WO2008034596A1

WO2008034596A1 - Installation and method for the production of fuels made of biogenic raw material

Info

Publication number: WO2008034596A1
Application number: PCT/EP2007/008139
Authority: WO
Inventors: Emil A. J. Wieser-Linhart
Original assignee: Lignosol Gmbh & Co. Kg
Priority date: 2006-09-20
Filing date: 2007-09-19
Publication date: 2008-03-27
Also published as: EP2082007A1

Abstract

The present invention relates to a method for the production of fuels made of biogenic raw material and to an installation for the execution of said method.

Description

Plant and process for the production of fuels from biogenic raw materials

The present invention relates to a process for the production of fuels from biogenic raw materials and to a plant for carrying out the process.

For the production of fuels from biogenic raw materials, various processes have been proposed according to the prior art.

One of the proposed methods is the flash pyrolysis of biomass in a hot sand fluid bed with subsequent rapid condensation of the resulting pyrolysis oils. Another proposed method is the so-called COREN method, which is a multi-step process. In the first stage, a gasification by means of oxygen, the so-called Carbo-V process for the production of synthesis gas (H2, CO, CO2). In the second stage, a synthesis gas purification and CO 2 ~ scrubbing takes place. In the third stage, the Fischer-Tropsch synthesis takes place, which ultimately leads to diesel by means of catalysis and condensation.

Also proposed is an entrained-flow gasification process in which coke, pyrolysis gas and pyrolysis oil are produced indirectly in an inert gas stream, without catalysis, in a plurality of process stages with subsequent condensation.

DE 100 49 377 C2 describes a process for lubricating plastics, fats, oils and other hydrocarbon-containing wastes. It can with the aid of a catalyst of sodium aluminum silicate in a circulation evaporator in the circulation with a base oil diesel be generated, which is subsequently separated by distillation and thus recovered.

DE 199 41497 describes an apparatus and a method for the catalytic leaching of wood by smoldering, burning the smoldered residues and burning the smoldering products in a container with honeycomb combustion catalysts at the top.

No. 4,648,965 describes a process for the preparation of liquid products from carbonaceous starting material which contains inorganic, catalytically active constituents.

US 4038172 describes a high pressure process for treating oxygenated starting materials, e.g. Wood, using a "red clay catalyst composition" in the presence of carbon monoxide.

WO2006131293 relates to methods for

Production of fuels from biogenic raw materials and a plant and catalyst composition for carrying out the process. The process disclosed therein comprises a two-step reaction sequence at 150-250 ° C ("Reaction") and 250-300 ° C ("Tire").

However, these various proposed methods have several disadvantages.

The disadvantage of flash pyrolysis with subsequent condensation is in the high

Reaction temperatures and the poor quality of the obtained pyrolysis oils. These contain too much tar, oxygen and water and are unsuitable as fuels. The CHOREN process requires a very complex and thus expensive investment technique and results in a very low energy yield of about 40%. from that This results in high operating costs, which uneconomically limit the process.

The entrained flow gasification process generates a large amount of gas and coke due to the high temperatures required, the oil yield is only half that of liquid oiling and the oil quality is insufficient.

The catalytic recycle evaporator method according to DE 100 49 377 C2 is unsuitable for biomass (such as wood) because biomass contains only a few hydrocarbons and is composed predominantly of carbohydrates such as lignin and cellulose. Furthermore, biomass is not dissolved quickly enough in the circulation process and thus largely excreted again via the disclosed solids sluice. In addition, a fossil carrier oil, which has to be supplemented on an ongoing basis, is required. In addition, the catalyst used "sodium aluminum silicate" (molecular sieve powder) is very expensive and thus increases the operating costs. Another disadvantage of this method is that due to the process, the heating surfaces tend to heavy deposit formation in wood and thus economic operation is not possible. Finally, when wood is used as raw material, a relatively large amount of coal is also produced as residue, whose economic utilization or disposal in the circulation steam process is problematic.

Due to the limited supplies of fossil fuels oil and gas, there is a need to produce fuels from renewable sources. In particular, there is a need to produce fuels such as gas oil, diesel fuel and gasoline from biomass, especially from wood.

An object of the present invention is to provide an alternative method and apparatus for producing fuels. Another object of the present invention is to provide a process for producing fuels from biogenic raw materials. A further object is to provide a system for carrying out this method which does not have the mentioned disadvantages. Of particular importance is to provide an economically operating plant that produces high quality products, works with good yield and meets applicable emission limits.

The above-outlined objects are achieved according to the independent claims. The dependent claims represent advantageous embodiments. The invention thus relates to a process for the production of fuels from biogenic raw materials. The invention further relates to a plant for the production of fuels from biogenic raw materials.

Unless otherwise stated in the direct context, the following terms have the meaning given here

"Biogenic raw materials" or "biomass" refers to the living organisms continuously biochemically synthesized organic substances and derived or extracted derived products. The biogenic raw materials can, depending on the producing organism, in the areas of plant, microbial and animal Biomass be broken down. Vegetable biomass includes, for example, wood, leaves, straw, bran, hay, cereals, press residues from fruit and viticulture, beet pulp, green waste, garden and agricultural waste, but also derived products such as residual wood products, starch,

Sugar, cellulose, waste paper, as well as vegetable fats and oils and their pressed residues. Microbial biomass includes, for example, dried sewage sludge, as well as fermenter and digestate. Animal biomass includes, for example, residues from animal husbandry, the

Fish industry and meat industry, residual products from the dairy and cheese industry but also animal meal, animal fats and animal oils. Biogenic raw materials can be liquid or solid. In the context of the present invention preferred in plant biomass. Solid biomass is furthermore preferred in the context of the present invention. Biomass is particularly preferably obtained from woody plants or annuals. Examples include wood, such as tree trunks, especially non-industrially exploitable tree trunks,

Tree branches, break wood, waste wood from wood processing plants; Garden waste and agricultural waste.

"Fuels" are known to those skilled in the art, and the term generally refers to hydrocarbon-containing compounds and mixtures as can be used in internal combustion engines.The term also includes those substances and mixtures which do not meet certain standards for fuels but are suitable as a precursor The term "mixtures of substances" includes C6-C25 aclans, C6-C25 alkenes, C6-C25 alkynes, C3-C25 cycloalkanes, C3-C25 cycloalkenes and / or C6-C25 aromatics, these definitions also include alkyl-substituted compounds such as Toluene or methylcyclohexane and branched compounds such as 2-ethylhexane.

"Carrier liquid" or "carrier oil" refers to a largely inert or inert liquid under reaction conditions. A liquid is then "substantially inert" if it remains at least 90% unchanged in a reaction cycle.) This liquid is suitable for suspending the catalyst and the biogenic raw material

Implementation of the inventive method continuously arises. Alternative carrier oils, suitable in particular when starting up a plant, are gas oil, diesel or a mixture thereof. Further alternative carrier oils are synthetic paraffinic base oils having a boiling range above 400 ° C., or polyethylene glycols with appropriate thermal stability. The carrier liquid is in direct contact with the biogenic raw material and the catalyst during the process. "Thermal oil" refers to a liquid for indirect heat transfer in the process according to the invention Suitable thermo oils are known to the person skilled in the art and can be based on silicone oils or hydrocarbons In the context of the present invention, any thermo oils adapted to the reaction temperature can be used Catalyst not in direct contact during the process.

"Mineral Catalyst" or "Catalyst" refers to a natural mineral clay which typically contains the active ingredients montmorriolite, illite and / or smectite. Preferably, the clay is first dried and finely ground. In In a further preferred embodiment, the finely ground alumina is mixed with carrier liquid such that the catalyst is in the form of a slurry ("catalyst slurry"). Clays containing at least 50% mass% of a layered silicate, more preferably montmorriolite, illite and / or or smectite.

The general, preferred and particularly preferred embodiments, ranges, etc. given in connection with the present invention may be combined with one another as desired. Likewise, individual definitions, embodiments, etc. may be omitted or not relevant.

Fig. 1 shows schematically an example of a system according to the invention. The invention, in particular the method and the system, will be explained in more detail below with reference to FIG. Shown in this scheme are the two main units for "Core Unit" and Energy Management ("Powerplant"), but not the raw material preparation and the utilization of the products coal, fuels, water.

A first aspect of the invention

Process for the production of fuels from biogenic raw materials, is explained in more detail below.

The invention relates to a process for the production of fuels from biogenic raw materials, characterized in that a mixture containing i) crushed, dried, biogenic raw material; ii) carrier liquid and iii) alumina mineral catalyst containing montmorriolite, illite and / or smectite contains, with heating to 300 - 400 ° C (especially: over 300 ° C to 400 ° C) is reacted and the resulting fuel is separated from the reaction mixture. The term biogenic raw material is explained above. Typically, the raw material "comminuted" is fed to the reactor, ie in the form of shavings, chips, chaff, shaped pieces or the like, so that a rapid and complete impregnation and / or reaction is possible.Which size is suitable depends on the biogenic material used off and can be in simple

Try to be determined. Typically, 90% of the biogenic raw material fed to the reactor is 0.01-10 cm 3, preferably 0.2-5 cm 3. When using wood, an edge length of approx. 0.5 * 1.0 * 1.0 cm has proven to be the upper limit. Straw chaff can be used as it is produced in agriculture. Typically, the raw material is dried, ie fed to the reactor with a residual moisture of less than 20%. The reaction products of the process according to the invention can be divided into 4 groups: i) non-condensable gases; ii) product oil; iii) coal and iv) process water. The resulting product oil either immediately fulfills the above-mentioned criteria of a "fuel" or has to be aftertreated (eg rectification, phase separation, degassing) in order to fulfill these criteria.The optimum reaction temperature depends inter alia on the type of biogenic raw material used Wood is the preferred reaction temperature at 350-370 ° C, for other raw materials it may be lower (eg straw) or even higher.The optimal temperature in each case can be determined by routine experimentation. A wide range of biogenic raw materials can be used in the present process. Thus, only solid biogenic raw materials can be used, or only liquid biogenic raw materials or mixtures of the two types of biogenic raw materials. If reference is made in the present invention to comminuted biogenic raw materials, this implies that at least part of the biogenic raw material used is solid. Accordingly, in an alternative embodiment of the process according to the invention, a liquid biogenic raw material is used instead of comminuted, dried, biogenic raw material.

In a further alternative embodiment, therefore, a liquid biogenic raw material is used in addition to the comminuted, dried, biogenic raw material.

In a further embodiment, the invention relates to a method as described above, characterized in that initially comminuted, dried, biogenic raw material at 150 - 200 ° C is impregnated with carrier liquid. The amount of necessary carrier liquid for the impregnation depends inter alia on the grain size and the structure of the respective biogenic raw material. Since the carrier oil typically both deposits on the surface of the raw material and draws into the pores, fine porous raw material binds more carrier oil as a raw material which is coarse and / or without pores. With mixed addition of solid and liquid biomass, the addition of the liquid biomass can take place both in the impregnator and in the reactor 1. A range of 100-300% carrier oil Absorbance, related to atro (absolutely dry) raw material, is typical. Since the impregnated raw material is subsequently fed into the reactor 1, and thus entrains carrier oil from the impregnator, this loss must be compensated by recycling of carrier oil. In this process variant impregnation and reaction are carried out in a plant, resulting in improved heat coupling and easier reaction. Alternatively, biogenic raw material can be externally impregnated and supplied with carrier liquid.

Impregnation is to be understood as the intimate mixing of carrier liquid with comminuted biogenic raw material, wherein the raw material is at least partially soaked in carrier liquid. Surprisingly, no significant decomposition of the biogenic material (in particular when using wood) is observed at the comparatively high temperatures of the impregnation. At the same time, a large part of the water present in the starting material is expelled at the start of the process, which results in an overall lower mass flow in the subsequent reaction steps.

With the sole addition of liquid biomass without solid biomass, e.g. Vegetable and animal fats and oils (which are typically present as triglycerides) can be dispensed with the impregnation, so that they can be added to the reactor 1, optionally together with the catalyst. At which point liquid biomass is introduced into the process depends i.a. from the design of the plant and the composition of the biomass (e.g., water content). The

Composition of the biomass (eg sulfur and nitrogen content) also influences the post-treatment steps for the production of fuels. In a further embodiment, the invention relates to a method as described above, characterized in that the gases formed during the impregnation are condensed separately. The gases formed in the impregnation contain predominantly water vapor, which arises from the evaporation of the capillary water (moisture) of the biogenic raw material, whereas the resulting in the reaction mixed steam contains only a water vapor content substantially corresponding to the resulting in the reaction itself chemical process water content. It has therefore proved to be advantageous to condense both gas streams separately and, if appropriate, to treat them separately.

In a further embodiment, the invention relates to a process as described above, characterized in that the reaction of i) crushed, dried, biogenic raw material; ii) carrier liquid and iii) mineral catalyst is carried out in two successive reaction steps, wherein the reaction temperature in the second reaction step 0 - 3O ° C higher than in the first reaction step. This process variant leads to an improved product mix, which leads to less coal and more fuels. In a further embodiment, the invention relates to a process as described above, characterized in that the gases formed during the reaction are condensed separately. As stated above, it may be advantageous to use the gases from the impregnator and the reactor (s) because of their different properties

Water content to condense separately and then subject to any necessary further treatment. In a further embodiment, the invention relates to a method as described above, characterized in that the gases formed during the reaction are condensed separately and the condensed gases are separated into their phases and further processed separately. The mixed vapor leaving the reactors typically forms, after condensation, a noncondensable gaseous phase (ie a phase whose components are predominantly gaseous at normal conditions) and three liquid phases: a product oil phase, an aqueous phase and a heavy oil phase. For optimum material and energy utilization in the process, it is advisable to separate these three liquid phases over the different densities and process them separately.

In a further embodiment, the invention relates to a method as described above, characterized in that the non-condensable gases formed in the process are partially or completely supplied to a gas engine. For the gases formed, various uses are open; they can either be flared, burned in a gas engine or dissolved / adsorbed in a carrier. The individual methods can also be combined with each other. Which use is made depends, inter alia. economic and (safety) technical considerations. Preferably, a major part or the total amount of gas produced is supplied to a gas engine, in order to enable optimal energy utilization (thermal / electrical) of the biogenic raw material used.

In a further embodiment, the invention relates to a method as described above characterized in that the fuels formed in the process are partially or completely supplied to a diesel engine. There are various uses for the fuels formed: they can either be commercialized (if necessary after further processing) or used further in the context of internal requirements. When supplied to a diesel engine, the own energy requirements of the system can be partially or completely covered. Which use is made depends, among other things, on economic considerations and product quality.

In a further embodiment, the invention relates to a method as described above, characterized in that the exhaust gases of the engines are supplied to a heat recovery. This measure improves the energy balance of the plant.

In a further embodiment, the invention relates to a method as described above, characterized in that the motors serve to generate electrical energy. In one embodiment, all of the resulting gases are used to generate energy. In a further embodiment, however, the diesel engine is used only to the extent that it is necessary for the energy consumption of the plant according to the invention.

In a further embodiment, the invention relates to a process as described above, characterized in that catalyst is added together with the biogenic raw material at the beginning of the process and / or after the impregnation and before the reaction. The catalyst can be fed into the reactor 1 as a solid or as a suspension / slurry. Optionally catalyst can be added again in reactor 2. The catalyst composition used in the process according to the invention is explained in more detail below: The catalyst composition contains i) alumina which contains montmorriolite, illite and / or smectite and ii) carrier liquid. The ratio of

Alumina to carrier liquid can be varied within a wide range. On the one hand, a high catalyst concentration is desirable, on the other hand, simple and safe handling in the plant must be ensured. Typically, the catalyst composition contains 10-90% by weight of clay, preferably 20-75% by weight, for example 50% by weight. As a suitable carrier liquid high-boiling heavy oil is called. The carrier liquid used is preferably high-boiling heavy oil, which continuously forms during the implementation of the process. The clay preferably contains 20-75% by mass of montmorriolite, illite and / or smectite and particularly preferably 50% by mass of montmorriolite, illite and / or smectite. In an alternative embodiment, an alumina is used as a catalyst containing other than the above-mentioned layered silicates. Preferably, the catalyst is added to the same as described above in an amount of 0.3-6.0% of the comminuted raw material. Preferably, the catalyst is added slurried in carrier oil.

In a further embodiment, the invention relates to a process as described above, characterized in that the coal formed as a reaction product is separated continuously. This separation can be done by means of a decanter.

Advantageously, the separation of the coal formed takes place in the flow-calmed lower part of the reactor 2. In a preferred embodiment, the separation takes place the coal from the reactor 2 together with adhering carrier oil; the coal / carrier oil mixture can be separated from one another in one or more subsequent treatment steps. This separation may be due to gravitational / centrifugal force and / or thermal (ie, evaporation of the heavy oil, possibly at reduced pressure); Both principles can also be used. Typically, both principles, first stage decanter, second stage evaporation, are applied one after the other.

In a further embodiment, the invention relates to a process as described above, characterized in that the carbon formed as a reaction product is separated continuously and the separated coal is mixed with emerging product water to exclude air. The mixture under exclusion of air is advantageous because the separated coal is initially very hot and would burn off automatically if air enters immediately. The formed coal sludge is a common form for the transport and the use of finely divided coal / coal dust. This process variant also allows the disposal of possibly contaminated product water without further purification of the same.

The individual steps of the process according to the invention can be summarized for solid biogenic material as follows: IgGf. Crushing and predrying of the biogenic material to less than 20% residual moisture

2. optionally impregnation of the obtained biogenic material with carrier oil at about 200 ° C and optionally separation of the resulting gases 3. Reaction of the impregnated biogenic material in the presence of the catalyst at 300-400 ° C in a first reactor and separation of the resulting mixed vapor 4. Further reaction of the resulting reaction mixture in a second reactor at a temperature increased by 0-30 ° C relative to the first reactor and separation of the resulting mixed vapor

5. optionally separating the carbon formed and the carrier oil from the reaction mixture

6. If necessary, separation of coal / carrier oil and recycling of the carrier oil.

The individual steps of the inventive method for the addition of exclusively liquid biogenic material can be summarized as follows: 1. Reaction of the biogenic material in the presence of the

Catalyst at 300-400 ° C in a first reactor and separation of the resulting mixed vapor 2nd optionally further reaction of the resulting reaction mixture in a second reactor at a 0-30 ° C compared to the first reactor elevated temperature and separation of the resulting mixed steam

3. optionally separating the carbon formed and the carrier oil from the reaction mixture

4. if necessary, separation of coal / carrier oil and recycling of the carrier oil.

An advantage of the process control according to the invention is the favorable energy and mass balance.

Another advantage of the process control according to the invention is the robustness of the process both in terms of fluctuations in the quality of the biogenic raw material as well as in relation to the necessary plant components.

A further advantage of the process control according to the invention is that all volatile components are evaporated in the reactor 1 and 2, and thus a separate evaporation tank can be dispensed with.

A further advantage of the process control according to the invention is that the comminution of the biogenic raw material must take place only at the beginning of the overall process and a comminution between the individual process steps can be dispensed with.

A second aspect of the invention, a plant suitable for carrying out the above process, is explained in more detail below.

In one embodiment, the plant according to the invention comprises:

^■ if necessary, a heated treater (in which the carrier liquid is mixed with the comminuted biogenic raw material) of which

^■ a heatable first reactor (in which, after addition of the catalyst, essentially the polymer structure and the lignin of the cellulose of the biogenic raw material are decomposed, the mixed vapor (containing H2O, CO, CO2 and carboxylic acids) is deposited and at the same time the polymerization of the resulting monomers takes place) followed, which of

^{■ followed by} a heatable second reactor (in which not yet fully reacted material has reacted), which may be replaced by

^■ a device for separating coal / oil mixtures (in which the carrier oil is partially or completely separated from the coal formed) followed. In an advantageous embodiment, the plant according to the invention comprises a comminution device (for comminution of the supplied biogenic raw material (in the case of wood to chips)) which precedes the impregnator.

In an advantageous embodiment, the system according to the invention comprises a thermal deoiler / entraining screw (for further separation of carrier oil and formed coal), which is connected downstream of the decanter or connected in parallel thereto.

In an advantageous embodiment, the system according to the invention comprises a heat exchanger (for separating the free and capillary water generated from the gas phase in the impragnator) which is assigned to the impragnator.

In an advantageous embodiment, the system according to the invention comprises a condenser (for separating the mixed steam produced in the reactors 1 and 2) which is assigned to the reactors 1 and 2.

In an advantageous embodiment, the system according to the invention comprises a three-phase separator (for separating the condensate generated in the converter) which is assigned to the condenser.

In an advantageous embodiment, the system according to the invention comprises a gas engine which burns some or all of the gases accumulating in the system (from impragnator, condenser, rectification, venting of the coal slurry tank) and thus serves to generate electricity and / or heat. In an advantageous embodiment, the system according to the invention comprises a diesel engine which burns some or all of the product oils produced in the system and thus serves to generate electricity and / or heat.

In an advantageous embodiment, the system according to the invention comprises a tank which is connected downstream of the de-oiler (for receiving a part or all of the coal produced and part or all of the aqueous phases produced in the system) and the generated

Suspension for further processing provides. Preferably, this tank is equipped with a stirring device. Preferably, this tank is designed airtight. These measures allow the simple production of a coal / water suspension.

In an advantageous embodiment, the plant according to the invention comprises screws for transporting the reaction mixture from the three container impregnator, reactor 1, reactor 2 into the respective downstream part of the installation. By this measure it is achieved that during transport of solids through the plant also non-dissolving coarse material such. Sand, metal parts etc. are safely guided through the plant. Thus, this measure serves to improve operational and plant safety. In a preferred embodiment, these coarse materials are freed of oil via the de-oiling screw, arrive as a solid in the coal sludge produced by adding the water condensate and can thus be safely disposed of.

The inventive system can be stationary or mobile. Depending on the size of the system, the throughput of mobile systems (for example, for land- Economy) 5 tons of biogenic raw material, with stationary plants up to several thousand tons biogenic raw material per day amount, obviously dependent on the dimensioning of the entire plant regarding their employment. The dimensioning of the system can be done by an enlargement / reduction of the individual plant parts or by parallel connection of system parts.

The individual plant parts of the plant according to the invention as described here (impregnator, reactor 1 and 2, decanter, deoiler, condenser, phase separator,...) Are known per se and are commercially available in whole or in part. The selection of suitable dimensions, materials, installations, etc. is within the scope of technical expertise. As is clear from the foregoing, the plant parts impregnator, reactor 1 reactor 2, decanters are connected in series one behind the other. For various reasons (for example, operational safety, flexibility), it may be desirable or necessary to supplement individual system parts with other system parts connected in parallel. Thus, e.g. two parallel operated impregnators may be followed by a reactor 1 or more reactors 2 may be followed by a decanter 1. This also applies to the ancillary plant components such as columns, connecting lines, pumps, etc. In the context of the present invention, such alternatives are included and are not named separately.

The inventive system can be operated with only one crushing device; In particular, a dispersion between impregnator and reactor 1 is not necessary. This can The amount of necessary carrier oil can be reduced and overall the heat balance can be improved.

The inventive system can be driven with a simple temperature profile. Each container (impregnator, reactor 1 and 2) is operated at a specific temperature; a stepped temperature control is not necessary. This increases plant safety and is also an advantage when scaling up.

Below, the individual parts of the system are described in detail and set out advantageous / preferred embodiments. The design of pipes, valves, actuators and measuring equipment is not described in detail, as this is within the general area of expertise. Generally it will be optimal

Heat utilization, by e.g. Waste heat is recirculated via heat exchangers of the plant and thermal insulation is provided at all relevant locations.

Crusher / pre-dryer: If the biogenic raw material used is not crushed to a sufficient extent, this is introduced into a first crushing device. This may for example be a hoe, a shredder or a mill, in which a reduction of the supplied raw material up to a particle size of 1 - 5 mm or smaller, takes place. In the case of wood chips are produced with dimensions in this area. If necessary, the shredded raw material is fed to a drying plant. In this, the raw material is pre-dried by means of warm air of usually a dry content of 50-60% to a dry matter content of over 80%. As If the raw material is pre-dried, it is not very critical and depends essentially on the design of the subsequent impregnator. The shredded and pre-dried raw material is entered from the drying plant via appropriate transport facilities with, for example, conveyor belts or screw conveyors in a lock. This lock serves to seal the air of the subsequent impregnator and can be designed as a rotary valve.

Impregnator: This is done in the impregnator

Soaking, impregnating and impregnating the shredded biogenic raw material. In the impregnator, essentially the remaining free and capillary water of the biogenic raw material is vaporized. The impregnator is advantageously heated indirectly by the generated waste heat of the exhaust gases of the gas engine / diesel engine via a thermal oil circuit to 150-200 ° C. It was found that up to 200 ° C no serious chemical change of the wood structure takes place and the highest possible temperature in the

Total impregnating tank saves energy in the following reactors. The steam is preferably condensed separately from the other condensation plants by means of a cooled with cooling water heat exchanger. The condensate can be diverted into a collecting tank together with the later developing process water. The non-condensing gas portion of the vapor can be passed (eg by means of a blower) to a gas engine. The discharge of carrier oil is preferably carried out only by adhering to the solid biogenic raw material. The amount of carrier oil discharged may be 100-300% of the amount of raw material raw material. The ultimately completely impregnated with carrier oil biogenic raw material decreases due to its higher density in the impregnation tank. In an advantageous embodiment, the determination of the throughput of biogenic raw material via a metering and weighing device in the still dry feed to the impregnator. In an advantageous embodiment, the impregnator is equipped with a stirrer in order to improve the heat transfer. In a further advantageous embodiment, the impregnator is provided in the gas space with bubble trays to minimize the formation of aerosol in the evaporation of water. Preferably, two bubble trays are provided. In an advantageous embodiment, the discharge of the impregnated raw material into the reactor 1 via a screw conveyor, wherein dripping carrier oil can be geodetically passed through a sieve back into the impregnation and the impregnated biogenic raw material is discharged into the following reactor 1 from above. In an advantageous embodiment, the carrier oil supply is level-regulated both from the bottom product of the rectification plant described below, as well as from the purified, re-heated centrate of the decanter described below.

Reactor 1: In reactor 1, after the catalyst has been added, essentially the decomposition of the catalyst is carried out

Polymer structure of the biogenic raw material (especially cellulose and lignin) to monomers. At the same time, the separation of the ring structures on the oxygen atom and the catalytic rearrangement of the oxygen atoms (dehydration and decarboxylation) essentially begin with H2O, CO, CO2 and carboxylic acids leaving the reactor via the gas phase. Furthermore, the conversion ("polymerization") of the resulting monomers to C6 to C25 alkanes take place. The addition of the catalyst slurry is preferably carried out at the ejection of the feed screw. The carrier oil supply to the reactor 1 advantageously takes place from the cleaned, re-heated reflux of the centrate of the decanter, possibly via the bubble trays installed in the gas space. The temperature in the reactor 1 is set by heating (eg electrically) to 300-400 ° C, preferably 350-370 ° C. It is advantageous to rapidly heat the raw material soaked in carrier oil (200 ° C. in the feed) to above 300 ° C., preferably to 350 ° -370 ° C., since this positively influences the product yield and minimizes coal production. In general, 90% of the reaction conversion (to product oil, water, coal and gas) is achieved within 2 min and within 10 min 100% of the

Reaction sales achieved. In an advantageous embodiment, the reactor 1 is equipped with a stirrer, so as to increase the turbulence in the container and to prevent the formation of deposits on the heating surfaces. It is advantageous to use a stirrer with attached wipers, so that thorough mixing is ensured and at the same time the cleanliness of the walls is ensured. In an advantageous embodiment, the reactor 1 is designed so that there is a flow-calmed zone in the lower region, in which the possibly formed granular coal settles together with not yet dissolved raw material. In an advantageous embodiment, the reactor 1 is equipped with one or more (preferably two) bubble trays, which minimize the aerosol formation and thus the carryover of carrier oil into the vapor phase. In an advantageous embodiment, the mixed steam of the reactor 1 (which substantially Water vapor, product oil vapor and entrained Trägeröl- aerosol (up to 50%) contains) the following condenser (possibly after combination with mixed steam of the reactor 2) supplied. The carrier oil excess together with finely suspended coal is fed to reactor 2. In an advantageous embodiment, this resulting reaction mixture is conveyed via a screw conveyor into the reactor 2.

Decanter: In the decanter, the educated

Coal separated from adhering carrier oil. In an advantageous embodiment, a screw decanter is used in which the coal is separated from the carrier oil by centrifugal force (e.g., at 3000-400 Og). Typically, a residual oil content of 10-20% by mass is achieved and free-flowing coal is obtained. This coal can be fed to a subsequent Entöler. In a preferred embodiment, the hot carbon-containing carrier oil (temperature at the end of the reactor 2: typically 37O ° C) is cooled to less than 100 ° C. Since at the same time the purified centrate of the decanter must be supplied at higher temperatures to both the impregnator (eg 200 ° C.) and the reactor 1/2 (for example 37 ° C.), a regenerative heat exchange carrier oil / centrate can be fed in the feed of the decanter by means of two Heat exchangers take place. Advantageously, a third cooling water-cooled heat exchanger is installed, which allows improved regulation of the inlet temperature of the decanter (for example, a maximum of 100 ° C.).

Reheater: In an advantageous embodiment, after the regenerative heat exchangers in Zentratrücklauf for the impregnator and the reactor 1/2 reheater are provided. Such reheater can be electrically heated for the impregnator with thermal oil and for the reactors 1/2.

De-oiler: In a preferred embodiment, the reactor 2 and / or the decanter are followed by a de-oiler (for example a de-oiling screw). In this de-oiling screw, the coal is strongly heated with the adhering carrier oil, e.g. to 500 - 600 ° C (preferably electrically heated) and thus completely evaporated the carrier oil. With upstream decanter the oil content of the incoming mixture is low, resulting in a low amount to be evaporated and therefore has a favorable effect on the energy balance. In order to close the steam room, rotary valves can be arranged at the entrance and at the exit of the deoiler. The resulting carrier oil vapor is preferably condensed; the resulting condensate can e.g. are returned to the reactor 2, the non-condensing gas fraction in the gas engine are supplied (for example sucked). It is also possible to operate the Entöler at reduced pressure.

Coal Mud Container: In a preferred embodiment, the glowing coal originating from the deoiler is fed to a coal slurry container and blended with (or quenched) part or all of the water condensate of the process to exclude air. Preferably, the entire water condensate is supplied. Any resulting gases are fed to the gas engine. The resulting coal sludge can be utilized as fuel. The container is advantageously equipped with a stirrer. Condensers: In a preferred embodiment, the resulting mixed steam from the reactor 1/2 is fed to a condensation plant. Advantageously, the condensation plant initially comprises a pipe heat exchanger cooled with product oil (for heating the product oil of the rectification plant and thus recovery of heat recovery), followed by a cooling water-cooled heat exchanger ("condenser") in which it is cooled to about 35 ° C. Typically, a mixture falls - Condensate of three phases The non-condensing gas component can be fed to the gas engine at the lower end of the condenser, eg via a mist eliminator and a downstream fan.

Phase Separator: In a preferred

In the embodiment, the mixed condensate obtained in the condenser is fed to a phase separator. The mixed condensate typically consists of an oily phase with a density of about 0.835 g / cm 3, an aqueous phase with a density of about 1. 03 g / cm 3 and a tarry heavy phase with a density of about 1.3 g / cm 3 and can be separated statically under the influence of gravity into three immiscible liquid phases. This can be done via dipping weirs and appropriately arranged overflows in a communicating separator due to the immiscibility and the density difference. Advantageously, the liquids obtained are fed to three intermediate containers in order then to be supplied to a further treatment.

Zwischenbehalter: The three products, the oily phase, the aqueous phase and the tarry heavy phase are treated differently or disposed of. Preferably, the three phases are further treated. The oily phase (consisting of the fuel components and up to 50% carrier oil) is advantageously first fed to a centrifugal separator in order to separate off heavy oil components and turbid substances, which can be supplied, for example, to the tarry heavy phase. The resulting concentrate can be fed to a preheater in the form of the tubular heat exchanger installed in the mixed steam flow and heated again and finally heated to 250-280 ° C. via a carrier oil-heated secondary heat exchanger. Thereafter, the heated oil relaxes into the rectification column where the fuel component evaporates. The aqueous phase is preferably fed to the coal slurry tank. The tarry heavy phase can be either pumped back into the reactors, or mixed with the coal sludge (external) disposed of.

Rectification: The purpose of rectification is to carry out the final separation of the fuel components from the carrier oil. The rectification of such product mixtures is known per se, the choice of apparatus and operating points is essentially determined by the desired product composition. Thus, for example, in a vacuum distillation column at a pressure of about 50 mbar absolute pressure due to the different Siedebetreiche of carrier oil and product oil separation by simple distillation is possible. At a controlled temperature of about 250 ° C, only the fuel component evaporates, the carrier oil component having a boiling range of 300-400 ° C remains in the bottom product and is partially or completely (preferably completely) recycled to the impregnator. Thereafter, the further fractional condensation in the upward flow carried out by means of an air-cooled, built into the column pipe heat exchanger to a separation temperature of 100-120 ° C, wherein the resulting middle distillate (diesel), for example, via a bubble tray and aftercooler is discharged into a tank. Thereafter, another air-cooled tube heat exchanger may be arranged, which cools the product vapor to eg 60 - 70 ° C and the light distillate (gasoline) is withdrawn through a further bubble tray in a tank. Thereafter, a head condenser cooled with cooling water can be arranged, with the product vapor being finally cooled to about 35 ° C. This liquid top product in a proportion of 2-3%, is often odor-laden, since it contains many aromatics and aldehydes, and can also be disposed of via a tank ultimately either in the gas engine, or in a torch, or in the coal sludge.

Energy generation: Plant parts for energy generation can be assigned to the plant according to the invention. The products of the plant (gas, product oil, coal or coal sludge) are suitable for energy production. Thus, energy can be generated via a gas engine into which all combustible residual gases (eg from the imprammer, the condenser, top gas of the rectification and the venting of the coal sludge tank) are carried. As a buffer, for example, a balloon-shaped gasometer can act, on the degree of filling of the gas engine is controlled. If the gasometer becomes full despite the 100% power of the gas engine, the excess gas can be discharged into the emergency flare, which also supplies the spring-loaded overpressure safeguards of all overpressure-hazarded plant components. As another power generator, a diesel engine operated with the product oil can function. In the exhaust pipe of the two engines, a thermal oil heater can be arranged, with which a flow temperature of about 350 ° C, with an exhaust gas temperature of the engine of about 400 ° C, is made possible. This thermal oil can be in a closed circuit and can be used to heat the indirectly heated impregnator, the reboiler of the product oil before the rectification and the reheater for the return Zertrat - decanter to the impregnator. Depending on the requirements of the system, the diesel combined heat and power plant can be designed either to meet the own energy needs of the oiling plant (electricity and heat) at maximum fuel production, or also to supply green electricity to a public grid for 100% on - site electricity generation. In any case, optimal heat recovery and possibly also a decoupling of low-temperature heat for external heating purposes are advantageous.

Cooling tower: A cooling tower can be provided for the cooling water supply to the condenser of the impregnator steam, the condenser of the reactor mixed steam and the top condenser of the rectification column. Further cooling points are possible product coolers in the course of the rectification column. Such cooling towers are well known; In connection with the plant according to the invention, a cooling water inlet temperature of about 30 ° C. at a return temperature of about 50 ° C. is advantageous. The evaporation evaporation loss is compensated by fresh water addition, to avoid salification about 10% of the additional water can be drained into a channel.

Expansion tank: On the one hand, an expansion tank can be used for initial filling with carrier oil, on the other hand for emptying the system (eg for maintenance purposes) are provided.

Depending on the requirements, the individual parts of the system can be heated directly or indirectly. Furthermore, the heating can be done electrically or by means of heat ^¬ carrier. These heating methods and their combinations are familiar to the person skilled in the art and are included in the present application. The reactors 1 and 2 are preferably electrically heated.

In a preferred embodiment, reactor 1 and reactor 2 A ^¬ directions for reducing the formation of aerosol are in the gas space of impregnator, see superiors. Such devices are familiar to the expert; As an example, bubble-cap trays, preferably 2 bubble-cap trays per apparatus, are mentioned.

In the case of the use of only liquid biogenic raw materials, the Imrägnator and also the second reactor can be omitted. The present invention therefore also relates, in an alternative embodiment, to a plant which does not contain these elements.

In a preferred embodiment

Decanter and Entöler connected in parallel, so that the decanter fine-grained coal, the coaleser coarse-grained coal is supplied.

If the sulfur content of the fuels produced is too high due to the raw material, a separate separate desulfurization stage can be provided in the fuel condensates. These are known from the prior art. The example below serves to further explain the invention; it is not intended to limit the invention in any way.

1st method:

The process according to the example comprises the subsections of material conversion, energy supply, waste material utilization, raw material supply.

1.1. Substance conversion (Core Unit):

The material conversion takes place catalytically with the addition of a mineral catalyst in an oily carrier liquid in several steps:

Impregnator: wood chips are indirectly heated to 200 ° C in about twice the amount of carrier oil, the free and capillary water is evaporated and the chips are completely saturated with oil. The derived vapor is condensed and the condensate is passed into a water tank after phase separation. The uncondensed gas component is fed to the gas engine. Because of the high density, the chips sink and are detected at the lower end of the impregnator by a conveyor and fed to the reactor 1.

Reactor 1: In the reactor 1, with a volume of 1500 1, the oil-impregnated wood is introduced into the electrically heated carrier oil at 370 ° C and distributed by means of a stirrer. Here, the main reaction takes place, the wood is divided into four phases: coal, product water, oil and gas. The oily and aqueous phase vaporizes and leaves the reactor via the steam line. The carbon phase remains in the carrier liquid and is conveyed into the reactor 2. Reactor 2: Raw material which has not yet reacted is aftertreated in reactor 2 (volume: 1500 l). Furthermore, here is the separation of coarse and fine coal, the fine coal is required in a decanter, the coarse coal dropped on a Forderer in the Entöler. Decanter: In the decanter, after cooling to 100 ° C via the centrifugal force, the carbon phase is separated from the carrier oil.

Entöler: In an electrically heated screw, the residual sol adhering to the coal is evaporated at 500-600 ° C, the dust is dedusted and then condensed. The condensate is returned to the carrier oil circuit.

Condensers: The mixed steam from reactor 1 and reactor 2 is first pre-cooled in a product refrigerator and then cooled in the condenser to about 35 ° C. The

Mixed phase of the condensate enters the phase separator, the gas phase is sucked to the gas engine.

Phase Separator: The resulting 3 phases (product oil, water and heavy oil) are separated by density and extracted into three tanks.

Rectification: The productol phase is first freed of heavier parts via a seperator and then reheated via the heat exchanger in the mixed steam. A re-heater with carrier oil and an electric heater allow a temperature of about 250 ° C with the product oil is relaxed in the rectification. The operating pressure here is about 50 mbar. In the column fall the phases Schwerol / Tragerol as the bottom phase, the middle distillate phase (diesel), the light distillate phase (gasoline) and the head phase as separate fractions. The individual fractions are derived or returned to the respective tanks, the uncondensed gas fraction is sucked into the gas engine. A cooling tower with automatic blowdown serves to recool the cooling water circuit. The fresh water requirement is about 600 l / h, Abschlammenge about 50 l / h.

1.2. Power Plant:

The plant is supplied with electricity and heat via the two integrated gas / diesel combined heat and power plants, which supply the plant with the necessary electricity and heat energy. In addition, a grid connection with approx. 500 kW is planned. Heat demand average: 100 kWth Electricity consumption average: 100 kWel The design is based on 50/450 kWel and the heat consumption on 200 kWth

1.3 Residual material utilization

The de-oiled coal is mixed with the resulting process water and, stored in a container and fed as sludge for further use.

1.4 Raw material supply

The supply of biogenic raw material (hops) takes place continuously in the impregnator. The supply of catalyst is carried out continuously at the ejection of the feed screw into the reactor. 1

2. Quantity balance After the experiments carried out, the following resulted

Quantity balance:

100m% wood = 43m% oil + 22m% water + 20m% gas + 15m% coal.

At 300 kg per hour of log entry (20 hours a day,

300 days per year) amount to the product quantities: 2.1 entry Wood: 300.0 kg / h 6.00 t / d = 1800 t / a 2.2 Discharge

POL: 122, 6 kg / h 2.45 t / d = 735, 6 t / a

Water: 77.7 kg / h 1.55 t / d = 466.2 t / a Coal: 42.7 kg / h 0.85 t / d = 256.2 t / a

Gas: 57.0 kg / h 1.15 t / d = 342.0 t / a

3. Energy balance:

After the experiments, the following energy balance was obtained: 100 e% wood = 70 e% oil + 7 e% gas + 20 e% coal + 3 e% V (V = thermal insulation losses).

4. Utilization of the products:

It results in the processing of 6 tons of wood chips per

Day 4 Products:

Charcoal powdered 850 kg / day

Product water (condensate) 1550 kg / day

Low gas in gas engine 1150 kg / day

Product oil in diesel engine: 2450 kg / day

The charcoal mixed with the product water is fed to a cogeneration plant.

The lean gas (about 700 Nm3 per day) is used in a gas engine with about 50 kWel; the waste heat of the exhaust gases is recovered as process heat.

The product oil (PÖL 2450 kg / day equivalent to 2934 l / day) is stored intermediately and used directly in a low-speed (1500 rpm) diesel engine to generate approximately 470 kWel of electricity. The engine waste heat of the exhaust gases is returned to the thermal oil heating and consequently as process heat in the system. With deduction of about 100 kWel of own electricity consumption, this results in a surplus of 300 - 420 kWel, which is to be fed as green electricity from biomass into the grid of the energy supply company.

Claims

claims

1. A process for the production of fuels from solid and / or liquid biogenic raw materials, characterized in that a mixture containing i) crushed, dried, biogenic raw material; ii) carrier fluid and ni) alumina mineral catalyst containing montmomolite, illite and / or smectite is reacted with heating to 300 - 400 ° C and the resulting fuel is separated from the reaction mixture.

2. The method according to claim 1, characterized in that first comminuted, dried, solid biogenic raw material at 150 - 200 ° C is impregnated with carrier liquid.

3. The method according to claim 2, characterized in that the gases formed during the impregnation are condensed separately.

4. The method according to any one of the preceding claims, characterized in that the reaction of i) crushed, dried, biogenic raw material; ii) carrier flow and iii) mineral catalyst is carried out in two successive reaction steps, the reaction temperature in the second reaction step being 0-30 ° C. higher than in the first reaction step.

5. The method according to any one of the preceding claims, characterized in that the gases formed during the reaction are condensed separately.

6. The method according to claim 5, characterized in that the condensed gases are separated into their phases and further processed separately.

7. The method according to any one of the preceding claims, characterized in that the non-condensable gases formed in the process are partially or completely supplied to a gas engine.

8. The method according to any one of the preceding claims, characterized in that the fuels formed in the process are partially or completely supplied to a diesel engine.

9. The method according to claim 7 or 8, characterized in that the exhaust gases of the engines are supplied to a Warmeruckgewmnung.

10. The method of claim 7, 8 or 9, characterized in that the motors are used to generate electrical energy.

11. The method according to any one of claims 2 to 8, characterized in that the catalyst is added both before and after the impregnation and before the reaction.

12. The method according to any one of the preceding claims, characterized in that the carbon formed as a reaction product is separated continuously.

13. The method according to claim 10, characterized in that the separated coal is mixed with emerging product water under exclusion of air.

14. Plant suitable for the production of fuels from biogenic raw materials comprising the following successive plant parts: heatable first reaction vessel with a device for metering catalyst; heated second reaction vessel.

15. Plant according to claim 14 comprising the following, consecutive plant parts: heatable impregnator, heatable first reaction vessel with apparatus for metering catalyst; heatable second reaction vessel; one or more apparatus (s) for separating coal / oil mixtures.

16. Plant according to claim 14 or 15, characterized in that the reaction vessels is associated with a condensation plant.

17. Plant according to claim 15 or 16, characterized in that the impregnator is associated with a condensation plant.

18. Plant according to claim any one of claims 15-17, characterized in that the device for separating oil comprises a decanter and / or a de-oiler.

19. Plant according to claim any one of claims 14 - 18, characterized in that the system is associated with a gas engine in which a part or all of the resulting non-condensable gases are utilized.

20. Plant according to claim any one of claims 14 - 19, characterized in that the system is associated with a diesel engine is the part or all of the resulting fuels used.

21. The method of claim 1, 4-10, 12, 13, characterized in that the reaction mixture contains i) liquid biogenic raw material and optionally crushed dried biogenic raw material.

22. The method according to claim 21, characterized in that the catalyst and liquid biogenic raw material are fed to the reaction simultaneously.

23. The method according to claim 1 -13, characterized in that the reaction mixture contains i) solid, crushed, dried biogenic raw material.

24. Plant suitable for the production of fuels from liquid biogenic raw materials, comprising the following successive plant components: heatable first reaction vessel with a device for metering catalyst and liquid biogenic raw material; optionally heatable second reaction vessel.