Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
  • C10G1/086—Characterised by the catalyst used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/16—Clays or other mineral silicates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
  • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

• the present invention relates to a process for the production of fuels from biogenic raw materials. It further relates to a plant for carrying out the process, catalyst compositions suitable for this process and the use of catalysts for the production of fuels from biogenic raw materials.
• 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.
• COREN method is a multi-step process.
• a gasification by means of oxygen the so-called Carbo-V process for the production of synthesis gas (H2, CO, CO2).
• synthesis gas H2, CO, CO2
• a syngas cleaning and CO2 scrubbing takes place.
• the Fischer-Tropsch synthesis takes place, which ultimately leads to diesel by means of catalysis and condensation.
• Entrained flow gasification process according to which in an inert gas stream indirectly heated, without catalysis, in several process stages with subsequent condensation coke, pyrolysis gas and pyrolysis oil is generated.
• DE 100 49 377 C2 describes a process for lubricating plastics, fats, oils and others hydrocarbon waste. In this case, it can be produced with the aid of a catalyst of sodium aluminum silicate in a circulation evaporator in the circuit with a base oil diesel, 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.
• US 4648965 describes a process for the preparation of liquid products from carbonaceous starting material containing inorganic, catalytically active ingredients.
• 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.
• the CHOREN process requires a very complex and thus expensive investment technique and results in a very low energy yield of about 40%. 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 circulation evaporator method according to DE 100 49 377 C2 is unsuitable for biomass (such as wood), since biomass contains only a few hydrocarbons and is composed mainly 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.
• a fossil carrier oil which has to be supplemented on an ongoing basis, is required.
• the catalyst used is "sodium aluminum silicate"
• 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. Another object is to provide a system for carrying out this method, which does not have the mentioned disadvantages. Of particular importance is that i) the plant operates at moderate process temperatures, and / or ii) causes low operating costs and / or iii) is economical through improved yield and / or iv) produces fuels of improved quality.
• 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.
• the invention further relates to a
• the invention further relates to the use of naturally occurring clays as catalysts for the production of fuels from biogenic raw materials.
• Biogenic raw materials or “biomass” refers to renewable vegetable raw materials. Biomass can be obtained from woody plants or annuals. Examples which may be mentioned are wood, such as tree trunks, in particular non-industrially exploitable tree trunks, branches, break wood, waste wood from wood processing plants; Garden waste and agricultural waste.
• the term also includes such substances and mixtures that do not meet certain standards for fuels but are suitable as a precursor.
• the term refers to mixtures of substances containing C6-C25 aclans, C6-C25 alkenes, C6-C25 alkynes, C3-C25 cycloalkanes, C3-C25 cycloalkylenes and / or C6-C25 aromatics; these definitions also include alkyl-substituted compounds such as e.g. Toluene or
• Carrier liquid or “carrier oil” denotes a liquid which is inert under reaction conditions. This liquid is suitable for
• Particularly suitable carrier liquid is heavy oil, which continuously arises when carrying out the process according to the invention.
• Alternative carrier oils are gas oil, diesel or their mixture. The carrier liquid is in direct contact with the biogenic raw material and the catalyst during the process.
• thermo oils 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.
• Catalyst refers to a natural mineral clay which typically contains the active ingredients montmorriolite, illite and / or smectite
• the clay is first dried and finely ground 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 smectite, are preferably used.
• the invention relates to a process for the production of fuels from biogenic raw materials, characterized in that a mineral catalyst of alumina, which contains montmorriolite, illite and / or smectite, with comminuted biogenic
• Raw material is reacted in a carrier liquid under heating to the reaction and the resulting fuel is separated from the reaction mixture.
• the mixture of shredded biogenic raw material and carrier liquid is subjected to the following treatment steps successively: soaking of the raw material in the carrier liquid and heating by circulating carrier oil; further reduction of the raw material to the microfibril; Mixing with the catalyst; further heating by means of circulating thermal oil for decomposing the polymer structure of the cellulose and the lignin; still further heating by circulating thermal oil for deoxygenation and polymerization of the resulting monomers; still further heating by circulating thermal oil to evaporate the resulting products; Finally, gradual cooling of the vaporized products to fuels.
• the method comprises the following steps (reference numbers, see Fig.
• Coarser solids separated in the separator are freed from the adhering carrier liquid in a heated discharge screw (54) and ejected.
• the exhaust gas flow from the combined heat and power plant (45) is fed to a termo oil boiler (49) in which circulating thermal oil for heating the containers (6, 11, 27, 34) is heated.
• the system according to the invention comprises: a mixing device (in which the
• Carrier liquid containing the comminuted raw material, the catalyst is mixed in) and a heated reaction vessel (in which essentially the polymer structure and the lignin of the Cellulose of the biogenic raw material) which of a
• the plant according to the invention comprises
• a first comminution device for comminuting the supplied biogenic raw material (in the case of wood into chips)
• comminuting device by a
• ⁇ dryer has followed, which dryer in turn is followed by a carrier liquid containing the heated impregnating container (in which a soaking, impregnation and impregnation of the supplied raw material), which impregnation of a
• ⁇ second mill is followed (is in which the structure of the raw material reduced to microfibril) which second comminuting device by a
• ⁇ mixing device used in which the carrier liquid mixed with the crushed raw material of the catalyst
• a ⁇ heated reaction vessel in which the polymer structure and the lignin of the cellulosic the biogenic raw material be decomposed and form monomers
• Heat exchanger which communicates via gas / steam lines with the impregnation tank, the reaction tank, the ripening container and the evaporation tank.
• the plant according to the invention comprises a first comminution device for comminuting the supplied biogenic raw material, in particular wood to chips, which comminution device has been followed by a dryer, which dryer in turn has been followed by a heated impregnation vessel containing the carrier liquid
• Ripening container and the evaporation container communicates.
• the exhaust pipe of the internal combustion engine extends to a thermal oil-waste heat boiler for heat exchange with circulating thermal oil, which is successively fed via a circulating heating line to one or more of the following containers: evaporation tank, maturing vessel, reaction vessel and impregnation vessel / these
• the inventive system can be stationary or mobile.
• a third aspect of the invention is explained in more detail below.
• the catalyst composition according to the invention 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, a simple and safe handling in the system must be ensured.
• the catalyst composition will contain 10-90% by weight of clay, preferably 20-75% by weight, for example 50% by weight.
• high-boiling heavy oil is called.
• high-boiling heavy oil is used as the carrier liquid, which constantly arises during the implementation of the method.
• 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.
• an alumina is used as a catalyst containing other than the above-mentioned layered silicates.
• the invention relates to the use of alumina or compositions containing such clays generally in the conversion of biogenic feeds to fuels.
• the invention also relates to the use of catalysts containing alumina which montmorriolite, illite and / or smectite, for the conversion of biogenic raw materials to fuels.
• Fig. 1 shows 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.
• Fig 1 mean: 1 source of raw material
• reaction vessel 12 gas / steam line of 6
• the reference number 1 denotes the source of raw materials with biogenic raw materials.
• This biogenic raw material is introduced into a first crushing device 2.
• This may for example be a hoe, a shredder or a mill, in which a reduction of the supplied raw material takes place up to a particle size of 1 - 5 mm, in the case of wood chips are produced with dimensions in this area.
• the throughput for mobile systems can be 5 tons of biogenic raw material, for stationary plants up to several thousand tons of biomass per day, obviously depending on the dimensioning of the entire plant with regard to their use.
• the crushed raw material is then fed to a drying plant 3.
• 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 90-95%.
• the warm air is supplied to the system 3 via a line 4 to be described by a heat source forth, wherein the exhaust air is returned via the line 60 to the heat source, which lines 4 and 60 together form a circulation line.
• the shredded and pre-dried raw material is from the drying plant 3 via appropriate transport facilities with, for example, conveyor belts or screw conveyors (not shown) in a
• Rotary valve 5 registered. This rotary feeder 5 serves to seal the air of the subsequent impregnating container 6.
• This impregnation container 6 is double-walled along its circumference, so that a
• Annular space 7 is formed, which is flowed through by a guided from a source to be described in the circulation thermal oil, which serves to heat the impregnating 6.
• the operating temperature of the impregnation is in the range of about 120-150 0 C.
• a recirculating carrier liquid for example a high-boiling heavy oil present. This carrier liquid with the raw material is thus heated in the impregnation container 6.
• the throughput of raw material is determined by a variable-speed drive (not shown) of the rotary valve 13.
• the Nachstructure of raw material in the impregnation 6 takes place automatically via the measurement of the level by means of the level probe 15th
• the biomass emerging from the further cellular wheel sluice 13 is fed via line 16 through the carrier fluid flowing through to a further, that is to say second comminuting device 17, for example in the form of a disperser, refiner or conical mill.
• second comminuting device 17 for example in the form of a disperser, refiner or conical mill.
• the structure of the biomass, including the chip, is comminuted to microfibril.
• a line 18 leads to a mixer 19.
• This mixer 19 is fed from a source 20, the catalyst slurry.
• the reaction vessel 11 is double-walled along its circumference, so that an annular space
• reaction vessel 21 is formed, which is traversed by a circulating from a source to be described later thermal oil, which serves to heat the reaction vessel 11.
• the operating temperature of the reaction vessel 11 is in the range of about 150 - 250 0 C.
• a stirring member 22 is mounted with attached wipers 23, so that thorough mixing of the mixture flowing from the mixer 19 ago mixture and simultaneously clean the heating surfaces of the annular space 21st is guaranteed.
• the reaction vessel 11 is provided with a
• Reaction vessel 11 as gases through the gas / vapor line 25.
• Other fission products remain either in the Carrier liquid of the mixture dissolved or also leave in gaseous form the reaction vessel through the
• the maturing container 27 is double-walled along its circumference, so that an annular space
• the operating temperature of the maturation container is in the range of about 250 - 300 0 C.
• the ripening container 27 through the gas / vapor line 30.
• the ripening container 27 is provided with a
• Level probe 29 equipped. This regulates via a pump (not shown) and the transfer line 33, the level in the maturation container 27 by controlled withdrawal of the mixture, the reaction liquid in the subsequent
• the evaporation container 34 is double-walled along its circumference, so that an annular space 35 is formed, which is guided by a circulating from a source to be described later thermal oil is flowed through, which serves to heat the evaporation tank 34.
• Evaporation tank 34 is in the range of about 300 - 370 0 C.
• the evaporation tank 34 is also equipped with a stirrer 36 with attached wipers 37.
• the evaporation tank 34 is used for the final evaporation of the resulting products, as well as the completion of the catalytic polymer reactions.
• the vaporized products leave the evaporation vessel 34 through line 38.
• the evaporation tank 34 is equipped with a level probe 39, which in this case the
• the number of necessary treatment steps or containers of 4 may change to a minimum of 3 or even 6 in the maximum case.
• the fuel condensates may have their own separate
• Desulfurization be provided. These are known from the prior art.
• the first outlet line 40 leads a first portion of the carrier liquid to a separator 41.
• the second outlet line 42 via a (not shown) pump, which serves as a return line, a second amount of the carrier liquid back to the impregnation 6.
• Outlet line 43 leads to a solids separator 44.
• a suitable device eg, a filter or a centrifuge. The separated particles are fed to the solids separator 44.
• the carrier liquid with the remaining particles smaller than 10-20 microns and high-boiling heavy oil that does not evaporate in the evaporation tank 34 are supplied as fuel to a cogeneration unit 45. This has a slow running
• Cogeneration plant 45 is suitable for coal slurry operation and drives a generator 46 for power generation 47 of the plant's own needs and also for delivery to the public grid.
• the cooling water 48 of the diesel engine is used for external heat purposes.
• the approximately 400 0 C hot exhaust gases of the diesel engine are fed to a thermal oil boiler 49.
• thermal oil boiler 49 there is a heat exchange between the exhaust gases and thermal oil.
• the heated thermal oil is sequentially supplied via a pump (not shown) and a circulation line 50 to the annulus 35 of the vaporizing vessel 34, the annulus 28 of the ripening vessel 27, the annulus 21 of the reaction vessel 11 and the annulus 7 of the impregnation vessel 6, and then flows through these annuli , now opposite sequence, back to the thermal oil boiler 49.
• the container 6, 11, 27 and 34 of the system are thus heated by the heat generated in the cogeneration unit 45, so that a thermally optimal operation is ensured.
• the cooled exhaust gas in the heat exchanger 49 is finally released via an exhaust filter 51 into the atmosphere.
• the deposited in the exhaust filter 51 filter dust is disposed of in a landfill.
• the third portion of the carrier liquid flows from the evaporation vessel 34 via the third outlet line 43 to the solids separator 44, to which also the separated solids in the separator 41 with a size greater than 10 microns via line 53 are supplied.
• the separation and regeneration of the catalyst can be carried out from the other solids in a separate process, so that this in turn can be returned to the process and thereby reduces the consumption of the fresh catalyst.
• the solids separator 44 consists of a sedimentation space and a heated discharge screw 54. Here are all the resulting mineral residues, as well as the added clay, freed by the heated discharge screw 54 of the adhering carrier liquid by evaporation.
• the heating unit is designated 55.
• the non-evaporated material ie the residue, is cooled and discharged after cooling in the cooler 56 via a cellular wheel 57 for external disposal.
• the oil vapor formed in the solids separator 44 and in the heated discharge screw 54 is fed via a line 52 to a heat exchanger, which has a first condenser 58 and a second condenser 59.
• the gas / vapor lines 12, 25, 30, 38 of the container 6, 11, 27, 34 open into a manifold 53, which extends to the first condenser 58 of the heat exchanger.
• this first capacitor called as
• This first capacitor 58 typically operates with an exit temperature of 160-200 0 C. This temperature is kept constant by regulating the quantity of cooling medium, that is the dry air. The said temperature determines the separation section between gas oil / diesel and gasoline / water, which substances from the various containers 6, 11, 27, 34 and the discharge screw 54 are supplied in vapor or gaseous form.
• the gas oil / diesel fraction 62 accumulates. This is then finely filtered and discharged as fuel into a storage tank (not shown).
• the gases not yet condensed in the liquid separator / aftercooler 61 are fed to the second condenser 59 and cooled therein to about 30 ° C. In this condenses the remaining water vapor together with the gasoline fraction. This fraction is then passed through line 63 into a water separator 64. In the water separator 64 gasoline and water separates statically due to the immiscibility and the density difference.
• the separated gasoline is through the
• Line 65 discharged, finely filtered and fed to a storage tank for use as fuel.
• the separated water is through the
• the non-condensed gases mainly CO2 and CO, but also C1-C4 alkanes, N2, are finally fed via line 8 of the combustion air supply to the diesel engine of the combined heat and power plant.
• Wood chips (dry) and 200 g / h alumina supplied and subjected to the novel process at 350 0 C for 10 h. It is isolated (based on the Ausgansmaterial, in wt .-%) 33-43% fuels; 15-20% coal, 20-25% water, 15-20% gas (43% CO2, 32% CO, 7% CH4, 9% N2, 1% H2). This corresponds to an energetic utilization (based on starting material 100%): 70-80% fuels, approx. 20% coal, cca 5-10% gas. The data varies, among others due to the variability of the used Ausgansmaterials.

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• 2006
  • 2006-06-06 CA CA002610876A patent/CA2610876A1/en not_active Abandoned
  • 2006-06-06 US US11/916,795 patent/US20090049738A1/en not_active Abandoned
  • 2006-06-06 WO PCT/EP2006/005350 patent/WO2006131293A1/de active Application Filing
  • 2006-06-06 AU AU2006257007A patent/AU2006257007A1/en not_active Abandoned
  • 2006-06-06 EP EP06743112A patent/EP1891182A1/de not_active Withdrawn
  • 2006-06-06 BR BRPI0611898-4A patent/BRPI0611898A2/pt not_active IP Right Cessation

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