater than 600 0 C in supercritical application, otherwise in the range around 500 0 C).
  • FIG. 18 shows the use of the biosynthesis gas as a chemical energy source for generating electrical energy in the gas turbine as a heat engine.
  • Another aspect is the generation of mechanical energy by internal combustion heat engines for driving large machinery, ships, and generating electrical energy.
  • Use of conditioned gas in engines is the generation of mechanical energy by internal combustion heat engines for driving large machinery, ships, and generating electrical energy.
  • the invention also expressly includes the use of the waste heat of the combustion processes in the waste heat boiler.
  • the technical synthesis gas is fed from the cooling / fine dedusting (integrated part of the SPOT process) directly to the turbocharger (s) of the large engine.
  • the conversion of the gas and the conversion into mechanical energy takes place with efficiencies of about 55%.
  • a waste heat utilization into which also the exhaust gases of the pulse burners are coupled.
  • Fig. 19 shows the use of the biosynthesis gas as a chemical energy source for generating mechanical energy in heat engines with internal combustion for driving ships and other large machinery and for power generation.
  • Another approach is the use of bio-synthesis gas as a chemical energy source using the water / steam process and the steam turbine as a heat engine and thermal power coupling.
  • this burner is used as a boiler
  • the heat is used in a heat engine with steam as the working medium (thermodynamic Rankine process) via a water / steam process.
  • the combination of gasification and boiler takes place both via the bio-synthesis gas part and also via the use of the heat of the flue gases of the impulse burner in the boiler.
  • a diagram of this process is shown in FIG. 19.

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  • Combustion & Propulsion (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de préparation d'énergie, de carburants et/ou de matières premières chimiques, comprenant les étapes suivantes : gazéification allothermique de la vapeur d'eau de matières premières renouvelables et/ou des gaz résiduaires des processus ultérieurs à l'aide d'un brûleur à impulsions; purification du gaz; refroidissement du gaz; condensation du gaz aux pressions nécessaires pour les processus ultérieurs; conversion catalytique du CO en H2, ajustement du rapport H2/CO des biogaz de synthèse bruts aux exigences du / des processus ultérieur(s); purification du gaz, élimination des traces qui sont des poisons de catalyseur pour les étapes suivantes du processus, par exemple selon le procédé Rectisol; production d'un ou de plusieurs des produits suivants : synthèse de méthanol pour la production de méthanol comme carburant et matière première pour produits chimiques et carburant; synthèse de Fischer-Tropsch et retraitement des produits en carburant; production de H2 sur la base du biogaz de synthèse.
EP08701376A 2007-01-23 2008-01-10 Procédé et dispositif de préparation d'énergie, de carburants ou de matières premières chimiques par mise en uvre de substances biogènes à bilan co2 neutre Pending EP2126006A1 (fr)

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DE102007004294A DE102007004294A1 (de) 2007-01-23 2007-01-23 Verfahren und Vorrichtung zur Herstellung von Energie, Treibstoffen oder chemischen Rohstoffen unter Einsatz von CO2-neutralen biogenen Einsatzstoffen
PCT/EP2008/050223 WO2008090028A1 (fr) 2007-01-23 2008-01-10 Procédé et dispositif de préparation d'énergie, de carburants ou de matières premières chimiques par mise en œuvre de substances biogènes à bilan co2 neutre

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