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EP1436367A1 - Procede de pyrolyse et de gazeification de biomasse - Google Patents

Procede de pyrolyse et de gazeification de biomasse

Info

Publication number
EP1436367A1
EP1436367A1 EP02801333A EP02801333A EP1436367A1 EP 1436367 A1 EP1436367 A1 EP 1436367A1 EP 02801333 A EP02801333 A EP 02801333A EP 02801333 A EP02801333 A EP 02801333A EP 1436367 A1 EP1436367 A1 EP 1436367A1
Authority
EP
European Patent Office
Prior art keywords
pyrolysis
oil
biomass
bio
coke
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.)
Withdrawn
Application number
EP02801333A
Other languages
German (de)
English (en)
Inventor
Edmund Henrich
Eckhard Dinjus
Dietrich Meier
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.)
Karlsruher Institut fuer Technologie KIT
Original Assignee
Forschungszentrum Karlsruhe GmbH
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 Forschungszentrum Karlsruhe GmbH filed Critical Forschungszentrum Karlsruhe GmbH
Publication of EP1436367A1 publication Critical patent/EP1436367A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0926—Slurries comprising bio-oil or bio-coke, i.e. charcoal, obtained, e.g. by fast pyrolysis of biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1643—Conversion of synthesis gas to energy
    • C10J2300/165—Conversion of synthesis gas to energy integrated with a gas turbine or gas motor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
    • 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
    • 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
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or 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
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the invention relates to a method for treating biomass according to the first claim.
  • biomass is to be understood to mean all agricultural and forestry residual and waste products, in particular straw, leaves, hay, residual wood and wood waste, which may be contaminated or blended with household waste, in particular with paper, cardboard and plastics ,
  • flash pyrolysis One method for the treatment of biomass is rapid pyrolysis, which is sometimes also referred to as "flash pyrolysis”.
  • shredded, dry biomass is rapidly heated to approximately 500 ° C. in the absence of air, the resulting sulfurized vapors quickly, that is to say
  • the process is carried out under normal or slight negative pressure and is therefore technically uncomplicated. It supplies carbonization gas, bio-oil and pyrolysis coke in products in varying proportions which can be influenced by the process parameters
  • the main product is generally bio-oil, the use of which as a fuel for the substitution of corresponding mineral oil products is discussed.
  • the carbonization gas is often used internally for heating purposes, while the usability of pyrolysis coke is limited.
  • bio oil In contrast to organic oils, bio oil typically contains 10 to 35% by weight of water. It is in petroleum products and non-polar organic solvents are insoluble, on the other hand miscible with water, the so-called pyrolysis lignin precipitating out with greater dilution. When distilling, almost half of the initial mass remains in the distillation residue.
  • Rapid pyrolysis is described in detail in a number of publications, for example in the article by A.V. Bridgwater. "An Introduction to Fast Pyrolysis of Biomass for Fuels and Chemicals” in Fast Pyrolysis of Biomass: A Handbook by A. Bridgwater et al, cpl-press, Aston University May 1999. This article also describes the devices for carrying out rapid pyrolysis.
  • the entrained flow gasifier consists of an outer cylindrical pressure jacket and an internally cooled, also cylindrical reaction chamber which is inserted into the upper part of the pressure jacket in such a way that an annular gap remains between the two components.
  • a pilot flame is maintained in the reaction chamber, which is filled with gas and technical oxygen is generated.
  • the fuel is fed separately into the flame zone.
  • the two input stages of the Noell conversion process include pyrolysis and entrained-flow gasification.
  • the following stages concern the cleaning of the resulting products and the waste water.
  • the pyrolysis is carried out in an externally heated rotary tube.
  • Solid pyrolysis coke and a raw pyrolysis gas are produced by pyrolysis.
  • the raw pyrolysis gas is cooled, with small amounts of condensed hydrocarbons being separated off, as well as any water and coke dust present.
  • Solid ingredients of the liquid hydrocarbons are separated in a decanter.
  • a further cooling stage and decanting result in an additional purification of the pyrolysis gas which is used in the subsequent entrained-flow gasification.
  • the pilot flame of the entrained-flow gasifier can be fed through the pyrolysis gas if required.
  • the pyrolysis coke from the upstream pyrolysis is used as fuel. This coke has to be ground very finely beforehand.
  • a specially developed pneumatic metering system is used to feed the entrained-flow gasifier.
  • a major advantage of the entrained flow gasifier is that the hot inside of the reaction chamber, which is provided with a silicon carbide lining, is covered during operation by a mineral so-called "slag fur", which protects the material from the corrosive conditions.
  • the invention has for its object to provide a multi-stage process for the treatment of biomass, which comprises a pyrolysis stage and a subsequent entrained flow pressure gasification, in which pyrolysis coke is used as a fuel which the feed of the pyrolysis coke can be made easier.
  • the fuel pyrolysis coke is fed to the entrained flow gasifier in the form of a pumpable slurry. This avoids the problems that arise when the fuel is fed in a dust-fine, solid form into an entrained-flow gasifier maintained at a high overpressure.
  • Bio oil is used as a slurry.
  • bio oil forms as the main product alongside the products pyrolysis gas and pyrolysis coke. Because of these proportions, the entire pyrolysis coke produced can be slurried in bio-oil.
  • the rapid pyrolysis is preferably carried out at operating parameters such that 40 to 80% by weight of bio oil and 10 to 30% by weight of pyrolysis coke are formed.
  • a slurry of the pyrolysis coke produced in the resulting bio-oil produces an oil sludge which is particularly suitable in terms of the pumping and feeding properties. Pressures in the range from atmospheric pressure to a rough vacuum and temperatures in the range from 400 ° C. to 600 ° C. are well suited for carrying out the rapid pyrolysis.
  • the residence time of the steam until condensation should be in the range of 0.5 to 5 seconds.
  • the entrained-flow gasification is carried out in the type of entrained-flow gasifier described in the publication mentioned at the beginning.
  • the operating pressure maintained in the entrained flow gasifier should be at least 50 bar; the maximum pressure results from the condition that supercritical conditions in the entrained-flow gasifier are avoided. Pressures of 50 bar and more are required, for example, for catalyzed low-pressure methanol synthesis if additional synthesis gas compressors are to be dispensed with. However, pressures up to 200 bar are possible.
  • a high operating pressure in the entrained-flow gasifier has the advantage that the synthesis gas can be cleaned more easily with a corresponding pressure at higher pollutant concentrations and in smaller devices. A high operating pressure ensures a high reaction speed and a high material turnover.
  • the temperature in the entrained flow gasifier should be in the range from 1200 ° C to 1800 ° C; this causes the slag fur to run as intended on the inner walls of the reaction space.
  • the method according to the invention enables the use of the entire usable energy content of the biomass for the synthesis gas generation in the subsequent entrained-flow gasification, without the need to provide more than one metering device for fuel on the entrained-flow gasifier.
  • the pyrolysis gas from rapid pyrolysis is suitable for maintaining the pilot flame or for atomizing oil sludge. It is particularly advantageous that cleaning steps or chemical preparation process for the bio-oil can be dispensed with, since it is mixed with the pyrolysis coke anyway.
  • all the condensates, in particular the “slurry products”, for example from decanters for cleaning synthesis gas can be added to the pyrolysis oil, so that the cleaning of the product streams from rapid pyrolysis is considerably simplified.
  • Bio oil or oil sludge is also easier to transport and store and more flexible to use than dusty pyrolysis coal.
  • the invention opens up the possibility of bringing together bio-oils or oil sludges from several decentralized rapid pyrolysis devices and further processing them in a large, central entrained-flow gasifier. In these cases it makes sense to use the pyrolysis gas directly in rapid pyrolysis.
  • the pyrolysis gas of a rapid pyrolysis usually contains only 10% or even less of the total calorific value of the starting biomass, so that 90% or more of the energy content of the original biomass still reaches the entrained-flow gasifier.
  • the figure shows a basic technical concept for the production of fuel and electricity from biomass.
  • the biomass After delivery and, if necessary, intermediate storage, the biomass is subjected to a pretreatment which includes comminution and post-drying. Then it is fed to rapid pyrolysis, which - as already mentioned above - can be carried out most easily at atmospheric pressure.
  • the operating temperature is around 500 ° C and is usually maintained via a heat transfer circuit.
  • Rapid pyrolysis products are carbonization gas, bio-oil and py- rolysekoks. These products can be obtained, for example, in a ratio of 15:60:25% by weight.
  • Use options for the carbonization gas are the use as fuel gas z. B. in the rapid pyrolysis itself, the power generation in gas engines or turbines and the use as an atomizing gas or fuel gas for the pilot burner of the subsequent entrained flow gasification.
  • the bio oil is used to make the coke slurry.
  • the pyrolysis coke is ground beforehand.
  • the biomass used contains high amounts of potassium and chlorine, such as straw or other rapidly growing biomass, it may be useful to remove potassium chloride and other soluble potassium / chlorine compounds from the pyrolysis coke, for example in a washing device, with water before the slurry.
  • the typical calorific value of pyrolysis coke is almost twice the calorific value of bio-oil, while the calorific value of pyrolysis gas is only roughly half of the calorific value of bio-oil.
  • the oil sludge that results from the slurry of the pyrolysis coke in the bio-oil is then pumped into the entrained-flow gasifier with the help of a high-pressure pump.
  • the entrained flow gasifier can be operated, for example, at a little over 50 bar and a temperature of 1500 ° C.
  • the pilot flame is e.g. B. operated with pyrolysis gas from rapid pyrolysis or with synthesis gas from the entrained flow gasifier and technical oxygen.
  • the proportion of oxygen should be about one third to one quarter based on the total oxygen requirement for the oxidation of the ingredients.
  • a sufficiently high reaction temperature must be guaranteed so that the chemical reaction proceeds as completely as possible and the operational drainage of the slag fur is guaranteed.
  • the raw synthesis gas leaving the entrained flow gasifier can be used as a high-temperature fuel gas or as a reducing gas. However, it can also be processed and converted into valuable chemical products, such as fuels.
  • the pure synthesis gas leaving the gas processing unit is suitable for methanol synthesis, as a fuel substitute or for other chemical syntheses, for example for carrying out oxosynthesis or, after a shift reaction, for hydrogenation.
  • the synthesis gas that is not converted during synthesis can be emitted in gas turbines, gas engines or GUD systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Sludge (AREA)

Abstract

L'invention vise à mettre en oeuvre un procédé simple de traitement de biomasse au cours duquel un gaz de synthèse est produit. Le procédé selon l'invention consiste a) à soumettre la biomasse à une pyrolyse rapide au cours de laquelle de la bio-huile et du coke de pyrolyse sont produits ; b) à former une boue d'huile à partir du coke de pyrolyse contenu dans la bio-huile ; c) à comprimer la boue d'huile dans un réacteur à lit entraîné maintenu en surpression ; et, d) à transformer ladite boue d'huile en un gaz de synthèse brut dans le réacteur à lit entraîné.
EP02801333A 2001-10-16 2002-10-12 Procede de pyrolyse et de gazeification de biomasse Withdrawn EP1436367A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10151054 2001-10-16
DE10151054A DE10151054A1 (de) 2001-10-16 2001-10-16 Verfahren zur Behandlung von Biomasse
PCT/EP2002/011437 WO2003033624A1 (fr) 2001-10-16 2002-10-12 Procede de pyrolyse et de gazeification de biomasse

Publications (1)

Publication Number Publication Date
EP1436367A1 true EP1436367A1 (fr) 2004-07-14

Family

ID=7702683

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02801333A Withdrawn EP1436367A1 (fr) 2001-10-16 2002-10-12 Procede de pyrolyse et de gazeification de biomasse

Country Status (3)

Country Link
EP (1) EP1436367A1 (fr)
DE (1) DE10151054A1 (fr)
WO (1) WO2003033624A1 (fr)

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