DE102011011158A1 - Preparing gasificationable bulk material from biogenous raw materials comprises delivery and acquisition of the materials dates, comminution of the materials, adjusting the moisture content and compaction of the comminute materials - Google Patents

Abstract

Preparation of gasificationable bulk material from biogenous raw materials comprises delivery and acquisition of the materials dates, comminution of the materials, adjusting the moisture content to a target range and compaction of the comminute materials. An independent claim is included for the gasification-capable bulk material from biogenous raw materials with many dimensionally stabilities and transportable solid individual bodies whose main ingredients are cellulose, hemicellulose, polysaccharides, peptides, lipids, resins and/or pectins.

Description

The invention relates to a method for producing gasifiable bulk material from biomass and a biomass-made, gasifiable bulk material.

The invention relates generally to the production of biogenic conditioned feedstocks which can be used in a gasification process for the production of energy and synthetic fuel (DME) as well as (chemical) feedstocks such as biosilica and nanostructured organic material (BioNanoMat). CO2-neutral, biogenic feedstocks, native or pretreated, and whose pyrolysis coke is capable of reacting or receiving, are used for the production of this synthesis gas. The starting substance for the production of the biogenic conditioned feedstocks is biomass, which can be characterized as being grown vegetable or animal substances as well as substances that have arisen through processing or use of the primary biomass.

When using a wide range of feedstocks as reactants of a gasification process, the supply processes including the metering and the introduction of the material, depending on the bulk density, must be illuminated in a special way. Restrictions inevitably arise due to the specifications of the process equipment. Serious variations in the feedstock used require extensive modification of the process equipment for the feed process, which in turn limits the actual core process - synthesis gas production. The aim of the present invention is to eliminate this problem by using bulk material according to the invention and to contribute to increasing the economic efficiency of the gasification process which the Applicant has developed.

The process according to the invention offers a comprehensive solution for this task, which makes it possible to modify all feedstocks which are suitable from a chemical point of view in such a way that the bulk material formed invariably for all the gasification processes of the Applicant with the patented dosing, entry and sluice system without adapting it to the varying raw materials is suitable. These systems are described in the DE 10 2006 017 355 A1 , of the DE 10 2006 017 353 A1 , of the DE 10 2006 022 265 A1 , of the DE 10 2006 039 622 A1 , of the DE 10 2007 004 294 A1 and the DE 10 2008 036 734 A1 which is fully incorporated by reference to the methods and equipment described therein.

The solution of the inventive process for the task outlined is the processing of biogenic raw material to produce a dimensionally stable intermediate, which is characterized by high bulk density, excellent shelf life and good transportability.

In the scientific literature such compaction processes are referred to as compaction to produce dimensionally stable bodies as agglomeration, and the physicochemical processes are described in detail (in particular, examples are given for the treatment of straw, hop umbels and bark).

In the process according to the invention, dimensionally stable parts are formed on the basis of the present substance mixture which differ in hardness and surface structure as a function of the manner of execution of the compaction and agglomeration. Preference is given to those materials which act as binding substances, ie as natural adhesives. In this way, agglomerated, dimensionally stable pellets can be obtained from biogenic feedstocks.

Depending on the embodiment of the processes used, the present substance mixture must meet specific conditions with regard to the geometrical size of the individual elements and the water content. In the inventive process, therefore, before the production of the bulk material according to the invention by compaction and agglomeration under optimal conditions, process stages for comminution and drying of the substance mixture are provided.

Due to the high evaporation enthalpy of the water, natural drying during storage by means of air (open storage and integration of solar energy for air heating) and the use of the residual heat of the exhaust gases of the exhaust gas are very expensive (and thus uneconomic) accounted for by the Applicant. By contrast, the mechanical processes of comminution and compaction as well as the agglomeration process are characterized by a moderate energy requirement.

In addition to the chemical composition and reaction kinetic specifications, which are characterized by the starting substances, the intermediate product shows very homogeneous properties in terms of logistic properties such as bulk solids density and solids density.

Various methods are already known from the prior art, with which biomass can be processed to industrially manageable bulk material. This bulk material is then usually burned for the purpose of energy, which is energetically unsatisfactory. Examples of forming processes are set forth in the patents and scientific reports listed below. So will in the DE 25 01 209 entitled "Process and Apparatus for Making Hop Pellets" by Johann Probst describes the production of moldings (pellets) by means of a special pelleting machine. In the final report Institute for Environmentally Sound Land Management IfUL, Müllheim; Institute of Process Engineering and Steam Boilers University of Stuttgart, Jürgen Maier, Dr. med. Reinhold Vetter, Volker Siegle, dr. Hartmut Spliethoff Research Project (Ord. No. 22-94.11) All rights: Ministry of Rural Areas Baden Württemberg, Stuttgart 1998 , The production of such shaped bodies from the cultivation of energy crops is considered closer. In the final report TU Bergakademie Freiberg, New applications for bark - through product development, Prof. Wolfgang Naundorf, dr. Ing. Ralf Wollenberg, Dipl.-Ing. Christian Warnecke, registration number 22009801, June 2005 , the production of moldings from biogenic feedstocks is investigated.

For a fundamentally different area of application, the following dissertation is based on the compaction (pressing) of biogenic raw material: "Process engineering solutions for milk production at remote feed production", Dissertation: Dr. med. Ing. Mulaw Bebreselassie, Humboldt University Berlin Institute of Agricultural and Horticultural Sciences, Dean Dr. Ing. Ernst Lindemann; December 2000 , Furthermore: "Basic Processes and Facilities - Powders and Bulk Materials - Flow Properties and Handling", Dietmar Schulze (Prof. Dr. Ing., University of Applied Sciences Braunschweig Wolfenbüttel, Institute for Recycling); Springer Verlag ISBN 10 3 540 34082 3 , and "Determination of the Compaction Behavior of Cohesive Compressible Bulk Materials with a Hydraulic Press", P. Müller, L. Grossmann, J. Thomas, Prof. Dr.-Ing. habil., Chair of Mechanical Process Engineering, Otto von Guericke University Magdeburg ,

The object of the invention is to provide a method for processing of biogenic raw material for producing a dimensionally stable intermediate, which is characterized by high bulk density, excellent storage stability and good transportability and is suitable for use in a gasification plant.

To achieve this object, the invention provides a method for producing gasifiable bulk material from biogenic raw materials by means of the following steps: delivery and recording of the material data; crushing; Setting the moisture content to a target range; and compaction. These steps make it possible to produce a homogeneous starting material from a wide variety of biomass, which can be delivered in different states, which can be stored, transported, dosed and used in a gasification plant as bulk material.

Preferably, it is provided that the detection takes place before the delivery, for example by taking samples of the raw material before loading. This makes it possible to adapt the logistics of the further treatment of the raw materials early on to the individual condition. For example, capacities for necessary drying processes can be provided in good time.

It is preferably provided that drying is carried out to set the moisture content to the desired value. In this way, the moisture content is brought to values of preferably 5 to 15% by weight, which facilitates further processing.

For drying, solar heat, process heat and / or open air drying are preferably used, so that the energy-intensive drying process can be carried out inexpensively. For drying, in particular heat can be used which is obtained by a feedback with an allothermal gasification plant.

In cases in which the raw material can not be further processed merely by compaction to bulk material, it is provided that the compaction is accompanied by an agglomeration. This makes it possible to process even such raw materials to pourable, abrasion-resistant and transportable individual bodies, in particular pellets, which do not contain adhesive substance for the necessary cohesion.

According to an alternative, a binder is added before compaction. This can be suitably selected depending on the respective raw materials to be processed.

Preferably, the binder is added by admixing biogenic raw materials. This is based on the recognition that some raw materials contain so high a content of sticking substances that they can be used to agglomerate other raw materials, which themselves can not be agglomerated. In other words, biogenic raw materials having high adhesiveness are suitably blended with biogenic raw materials having low adhesiveness so that the mixture can be agglomerated. Thus, no "foreign" binder must be added, which has an advantageous effect on the overall energy balance.

According to one embodiment, it is provided that the bulk material is dried and / or cooled after compaction. Preferably, the cooling can take place in the form of post-drying. In this way, the introduced into the bulk material during the compaction heat dissipated, which protects the equipment used from damage and prevents thermal decomposition of the pellets.

According to one embodiment of the invention, it is provided that the energy required for the production of the bulk material is obtained by power generation of previously produced bulk material. In other words, the production of the pellets is fully integrated into the operation of the gasification and electricity generation plant, which converts the biogenic raw materials into electrical energy. This leads to a very advantageous overall energy balance.

The above object is also achieved by a gasifiable bulk material from biogenic raw materials, which consist of a variety of dimensionally stable, transport-resistant individual bodies whose essential ingredients are cellulose, hemicellulose, polysaccharides, peptides, lipids, resins and / or pectins.

It is preferably provided that the bulk material has a bulk density in the order of 500 kg / m ³ to 800 kg / m ³ . This allows a rational storage and a rational transport due to the high specific gravity of the pellets.

According to a preferred embodiment of the invention it is provided that the bulk material has a residual moisture in the order of 5 to 15% by mass. Such a low residual moisture content allows a long storage time and ensures that each unit of weight contains a high proportion of gasifiable material in the bulk material.

The bulk material may be in the form of pellets or briquettes. In both cases, it can be easily transported and dosed.

An essential part of the process according to the invention is compaction and agglomeration. In the prior art, the processes of shaping and forming a mold (molding) by briquetting (formation of briquette in predetermined forms), pelletizing (formation of pellets) or granulation (grain formation) are described. The processes of shaping do not distinguish the change in the "internal" properties, density and formation of chemical or mechanical bridge bonds; these processes are thus sub-processes of compaction and agglomeration.

For the process according to the invention, however, it is crucial that both compaction and agglomeration take place. Selected shaping processes and their assignment to the agglomeration and compaction processes are described below.

Briquetting is the shaping of particulate, mostly powdery solids in predetermined forms under high pressure. The process is characterized by the fact that the suitable solids to be treated are agglomerated even without addition of binder to extremely fracture and abrasion resistant moldings. The quality of the moldings is determined by the pressure, the temperature and the mechanical and chemical properties of the mixture used.

Pelleting as a shaping process refers to the production of spherical shaped bodies using agglomeration processes (production of iron ore pellets in the pelletizing plate) or of mostly cylindrical pellets by compaction and agglomeration in the extrusion press pelletizing.

Product properties of the pellets can be adjusted by temperature, pressure, residence time, constructive design of matrix and Koller and functional auxiliaries (binders) and material create structural properties, such as a shiny surface. For the pelleting of the highest interest are biogenic substances with excellent binding properties, such. B. bran, molasses or others. A mixture of the substances to be pelleted with such as binders to be designated biogenic substances leads to excellent products. By selecting a suitable mixture of raw materials, pellets or briquettes can be produced from biogenic raw materials that are suitable for the production of BioSilika as well as nanostructured BioNanoMat and in addition with admixture of z. As lime (suspension of calcium bicarbonate / calcium carbonate) as catalysts for gasification application.

With regard to a good overall energy balance, the process according to the invention integrates the pretreatment of the raw materials and the selective production of the pellets or briquettes from biogenic raw materials. The most important economic effect is the simplicity and high flexibility in the selection of biogenic feedstocks.

The generation of the energy required for the agglomeration compaction, shaping and the preparatory process steps such as crushing takes place as feedback from the parallel connected allothermic gasification plant (s) with power generation by a supercharged internal combustion engine with exhaust heat recovery and is thus integrated into the overall process. The integration of the processes agglomeration-compaction and shaping also allows the use of waste heat for efficient product drying.

The raw materials for the production of biogenic conditioned feedstocks include the existing spectrum of various biogenic feedstocks, as far as they are present at a residual moisture content below 60 mass percent (based on the total mass) or are mechanically dewatered and with the introduction of mechanical energy to dimensionally stable and abrasion-resistant body can be pressed (compacted). Critical to the gasification process is the size of the pellets, as a guide to the reactivity of the coke produced by pyrolysis and the carbon conversion at a given (optimal) temperature.

Basically, biogenic raw materials and products must be characterized by their chemical composition and the directly derivable data such as the formation and combustion enthalpy, the HHV Higher Heating Value and the structural and mechanical properties.

The starting materials for the production of the biogenic conditioned feedstocks are biogenic raw materials that are produced either directly after harvesting or after preceding antgenic processes.

The chemical composition is determined by the mixture of different raw materials and corresponds to the sum of the corresponding raw materials, since the process essentially proceeds without chemical conversion

In addition, the chemical reactivity of the pyrolyzed biogenic conditioned feedstocks is essential, depending both on the properties of the raw materials and on the bulk mechanical properties. This reactivity is modeled by standardized laboratory-scale model experiments, since direct measurement is inadequate during the technical operation of the gasification unit. The chemical and molecular properties, with the exception of the water content, are not changed.

Biogenic raw materials include carbon, water and oxygen as well as traces of nitrogen and sulfur as elemental building blocks. Typically this can be summarized as follows: C _(35-45) H _(50-60) O _(23-28)

With respect to the individual components, the variance is larger and has a range of (C _(35-45) H _(50-60) O _(23-28) ) _n cellulose to esters of saturated and unsaturated fatty acids (fatty acid esters) on C ₁₅ H ₃₀ O ₂ -C ₁₉ H ₃₈ O ₂ .

These feedstocks comprise the following main components: cellulose, hemicellulose, lignin, polysaccharides (poly-sugars, starch), pectins, proteins, fats, resins and bio-silicas. The typical molecular components of feedstock raw materials and their key biogenic resources are shown in the table below: Typical molecular component Important biogenic resource Cellulose hemicellulose lignin Lignocelluloses, e.g. B. bamboo straw of cereals, rice straw fruit peel, z. Peanut shells, coconut shells Polysacharride strength Wheat, rye, barley, triticale potatoes Polysaccharide Poly Sugar Sugar cane Molasses residues Sugar beet pulp Proteins (protein) legumes pectins Fruit, z. Apples and pears fats Rapeseed oil Palm oil Yatropha oil resins Softwoods, conifers Biosilika rice straw

From a molecular point of view, the substances are usually oligo- or polymers with complex spatial structures that form various aggregations, such as by way of example cells, cell aggregates and others.

If raw materials selected for the production of gas are used, biogenic precursors can be produced, which can be upgraded to biosilica or BioNanoMat (a carbon-based nanomaterial) by the gasification process developed by the notifying party. The aim of the production of biogenic conditioned feedstocks is to produce a largely homogeneous and defined product, in particular with regard to geometry (shape), mechanical, hygienic and logistical properties (bulk density).

The periodic harvesting of biogenic input materials requires the necessity of subjecting these substances to intermediate storage - in heap or partially compacted (without agglomeration) outdoors. The disadvantage of untreated raw materials in terms of bulk-mechanical properties is evident.

The present invention solves this problem by producing the biogenic conditioned feedstocks as feedstock with optimum bulk mechanical properties for the entry process into the gasification reactor. The process begins with the delivery of the raw materials, which typically takes into account packs such as bales, packings or (bulk) in bulk containers from different suppliers. The heterogeneous material is preferably supplied to the production process close to the site.

The necessary process steps include the uptake of the crude products, if necessary comminution, drying, compaction and agglomeration preferably by pelleting (compression) by way of example in a flat die press by forming extrudates, for the production of pressure and dimensionally stable solids as final products (pellets).

Downstream of the compaction and agglomeration (preferably pelletizing) is a further drying step in order to reduce the starting materials to the optimum residual moisture content of 10 to 15 mass percent, to cool the molded articles heated during this process and to optimize the shelf life and transport weight. This process step is necessarily closely interlinked with the (low temperature) waste heat heating and energy production in the gasification plant developed by the Applicant. Further steps include fertilizer return to agricultural land and the provision of synthetic fuel (DME) for the farm.

In 1 the production process of the pellets or briquettes according to the invention (referred to therein as power greenies) is shown schematically as a process flow diagram; the production starts with the delivery of the raw material obtained after the harvest or previous processing stages (food production). The delivery usually takes place in transportable containers as bulk material or in suitable transport containers. It is assumed that the materials are in shredded form through appropriate processing.

The characteristic properties of the raw materials vary considerably with regard to the bulk density, the geometric dimension and the humidity, so that the processes of comminution and drying must be aligned to the requirements of the pelleting. For this purpose, in the first step, the relevant data are recorded in the form of an operational analysis and the delivered materials, the sampling of which has preferably already taken place during the loading, are forwarded directly to the respective sub-process. Optionally there is the possibility of temporary storage to bridge weather-related delivery bottlenecks and the time span to the operational analysis classification.

This is followed by drying by the waste heat from energy generation and the gasification process, as well as by the integration of solar energy (via a belt dryer). Alternatively, the drying can be done by directly or indirectly heated drum dryer. After drying, the starting materials are used for comminution for the subsequent (optimal) pelleting in order to comminute in particular excessively long, chalky material to the optimum dimensions for pelleting or directly into an intermediate storage facility. The crushing process is designed so that the geometric dimensions of the lumpy material are optimally matched to the specifications of the shaping process, since z. B. pelletizing means Koller- and flat die requires further crushing of the feed mixture.

From this intermediate storage, the raw materials go directly to a mixing unit (screw), in which the different components and possible additives are homogenized. The subsequent pelleting process in the form of press-strand granulation is used to produce biogenic conditioned feedstocks, a compacted, solid and dimensionally stable gasification material from a wide variety of biogenic materials. The starting materials are compressed under pressure (also higher temperature). Due to the existing substances with adhesive properties such as pectins, protein, carbohydrates (starch, poly-sugar), resins. Lignins, etc. result in abrasion-resistant pellets of considerable mechanical strength or high density (over 500 kg / m ³ ).

The moisture required for this process is preferably "supplied" by the raw material used or by mixing batches of different moisture content. An additional moistening is only optional, to z. B. to support operational problems during shaping by pelleting, since the subsequent drying adversely affects the thermodynamic efficiency. For the design of the device (die-press ring or flat) in addition to the pelleting and the parallel shredding plays the crucial role.

The pellets are subjected to an additional increase in temperature due to the energy dissipation of the pressing process. In this respect, a cooling in the form of post-drying takes place after processing, on the one hand to protect the equipment used from damage and on the other hand, the pellets against thermal decomposition. Then the end product passes through the conveyors directly into the carburetor developed by the applicant or in interim storage.

The carbon atoms of a hydrocarbon compound can be characterized by oxidation numbers based on their chemical properties as outlined in the following table of five examples.

The chemical reactions on which the processes according to the invention are based can be described as oxidation reactions based on formal oxidation numbers, the reactants, ie the starting materials, being oxidized while the oxidizing agents, essentially water vapor and oxygen, are reduced. connection Chem. Formula Oxidation number of the C atom methane CH4 -4.0 Ethan C2H6 -3.0 pentane C5H12 -2.4 fatty acid methyl ester C ₁₅ H ₃₀ O ₂ -1.7 cellulose (C ₆ O ₅ H ₁₀ ) ₁₀ 0 Carbon monoxide CO +2.0 carbon dioxide CO2 +4.0

As oxidation, this change of state is indicated by the increase in the oxidation number of the oxidized molecule, for the reduction, it applies accordingly. The essential products which are formed from the starting materials by the process according to the invention are CO, H ₂ and CO ₂ . While CO and CO _{2 are formed} by oxidation from the carbon compound, H _{2 is formed} by the reduction of H molecules within the hydrocarbon compound and the oxidant water vapor. The oxygen molecules O ₂ present in the reaction system are reduced. In Examples 1 and 2, these processes are exemplified for the present processes: Example 1 Oxidation of Reactants Cellulose (C ₆ O ₅ H ₁₀ ) ₁₀ from oxidation number 0 to oxidation number +2 or +4 fatty acid methyl ester C ₁₅ H ₃₀ O ₂ from oxidation number -2 to oxidation number +2 or +4

Example 2 Reduction of the oxidizing agent

• Oxygen O ₂ from oxidation number +0 to oxidation number -2 H Water vapor molecules from oxidation number +1 to oxidation number 0

In addition, the process allows the production of biosilka and, with appropriately conditioned feedstocks and modification of the process parameters (reaction conditions), the production of nano-structured organic carbonaceous products.

In 2 a process flow diagram is shown, from which the most important balance data results. Based on the selected module size (2 standard modules gasification and 1 standard module power generation INCOX100, so a supercharged internal combustion engine with exhaust heat recovery) are processed in the selected typical case 412 to / h raw raw materials for bulk material according to the invention with a residual moisture content of 14%. With additional use of solar energy residual moisture in the range between 10 and 12.5% can be achieved. The result is 400 to / h daf (dry and ash-free).

The biogenic conditioned feedstocks produced on the basis of this invention are characterized by a high bulk density between 500 and 800 kg / m ³ and correspondingly optimized storage or transport volume.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102006017355 A1 [0004]
• DE 102006017353 A1 [0004]
• DE 102006022265 A1 [0004]
• DE 102006039622 A1 [0004]
• DE 102007004294 A1 [0004]
• DE 102008036734 A1 [0004]
• DE 2501209 [0011]

Cited non-patent literature

• Institute for Environmentally Sound Land Management IfUL, Müllheim; Institute of Process Engineering and Steam Boilers University of Stuttgart, Jürgen Maier, Dr. med. Reinhold Vetter, Volker Siegle, dr. Hartmut Spliethoff Research Project (Ord. No. 22-94.11) All rights: Ministry of Rural Areas Baden Württemberg, Stuttgart 1998 [0011]
• Prof. Wolfgang Naundorf, dr. Ing. Ralf Wollenberg, Dipl.-Ing. Christian Warnecke, registration number 22009801, June 2005 [0011]
• "Process engineering solutions for milk production at remote feed production", Dissertation: Dr. med. Ing. Mulaw Bebreselassie, Humboldt University Berlin Institute of Agricultural and Horticultural Sciences, Dean Dr. Ing. Ernst Lindemann; December 2000 [0012]
• "Basic Processes and Facilities - Powders and Bulk Materials - Flow Properties and Handling", Dietmar Schulze (Prof. Dr. Ing., University of Applied Sciences Braunschweig Wolfenbüttel, Institute for Recycling); Springer Verlag ISBN 10 3 540 34082 3 [0012]
• "Determination of the Compaction Behavior of Cohesive Compressible Bulk Materials with a Hydraulic Press", P. Müller, L. Grossmann, J. Thomas, Prof. Dr.-Ing. habil., Chair of Mechanical Process Engineering, Otto von Guericke University Magdeburg [0012]

Claims (15)

Process for the production of gasifiable bulk material from biogenic raw materials by means of the following steps: - delivery and collection of material data; - crushing; - Setting the moisture content to a target range; - Compaction. A method according to claim 1, characterized in that the detection of the material data takes place before delivery. Method according to one of the preceding claims, characterized in that drying is carried out to set the moisture content to the desired value. A method according to claim 3, characterized in that for drying solar heat, process heat and / or an open drying in air is used. A method according to claim 3 or claim 4, characterized in that heat is used for drying, which is obtained by a feedback with an allothermal gasification plant. Method according to one of the preceding claims, characterized in that the compaction is accompanied by an agglomeration. A method according to claim 6, characterized in that before the compaction, a binder is added. A method according to claim 7, characterized in that the binder is added by admixing biogenic raw materials. Method according to one of the preceding claims, characterized in that the bulk material is dried and / or cooled after compaction. Method according to one of the preceding claims, characterized in that the energy required for the production of the bulk material is obtained by power generation of previously produced bulk material. Gastreatable bulk material from biogenic raw materials, which consist of a plurality of dimensionally stable, transport-resistant individual bodies whose essential ingredients are cellulose, hemicellulose, polysaccharides, peptides, lipids, resins and / or pectins, preferably prepared by a method according to one of the preceding claims. Bulk material according to claim 11, characterized in that it has a bulk density in the order of 500 kg / m ³ to 800 kg / m ³ . Bulk material according to claim 11 or claim 12, characterized in that it has a residual moisture in the order of 5 to 15% by mass. Bulk material according to one of claims 11 to 13, characterized in that it is in the form of pellets. Bulk material according to one of claims 12 to 13, characterized in that it is in the form of briquettes.

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