EP2126006A1

EP2126006A1 - Method and device for the production of energy, fuels, or chemical raw materials using co2-neutral biogenic starter materials

Info

Publication number: EP2126006A1
Application number: EP08701376A
Authority: EP
Inventors: Oliver Neumann
Original assignee: Spot Spirit Of Technology AG
Current assignee: SPIRIT OF TECHNOLOGY AKTIENGESELLSCHAFT
Priority date: 2007-01-23
Filing date: 2008-01-10
Publication date: 2009-12-02
Also published as: WO2008090028A1; DE102007004294A1

Abstract

A method for the production of energy, fuels, and/or chemical raw materials, comprising the following steps: allothermic steam gasification of renewable raw materials and/or waste gases of the subsequent process by means of an impulse burner; gas scrubbing; gas cooling; gas compression to the levels required for the subsequent processes; shift reaction for converting the CO to H2, adjustment of the H2/CO ratio of the raw biosynthesis gas to the requirements of the; gas scrubbing, removal of trace materials which are catalyst poisons for the following process steps; for example, described according to the Rectisol process; production of one or several of the following products: methanol synthesis for the production of methanol as a fuel and raw material for chemical products and fuels; Fischer-Tropsch synthesis and workup of the products to make fuel; production of H2 based on the biosynthesis gas.

Description

Method and device for producing energy,

Fuels or chemical raw materials using CO2-neutral biogenic feedstocks

Field of the invention:

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

For the commercial gasification of biomass, primarily the fixed bed gasifier and the fluidized bed gasifier were further developed.

Of the many different technical approaches in the field of fixed-bed gasification, the Carbo-V process is shown here as an example.

Literature for fluidized-bed gasification which forms part of this application can be found in the following literature: Wolfgang Adlhoch, 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 ^Vλ ; R. Rauch, H. Hofbauer; Lecture University of Leipzig 2004. "Circulating Fluid 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 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 found in the following literature: 30 MV Carbo V Biomass Gasifier for Municipal CHP; The CHP Project for the City of Aachen Matthias Rudioff; Lecture Paris October 2005.

Literature for combination for the fixed-bed gasification (slag-down gasifier), 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.

In the Carbo-V process, gasification takes place in two stages. First, 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.

Due to the high technical and economic costs, due to the high pressure level (up to 40 bar), these carburettor types are completely unsuitable for the gasification of biomass (which is regionally produced and has a significant impact on the costs of logistics and processing).

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.

In Güssing (Austria), an allothermal, circulating fluidized bed gasification plant was put into operation in early 2002. The biomass is gasified in a fluidized bed with steam as the oxidant. To provide heat for the gasification process, part of the charcoal produced in the fluidized bed is burned in a second fluidized bed. The gasification under steam produces a product gas. Disadvantageous are the high initial costs of the system technology and an excessive effort for the process control.

In order to overcome the problems of the prior art, the Applicant has already filed a number of applications in the field, the disclosure content of which is part of this application. These applications are 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 pulse burners, which allow an indirect heat input into the fluidized bed located in the reactor. Hereinafter, 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 the following process steps can be refined:

method

As a result, it should be noted that 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

Steam converter or directly in the corresponding gas line.

The pollutant components to be removed from the product gas

(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 feedstocks by the addition of the adsorbent to the gasification reactor. This immediate adsorption immediately after release of the pollutant components is referred to as "in situ" gas purification (in the case of removal of sulphurous components as desulphurization) The sulfur component in question is thus directly at the place of formation, ie in the reaction zone of the gasification by means of the additive (practical during its formation), the sulfur (or the homologues selenium and telur) react to the sulfides, selenides and telurides, which is known from applications in combustion processes and similar gasification processes (Lit .: 6; 7) for other burns and gasification in the literature has been described.

In a first step, 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.

In addition to the removal of sulfur-containing components, 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

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.

In the second step, 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

(For example, the 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. In addition to a direct task either as a supplement to the feedstock or the direct metering in the steam converter, the injection into the external cyclone is expedient, especially to find suitable reaction conditions for the case of chlorine absorption. In general, 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.

The deposition of dust as a further step in the synthesis gas makes special demands on the deposition of extremely fine, high-carbon dust. In the context of the process according to the invention, after intermediate cooling to temperatures between 150 and 700 ° C. (above the dew point of the synthesis gas), 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

Filter unit. 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. At these forms of the candles of the non-separated in the multicyclone stage dust and laden Adsorbensanteilen 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. In addition, it is possible to selectively meter adsorbent in this area again. Layer thickness and the low flow rate of the cake are essential parameters.

Overview of the invention:

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.

This object is achieved by a method and an apparatus having the features of the independent claims.

The underlying gasification process allothermal steam gasification with pulse burner is the most different types of renewable resources suitable, including the patented SPOT Power for ^"

Greenies to produce by chemical synthesis

Convert fuels, chemical products and as a feedstock for the production of energy, combustion in boilers, gas turbines or internal combustion heat engines suitable described ibid bio-synthesis gas.

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. Due to the basic reaction conditions, 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. Moreover, 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.

The inventions described below deal with the circuit of the process routes that allow the biosynthesis gas of the SPOT gasifier to be used to generate energy, fuels and chemical products. These Routes are characterized by the integrated use of the purge

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.

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 utilization by steam turbine process)

5.7 Generation of ammonia based on the H2 of the biosynthesis gas, conversion of the ammonia by addition to CO2

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 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;

Brief Description:

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;

5 shows the gas compression to the pressure level necessary for the down-stream processes; Fig. 6 shows a further overview for dedusting, the

Quench cooling and compression;

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;

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

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

Electricity generation and combined heat and power 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 biosynthesis gas, as can be seen from FIGS. 1 a to 1 c.

The use of residual gases (off-gases, purge gases) of the downstream processes (down-stream processes) as fuel for the pulse burners is discussed below.

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. By integrating the off-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

Normal operation of the gasification plant with bio-synthesis gas, natural gas and propane as well as the various exhaust gases of the subsequent processes. The concept also allows starting with the help of bio-synthesis gas from the parallel carburettors, even with parallel carburettors.

The use of a mechanical gas cleaning and fine dedusting by means of multi-cyclone and sintered metal filter (gas conditioning before compression of the biosynthesis gas in turbocompressors) is provided.

It is a compaction of the biosynthesis gas required and in consequence of thermodynamic and mechanical engineering requirements out the cooling of the product gas to a temperature range preferably below 100 ° C required. In this temperature range, condensable hydrocarbons present in traces in the biosynthesis gas condense, in particular during startup operation.

The concept described below, the mechanical purification of the biosynthesis gas in the process stage described in (FIG. 3) and the cooling in the process stage preferably operated with oil, bio-diesel or other suitable washing and cooling media ensure 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. As part 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 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. These variations allow flexibility to respond to characteristic requirements through the downstream process stages or to varying properties of the starting materials.

Quenching and gas cooling to remove condensable trace amounts in the biosynthetic gas (gas conditioning prior to compression of the biosynthetic gas in piston or turbo compressors) is another approach to optimized use of the system. After the mechanical cleaning stage described above, 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. In the quench part of this process, the admission of the gas takes place with the Ouench medium, the gas cooling takes place here by evaporative cooling. Thereafter, 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

Quench / cooling medium is fed 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 exemplary circuit shown in FIG. 4, 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. By 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.

In the template of this stage, i. in the washing / cooling medium, the washed-out portions of hydrocarbons and other impurities accumulate to limit the maximum

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

Cooling)

This is followed by gas compression to the pressure stages necessary for the subsequent processes. The compression of

Process levels depend on the requirements of subsequent processes and will be required when the

Process pressure of this subsequent process stage above the

Gasification is concerned, these are processes with separate compression. This level can be directly into the

Process stage integrated or executed separately. in the

Some of these processes can be described as follows:

• Subsequent processes at the pressure level of the gasification unit: pressureless 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, such as the two-stroke engine used to 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. In addition to the mentioned use in gas turbine plants, these include the use in synthesis plants which are normally operated at a pressure level in the range from 20 to 30 bar a. 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. Depending on the gas volume and the overall circuit, either flow machines (turbo compressors) or reciprocating compressors (preferably Roots compressors) are used.

Another aspect is the production of input materials for

Energy production (hydrogen), synthetic fuels and

Chemistry products via direct synthesis or with methanol as an intermediate. In the following, the processes for the synthesis of gasoline via the methanol route and of diesel over the Fischer-Tropsch route, the production of H2 based on biosynthesis gas and other routes for the production of chemical products are described. 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. FIG. 1 gives an overview of the routes discussed.

In the CO shift reaction for the conversion of CO to H2, 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

Gases deleted. Depending on the catalyst system, the process operates in the range of 200 ° C to 500 ° C. With a suitable choice of reaction conditions and the catalyst system can be achieved very low residual CO contents.

To generate 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, 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. As a typical representative of process units for the purification of gases for the purposes mentioned, the Rectisol process for physical washing is exemplified. These methods work on the absorption principle.

The 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 the washing liquid is loaded with it. In the regenerator these substances are separated from the washing liquid. The eluate is recycled and the separated products are processed further.

The following describes the Rectisol process. With the help of this washing process, a total purification of synthesis gas can be carried out. As Absorbens serves

Methanol. The removal of hydrogen sulfide, organic

Sulfur compounds, CO2 (carbon dioxide), ammonia, hydrocyanic acid,

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

+10 ⁰ C and -80 ⁰ C with methanol washed out. The loaded one

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. Depending on the composition of the raw gas, 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. As a process route here is the world selected low pressure method. The catalytic

Method works with recycle gas to control the reaction conditions and to adjust the reaction temperature of the highly exothermic reactions. As by-products arise steam (removal of the heat of reaction) and an off-gas. The steam is used to supply the process with electrical energy as an energy source for the compression of the biosynthesis gas, the off-gas is used within the SPOT gasification process to generate the heat of reaction of the endothermic process; the process route becomes an integrated process. The specific advantages of the outlined process chain, due to the use of hydrogen-rich renewable raw materials, lies in the high material conversion. As a result, it should be noted that from 100 to renewable raw materials 27 to methanol can be produced.

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

Furthermore, further processing of the methanol to chemical products can take place.

Through the intermediate stage of methanol, which is obtained by itself an excellent fuel, the range of production processes for the production of gasoline is open. Further syntheses in 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 further synthetic fuels and as a chemical raw material with its secondary products.

The Fischer-Tropsch synthesis for the production of hydrocarbons is another alternative. In the following, 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 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. 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 + l) OH + (nl) H2O Alcohols

Current developments aim to convert the CO2 present in the syngas with H2 to methanol.

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.

The following describes the generation of H2 by 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:

• H2 (pure) generation by burning off the CO2 by gas scrubbing (e.g., 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)

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, and 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

Fuel cells for generating 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 a steam turbine and generator, whereby the possibility exists, by the extraction of heat from the

Steam turbine process, a combined heat and power with the

Increase the efficiency use. 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. 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 using bio-syngas as fuel. In addition to the direct generation of electricity via the fuel cell, 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.

In addition to these processes, the use of 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. Depending on 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

(Flow or piston engines) with internal combustion for

Generation of mechanical energy (in the case of

Drive machines such as marine propulsion) 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 fed from the cooling / fine dedusting (integrated part of the SPOT process) directly to the turbocharger (s) of the large engine. In these heat engines, the conversion of the gas and the conversion into mechanical energy takes place with efficiencies of about 55%. Integrated into this system is 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.

The simplest form of conversion of bio-synthesis gas into electrical energy is the use as a fire for a boiler (parallel industrial furnace use, 1st part).

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 diagram of this process is shown in FIG. 19.

Claims

claims

1. A 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 subsequent processes by a pulse burner;

- gas purification; - gas cooling;

- Gas compression on the subsequent processes by pressure stage

- Shift reaction for the conversion of the CO to H2, adjustment of the H2 / CO ratio of the crude biosynthesis gas to the requirements of the /

- Gas purification, removal of trace substances that 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 methanaol as

Fuel and raw material for chemical products and fuel; Fischer-Tropsch synthesis and processing of the products into fuel; Generation of H2 based on the biosynthesis gas.

2. The method according to one or more of the preceding claims, comprising

the production of ammonia on the basis of the H2 of the biosynthesis gas,

- Implementation of ammonia by addition of CO2 to urea and other products.

3. The method according to one or more of the preceding claims, wherein the gas cleaning comprises a mechanical gas cleaning and / or Feinstentstaubung.

4. The method according to the preceding claim, wherein the hydrogen is used in fuel cells for generating electrical energy.

5. The method according to the preceding claim, wherein a waste heat utilization takes place by means of steam turbine process.

6. The method according to one or more of the preceding claims, wherein the gas cleaning comprises a mechanical gas cleaning and / or Feinstentstaubung.

7. The method according to one or more of the preceding claims, comprising a gas quench.

8. The method according to one or more of the preceding claims, wherein the gas cooling is combined with a removal of condensable trace amounts in the biosynthesis gas.

9. The method according to one or more of the preceding claims, wherein electrical energy is generated by combustion of the biosynthesis gas in one or more of the following systems: in the combustion chamber of a gas turbine, waste heat utilization and thermal power coupling; Generation of electricity and useful heat; - In a boiler for steam generation, use of steam by steam turbine and thermal power, generation of electricity and useful heat; in the gas engine for generating mechanical energy (propulsion of ships, for example)

Generation of electricity by means of internal combustion heat engines including utilization of the residual heat of the flue gases by a downstream steam turbine process.

10. Use of the starting materials produced according to one or more of the preceding claims for driving a marine engine.