DE102007004294A1 - Process and device for the production of energy, fuels or chemical raw materials using CO2-neutral biogenic feedstocks - Google Patents

Abstract

Process for the production of energy, fuels and / or chemical raw materials, comprising the steps of: - allothermic water vapor gasification of renewable raw materials and / or residual gases of the subsequent processes by a pulse burner; - gas purification; - gas cooling; Gas compression to that for d for conversion of CO to H2, adaptation of the H2 / CO ratio of the crude biosynthesis gas to the requirements of the gas purification, removal of trace substances which are catalyst poisons for the subsequent process stages; exemplified by the Rectisol process; - production of one or more of the following products: methanol synthesis for the production of methanol as fuel and raw material for chemical products and fuel; Fischer-Tropsch synthesis and processing of the products into fuel; Generation of H2 on the basis of biosynthesis gas.

Description

Field of the invention:

The Development of thermal gasification processes has essentially produced three different carburetor types, the entrained flow gasifier, the fixed bed gasifier and the fluidized bed gasifier

For The commercial gasification of biomasses were primarily the fixed bed gasifier and the fluidized bed gasifier further developed.

From the many different technical approaches in the field the fixed bed gasification is at this point the Carbo-V process exemplified.

Literature for fluidized bed gasification which is part of this application can be taken from the following literature: Wolfgang Adlhoch, Rheinbraun AG, Hisaaki Sumitomo Heavy Industries, Ltd., Joachim Wolff, Karsten Radtke (speaker), Krupp Uhde GmbH, Gasification Technology Conference, San Francisco, California, USA, "High-Temperature Winkler Gasification of Municipal Solid Waste"; October 8-11, 2000; Conference Proceedings

Literature for circulating fluidized bed in the composite system which is part of this application can be taken from the following literature: "Decentralized power and heat generation based on biomass gasification", R. Rauch, H. Hofbauer, lecture University of Leipzig 2004 , "Circulating fluidized bed, gasification with air Operation Experience with CfB - Technology for Waste Utilization at a Cement Production Plant" R. Wirthwein, P. Scur, K.-F. Scharf - Ruedersdorfer Zement GmbH, H. Hirschfelder - Lurgi Energie und Entsorgungs GmbH 7th International Conference on Circulating Fluidized Bed Technologies; Niagara Falls May 2002 ,

Literature for combination fixed bed (rotary tube) which is part of this application can be taken from the following literature: 30 MV Carbo V Biomass Gasifier for Municipal CHP; The CHP Project for the City of Aachen Matthias Rudloff; Lecture Paris October 2005

Literature for combination for the fixed bed gasification (Schlackeabstichvergaser) which is part of this application can be taken from the following literature: Operation Results of the BGL Gasifier at Schwarze Pumpe Hans-Joachim Sander SVZ; Dr. Georg Daradimos, Hansjobst Hirschfelder Envirotherm; Gasification Technologies 2003; San Francisco California; October 12-15 2003; Conference Proceedings

at The Carbo-V process gasification takes place in two stages. First, the biomass at 500 ° C in their volatile and solid components split. The result is a tar-containing Gas and additionally "charcoal". The gas is at temperatures burned by more than 1200 ° C, the tars in CO2 and H2 decay. With the hot flue gas and the charcoal Subsequently, a CO and H2-containing product gas is generated.

by virtue of the high technical and economic effort, conditional due to the high pressure level (up to 40 bar), these carburettor types are for the gasification of biomass (generated regionally) and significant impact on logistics and processing costs has) completely unsuitable.

The Fluidized bed gasifiers can be subdivided into two processes, which differ in the warming up of the fluidized bed, the circulating fluidized bed gasifier and the stationary fluidized bed gasifier.

Literature for desulfurization in a fluidized bed gasification which is part of this application can be taken from 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 Palo Alto Californic: ZWS Pressure Gasification in Combi-Block Final Report BMFT FB 03 E 6384-A; P. Mehrling LURGI GmbH; Bewag

In Güssing (Austria) became an allotherme in early 2002, circulating fluidized bed gasification plant put into operation. The biomass is in a fluidized bed with steam as the oxidant gassed. For heat supply for the gasification process Part of the charcoal produced in the fluidized bed is in burned a second fluidized bed. By the gasification under Steam, a product gas is generated. The disadvantages are the high ones Acquisition costs of the system technology and an inflated Expense for the process control.

Of the Applicant has to overcome the problems of the state of Technique already filed some applications in the field, whose Disclosure content is part of this application. In these Applications are the 10 2006 017 353.8, 10 2006 017 355.4, 10 2006 019 999.5, 10 2006 022 265.2, 10 2006 039 622.7.

From these applications it is known that the present gasification of the biomass also in a fluidized bed with steam as the reaction and fluidizing medium. However, this is a stationary fluidized bed with two specially developed flared pulse burners, which allow an indirect heat input into the fluidized bed located in the reactor. In the following, this method is referred to as SPOT method.

Of the Advantage compared to the fixed bed carburetor and the circulating Fluidized bed is the absence of pronounced temperature and Reaction zones. The fluidized bed consists of an inert bed material. This will be a simultaneous flow of the individual partial reactions and a homogeneous temperature (about 800 ° C) guaranteed. The process is almost without pressure (up to a maximum of 0.5 bar) and is thus technically easy to implement. It is characterized by a high Economy out. The acquisition costs are below the aforementioned carburettor types.

starting point for further use as fuel is the medium calorie Gas from the bio synthesis gas plant (based on renewable Raw materials), which becomes more condensable after dedusting and washing out Hydrocarbons (oil quench) via a turbo compressor on compressed about 20 bar and refined by the following process steps can be:

method

When Result remains to be noted that the inventive Process based on the synthesis gas is able to off 100 to biomass 23 to produce high quality fuel.

The inventive method and the corresponding Devices require a purification of the generated synthesis gas, to do this in specially designed pulse burners (including Pilot burner) energetically implement. The system is based on the "in-situ removal" the gaseous pollutants in the reaction space of the steam converter or directly in the corresponding gas line.

The from the product gas to be removed pollutant components (sulfur) are released directly during the gasification process. Essential part of the presently described process is the direct chemical Bonding of these with the components released from the starting materials the addition of the adsorbent in the gasification reactor. These Immediate Adsorbtion immediately after release of the pollutant components is called "in-situ" gas cleaning (in the case of removal sulfuric Components as desulfurization). The sulfur component in question is thus directly at the place of origin, d. H. in the reaction zone the gasification by means of the additive (practically during the Origin) adsorbed, the sulfur (or the homologues selenium and Telur) react to the sulphides, selenides and telurids. This procedure is from applications in combustion processes and similar gasification processes known (Ref .: 6; 7). Similar Processes are for other burns and gassings described in the literature.

In a first step is the goal, the sulfur-containing gas components (mainly H2S) with the help of aggregate materials such as limestone, Dolomite or similar recycled or natural to remove occurring aggregates.

Next the removal of sulfur-containing components can be apply this method also for the substances accompanying the sulfur the same main group of the periodic table Se (selenium) and Te (Telur).

investigations These methods show that the reaction temperatures prevailing in the steam splitter due to the thermodynamic stability of the pollutants Sulfur, telur selenium can be deposited directly with high efficiency, while the adsorption of chlorine once more reactive adsorbents requires and an adaptation to the reaction temperatures. The gaseous themselves in the conversion of the input materials forming (in situ) pollutant components be on the solid particles of the adsorbents in the form of a Two - phase reaction (gas - solid) by convection and Diffusion of the pollutant transported to the adsorbent particle and react there to a thermodynamically stable salt. These Particles are discharged with the ash or partly in the in the gas path downstream gas purification stages, in particular in Multicyclone and the sintered metal fine filters deposited and there selectively removed.

in the second step is the goal, the absorption respectively the distance of chlorine, which is present as chlorine radical and comes from organic chlorine compounds. Other chlorine compounds (eg the chlorine salts chlorides) are in the Meaning of the method according to the invention less relevant.

The Method can be applied to the group of halogens (Cl, J, Br, F) according to the thermodynamic properties of the individual Expand components.

The Adsorbents or reactants are process engineering at the for the respective task most appropriate place introduced. In addition to one direct task either as a supplement to the input material or the direct metering into the steam converter is the injection in the external cyclone purposeful, especially for find the case of chlorine absorption suitable reaction conditions.

As a general rule is the regulation of the dosage of additives either over a ratio control with variable ratio between feedstock and additive or via a trim-back control, where the reference variable is the synthesis gas measured pollutant concentration reflects.

The Separation of the dust particles as a further step in the synthesis gas places special demands on the deposition of the extremely fine, high carbonaceous dust. In the context of the invention Process takes place after intermediate cooling to temperatures between 150 and 700 ° C (above the dew point of the synthesis gas) the dedusting in a multi-cyclone and a downstream Battery of sintered metal filters.

These Gas purification stage (dedusting) consists of a multi-cyclone as Vorreingungsstufe and downstream of a filter unit. The multicyclone consists of a battery of small cyclones housed in a housing are mounted on a support plate. The entering Product gas (containing dust and adsorbent), distributed almost corresponding to the flow resistances evenly on the individual elements of the multi-cyclone. In these elements, the separation of a partial stream of dust occurs (together with the adsorbent). The gas leaves the apparatus, the dust collects together with the also deposited Adsorbent in the funnel of the apparatus, from where the deposited Substances are discharged.

The second stage this hot gas cleaning and dedusting consists of fine filters with sintered metal candles. At these forms on the candles of those not deposited in the multicyclone stage Dust and loaded Adsorbensanteilen a filter cake, the next the dust separation, in particular in the case of the deposition of chlorine - containing Pollutants without significant increase in pollutant adsorption causes. There is also the possibility again targeted to dose adsorbent in this area. Layer thickness and the low flow rate of the cake are essential parameters.

Overview of the invention:

The The present invention has the production of chemical raw materials, fuels and energy from renewable raw materials by means of other applications Subject to the described SPOT procedure.

Solved This object is achieved by a method and a device with the features of the independent claims.

The Underlying gasification processes of allothermal steam gasification with impulse burner is for the most different types suitable for renewable raw materials, including for SPOT's patented Power Greenies for chemical synthesis for the production of fuels, chemical products and as a feedstock for Generation of energy, combustion in boilers, gas turbines or Heat engines with internal combustion suitable to convert the described biosynthesis gas.

The SPOT procedure allowed on a large scale from renewable Raw materials or biomass Energy, fuels and chemical intermediates which in turn is the starting substance for the entire range of today based on the petrochemistry manufactured products. The indicated in the following description proposed process routes are thus exemplary for the possibilities, but also the key processes, the interface between the renewable resources and the other chemical processes based on a closed Form a cycle.

feedstocks All resources are renewable, and that's the only one theoretical limitation, to residual moisture content on preferably below Bring 35% mass - with an energy expenditure, which is significantly lower than the substance bound, chemical Energy or the corresponding calorific value. Unsuitable is the process thus, due to the basic reaction conditions, for very watery, only a few percent by mass Biomass containing solids (eg manure).

The remaining renewable biomass, power greenies, feed also plant waste, wood All varieties and species can be identified with this process, the specific Adjustments z. B. the feed preparation and the entry in the gasification reactor and bed management are marginal, to implement a circumferentially usable intermediate. Carrying out the gasification process as allothermer Gasification process also allows the highest to efficiently produce a synthesis gas that otherwise only through Gasification by means of oxygen is available. The latter way leads over the technically complex, energetic through the thermodynamic conversion processes, efficient generation of electrical energy and the subsequent production of oxygen.

This concept therefore allows all energies required for production to be CO2-neutral, ie as a net CO2 consumer, by As urea synthesis or more modern variants of the Fischer-Tropsch methanol synthesis, by the Increased CO2 content of the synthesis gas and this proportion of CO2 is reacted to produce.

The inventions described below deal with the circuit of the process routes that allow the biosynthesis gas of the SPOT carburetor for the production of energy, fuels and chemical Use products. These routes are characterized by the integrated Use of the purge gas (essentially methane) as fuel for generating the heat of reaction of the gasification process in the SPOT gasification process, through energy efficiency and high material use of the input materials.

• 1. Nutzung von Restgasen (Off-Gasen, Purge-Gasen) der Folgeprozesse (Down-Stream Prozessen) als Brennstoff für die Impulsbrenner;
• 2. Mechanische Gasreinigung und Feinstentstaubung mit integrierter Kühlung;
• 3. Gas-Quench und Gaskühlung mit Entfernung kondensierbarer Spurenanteile im Bio-Synthesegas;
• 4. Gasverdichtung auf die für die Folgeprozesse notwendigen Druckstufe;
• 5. Produktion von Einsatzstoffen zur Energieerzeugung (Wasserstoff), synthetischen Treibstoffen und diverse chemische Produkte über direkte Synthese oder mit Methanol als Zwischenprodukt durch: 5.1 Shift Reaktion zur Konvertierung des CO zu H2, Anpassung des H2/CO Verhältnisses des rohen Bio-Synthesegases an die Erfordernisse des/der Folgeprozesse(s); 5.2 Gasreinigung, Entfernung von Spurenstoffen, die Katalysatorgifte für die nachfolgenden Prozessstufen sind; beispielhaft beschrieben nach dem Rectisol-Prozess; 5.3 Erzeugung von Methanol als Treibstoff und Rohstoff für chemische Produkte und Treibstoff; 5.4 Fischer-Tropsch-Synthese und Aufarbeitung der Produkte zu Treibstoff; 5.5 Erzeugung von H2 auf der Basis Bio-Synthesegas nach verschiedenen Prozessrouten (Anm.: mit/ohne CO-Shift, chemische Wäsche, Tieftemperatur oder PSA Gastrennung) 5.6 Einsatz von Wasserstoff in Brennstoffzellen zur Erzeugung von elektrischer Energie (Anm.: einschließlich Abwärmenutzung mittels Dampfturbinenprozess) 5.7 Erzeugung von Ammoniak auf der Basis des H2 des Bio-Synthesegases, Umsetzung des Ammoniak durch Addition an CO2 zu Harnstoff und anderen Produkten
• 6. Erzeugung von elektrischer Energie durch Verbrennung des Bio-Synthesegases in: 6.1 der Brennkammer einer Gasturbine, Abhitzenutzung und Wärmekraftkopplung; Erzeugung von Strom und Nutzwärme; 6.2 einem Kessel zur Dampferzeugung, Nutzung des Dampfes durch Dampfturbine und Wärmekraftkopplung, Erzeugung von Strom und Nutzwärme; 6.3 dem Gasmotor zur Erzeugung von mechanischer Energie (Antrieb z. B. von Schiffen) oder Erzeugung von Strom mit Hilfe von Wärmekraftmaschinen mit innerer Verbrennung einschließlich Nutzung der Restwärme der Rauchgase durch einen nachgeschalteten Dampfturbinen-Prozess;

In detail, the following points are considered:

• 1. Use of residual gases (off-gases, purge gases) of the downstream processes (down-stream processes) as fuel for the pulse burners;
• 2. Mechanical gas cleaning and fine dedusting with integrated cooling;
• 3. gas quenching and gas cooling with removal of condensable trace amounts in the biosynthesis gas;
• 4. Gas compression to the pressure required for the subsequent processes pressure stage;
• 5. Production of input materials for power generation (hydrogen), synthetic fuels and various chemical products via direct synthesis or with methanol as an intermediate: 5.1 Shift reaction for the conversion of CO to H2, adaptation of the H2 / CO ratio of the crude biosynthesis gas to the Requirements of the follow-up process (s); 5.2 gas purification, removal of trace substances that are catalyst poisons for the subsequent process stages; exemplified by the Rectisol process; 5.3 production of methanol as fuel and raw material for chemical products and fuel; 5.4 Fischer-Tropsch synthesis and processing of the products into fuel; 5.5 Generation of H2 based on Bio-Synthesis gas according to different process routes (Note: with / without CO shift, chemical scrubbing, low temperature or PSA gas separation) 5.6 Use of hydrogen in fuel cells to generate electrical energy (Note: including waste heat recovery by means of Steam turbine process) 5.7 Generation of ammonia based on the H2 of the biosynthesis gas, conversion of the ammonia by addition of CO2 to urea and other products
• 6. Generation of electrical energy by combustion of the biosynthesis gas in: 6.1 the combustion chamber of a gas turbine, waste heat utilization and thermal power coupling; Generation of electricity and useful heat; 6.2 a boiler for steam generation, use of steam by steam turbine and combined heat and power, generation of electricity and useful heat; 6.3 the gas engine for the generation of mechanical energy (propulsion of ships, for example) or the generation of electricity by means of internal combustion heat engines, including the use of the residual heat of the flue gases through a downstream steam turbine process;

Brief Description:

1a - 1c show an overview of the different process routes;

2 shows the circuit variant supply the pulse burner with fuel gas;

3 shows an overview of dedusting, quenching, cooling and compaction

4 shows the syngas configuration, cooling by quenching and stripping;

5 shows the gas compression to the pressure level necessary for the down-stream processes;

6 shows another overview for dedusting, quench cooling and compression;

7 shows a biosynthesis gas Rohgas conversion (Crude Gas Shift);

8th shows the gas scrubbing using the example of the Rectisol process for the total purification of the biosynthesis gas before use in catalytic systems;

9 shows the synthesis of methanol from biosynthesis gases;

10 shows the production of methanol from biosynthesis gas as a basis for other synthetic fuels and chemical raw materials with its derivatives;

11 shows the fish-Tropsch synthesis based on the biosynthesis gas for the production of synthetic fuels and chemical raw materials;

12 shows the production of hydrogen from biosynthesis gas by decomposition by gas scrubbing, pressure swing adsorption or cryogenic decomposition;

13 shows the possible uses of Hydrogen as an intermediate for various technical syntheses;

14 shows the use of hydrogen from biosynthesis gas as fuel for fuel cells;

15 shows the ammonia synthesis with subsequent urea production through the use of hydrogen from biosynthesis gas;

16 shows a possible use of biosynthesis gas as fuel of a gas turbine plant with waste heat utilization and thermal power coupling;

17 shows the use of biosynthesis gas as Brennsoft for large engines for propulsion of ships and for the production of electricity;

18 shows the use of biosynthesis gas as fuel for large engines to propel ships;

19 the use of biosynthesis gas as a fuel for power generation and thermal power coupling by means of steam generation and steam turbine process.

Detailed description of the embodiments:

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 bio-syngas, as they are known from the 1a to 1c can be seen.

The Use of residual gases (off-gases, purge gases) of the subsequent processes (Down-stream processes) as fuel for the pulse burner will be discussed below.

The Execution of the SPOT gasification plant allows the use in the process routes described below resulting, high calorific off-gases, as in said processes arise as residual gases or purge gases from cycles, as fuel for the impulse burner system (impulse burner and integrated pilot burners).

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. By integrating the off-gases, the processes become an integrated element of the SPOT carburetor, the process steps to a directly unmistakably connected unit. (please refer 2 Circuit variants Supply the pulse burner with fuel gas.

The technical equipment allowed for starting the normal operation of the gasification plant with biosynthesis gas, natural gas and propane and the various exhaust gases of the subsequent processes. The concept allows starting even with carburetors connected in parallel Help of bio-synthesis gas from the parallel carburettors.

Of the Use of a mechanical gas cleaning and dedusting by means of Multicyclone and sintered metal filter (gas conditioning before compression the bio-synthesis gas in turbocompressors) is provided.

It a compaction of the biosynthesis gas is required and in consequence due to thermodynamic and mechanical requirements the cooling of the product gas to a temperature range preferably below 100 ° C required. In this temperature range condense, especially in start-up operation, in traces in the biosynthesis gas existing condensable hydrocarbons.

The concept described below, the mechanical purification of the biosynthesis gas in the ( 3 ) and the cooling in the preferably operated with oil, bio-diesel or other suitable washing and cooling media process stage ensures the required purity and the necessary cooling. The concept avoids the accumulation of technically unusable waste streams.

Mechanical gas cleaning is an important point to keep in mind. The separation of the dust content of the biosynthesis gas places special demands on the separation devices because of the extremely fine, carbonaceous dust. In the context of the SPOT process, after the intermediate cooling of the biosynthesis gas to preferably 250 to 450 ° C (design 310 ° C), the cooling to temperatures between preferably 150 ° C and 200 ° C (design 170 ° C) and the mechanical dedusting in a multicyclone and a downstream battery of sintered metal filters. (please refer 3 Concept of dedusting in the SPOT process). The cooling of the gas can be as in 3 shown in one or more stages before gas cleaning, partly in front of the multicyclone, partly between multicyclone and gas filters. These variations allow flexibility for characteristic requirements by the downstream process stages or to varying properties the input materials.

The Quenching and gas cooling to remove condensable Trace content in the bio-synthesis gas (gas conditioning before compression of the biosynthesis gas in piston or turbo compressors) is another approach to optimized use of the system.

To The mechanical cleaning step described above becomes the gas two-stage by quench and by direct countercurrent cooling in the Wash tower cooled to temperatures preferably below 100 ° C. This two-stage process is divided into evaporative cooling in the quench, not with oil or other suitable aqueous media, and the subsequent Cooling in the scrubbing tower, the coolant can be performed in counter-DC, or cross-current. quenching stands for an injection cooling.

The Gas is introduced into the quench, with the flow of the process apparatus by the integration vertically from above, laterally or from below. In the quench part of this process is done the admission of the gas with the quench medium, the gas cooling done here by evaporative cooling. After that it will be Gas in a column with internal internals and in direct contact further cooled with the cooling medium. That in the quench injected and abandoned in the washing and cooling column Coolant collects in template, either as integrated Part of the column or designed as a separate container is. The used in the process quench / cooling medium is refilled in this template.

This medium is passed through a cooling circuit by means of air cooler and water cooler and fed to the wash column. In addition to the in 4 variants shown are possible, which provide for the separation of quench and scrubber sump. 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 added to the cooling / washing column gets into the sump after passing the internals. Out of this swamp the quench is also supplied with cooling medium. This Cooling system allows the cooling of the pump sump by recycling this stream.

The in the gas existing condensable organic components are in the process described cooled, deposited and in the Enriched washing / cooling medium. Through a downstream demister (Entnebler for the removal of fine spray mist) becomes the gas stream of adhering, entrained wash / cool medium freed. The gas has thereby through this process for the subsequent process stages required temperature level.

In the submission of this stage, d. H. in the washing / cooling medium the washed-out portions of hydrocarbons and others Impurities, to limit the maximum concentration a partial flow must be expelled from this cycle. This purge stream is recycled and in the gasifier implemented together with the feedstock to bio-syngas.

The dust and condensate-free gas is fed to the compression stage.
(please refer 4 Flow diagram gas conditioning by quench with cooling)

• • Folgeprozesse auf dem Druckniveau der Vergasungseinheit: Drucklose und nahe atmosphärische Prozesse, wie die Verbrennung des Produktgases in Kesseln oder die Feuerung von Industrieöfen (z. B. Drehrohröfen zur Herstellung von gebranntem Kalk, Zementöfen etc.)
• • Folgeprozesse mit erhöhtem Druck
• • Prozesse mit integrierten Verdichtern (z. B. Turboladern) Als Beispiel sei hier der Einsatz des Bio-Synthesegases in Großmotoren angezeigt, wie sie zum Beispiel als Zweitaktmaschinen dem Antrieb großer Schiffe (Motorengröße zur Zeit bis etwa 100 MW mechanisch) dienen.
• • Prozesse mit externer Verdichtung, um den Synthesegasvordruck auf die für die nachfolgenden Prozesse notwendigen Reaktionsdruck zu heben. Hierzu zählen neben dem erwähnten Einsatz in Gasturbinenanlagen der Einsatz in Syntheseanlagen, die im Regelfall bei einem Druckniveau im Bereich 20 bis 30 bar a betrieben werden

This is followed by gas compression to the pressure stages necessary for the subsequent processes. The compression of the process stages depends on the requirements of the following processes and becomes necessary when the process pressure of this subsequent process stage is above that of the gasification, ie processes with separate compression. This stage can be integrated directly into the process stage or executed separately. In detail, these processes can be described as follows:

• • Subsequent processes at the pressure level of the gasification unit: Pressure-free and near-atmospheric processes, such as the combustion of the product gas in boilers or the firing of industrial furnaces (eg rotary kilns for the production of quicklime, cement kilns, etc.)
• • Follow-up processes with increased pressure
• • Processes with integrated compressors (eg turbochargers) As an example, the use of biosynthesis gas in large engines is indicated, as they serve as a two-stroke engines, the drive large ships (engine size currently up to about 100 MW mechanical).
• • External compression processes to increase the synthesis gas pressure to the reaction pressure required for subsequent processes. These include, in addition to the mentioned use in gas turbine plants, the use in synthesis plants, which are usually operated at a pressure level in the range 20 to 30 bar a

The 5 shows a flow diagram with compression level. The actual compression is carried out either as an integrated stage of the downstream heat engine (large engine, turbocharger) as an integrated compression stage in gas turbine plants, as a separate stage or in a mixed form. Depending on the gas volume and the overall circuit, either flow machines (turbo compressors) or reciprocating compressors (preferably Roots Ver denser).

One Another aspect is the production of input materials for energy production (Hydrogen), synthetic fuels and chemical products direct synthesis or with methanol as an intermediate.

in the Following are the processes for the synthesis of gasoline the methanol route and diesel over the Fischer-Tropsch route, the production of H2 based on bio-syngas as well as other routes for the production of chemical products.

In addition to the CO conversion (Crude-Gas-Shift reaction), the gas scrubbing, the process routes each include the entire gas generation according to the SPOT process with the purification stages and the compression. The following descriptions focus on the respective core processes in terms of a modular approach. In 1 is given an overview of the routes discussed.

at the CO shift reaction for the conversion of CO to H2 is a Adjustment of the H2 / CO ratio of the biosynthesis gas to the requirements of the follow-up process.

The technical bio-synthesis gas is after conditioning, compression by reacting a portion of the CO contained in the gas with water H2 and CO2 (homogeneous water gas reaction) on catalyst systems, z. For example, iron oxide-chromium oxide catalysts or equivalent catalyst systems, implemented. This conversion, the so-called raw gas conversion (Crude gas shift reaction), has the advantage of being in the synthesis gas contained water vapor as a reactant available is and saturation of the gas is eliminated. Dependent From the catalyst system, the process operates in the range of 200 ° C up to 500 ° C. With a suitable choice of reaction conditions and the catalyst system can achieve very low residual CO levels.

to Generation of H2 from the CO portions of the biosynthesis gas the entire synthesis gas stream is treated to produce methanol or Hydrocarbons after the Fischer-Tropsch synthesis is used for adjustment a certain proportion of CO / H2, only a partial stream of the biosynthesis gas converted.

One special feature of the process route described here is the possibility of adjusting the operating parameters the SPOT process on their reaction to influence the H2 to CO ratio so that the to be converted Proportion of gas flow is minimized.

The 7 shows the circuits of CO-shift processes / processes, complete shift or partial shift reaction.

The Gas cleaning by physical washing (Rectisol) is another process step.

The Bio-syngas, as is the conditioning and compression stage the plant operating according to the SPOT process and the crude shift reaction leaves, requires before further processing to H2, fuels or chemical products one to the requirement of the downstream Facilities adapted gas cleaning. In particular, the distance plays here of catalyst poisons and the adjustment of stoichiometry the reactions as a basis for the requirements of the Feed gas is the decisive role. As a typical representative of Process units for the purification of gases for the said Purpose is exemplified the Rectisol method for physical Laundry listed.

These Procedures work according to the absorption principle. Main elements of the Process are the absorber (wash tower) and the regenerators. In the absorber the interfering gas components are washed out in countercurrent and, load the washing liquid with it. In the regenerator These substances are separated from the washing liquid. The eluate is recycled and the separated Products are processed further.

in the The following describes the Rectisol process. With the help of this Washing process can be a total purification of synthesis gas carry out. The absorbent used is methanol. The distance of hydrogen sulphide, organic sulfur compounds, CO2 (carbon dioxide), Ammonia, hydrogen cyanide, resin pictures, higher hydrocarbons (naphtha, Crude benzene, iron and Metallcarbonyle) and water can be in perform this one process step. That under medium pressure from 5 to 40 bar ü standing raw gas is at temperatures between + 10 ° C and -80 ° C with methanol washed out. The loaded methanol is released by venting, evacuating and heating regenerated and then reused.

The Product of this stage is a gas with synthesis unit for Downstream processes such as methanol synthesis, ammonia synthesis or the hydrocracking process. Depending on the composition of the raw gas fall as by-products of naphtha, pure CO2 (z. For urea synthesis) and H2S rich gas.

The 8th 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 and by converting a partial flow to a H2 / CO ratio of 2 set and compressed to 20 to 25 bar ü Bio-synthesis gas is converted to methanol in the methanol process. When The process route becomes the world's leading low-pressure process selected. The catalytic process works with recycle gas for controlling the reaction conditions and for adjusting the reaction temperature the strongly exothermic reactions. By-products are steam (Removal of the reaction heat) and an off-gas. The steam is used to supply the process with electrical energy as an energy source used for compression of the biosynthesis gas, the off-gas is within the SPOT gasification process to generate the heat of reaction used the endothermic process; the process route becomes so to an integrated process. The specific advantages of the outlined Process chain, with due to the use of hydrogen-rich renewable resources, lies in the high material conversion. When The result remains to be noted that 100 tons of renewable resources 27 to methanol can be generated.

The 9 shows the synthesis of methanol from biosynthesis gas, gas was conditioned via the preceding stages for the synthesis, it is only the pure MeOH process shown.

Further a further processing of the methanol to chemical products can take place.

about the intermediate of methanol, recovered by itself is an excellent fuel, is the range of Production process for the production of gasoline open. Further syntheses from the field of organic chemistry also emphasize the role of this Substance as an intermediate.

10 shows the use of methanol from biosynthesis gas as the basis of other synthetic fuels and as a chemical raw material with its derivatives.

The Fischer-Tropsch synthesis for the production of hydrocarbons is another alternative.

in the Following is the production of diesel via the Fischer-Tropsch route described.

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 becomes hydrocarbon in the catalytic Fischer-Tropsch synthesis implemented. The reaction taking place on the solid catalyst proceeds in the temperature range between 200 ° C and 350 ° C from and at pressures between 20 and 30 bar ü.

Reaction equations for this are: nCO + (2n + 1) H2 ==== CnH (2n + 2) + nH2O parrafins nCO + (2n) H2 ==== CnH (2n + 2) + nH2O olefins nCO + (2n) H2 ==== CnH (2n + 1) OH + (n - 1) H2O Alcohols

current Developments are aimed at, even those present in the synthesis gas Convert CO2 with H2 to methanol.

The Product gas of the Fischer-Tropsch process is a mixture and is usually used in a hydro-cracker / diesel production processed with the highest cetane.

The Fischer Tropsch process supplies in addition to diesel (fuel), naphtha (Chemical.-Gasoline) LPG also waxes (oligomeric hydrocarbons).

The 11 describes the Fischer Tropsch synthesis from bio-syngas as a basis for synthetic fuels and as a chemical raw material with its derivatives.

This can by generation or direct separation or after complete Shift reaction done.

in the Following is the generation of H2 through complete Shift reaction described. H2 in pure form can be from bio-syngas over the described process steps receive. The by-product of the shift reaction CO2 is used in the subsequent gas purification process (eg Rectisol process) separated.

• • H2 (rein) Erzeugung durch Abrennen des CO2 mittels Gaswäsche (z. B. Heißpottasche-Wäsche)
• • H2 (rein) Erzeugung durch Abtrennung des H2 aus dem Gasstrom nach der Shift-Reaktion durch PSA (Pressure Swing Adsorption)
• • H2 (rein) Erzeugung durch Abtrennung des H2 aus dem Gasstrom nach der Shift-Reaktion durch PSA (Pressure Swing Adsorption oder Druckwechseladsorption)

Basically, here are three different processes:

• • H2 (pure) Generation by burning off the CO2 by gas scrubbing (eg hot potash scrubbing)
• • H2 (pure) Generation by separation of the H2 from the gas flow after the shift reaction by PSA (Pressure Swing Adsorption)
• • H2 (pure) Generation by separation of the H2 from the gas flow after the shift reaction by PSA (pressure swing adsorption or pressure swing adsorption)

The 12 shows the production of hydrogen (H2) from biosynthesis gas, by gas scrubbing, pressure swing adsorption or cryogenic decomposition.

The Possible uses of hydrogen based on bio-syngas are diverse. In addition to use in fuel cells For the direct generation of electricity, the hydrogen can be directly added to the Synthesis z. B. of ammonia and as an intermediate for a variety of chemical syntheses are used.

12 shows different process routes for hydrogen production from biosynthesis gas, and 13 gives an excerpt of the possibilities for the use of this gas as a reaction partner in chemical syntheses.

One Another aspect is the use of hydrogen in fuel cells for generating electrical energy.

The 14 shows the use of the hydrogen produced from renewable resources as fuel in fuel cells to generate electrical energy. The process heat, which arises in the fuel cell process, is used via a water / steam process to generate electricity by means of steam turbine and generator, with the possibility exists, by decoupling heat from the steam turbine process, a combined heat and power with the increase of Use efficiency.

One Another process step may be based on the use of ammonia of bio-synthesis gas (hydrogen production) and implementation 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. in the 15 this process is shown. In a subsequent reaction, the ammonia produced can be further processed to urea with the CO2 produced in the gas purification stage.

generation of electrical energy by means of thermodynamic processes Bio-syngas as fuel. In addition to the direct generation of electricity over the fuel cell can absorb electrical energy the basis of bio-syngas over the classic thermo-dynamic Create processes. These classic routes include generation of steam in a gas boiler and the use of the water vapor generated thereby in the steam turbine and the use of the gas in the gas turbine in the form of a combined process. This is where the electrical energy gets once directly through the generator driven by the gas turbine generates and the waste heat of the combustion gases of this turbine used for steam generation. The transformation of the steam thus generated to electrical energy by means of steam turbine and generator.

Next These processes offer the use of bio-synthesis gas as Fuel for heat engines with inner Burning on. These machines, as a two-stroke diesel engines z. B. are used in the field of propulsion of ships are today with 100 MW state of the art technology.

The technical bio-synthesis gas, as it is after conditioning before or after the compression stage accumulates, can directly without Further workup be used as a fuel gas. Dependent from these consumers, such as B. boiler systems or as industrial furnaces (Kalkdrehrohröfen), there is beyond the Possibility to further simplify the conditioning process.

One 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 process type is characterized by the use of the efficiency advantage due to the temperature operating point of the gas turbine and the waste heat utilization, which operate by post-firing at its optimum point leaves. (Working temperature gas turbine up to 1500 ° C, Steam turbine greater than 600 ° C at supercritical Application, otherwise in the range around 500 ° C).

The 18 shows the use of bio-synthesis gas as a chemical energy source for generating electrical energy in the gas turbine as a heat engine.

One Another aspect is the generation of mechanical energy by Heat engines with internal combustion to drive of large machinery, ships and for the production of electrical energy.

Use of the conditioned gas in internal combustion engines (flow or piston engines) to generate mechanical energy (in the case of propulsion engines, eg marine propulsion systems) or the generation of 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 taken from the cooling / fine dedusting (integrated part of the SPOT process) directly to the Turbola the (s) of the large engine supplied.

In These heat engines find the implementation of the gas and the conversion into mechanical energy with efficiencies of about 55 instead. Integrated into this system is a waste heat utilization, in which the exhaust gases of the pulse burner are coupled.

The 19 shows the use of bio-synthesis gas as a chemical energy source for generating mechanical energy in internal combustion heat engines for propulsion of ships and other large machinery and for power generation.

One Another approach is the use of biosynthesis gas as a chemical Energy source using the water / steam process and the steam turbine as a heat engine and thermal power coupling.

The simplest form of conversion of biosynthesis gas into electrical Energy is the use as fire for a boiler (parallel Industrial furnace use, part 1).

If 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 schematic of this process shows 19 ,

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited non-patent literature

• Wolfgang Adlhoch, Rheinbraun AG, Hisaaki Sumitomo Heavy Industries, Ltd., Joachim Wolff, Karsten Radtke (speaker), Krupp Uhde GmbH, Gasification Technology Conference, San Francisco, California, USA - "High-Temperature Winkler Gasification of Municipal Solid Waste" October 8-11, 2000; Conference Proceedings [0004]
• - "Decentralized power and heat generation based on biomass gasification", R. Rauch, H. Hofbauer, lecture University of Leipzig 2004 [0005]
• - "Circulating Fluidized Bed, Gasification with Air Operation Experience with CfB - Technology for Waste Utilization at a Cement Production Plant" R. Wirthwein, P. Scur, K.-F. Scharf - Ruedersdorfer Zement GmbH, H. Hirschfelder - Lurgi Energy and Disposal 7th International Conference on Circulating Fluidized Bed Technologies; Niagara Falls May 2002 [0005]
• - 30 MV Carbo V Biomass Gasifier for Municipal CHP; The CHP Project for the City of Aachen Matthias Rudloff; Lecture Paris October 2005 [0006]
• - Operation Results of the BGL Gasifier at Schwarze Pumpe Hans-Joachim Sander SVZ; Dr. Georg Daradimos, Hansjobst Hirschfelder Envirotherm; Gasification Technologies 2003; San Francisco California; October 12-15 2003; Conference Proceedings [0007]
• 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 Palo Alto Californic: ZWS Pressure Gasification in Combi-Block Final Report BMFT FB 03 E 6384-A; P. Mehrling LURGI GmbH; Bewag [0011]

Claims (10)

Process for the production of energy, fuels and / or chemical raw materials, comprising the steps: - Allothermic Water vapor gasification of renewable raw materials and / or residual gases of the Follow-up processes by a pulse burner; - gas purification; - gas cooling; - gas compression on the for the following processes by pressure stage - Shift Reaction to the conversion of the CO to H2, adjustment of the H2 / CO ratio of the crude biosynthesis gas to the needs of the / - gas cleaning, Removal of trace substances, the catalyst poisons for the subsequent process stages are; described by way of example the Rectisol process - Generation of one or more one of the following products: methanol synthesis for the production of methanaol as a fuel and raw material for chemical products and Fuel; Fischer-Tropsch synthesis and work-up of the products to fuel; Generation of H2 based on the biosynthesis gas. The method according to one or more of the preceding Claims, comprising - the production of Ammonia based on the H2 of the biosynthesis gas, - Implementation of ammonia by addition of CO2 to urea and other products The method according to one or more of the preceding Claims, wherein the gas cleaning a mechanical gas cleaning and / or Feinstentstaubung includes. The method of the preceding claim, wherein the hydrogen in fuel cells to produce electrical Energy is used. The method of the preceding claim, wherein a waste heat using steam turbine process takes place. The method according to one or more of the preceding Claims, wherein the gas cleaning a mechanical gas cleaning and / or Feinstentstaubung includes. The method according to one or more of the preceding Claims comprising a gas quench. The method according to one or more of the preceding Claims, wherein the gas cooling is combined with the removal of condensable trace amounts in the biosynthesis gas. The method according to one or more of the preceding Claims, wherein electrical energy by combustion of the biosynthesis gas in one or more of the following systems is produced: In the combustion chamber of a gas turbine, Waste heat utilization and thermal power coupling; Generation of electricity and useful heat; - in a steam boiler, Utilization of steam by steam turbine and thermal power coupling, Generation of electricity and useful heat; - by doing Gas engine for generating mechanical energy (drive eg from ships) - Generation of electricity by means of heat engines with internal combustion including use of residual heat the flue gases through a downstream steam turbine process. Use of according to one or more of the preceding Claims generated starting materials to drive a Ship engine.