US20130153394A1 - Facility and Method for Production Fuels from Biomass/Plastic Mixtures - Google Patents

Facility and Method for Production Fuels from Biomass/Plastic Mixtures Download PDF

Info

Publication number
US20130153394A1
US20130153394A1 US13/812,077 US201113812077A US2013153394A1 US 20130153394 A1 US20130153394 A1 US 20130153394A1 US 201113812077 A US201113812077 A US 201113812077A US 2013153394 A1 US2013153394 A1 US 2013153394A1
Authority
US
United States
Prior art keywords
reactor
oil
biomass
phase
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/812,077
Other languages
English (en)
Inventor
Emil A.J. Wieser-linhart
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of US20130153394A1 publication Critical patent/US20130153394A1/en
Abandoned legal-status Critical Current

Links

Images

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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
    • 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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • 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
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a method for producing fuels from mixtures containing biomass and plastics, and facilities for carrying out the method.
  • Wieser (WO 2006/131293) describes a catalytic method for producing fuel from biogenic raw material, using carrier oil.
  • Koch (EP 1538191) describes a method for producing fuels from residual materials by catalytic depolymerization, using a specific reactor.
  • One disadvantage of this method, among others, is that a specific reactor which is susceptible to malfunction must be used.
  • Goessler et al. (WO 2010/031803) describe a method for extracting fuels from mixtures containing biomass and heavy fuel oil.
  • One disadvantage of this method, among others, is that the biomass used must meet high quality requirements.
  • the aim of this method is essentially to process heavy fuel oils, not to enable utilization of biomass.
  • Spitzauer et al. (WO 2009/131590) describe a catalytic method for providing fuels from a plurality of possible starting materials in the liquid phase, using a carrier oil.
  • Molinari et al. (WO 2009/095888) likewise describe a catalytic method for providing fuels from a plurality of possible starting materials in the liquid phase, using a carrier oil.
  • Tschirner (DE 102006052995) describes a method for producing gas oil from organic residual materials and renewable raw materials by reaction control and energy input by means of process-integrated cavitation/friction. The addition of hydrogen is not disclosed in this document.
  • Miller discloses a method for producing pyrolysis oil (40) from biomass (25) and waste plastic according to the “flash pyrolysis” principle. Thus, the reaction described therein is not carried out in the liquid phase, nor is carrier oil recycled.
  • Wada discloses a catalytic method for producing oils from plastics, whereby plant or animal oils may also be added to the starting material. Neither recycling of a carrier oil nor the use of solid biomass is described.
  • Miyoshi et al. disclose a recycling process which may be connected to a refinery, in which a pyrolysate mixture is produced from various starting materials such as waste plastic and biomass according to the fluidized bed pyrolysis principle. In this process a portion of the starting materials is combusted, thus generating the required heat of reaction.
  • Wilms (DE 102008047563) likewise discloses a method for producing petrochemical intermediate products from (waste) plastics according to the fluidized bed pyrolysis principle, whereby biological (BTL) residual materials may also be added to the starting material.
  • the ratio of plastic to biomass is stated as 90:10 to 10:90.
  • the reaction does not take place in the liquid phase, and solids are mentioned as the carrier medium.
  • Steinberg U.S. Pat. No. 5,427,762 discloses a method for producing methanol, not fuels, from biomass, optionally in the presence of plastics.
  • the described method is likewise a fluidized bed pyrolysis process.
  • a disadvantage of the referenced methods in the liquid phase is that a carrier liquid must be added to the process.
  • the carrier liquid is not sufficiently stable under the given reaction conditions, and therefore must be continually replenished.
  • a disadvantage of the referenced methods in the gas phase is that the selectivities and/or yields of product oil are unsatisfactory. There is a need to reduce the quantity of by-products, in particular coal, CO, CO 2 , and process water, formed in this process. Furthermore, control of the facilities for the referenced methods is laborious and complicated, so that there is also a need for facilities which operate reliably and have a simple design.
  • the invention relates to a method for producing fuels from mixtures containing biogenic raw materials and plastics.
  • the invention further relates to a facility for producing fuels from such starting materials.
  • Biogenic raw materials refers to the organic substances continuously biochemically synthesized by living organisms, and secondary products produced or extracted therefrom.
  • the biogenic raw materials may be divided into the areas of plant, microbial, and animal biomass, depending on the producing organism.
  • Plant biomass includes, for example, wood, foliage, straw, bran, hay, grains, pressing residues from fruit and wine crops, beet pulp, green waste, gardening and agricultural waste, as well as secondary products such as scrap wood products, starch, sugar, cellulose, and waste paper.
  • Microbial biomass includes, for example, dried sewage sludge as well as fermenting waste and digestate.
  • Animal biomass includes, for example, waste from animal husbandry and the fish and meat industries, waste products from the milk and cheese industry, and meat and bone meal.
  • biomass is preferred.
  • Biomass containing lignocellulose (“lignocellulosic biomass”) is particularly preferably used, typically having a cellulose content of greater than 30% by weight, in particular greater than 60% by weight, or composed essentially of lignocellulose.
  • Such preferred biomass may be composed of or extracted from woody plants or annual plants; examples are wood from various sources (such as tree trunks, in particular tree trunks that are not industrially recoverable, branches, fallen timber, scrap wood from wood processing plants); and garden waste and agricultural residues (such as straw, bran, and dried beet pulp).
  • biomass which contains or is composed of carbohydrates is particularly preferred.
  • Biogenic raw materials may be present in liquid or solid form. Within the scope of the present invention, solid biomass is preferred.
  • Plastics are known to those skilled in the art; the term refers in general to macromolecular semi-synthetically and in particular synthetically produced solids.
  • the term includes thermoplastics, duroplastics, and elastomers. Plastics may be present as pure substances or as substance mixtures/blends. In addition, plastics may be present in various degrees of purity; therefore, the term also includes plastic-containing mixtures.
  • “Fuels” are known to those skilled in the art; the term refers in general to hydrocarbon-containing compounds and mixtures as may be used in internal combustion engines.
  • the term refers to substance mixtures containing C6-C25 alkanes, C6-C25 alkenes, C6-C25 alkynes, C3-C25 cycloalkanes, C3-C25 cyloalkenes, and/or C6-C25 aromatics; these definitions also include alkyl-substituted compounds such as toluene or methylcyclohexane, as well as branched compounds such as 2-ethylhexane.
  • Such substances and substance mixtures which do not meet certain standards for fuels but which are suitable as precursor product are referred to as product oil or fuel, depending on the context.
  • Carrier liquid or “carrier oil” refers to a liquid which is largely inert or inert under reaction conditions.
  • a liquid is considered as “largely inert” if it does not boil at the prevailing reaction temperatures (in particular if it has a boiling point >380-400° C.).
  • Such carrier liquids for which at least 90% remains unchanged in a reaction cycle are preferred.
  • This liquid is suitable for suspending the biogenic raw material.
  • a particularly suitable carrier liquid is heavy fuel oil, which is continuously generated while carrying out the method according to the invention.
  • Alternative carrier oils such as gas oil, diesel, or a mixture thereof are suitable in particular for running a facility. The carrier liquid is in direct contact with the starting materials during the process.
  • Thermal oil refers to a liquid for indirect heat transfer in the method according to the invention. Suitable thermal oils are known to those skilled in the art, and may be based on silicone oils or hydrocarbons. Within the scope of the present invention, any given thermal oils which are adapted to the reaction temperature may be used. The thermal oil is not in direct contact with biogenic raw material or catalyst during the process.
  • FIG. 1 schematically shows an example of a facility according to the invention.
  • This diagram shows the main unit for material conversion, but not auxiliary units such as raw material preparation and recovery of the products coal, fuels, gases, and water.
  • the terms have the following meanings: biomass silo (S B ), plastics silo (S K ), biomass screw heater (H B ), plastics screw heater (H K ), disperger (DIS), reactors R (main reactor (R 1 ), hydrogenation reactor (R 2 ), anaerobic reactor (R 3 )), vacuum evaporator (VVD), condensers (K 1 , K 2 , K 3 ), phase separator (PT), separators ((S 1 ) for oil phase and (S 2 ) for aqueous phase), rectification column (RKT), and gas engine/gas turbine (GM).
  • biomass silo S B
  • plastics silo S K
  • biomass screw heater H B
  • plastics screw heater H K
  • disperger disperger
  • the products of the method or of the facility are denoted by P coal (product coal), P H2O (product water), P oil (product oil/fuels), and P E (thermal energy/heat, electrical power).
  • the starting materials of the method or of the facility are denoted by B (biomass) and K (plastics).
  • B biomass
  • K plastics
  • the product flow from the starting materials to the fuels which are the primary product is highlighted.
  • the recirculation of intermediate products (in the reactor, for example) is not shown in FIG. 1 .
  • the recycling of carrier oil from the vacuum evaporator VVD into the disperger DIS is clearly apparent.
  • FIG. 2 schematically shows an example of an alternative facility according to the invention.
  • the reactor R 1 and a sump phase hydrogenation reactor R 4 are expanded, in which a portion of the sump phase (heavy fuel oil+coal) is hydrogenated by supplying hydrogen, and the reaction product is directly recycled into R 1 .
  • R 1 is replaced by R 1 +R 4 in this variant; the remaining parts of the facility correspond to those in FIG. 1 and are not illustrated in full.
  • the invention in particular the method and the facility (facilities), is/are explained in greater detail below with reference to the figures.
  • the method according to the invention is first explained in its embodiment as an independent process, followed by a description of method variants which involve integration into a larger production system. Lastly, facilities which are suitable for this purpose are described, and exemplary embodiments are explained.
  • a first aspect of the invention a method for producing fuels from biogenic raw materials and plastics, is explained in greater detail below.
  • the invention relates to a method for producing fuels from biomass and plastics, characterized in that in a first step biomass and plastics are provided and dispersed at 300-400° C., optionally in the presence of recycled carrier oil; in a second step the obtained mixture is brought to reaction at 300-400° C.; in a third step the resulting gaseous, liquid, and solid products are separated from one another and optionally further processed.
  • the method according to the invention represents for the first time a method for the joint oiling of plastics and biomass. Additional continuous supplying of (fossil) carrier oil may thus be avoided. It is assumed that continuous external addition of carrier oil is thus unnecessary, since the supplied plastic, due to its simultaneous splitting inherent to the process, takes over the function of the carrier oil.
  • the invention relates to a method as described herein which is carried out without externally supplying carrier oil.
  • biomass lignocellulose, for example
  • hot carrier oil paraffinic carrier oil such as HFO or VGO, for example
  • a diesel-like cracking product typically results as condensate, of which approximately 50% originates from biomass and 50% originates from carrier oil.
  • the yield relative to the dry biomass charged is typically 30-40% by weight, so that 15-20% of the product originates from the biomass, and the same quantity originates from the carrier oil. Since both reactants are polymers, the result is that not only the biomass, but also the carrier oil is depolymerized (cracked). Therefore, the carrier oil cannot be referred to as inert.
  • the splitting of the carrier oil (“depolymerization”) may be definitively verified by precise balancing and concurrent checking using the C14 method.
  • the cracking of carrier oil is an undesired reaction, since continuous addition of the carrier oil is necessary.
  • supplying carrier oil may be dispensed with altogether, which is a major advantage compared to the known methods.
  • the invention relates to a method as described herein in which the stated second step is carried out without externally adding catalyst.
  • a method without addition of catalyst results in simplified process control, since it is not necessary for catalyst to be either metered in or separated. Without being bound to a theory, it is assumed that the biomass supplied to the process forms catalytically active material in the form of coal.
  • the invention relates to a method as described herein which is carried out semicontinuously or continuously.
  • the method according to the invention is advantageously designed in such a way that steps 1, 2, and 3 are carried out continuously.
  • the continuous process is efficient, and allows integration into larger facility systems.
  • the invention in another advantageous embodiment (“sump phase hydrogenation”), relates to a method as described herein in which in a further step, a portion of the sump phase (10-90%, for example) formed in the second step is removed from the reactor, hydrogenated, and subsequently recycled to the reactor.
  • a portion of the sump phase (10-90%, for example) formed in the second step is removed from the reactor, hydrogenated, and subsequently recycled to the reactor.
  • at least two recycling circuits are present: one for carrier oil into the disperger and one from the hydrogenated sump phase into the reactor R 4 ( FIG. 2 ).
  • the invention relates to a method as described herein in which the ratio of biomass to plastic is in the range of 80:20 to 10:90% by weight. It has surprisingly been found that for a proportion of plastics of at least 20% by weight of the supplied quantity of raw material (biomass+plastic), it is not necessary to supply additional carrier oil to the process. Without being bound to a theory, it is assumed that plastics in the reactor are continuously biocatalytically split into carrier oil in exactly the same way as carrier oil, and are subsequently converted into the product oil by further cracking. Therefore, plastics or carrier oil may be considered as hydrogen donors, and biomonomers may be considered as hydrogen acceptors.
  • biogenic raw material and “plastic” have been discussed above.
  • the raw material is typically supplied to the reactor in “comminuted” form, i.e., in the form of chips, shavings, cuttings, molded pieces, or the like, thus enabling a rapid, complete reaction.
  • the particular size that is suitable depends on the biogenic material used, and may be determined in simple tests.
  • 90% of the biogenic raw material supplied to the reactor has a particle size less than 10 mm, preferably greater than 3 mm.
  • substitute fuels from a waste sorting plant When substitute fuels from a waste sorting plant are used, a particle size of approximately 5 mm has proven satisfactory. Chopped straw as it occurs in agriculture may be used in this way.
  • the raw material is typically dried in screw heaters, i.e., is supplied to the reactor with a residual moisture of less than 5%.
  • the invention relates to a method as described herein in which the stated plastic is a mixture comprising (i.e., containing or composed of) PE, PP, and/or PS. It is advantageous for the method when the plastics used have a minimum content of 50% by weight, preferably 65% by weight, of the stated plastics. Since plastics such as polyethylene (PE), polypropylene (PP), and polystyrene (PS) are chemically related to the paraffins, are essentially different with regard to chain length and crosslinking, and are saturated with hydrogen due to their stability, they may meet the cracking-related continuous oil requirements when added concurrently with biomass.
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • plastics such as polyethylene terephthalate (PET), polyurethane (PU), and polyvinyl chloride (PVC) are also typically contained in lower concentrations in mixed plastics. These plastics may be either (i) supplied to material recycling beforehand by suitable separating methods or (ii) supplied to the process. The plastic used may therefore have variable contents of heteroatoms such as S, O, N, and Cl. These plastics may be partially converted into product oil, and would therefore be classified as impurities. Such impurities may be removed in an additional hydrogenation step (rectification column (RKT); see above).
  • RKT rectification column
  • the invention relates to a method as described herein in which the stated biomass is a mixture comprising (i.e., containing or composed of) lignocellulose, carbohydrates, and/or derivatives thereof.
  • the invention relates to a method as described herein in which the so-called “high heating value fraction” of a mechanical biological waste sorting plant is used as raw material.
  • This fraction is also referred to as “substitute fuel,” and already contains at least 20% mixed plastics, as well as waste paper as biomass.
  • Substitute fuel is suitable for the method according to the invention from both a technical standpoint (chemical composition, availability) and an economic standpoint (disposal fees).
  • the invention relates to a method as described herein in which other raw materials, for example wood, straw, and biogenic residual materials, with addition of at least 20% plastic are used as starting material.
  • other raw materials for example wood, straw, and biogenic residual materials, with addition of at least 20% plastic are used as starting material.
  • the plastics used are initially liquefied/melted; this is possible at 150-200° C. and may be carried out, for example, by charging from a silo into a disperger via a screw heater. Any vapors generated are discharged and further processed as described below.
  • the biomass used is initially heated and dried; this is possible at 150-200° C. and may be carried out, for example, by charging from a silo into a disperger via a screw heater. Generated vapors are discharged and further processed as described below.
  • the starting materials which are heated to 150-200° C. and predried are dispersed with addition of carrier oil at a temperature of 300-400° C., and at the same time are heated to form a suspension.
  • This dispersion is advantageously carried out with addition of carrier oil which, among other things, is formed in the second step and is partially or completely recycled. It has proven advantageous when the suspension that is formed is immediately transferred to the reactor (second step); typical residence times for solids in the area of the dispersion are 0.1-1.0 sec, and in the area of the reactor, 10-30 min.
  • the invention further relates to a method, characterized in that in a first step biomass and plastics are initially provided, then dried/liquefied at 150-200° C., and then dispersed at 300-400° C., optionally in the presence of carrier oil (preferably recycled carrier oil).
  • carrier oil preferably recycled carrier oil
  • the invention relates to a method as described herein in which the stated second step is carried out in the liquid phase.
  • Suitable reaction temperatures for the present method may vary over a wide range.
  • the optimal reaction temperature depends, among other factors, on the type of raw material used, and is typically 300-400° C.
  • the optimal temperature in the individual case may be determined by routine testing.
  • the product oil is therefore initially present in gaseous form, thus providing for easy separation.
  • Suitable reaction pressures for the present method may vary over a wide range.
  • the invention relates to a method as described herein in which the stated second step is carried out without pressure, i.e., in a reactor at standard pressure.
  • a slight positive pressure of 20-40 mbar for example, is typically set.
  • the term “unpressurized” is understood to mean a maximum of 100 mbar above standard pressure. According to the prior art, such pressures may be set using standard pressure relief valves. The purpose of the slight positive pressure is to minimize the penetration of ambient air, and thus the risk of forming explosive gas mixtures.
  • the invention further relates to a method in which inerting with CO 2 is carried out at least in step 1 or 2, and in which the inerting is preferably automatically regulated.
  • Suitable residence times for the present method may vary over a wide range.
  • the optimal residence time depends, among other factors, on the type of raw material used, and is typically 10-20 min.
  • the average residence time in the reactor is typically greater than in the disperger by a factor of 1000.
  • the optimal residence time in the individual case may be determined by routine testing.
  • the present method may be carried out uncatalyzed or catalyzed.
  • the invention relates to a method as described herein, characterized in that no catalyst is externally added to the process (“uncatalyzed”).
  • This embodiment is particularly advantageous for biogenic material having a high lignocellulose and/or ash content. It is assumed that under the given reaction conditions a catalytically active material (coal) forms from the biogenic material, in particular from the lignin component. If the reaction is carried out catalyzed, the catalysts known from the prior art for oiling reactions may be used.
  • the reaction products of the method according to the invention may be divided into four groups: i) noncondensable gases P G ; ii) product oil P oil ; iii) process water P H2O , and iv) coal P coal .
  • the resulting gaseous, liquid, and solid products are typically separated from one another and optionally further processed. The separation of these individual groups is known per se.
  • the products which are gaseous under the reaction conditions are initially separated, the noncondensable gases are then separated from this product stream, and lastly, the aqueous phase (process water) is separated from the nonaqueous phase (product oil).
  • Suitable devices for the individual operations are known to those skilled in the art, and may be designed based on the product streams.
  • the resulting product oil either immediately meets the above-mentioned criteria for a “fuel,” or must be further treated (phase separation, separation, rectification, and hydrogenation, for example) in order to meet these criteria.
  • the products which are gaseous under the reaction conditions are advantageously discharged overhead from the reactor, while the products which are liquid and solid under the reaction conditions (“sump phase”) are discharged via the reactor sump.
  • the products discharged overhead are subsequently advantageously separated into a gaseous phase, an aqueous phase, and an oil phase, and further processed separately.
  • the products discharged from the reactor sump are subsequently advantageously separated into solid products (coal) and liquid products and further processed, whereby the liquid products (“carrier oil”) which arise there may be completely or partially recycled to the reactor.
  • products discharged from the reactor sump may undergo a hydrogenation step (“sump phase hydrogenation”), as explained below.
  • 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 optionally separated into their phases and further processed separately.
  • the mixed vapor exiting from the reactors typically forms a noncondensable gaseous phase (i.e., a phase whose components are predominantly gaseous at standard conditions) and two liquid phases: a product oil phase and an aqueous phase.
  • a noncondensable gaseous phase i.e., a phase whose components are predominantly gaseous at standard conditions
  • two liquid phases i.e., a phase whose components are predominantly gaseous at standard conditions
  • Noncondensable gases in another embodiment, relates to a method as described above, characterized in that the noncondensable gases formed in the process are partially or completely supplied to a gas engine and/or a gas turbine.
  • gases that are formed they may either be flared, converted into electrical power in a gas engine/gas turbine, or dissolved/adsorbed in a carrier.
  • the individual methods may also be combined with one another. The particular use depends, among other factors, on the economic and (safety-related) technical considerations.
  • Most or all of the quantity of gas that arises is preferably supplied to a gas engine/gas turbine to allow optimal energy utilization (thermal/electrical) of the biogenic raw material used.
  • the invention thus relates to a method as described herein in which the gaseous products that are formed are supplied, optionally after conditioning, to a gas engine or a gas turbine.
  • the solids formed in the method according to the invention are essentially coal having a comparatively high internal surface and high porosity, and mineral substances.
  • the coal that is formed may be separated from the remaining reaction mixture (essentially in the carrier oil) in a manner known per se. Continuous separation is preferably carried out, for example by means of a vacuum evaporator VVD heated by a carrier oil.
  • the separation of the coal that is formed is preferably carried out in the steady-flow lower section of the reactor (“reactor sump”).
  • the separation of the coal from the reactor takes place together with the phase which is an oil phase under the reaction conditions.
  • This coal/oil phase mixture may be further treated in one or more subsequent steps, and/or the mixture constituents may be separated from one another.
  • Hydrogenation processes are suitable for further treatment of coal/oil, while thermal separation operations (i.e., vaporization of heavy fuel oil, optionally at reduced pressure) are suitable for separating coal/oil.
  • the separation of the coal/oil phases is carried out by extractive separation, followed by thermal separation.
  • extracting agents aromatic solvents (toluene, for example), aliphatic solvents (hexane, heptane, cyclohexane, for example), or mixtures thereof.
  • a suitable quantity of extracting agent is 100-500% by weight of the carrier oil content, typically 300% by weight of the carrier oil content.
  • the liquid phase obtained in the extraction (“miscella”) is optionally filtered and subsequently distillatively separated into solvent and carrier oil.
  • Such extraction methods are generally known, and are used in the area of residual oil removal from oilseeds.
  • the remaining dry coal is thermally treated (“toasted”) in an additional step to further reduce the residual solvent content.
  • a content of solvent in the coal of ⁇ 0.5% by weight is typically achieved; this loss of solvent may be compensated for by external supply, or preferably by the light fraction of the product oil that is formed.
  • Thermal integration of the mentioned distillation and toasting steps into the overall process improves the energy balance.
  • reaction gases generated during the coal preparation such as H 2 O, H 2 S, NH 3 , HCl, etc., may be continuously discharged into the product gas line.
  • the oil phase obtained in the coal preparation is preferably supplied back to the process (recycled) and/or further processed together with the above-mentioned product oil (ii).
  • the dried coal obtained in the coal preparation may be further processed as described below, in particular in the form of a coal gasification step for formation of fuel gas which is additionally supplied to a gas engine (which improves the energy balance of the process) and/or in the form of a steam reforming step for formation of water gas (which meets the hydrogen requirements of the facility).
  • the invention further relates to a method as described herein in which the solid products that are formed, optionally after drying, are provided to separate further processing.
  • the method according to the invention may be supplemented by further steps, in particular hydrogenation of the product oil that is formed (see fourth step below), and coal preparation (see fifth step below).
  • the product oil i.e., the liquid products formed during the reaction
  • the product oil may be hydrogenated in the method according to the invention, although this is not mandatory. It has proven advantageous to catalytically hydrogenate the product oil.
  • This method step improves the quality of the product oil, since alkenes which may be present are converted into the corresponding alkanes, and at the same time, undesired accompanying substances which may be present are removed. As the result of this method step, it may be ensured that the generated product oil meets the current commercial standards for fuels.
  • the quality criteria for standard diesel for example, for phosphorus, nitrogen, sulfur, chlorine, and water content, as well as oxidation stability, according to currently applicable DIN EN 590 may be met.
  • the hydrogen required for the hydrogenation step may be externally supplied or generated in the process itself (see steam reforming, water-gas shift below).
  • the hydrogenation of the product oil preferably takes place after the rectification. Suitable hydrogenation units for the substance mixtures that are present are known per se, and [are used in the] prior art in oil refineries, for example.
  • Suitable catalysts for the substance mixtures that are present are known per se and commercially available; heterogeneous catalysts in which the catalytically active metal/active metal compound is applied to an inert carrier are advantageous.
  • the catalyst is set up as a fixed bed in two parts, whereby the two parts contain different hydrogenation catalysts; typical heights of the catalyst bed are 20-200 cm.
  • the upper area is preferably designed as an Ni/MoS fixed bed.
  • the lower area is preferably designed as a Pd/Pt fixed bed. This division results in particularly good results, since the upper area having a “robust” catalyst brings about the deposition of catalyst poisons (in particular sulfur-containing compounds), whereas the lower area ensures alkanization with high efficiency.
  • the invention thus further relates to a method as described herein, characterized in that the liquid products that are formed (in particular the fuel fraction) undergo rectification followed by hydrogenation.
  • the invention further relates to a method in which these quantities of hydrogen are supplied.
  • the hydrogenation step of the product oil hydrogenation is designed in such a way that after hydrogenation is complete, the product oil has sufficient oxidation stability according to DIN EN 12205.
  • an infrared spectrometric measuring device is situated in the discharge line of the alkanic oil. This measure provides simple and efficient monitoring of the hydrogenation, and on the basis of this measurement provides the option of adjusting the process parameters of the hydrogenation.
  • any given hydrogen sources known to those skilled in the art including pure H 2 and H 2 -containing gas mixtures, may be used.
  • hydrogen is used which is generated from the reaction of the solid, and is separated in the process by steam reforming, followed by water-gas shift; “heat pipe reformers,” for example, would be suitable as reactors for this purpose. Details concerning this embodiment are provided below in the “coal recovery” section.
  • hydrogen is used which is produced from natural gas by steam reforming with a subsequent water-gas shift reaction. This method procedure may be appropriate when the overall capital and facility operating costs are taken into consideration.
  • the coal that is formed is the important solid reaction product of the method according to the invention, and may be reused in various ways.
  • the invention relates to a method as described above, characterized in that the coal that is formed, optionally with oil removed, undergoes steam reforming with water, preferably with the product water that is generated, followed by a water-gas shift reaction.
  • This method variant provides hydrogen which may be required for the method, in particular for the mentioned hydrogenation steps (hydrogenation of the sump phase, hydrogenation of the product oil).
  • the invention in another embodiment relates to a method as described above, characterized in that the coal that is formed, optionally with oil removed, is gasified.
  • the coal that is formed is converted into fuel gas, a mixture containing CO, H 2 , and methane (in varying quantities, depending on the coal gasification process selected).
  • This fuel gas may meet part or all of the process energy requirements in an associated gas engine.
  • the invention in another embodiment, relates to a method as described above, characterized in that the coal that is formed is continuously separated and mixed with product water that is generated, with exclusion of air.
  • the mixing with exclusion of air is advantageous, since the separated coal is initially very hot and would immediately combust on its own upon entry of air.
  • the coal slurry that forms is a common form for the transport and use of fine-particle coal/coal dust.
  • this method variant allows disposal of possibly contaminated product water without further purification.
  • the required hydrogen may come from any desired source, for example from a natural gas reformer as previously described.
  • the hydrogenation may be carried out under conditions that are known per se; catalyst-free hydrogenation by means of ultrasound is advantageous.
  • three hydrogenation options may be used, independently of one another or together, in the method according to the invention: the H donor function of the plastic used, the hydrogenation of the product oil, and the hydrogenation of the sump phase.
  • the sump phase hydrogenation thus allows intervention into and optimization of the actual oiling process in the reactor.
  • This embodiment is therefore particularly advantageous.
  • the hydrogenation of the sump phase is carried out by ultrasound.
  • ultrasound essentially produces two effects: (A) At a temperature greatly below the vaporization temperature of the coal/oil suspension (for example, 100° C. or less), cavitation occurs in the liquid with subsequent implosion of the microbubbles, resulting in a very high pressure (up to 1000 bar) and a very high temperature (up to 2000° C.), which are temporary and locally limited.
  • the hydrogenation reaction is accelerated by ultrasound, essentially due to activation of the hydrogen and/or activation of the coal.
  • Complete hydrogenation i.e., elimination of all double bonds and all heteroatoms, is not necessary in this step; partial hydrogenation, for example to 10-90% of the theoretical value, is sufficient, depending on the other reaction parameters and the starting materials used.
  • the mechanical sound energy introduced in this hydrogenation step is ultimately converted into heat, which may also contribute to the heating of the reactor.
  • step 1 Optional comminution and predrying of the biogenic material to less than 5% residual moisture (step 1) 2. Optional comminution and predrying of the plastic to less than 5% residual moisture (step 1) 3. Admixture of the prepared raw materials and continuous supply to the reactor (step 1) 4. Unpressurized reaction of the supplied material and continuous overhead separation of the resulting mixed vapor (step 2) 5. Continuous separation of the formed coal and the formed oil phase from the reactor sump (step 3) 6. Separation of the oil phase from the coal, and recycling of the oil phase to the reactor 7. Optional steam reforming and water-gas shift reaction of the coal that is formed, and supplying the formed hydrogen in step 8 8. Isolation and optional hydrogenation of product oil from the mixed vapor of step 4.
  • step 1 Optional comminution and predrying of the biogenic material to less than 5% residual moisture (step 1) 2. Optional comminution and predrying of the plastic to less than 5% residual moisture (step 1) 3. Admixture of the prepared raw materials and continuous supply to the reactor (step 1) 4. Unpressurized reaction of the supplied material in the liquid phase and continuous overhead separation of the resulting mixed vapor (step 2) 5. Continuous separation of the resulting sump phase (containing coal and the heavy fuel oil phase that is formed) from the reactor sump (step 3) 6. Separation of a portion of the sump phase, followed by hydrogenation and recycling to the reactor 7. Separation of the remaining sump phase into coal and oil phases, and recycling of the oil phase to the reactor or disperger 8. Optional steam reforming and water-gas shift reaction of the coal that is formed, and supplying the formed hydrogen in steps 9 and/or 6. 9. Isolation and optional hydrogenation of product oil from the mixed vapor of step 4.
  • the invention thus relates to a method as described herein which is integrated into a production system, in particular a method which is coupled to a waste/refuse disposal process.
  • the method according to the invention and the corresponding facility may be configured as an individual process or facility (“stand-alone”), or may be coupled to a further process or facility.
  • This flexibility represents a fundamental advantage of the present invention.
  • the term “coupling” is understood to mean the production system between facilities in which the material and/or energy flows are exchanged.
  • the invention relates to a method for producing fuels as described above, characterized in that the stated starting materials are supplied directly from a waste sorting plant to the process, optionally with temporary storage.
  • a third aspect of the invention a facility that is suitable for carrying out the above methods, is explained in greater detail below.
  • the facility according to the invention includes the following (see FIG. 1 ):
  • the facility according to the invention also includes a comminution device, situated upstream from the screw heaters, for comminuting the supplied biogenic raw material (in the case of comminuting wood into chips) and/or the supplied plastic.
  • a comminution device situated upstream from the screw heaters, for comminuting the supplied biogenic raw material (in the case of comminuting wood into chips) and/or the supplied plastic.
  • the facility according to the invention includes a separate condenser (K 1 ) for separating the free and capillary water evaporated in the screw heaters, as well as other volatile components.
  • the facility according to the invention includes a condenser (K 2 ), associated with the reactor, for separating the mixed vapor generated in the reactor.
  • K 2 condenser
  • the facility according to the invention includes a phase separator (PT), associated with the condenser (K 2 ), for separating the condensate generated in the condenser (K 2 ).
  • PT phase separator
  • the facility according to the invention includes an additional gas engine and/or gas turbine (GM) which combust(s) part or all of the gaseous products generated in the facility, and which is/are thus used for generating electrical power and/or heat.
  • GM gas engine and/or gas turbine
  • the facility according to the invention includes an additional anaerobic reactor (R 3 ), associated with the separator (S 2 ), which reduces the organic fractions of the aqueous phase with formation of biogas.
  • the facility according to the invention includes one or more heated screws (H K ), (H B ) for transporting the starting materials into the disperger (DIS).
  • the facility according to the invention may have a stationary, modular design.
  • the daily throughput for small facilities may be 5 metric tons of biogenic raw material, and for large facilities, may be up to several thousand metric tons of biogenic raw material, obviously as a function of the dimensioning of the overall facility with regard to its charging.
  • the facility may be dimensioned by increasing/decreasing the size of the individual facility parts, or by connection of facility parts in parallel.
  • the facility parts disperger (DIS), reactor (R 1 ), and vacuum evaporator (VVD) are connected in series.
  • DIS facility parts disperger
  • reactor R 1
  • VVD vacuum evaporator
  • two dispergers operated in parallel may be followed by a reactor.
  • ancillary facility parts such as columns, connecting lines, pumps, etc.
  • Such alternatives are encompassed within the scope of the present invention, and are not named separately.
  • the reactor may be replaced by two reactors 1 and 2 connected one behind the other, the second reactor advantageously being operated at a temperature that is 0-30° C. higher.
  • the facility according to the invention may be operated with a simple temperature profile. Each container is operated at a specific temperature; stepped temperature control is not necessary. This increases the safety of the facility, and is also advantageous for scale-up.
  • Raw material preparation and storage The raw materials are delivered either in wrapped bales (substitute fuel) or in bulk. In general, precomminution to particle sizes ⁇ 5 mm is carried out, as well as predrying to a moisture level ⁇ 20% if necessary.
  • the raw material is subsequently introduced into one or more, for example two, silos for temporary storage, and optionally inerted there using N 2 and/or CO 2 , for example.
  • Plastic fraction In the method according to the invention, the plastic fraction must be at least 20% but no greater than 90%.
  • the biomass fraction should therefore likewise be at least 10%, and 80% at most.
  • the method according to the invention is designed with one or multiple lines, preferably two lines.
  • the plastic content may also fluctuate in substitute fuel, and if this value drops below 20%, the resulting deficit may be compensated for via a second line.
  • a higher plastic content (up to 90%) is not harmful, but, rather, increases the yield considerably. If the first line is operated only with biomass, the addition of plastic via the second line is controlled in such a way that no carrier oil deficiency occurs, and the yield is maximized.
  • Screw heaters The screw heaters (H K ), (H B ) are designed as twin screws, and are preferably indirectly heated to 130-200° C. using thermal oil.
  • the moisture present in the raw material evaporates, and is preferably subsequently condensed in a condenser (K 1 ).
  • the condensate together with any stripped substances contained therein passes into the phase separator (PT), and noncondensing gases are supplied to the gas engine (GM) via the shared gas system.
  • the biomass is preheated, and the plastic is plasticized or also melted, in the screw heaters.
  • Disperger The purpose of the disperger is to quickly mix the biomass and plastic raw materials with the circulated carrier oil, while at the same time raising the temperature to approximately 330-380° C. It is assumed that the material gradient and the speed are of great importance for the success of the overall process.
  • the disperger is advantageously composed of a motor-driven inline mixing unit having a high shear gradient. These types of dispergers ensure that the raw materials are quickly mixed with the circulated carrier oil.
  • the facility according to the invention is designed with two lines up to the disperger.
  • the mixing ratio of the biomass and plastic raw materials may be freely set.
  • the reactor (R 1 ) is preferably equipped with an agitator and circulation pump.
  • the reactor is preferably composed of a double-wall container, and is heated to 300-400° C., for example 330-380° C., using thermal oil.
  • the reactor is designed as a loop reactor, and for this purpose is equipped with an agitator.
  • the level in the container is advantageously monitored and regulated (for example, if the level drops, the continuously added fraction of plastic may be increased; if the level rises, the addition of the total quantity of raw materials may be restricted).
  • a circulation pump draws in carrier oil in the lower section [of the reactor] and supplies the disperger with the required mixed oil, optionally after purification.
  • the consistency of the circulation oil is continuously monitored, and is set to 20-50% dry matter by varying the discharge into the vacuum evaporator.
  • the degassing takes place in the upper section of the reactor; the resulting mixed vapor is advantageously purified via an aerosol separator and subsequently supplied to a condenser (K 1 ).
  • the resulting liquid phase passes into a static phase separator (PT), and the noncondensing gas fraction is supplied to the gas engine (GM).
  • the facility according to the invention thus includes a reactor (R 1 ) which is indirectly heated by thermal oil, and which has internal loop conduction via an agitator and a circulation pump for returning carrier oil to the disperger.
  • Vacuum evaporator solids The vacuum evaporator (VVD) is preferably provided as a film evaporator having scrapers.
  • the vacuum evaporator (VVD) is preferably indirectly heated by thermal oil.
  • the 20-50% dry matter coal-carrier oil suspension is conducted from the reactor via a pump, and the oil is vaporized at approximately 360° C. and a pressure of approximately 5 mbar. Oil contents of ⁇ 1% in the residual coal are thus possible.
  • the coal-mineral substance mixture is discharged as a powder via a pressure lock with wetting by water, the resulting oil vapor is condensed under vacuum, the condensate is supplied to the phase separator, and the residual gas is conducted via the vacuum pump and recondensed at standard pressure. The remaining noncondensing fraction is discharged to the gas engine.
  • Condensers The condensation of the mixed vapors is advantageously carried out in spray coolers which are preferably irrigated with cooled circulation condensate.
  • Static phase separator All condensates are combined in the static phase separator (PT).
  • PT static phase separator
  • the oil phase is separated from the aqueous phase in a gravitational field, the separation zone is continuously measured, and the withdrawal of the two phases is appropriately regulated.
  • Partially emulsified denser subphases are present in both the aqueous phase and the oil phase, in the crude oil (in particular heavy fuel oil) and in the water (in particular tars and solids). These subphases are preferably separated via the two separators (S 1 ), (S 2 ) and returned to the reactor.
  • the crude oil from S 1 is advantageously discharged to the rectification (RKT) as the lighter phase, and the heavy fuel oil is returned to the reactor R 1 .
  • the water from S 2 is advantageously discharged to an anaerobic reactor (R 3 ), and the heavy fuel oil/tar is returned to the reactor R 1 .
  • Rectification The purpose of the rectification column (RKT) is to provide a suitable boiling fraction of the resulting alkanes/alkenes, for example for C20-C23 alkanes/alkenes. This is possible by means of the different boiling characteristics, as a function of the chain length.
  • Nonvaporizing oils remain in the sump and are returned to the reactor.
  • the vaporizing portion is advantageously once again condensed, for example in a packed separation column, and supplied to the hydrogenation process.
  • Typical operating conditions for the rectification are approximately 210° C. sump temperature at approximately 20 mbar.
  • the sump is advantageously heated by thermal oil.
  • Anaerobic reactor The resulting process water, in particular from the separator (S 2 ), contains all polar, water-soluble substances which occur in the process. These include primarily carboxylic acids, aldehydes, and alcohols. The COD value is very high, typically 100-200 g/L, and the degradability is very good.
  • the biogas generated in the anaerobic reactor (R 3 ), having methane as the main component, is discharged into the gas supply system and ultimately supplied to the gas engine.
  • the anaerobically purified wastewater is advantageously delivered to an activated sludge plant for final cleaning.
  • Hydrogenation (product oil): The purpose of hydrogenation is to cover the hydrogen deficit which arises, since this is not possible using the plastic fraction alone, and therefore also depends on the biomass/plastic mixing ratio.
  • the expected hydrogen consumption is 3-6%, relative to the crude oil feed.
  • the hydrogenation reactor (R 2 ) is a catalyst-filled pressurized reactor, into which the hydrogen is supplied from the bottom and the crude oil is supplied from the top. Typical operating conditions are 330-360° C. and 30-60 bar.
  • heteroatoms such as S, O, N, Cl are hydrogenated, and are discharged in gaseous form in the so-called “purge gas.”
  • the ultrasound hydrogenation unit (hydrogenation reactor R 4 ) is composed of (i) an outlet of a substream of the coal-carrier oil suspension from the reactor sump R 1 , (ii) a heat exchanger for setting the optimal acoustic irradiation temperature), (iii) a solid-tolerant, controllable circulation pump for setting the circulation volume, (iv) a metering point for gaseous hydrogen (H 2 ), (v) an ultrasound generator having 1-5 sonotrodes with an integrated reaction chamber, and (vi) a return line to the reactor R 1 .
  • Hydrogenation reactors that are operated using ultrasound are known and commercially available, for example from Hielscher. These ultrasonic hydrogenation reactors operate in the liquid phase, and require no additional catalyst.
  • R 4 Energy input is provided in R 4 by an external ultrasound generator having sonotrodes present in the circulation flow, each sonotrode being composed of an electromagnetic sound generator with mechanical sound transmission into the liquid.
  • each sonotrode being composed of an electromagnetic sound generator with mechanical sound transmission into the liquid.
  • the stated ultrasound generator has major advantages with regard to the expected abrasion and the control characteristics.
  • the invention further relates to a facility having a hydrogenation reactor (R 4 ) which is an ultrasonic hydrogenation reactor that is connected to the sump phase of the reactor (R 1 ) for supplying the starting material, and is connected to the head phase of the reactor (R 1 ) for delivering the hydrogenated product.
  • a hydrogenation reactor (R 4 ) which is an ultrasonic hydrogenation reactor that is connected to the sump phase of the reactor (R 1 ) for supplying the starting material, and is connected to the head phase of the reactor (R 1 ) for delivering the hydrogenated product.
  • Reformer The reformer is used to produce hydrogen from natural gas; for this purpose, methane and steam are brought to reaction, and the concurrently generated CO 2 is discharged. Natural gas reforming constitutes prior art, and therefore is not explained in greater detail.
  • Gas engine/gas turbine All gases are advantageously collected, purified, and initially conducted to a gasometer. A gas flare ensures safety in the event of surplus gas.
  • the fuel gas is ultimately supplied to the gas engine.
  • the fuel gas has an average heating value of 13 MJ/Nm 3 , and is thus just as good a fuel as biogas, and therefore is well-suited as a fuel for gas engines as well as gas turbines.
  • Waste heat boiler The exhaust gas from the gas engine is present at approximately 450° C., and is advantageously supplied to a waste heat boiler.
  • the flow temperature of the thermal oil is approximately 400° C.
  • the return flow temperature is approximately 250° C.; the boiler is therefore advantageously provided with coiled heating tubes.
  • an auxiliary burner may be provided, in particular for start-up and for controlling the thermal balance of the facility according to the invention.
  • Cooling tower An appropriately dimensioned central cooling tower unit advantageously provides the cooling water required in the process at a flow temperature of approximately 25° C.
  • the cooling water is necessary in particular for operating the condensers.
  • Inerting The overall facility is operated at a slight positive pressure of 20-30 mbar. If this pressure drops in any area, an inert gas such as N 2 or CO 2 is automatically fed. Inerting is also performed in start-up and shutdown operations for safety reasons.
  • the present invention describes for the first time a method and a facility for oiling of carbohydrate-hydrocarbon mixtures, in which the hydrocarbon is dehydrogenated with transfer of H 2 to the carbohydrate, and is simultaneously depolymerized. It is assumed that the carbohydrate is hydrogenated with splitting of C, CO, CO 2 , and H 2 O and is simultaneously depolymerized.
  • This method may be used in a particularly advantageous manner when the carbohydrate is composed predominantly of biomass, and the hydrocarbon is composed predominantly of plastics.
  • a significant advantage of the method according to the invention as well as the facility according to the invention is that the continuous external addition of carrier oil and/or catalyst during the conversion of biomass to fuels may be dispensed with.
  • Another advantage of the present invention is the good availability of the starting material and the cost-effective procedure.
  • a further advantage of the present invention is the robustness of the process with regard to quality fluctuations of biomass and plastic, as well as the necessary facility parts.
  • Another advantage of the present invention is the favorable energy and mass balance.
  • Biogenic raw material and plastic are supplied continuously in two parallel lines via the silo and screw heater to the disperger, and from there are supplied directly to the reactor according to FIG. 1 .
  • No catalyst is added. There is no addition of carrier oil after the facility starts up.
  • Mass balance 800 kg dry biomass+200 kg dry mixed plastic result in 300 kg product oil, corresponding to 360 L product oil (17.5% biogenic yield, 80% plastic yield, product oil density 0.833 kg/L). It is not necessary to add additional carrier oil, since the oiling process according to the invention is balanced. The difference from 1000 kg is composed of the outflow of gas, product water, and coal.
  • Biogenic raw material and plastic are supplied continuously in two parallel lines via the silo and screw heater to the disperger, and from there are supplied directly to the reactor according to FIG. 2 .
  • No catalyst is added, either in R 1 or R 4 .
  • the sump phase is continuously withdrawn from R 1 (100-1000 L/h; solids consistency: 5-20 mass-%, temperature: 50-380° C.), and is hydrogenated in R 4 at 0-10 bar positive pressure (ultrasound parameters: frequency: 18-30 kHz, power parameters: 300-3000 W/L).
  • the reaction product obtained is recycled to the reactor R 1 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US13/812,077 2010-07-26 2011-07-14 Facility and Method for Production Fuels from Biomass/Plastic Mixtures Abandoned US20130153394A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10007739.5 2010-07-26
EP10007739 2010-07-26
PCT/EP2011/003511 WO2012016633A2 (de) 2010-07-26 2011-07-14 Anlage und verfahren zur erzeugung von treibstoffen aus biomasse / kunststoff - gemischen

Publications (1)

Publication Number Publication Date
US20130153394A1 true US20130153394A1 (en) 2013-06-20

Family

ID=43086461

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/812,077 Abandoned US20130153394A1 (en) 2010-07-26 2011-07-14 Facility and Method for Production Fuels from Biomass/Plastic Mixtures

Country Status (9)

Country Link
US (1) US20130153394A1 (ja)
EP (1) EP2598605A2 (ja)
JP (1) JP2013535539A (ja)
KR (1) KR20130102545A (ja)
CN (1) CN103080274A (ja)
BR (1) BR112013002000A2 (ja)
CA (1) CA2805521A1 (ja)
EA (1) EA201390160A1 (ja)
WO (1) WO2012016633A2 (ja)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104531194A (zh) * 2014-12-19 2015-04-22 东北林业大学 一种木塑复合材料催化裂解制备苯系液相产物的方法
EP2876146A1 (de) * 2013-10-14 2015-05-27 Gerold Weser Verfahren und Anlage zum Aufbereiten von Kunststoffwertstoffen
CN105419848A (zh) * 2015-11-18 2016-03-23 江苏大学 一种藻类和废弃橡胶共热解催化加氢制备生物油的方法
US20200080009A1 (en) * 2016-12-08 2020-03-12 Shell Oil Company A method of pretreating and converting hydrocarbons
CN112094664A (zh) * 2020-08-21 2020-12-18 广东石油化工学院 一种生物质油低温催化加氢脱氧反应系统及方法
EP3642305A4 (en) * 2016-06-27 2021-01-27 CDP Innovations PTY Ltd METHOD OF MANUFACTURING DIESEL
IT202000027323A1 (it) * 2020-11-16 2021-02-16 Alberto Zucchelli Impianto e procedimento per la produzione di idrocarburi liquidi attraverso l'utilizzo di biomasse residuali
US10968130B2 (en) * 2016-06-02 2021-04-06 Akw A+V Protec Holding Gmbh Method and device for treating wastewater containing organic matter and/or wet waste containing organic matter, in particular for treating sanitary wastewater in trains
US11046891B2 (en) * 2019-07-22 2021-06-29 Jürgen Buchest Method of recycling waste plastic material
CN113462410A (zh) * 2021-07-30 2021-10-01 重庆大学 一种红外快速加热医疗废弃物的热解多联产系统
RU2758375C2 (ru) * 2017-01-03 2021-10-28 Д.М.С Способ и устройство для получения энергетических продуктов путем каталитического крекинга твердого углеводородного материала без образования кокса
US11891574B2 (en) 2019-04-18 2024-02-06 Shell Usa, Inc. Recovery of aliphatic hydrocarbons

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013170224A (ja) * 2012-02-21 2013-09-02 Nihon Univ 石油代替液体燃料の製造方法
DE102012010763A1 (de) * 2012-03-26 2013-09-26 Axel Trautmann Vorrichtung und Verfahren zur katalytischen Depolymerisation von Kohlenstoff enthaltendem Material
CA2816195C (en) * 2013-05-22 2021-11-02 Bfcc Tech Ltd. Hydrothermal decomposition method and apparatus for making pyrolysis liquid in the range of diesel fuel
JP6445832B2 (ja) * 2014-10-20 2018-12-26 株式会社Kri バイオピッチの製造方法
CN104862000A (zh) * 2015-05-21 2015-08-26 张敬伟 一种废料的加工方法
WO2019038276A1 (de) * 2017-08-23 2019-02-28 Karl Morgenbesser Vorrichtung und verfahren zur katalytischen und/order drucklosen verölung
CN108355711B (zh) * 2018-02-11 2019-07-23 北京石油化工学院 一种催化裂解催化剂及其制备方法和应用
CN108273558B (zh) * 2018-02-11 2019-07-23 北京石油化工学院 催化裂解催化剂及其制备方法和应用
KR102068337B1 (ko) 2018-04-03 2020-01-20 한국기계연구원 바이오매스와 합성수지의 혼합 열분해를 위한 바이오 원유 제조 시스템
CN110229685B (zh) * 2019-06-12 2020-08-25 中国科学院广州能源研究所 一种废塑料高压热转化制备燃油的方法
CN112280582B (zh) * 2019-07-24 2022-08-30 中国石油天然气集团有限公司 一种含油浮渣的深度资源化处理系统及方法
CN110564436A (zh) * 2019-10-03 2019-12-13 环宇瑞驰(北京)科技有限公司 一种生物质综合处理的方法
KR20210072217A (ko) * 2019-12-06 2021-06-17 현대오일뱅크 주식회사 안정화된 연료유의 제조방법 및 그로부터 얻는 안정화된 연료유
CN112480965A (zh) * 2020-11-20 2021-03-12 张俊霞 采用废塑料和生物质制备生物氢烷和活性炭的装置及方法
WO2023247286A1 (en) * 2022-06-21 2023-12-28 Basell Poliolefine Italia S.R.L. Process for the depolymerization of plastic waste material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753086A (en) * 1993-03-10 1998-05-19 The University Of Wyoming Research Corp. Process for waste plastic recycling
US5836524A (en) * 1996-10-01 1998-11-17 National Science Council Liquefaction of wastes with product oil recycling
US5917102A (en) * 1994-05-20 1999-06-29 Veba Oel Ag Device for depolymerizing used and waste plastics
US20100270209A1 (en) * 2008-01-05 2010-10-28 Bio-Energy-Holding Ag Process and device for generating middle distillate from hydrocarbonaceous energy sources

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5427762A (en) * 1987-05-27 1995-06-27 Hydrocarb Corporation Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol
CN1332230A (zh) * 2001-08-19 2002-01-23 李家辉 利用废弃的有机物制造再生可燃液化气的工艺方法
US20050075521A1 (en) * 2002-01-25 2005-04-07 Yoichi Wada Method and plant for converting plastic into oil
US20060194990A1 (en) * 2003-08-29 2006-08-31 Norihisa Miyoshi Recycling method and system
DE10356245B4 (de) 2003-12-02 2007-01-25 Alphakat Gmbh Verfahren zur Erzeugung von Dieselöl aus kohlenwasserstoffhaltigen Reststoffen sowie eine Vorrichtung zur Durchführung dieses Verfahrens
WO2006131293A1 (de) 2005-06-09 2006-12-14 Lignosol Gmbh & Co. Kg Verfahren zur erzeugung von treibstoffen aus biogenen rohstoffen sowie anlage und katalysatorzusammensetzung zur durchführung des verfahrens
US20080072478A1 (en) * 2006-09-22 2008-03-27 Barry Cooper Liquefaction Process
DE102006052995B4 (de) 2006-11-10 2008-12-18 Tschirner, Erhard, Dr. Verfahren zur Herstellung von Gasöl aus kohlenwasserstoffhaltigen organischen Reststoffen und nachwachsenden Rohstoffen durch Reaktionsführung und Energieeintrag mittels prozeßintegrierter Kavitation/Friktion
US7834226B2 (en) * 2007-12-12 2010-11-16 Chevron U.S.A. Inc. System and method for producing transportation fuels from waste plastic and biomass
ITBO20080072A1 (it) 2008-02-01 2009-08-02 Vuzeta Brevetti S R L Apparato per il trattamento di materiali di rifiuto
CN101265412A (zh) * 2008-04-09 2008-09-17 江华鹏 生物质与废塑料共热解制取燃料油的方法
US20090267349A1 (en) 2008-04-23 2009-10-29 Spitzauer Michael P Production Processes, Systems, Methods, and Apparatuses
DE102008047563A1 (de) * 2008-09-16 2010-04-15 Zeppelin Silos & Systems Gmbh Verfahren und Vorrichtung zur Aufbereitung von kunststoffhaltigen Stoffen
TW201026837A (en) 2008-09-17 2010-07-16 Bdi Bio Diesel Internat Ag Process for obtaining combustibles and fuels, respectively
DE102008058967A1 (de) * 2008-11-25 2010-06-10 Wenzel Bergmann Verfahren zur Herstellung von Synthesegas und/oder flüssigen Rohstoffen und/oder Energieträgern aus Abfällen und/oder Biomassen
CN101508619B (zh) * 2009-03-12 2013-03-27 浙江大学 生物质与聚合物催化共裂解制取碳氢化合物的方法
CN101659875A (zh) * 2009-09-16 2010-03-03 浙江林学院 一种制备生物燃油的方法
CN101691494B (zh) * 2009-10-16 2012-07-11 江南大学 一种植物生物质和废弃聚酯混合超临界流体循环液化的方法
CN101735844A (zh) * 2010-01-06 2010-06-16 浙江大学 一种生物质自催化共裂解制备烃类物的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753086A (en) * 1993-03-10 1998-05-19 The University Of Wyoming Research Corp. Process for waste plastic recycling
US5917102A (en) * 1994-05-20 1999-06-29 Veba Oel Ag Device for depolymerizing used and waste plastics
US5836524A (en) * 1996-10-01 1998-11-17 National Science Council Liquefaction of wastes with product oil recycling
US20100270209A1 (en) * 2008-01-05 2010-10-28 Bio-Energy-Holding Ag Process and device for generating middle distillate from hydrocarbonaceous energy sources

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WO 2009/086908 (published 07-16-2009) English Abstract *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2876146A1 (de) * 2013-10-14 2015-05-27 Gerold Weser Verfahren und Anlage zum Aufbereiten von Kunststoffwertstoffen
CN104531194A (zh) * 2014-12-19 2015-04-22 东北林业大学 一种木塑复合材料催化裂解制备苯系液相产物的方法
CN105419848A (zh) * 2015-11-18 2016-03-23 江苏大学 一种藻类和废弃橡胶共热解催化加氢制备生物油的方法
US10968130B2 (en) * 2016-06-02 2021-04-06 Akw A+V Protec Holding Gmbh Method and device for treating wastewater containing organic matter and/or wet waste containing organic matter, in particular for treating sanitary wastewater in trains
EP3642305A4 (en) * 2016-06-27 2021-01-27 CDP Innovations PTY Ltd METHOD OF MANUFACTURING DIESEL
US20200080009A1 (en) * 2016-12-08 2020-03-12 Shell Oil Company A method of pretreating and converting hydrocarbons
US11920094B2 (en) * 2016-12-08 2024-03-05 Shell Usa, Inc. Method of pretreating and converting hydrocarbons
RU2758375C2 (ru) * 2017-01-03 2021-10-28 Д.М.С Способ и устройство для получения энергетических продуктов путем каталитического крекинга твердого углеводородного материала без образования кокса
US11891574B2 (en) 2019-04-18 2024-02-06 Shell Usa, Inc. Recovery of aliphatic hydrocarbons
US11046891B2 (en) * 2019-07-22 2021-06-29 Jürgen Buchest Method of recycling waste plastic material
CN112094664A (zh) * 2020-08-21 2020-12-18 广东石油化工学院 一种生物质油低温催化加氢脱氧反应系统及方法
IT202000027323A1 (it) * 2020-11-16 2021-02-16 Alberto Zucchelli Impianto e procedimento per la produzione di idrocarburi liquidi attraverso l'utilizzo di biomasse residuali
CN113462410A (zh) * 2021-07-30 2021-10-01 重庆大学 一种红外快速加热医疗废弃物的热解多联产系统

Also Published As

Publication number Publication date
CA2805521A1 (en) 2012-02-09
EA201390160A1 (ru) 2013-06-28
KR20130102545A (ko) 2013-09-17
CN103080274A (zh) 2013-05-01
WO2012016633A2 (de) 2012-02-09
BR112013002000A2 (pt) 2016-06-14
EP2598605A2 (de) 2013-06-05
WO2012016633A3 (de) 2012-12-06
JP2013535539A (ja) 2013-09-12

Similar Documents

Publication Publication Date Title
US20130153394A1 (en) Facility and Method for Production Fuels from Biomass/Plastic Mixtures
Xu et al. Conversion of secondary pulp/paper sludge powder to liquid oil products for energy recovery by direct liquefaction in hot-compressed water
US8940949B2 (en) Hydrothermal conversion of biomass to hydrocarbon products
EP2661477B2 (en) Processing of organic matter
Demirbas Hydrogen-rich gas from fruit shells via supercritical water extraction
EP2718403B1 (en) Process for producing liquid hydrocarbon
EP2718404B1 (en) Process for producing liquid hydrocarbons
US9181158B2 (en) Methods for conversion of a glycol reaction product obtained from hydrothermal digestion of cellulosic biomass solids into a dried monohydric alcohol feed
CA2801429C (en) Process for the production of biofuel
Demirkaya et al. Liquefaction of waste hazelnut shell by using sub-and supercritical solvents as a reaction medium
CA2816195C (en) Hydrothermal decomposition method and apparatus for making pyrolysis liquid in the range of diesel fuel
WO2015092143A1 (en) Intergrated pyrolysis process
US20150148553A1 (en) Hydrothermal Conversion of Biomass to Hydrocarbon Products
US10208255B2 (en) Method for producing light oil through liquefying biomass
US9822048B2 (en) Method of extending biomass conversion catalyst life
US20150051427A1 (en) Integrated process for the production of renewable drop-in fuels
WO2022220246A1 (ja) 有機原料の分解方法、それを利用した液体燃料、固体燃料、又は活性炭の製造方法
WO2023175493A1 (en) Process and apparatus for the production of bio-oil from lignocellulosic biomass
Sarwono Hydrothermal Process for Cellulosic Waste Degradation Into Valuable Chemicals
Baloyi et al. A review of the co‐liquefaction of biomass feedstocks and plastic wastes for biofuel production

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION