SE1051238A1 - Process for generation of renewable liquid materials and fuels using steam pyrolysis of carbonaceous solid waste materials and biomass feedstock using ultra high temperature steam - Google Patents

Abstract

_19- ABSTRACT An advanced process concept for upgraded bio-oil production from carbona-ceous, solid waste materials and biomass materials, especially a lignocellulosic rawmaterial, in a one step method is proposed. Introduction of high-temperature steamin biomass pyrolysis process results in a low oxygen content upgraded bio-oil withan O / C ratio less than 0.2. The introduction of high-temperature steam allows thereforming and cracking of heavy bio-oil molecules to lower molecular weight sub-stances while the hydrogen radicals that are present due to steam dissociation re-actions are taking part in the hydrodeoxygenation (HDO) of the primary oxygenated species resulting from the pyrolysis.

Description

A METHOD OF GENERATING RENEWABLE LIQUID MATTERS AND FUELS USINGULTRA HIGH TEMPERATURE STEAM PYROLYSIS OF CARBONACEOUS, SOLIDWASTE MATERIALS AND BIOMASS RAW MATERIALS FIELD OF THE INVENTION The present invention generally relates to the exploitation of carbonaceous, solidwaste materials, and biomass, especially lignocellulosic materials for bio-oil produc-tion, and in particular to an advanced one step process that can produce upgradedbio-oil directly from solid waste materials or biomass by hydrodeoxygenation (HDO)using high-temperature steam, as well as an arrangement for carrying out the in- ventive process.

DESCRIPTION OF THE PRIOR ART Biomass is a renewable energy source With increasing potential in the worldwideenergy market, and its net carbon dioxide emissions are essentially neutral, thusnot contributing to the greenhouse effect. Moreover, its very low nitrogen (N) and sulfur (S) contents add to the environmental friendly character of such a material.

Municipal solid wastes also to a large extent comprises biomass and offer increasedsustained potential for biofuel production, with cleaner environment. The plasticsfrom municipal solid wastes also offer clean biofuel production With characteristics similar to that of biodiesel liquids.

The most important advantage of biomass, apart from its neutral C02 net charac-teristic, is that it can be converted to liquid, solid, or gaseous fuels, unlike otherrenewable sources of energy (e.g. wind, and solar energy), which only give heat and power.

Similarly, the municipal solid wastes that are also biomass can be converted to liq-uid fuels for use in propulsion and power systems. The dumping of plastics in land-fill causes environmental issues, since the plastics are not biodegradable. The en- ergy content in plastics is much higher than in biomass materials, so that its fuel _2_ reforming would offer benefits of negative cost fuels from such wastes, improved environment, and a permanent solution to the plastic wastes.

Therefore, biomass, solid wastes and plastics can be considered as a renewable re-source which could be directly transformed into liquid fuel and value added prod- ucts and chemicals.

The research in the area of transforming biomass has mostly focused on two as-pects of thermochemical and bio-chemical processes. Biomass pyrolysis has at-tracted the highest interest amongst the thermochemical conversion technologies asit offers renewable liquid, gaseous and solid products converted by optimized tech- nologf conditions.

There are basically two methods being used to produce oil from biomass: high pres-sure liquefaction (typically hydrothermal for biomass), and atmospheric pressurefast pyrolysis. Available biomass pyrolysis technology for bioliquid production is to convert organics to solid, liquid and gas by heating in the absence of oxygen.

Fast pyrolysis of biomass is one way to generate liquid from biomass. This is themost intensively investigated pyrolysis process at present. The key issues are rapidheating and rapid quenching in order to obtain as much liquid as possible. Externalheat is generally supported by sand in fluidized-bed reactors, or by a hot wall, suchas in ablative (vorteX and rotating blade) reactors. The main heat transfer modes areconduction and convention. Fast pyrolysis has been developed relatively recently.Intensive studies were carried out in 70s. Presently, many laboratories around theworld are trying to commercialize ”fast wood pyrolysis” to liquid. Demonstrationplants include 400 kg/h at Dynamotive with fluidized bed reactor, 1,000 kg/h CFBat Red Arrow, and 20 kg/ h at VTT. 120 kg/ h of rotating cone reactor at BTG, (Neth-erlands), 3,500 kg/ h at Pyrovac with a vacuum reactor, 350 kg/ h at Fortum,Finland with an ablative reactor, a 200 kg/h auger reactor at Mississippi State Uni-versity, USA. _3_ However, bio-oil, directly derived from these traditional processes, is usually of highviscosity and exhibits a high content of oxygenic components, with low stability andheat value, and thus further processing and upgrading of the bio-oil is required.The oxygenated compounds present in raw bio-oil impart a number of unwantedCharacteristics, such as thermal instability (reflected in increasing viscosity uponstorage), corrosiveness and low heating value. This instability is associated with thepresence of reactive chemical species, mainly aldehydes, ketones, carboxylic acids,alkenes and guaiacol-type molecules. During prolonged storage, condensation reac-tions involving the above mentioned functional groups result in formation of heavier compounds due to polymerization reactions.

From all the above it can be understood that upgrading biomass-derived oils to hy-drocarbon fuels requires oxygen removal and water content and molecular weightreduction. In order to improve quality of the thus obtained bio-oil usually processessuch as cracking, hydrogenation, and steam reforming are involved. An upgradingprocess of this kind of oil is needed. The concept of achieving a conversion of ligno-cellulosic biomass into liquid biofuels that are physically and chemically compatible with petroleum-based hydrocarbon fuels can be expressed by the formula: Biomass 9 Volatile (CxHyOZ)+ Char (C) +H, CXHyOZ > -CHZ - 2 Upgrading biomass-derived oils to hydrocarbon fuels requires oxygen removal andmolecular weight reduction. This requires that hydrogen is added in the process to increase the H/ C ratio of the product and to remove excess oxygen as water.

To date, two main deoxygenation methods have been investigated. The first com-prises bio-oil cracking at atmospheric pressure, resulting in simultaneous dehydra- tiondecarboxylation.

On account of the thermal instability of bio-oil, the off-line cracking process utilizespyrolysis derived bio-oil as raw material. However, the bio-oil must be vaporizedbefore cracking, which causes coke formation reactions and condensation reac- tions. On the other hand, online cracking is not only available to avoid the energf _4_ intensive vaporization process, but also to avoid undesired reactions. However, ifcatalytic cracking is employed severe coking and therefore deactivation of the cata- lysts put a limitation in their application.

The second method for bio-oil upgrading utilizes typical hydrotreating conditions,i.e., high hydrogen pressures for the hydrogenation of unsaturated groups (withelimination of oxygen as water) and hydrogenation-hydrocracking of large mole-cules. Although hydrotreating is extremely effective, techno-economic analyses re-veal its economics to be unfavorable for the production of the fuel-type products itaffords. Hydrogen is typically derived from steam methane reforming, which is de-pendent on methane, and is therefore not normally considered a renewable source.Alternative methods of hydrogen production include the use of water electrolysis.

The prior art methods of producing hydrogen are relatively costly.

The most suitable and effective method for upgrading bio-oil is hydrodeoxygenation(HDO). During HDO, oxygen in the feed is converted to H20 which is environmen-tally benign.

The main problem with the upgrading methods described above is the coke deposi-tion, and as a result, catalyst deactivation, even though several catalysts have beentested, as well as the hydrogen availability and complexity of high pressure proc- CSSCS.

A method solving the above problems has recently been disclosed by Kantarelis, E.,Liu, J., Yang, W., and Blasiak, W., Sustainable Valorization of Bamboo via High-Temperature Steam Pyrolysis for Energy Production and Added Value Materials,Energy Fuels 2010 (DOI:10.1021/ef100875g published on 1 November 2010, ac-cessible from http :¿ fptilësacsaärfl, ), the contents of which is incorporated herein in its entirety by reference.

The inventive method is a fast pyrolysis process for the production of bio-oil from acarbonaceous, solid raw material selected from waste materials and biomass mate-rials, or a miXture thereof, and especially lignocellulosic raw materials. The methoduses high-temperature steam to pyrolyse the raw material. By virtue of the presenceof high-temperature steam during the pyrolysis, deoxygenation of oxygenated spe- cies in the pyrolysis gas will also be accomplished at the same time.

It has recently been found by same inventors, that the deoxygenation can be furtherenhanced by means of providing additional hydrogen radicals (H*) to the process,which radicals can be readily generated, using electrical means, from the high- temperature steam.

According to the invention, upgraded bio-oil can be produced in a one-step process.

SUMMARY OF THE INVENTION The present inventors have found that, when high-temperature steam is used forpyrolysis of a lignocellulosic raw material, the degree of oXygenation in the resultingpyrolysis gases will be reduced. As alluded to in the article by Kantarelis et al.above, hydrogen may be transferred to the oxygenated or unsaturated molecules, and this generally enhances the quality of the resulting bio-oil.

While the present invention as described herein has been focused on using lignocel-lulosic raw materials, the present inventors also believe that the inventive methodcould be used for converting carbonaceous solid waste materials and biomass ma-terials in general, such as municipal solid waste, waste plastics, waste tyres, andbiomass, such as e.g. lignocellulosic biomass. The oxygen content of waste plasticsand waste tyres is likely to be comparatively low in general, and therefore, whensuch materials are being used as the sole raw material for the process, the deoxy-genation capacity of the inventive process will not be taken full advantage of. Ac-cordingly, it is preferred that the raw material, or miXture of raw materials, for theprocess contains a substantial amount of oxygen containing compounds. Prefera-bly, municipal solid waste and/ or biomass is used as the raw material in the inven- tive process, and more preferably biomass, especially lignocellulosic biomass.

Accordingly, in a first aspect, and with reference to Figure 1, the invention relates toa method of producing bio-oil 120 from a carbonaceous, solid raw material 40 se-lected from waste materials and biomass, and mixtures thereof, which method in itsmost generic embodiment comprises the steps of: (a) providing a carbonaceous, sol-id raw material 40; (b) subjecting the carbonaceous, solid raw material to conditionseffective for accomplishing fast pyrolysis of said carbonaceous, solid raw material; (c) subjecting the oxygenates formed in step (b) to conditions effective for accom- _6_ plishing deoxygenation of said oxygenates; and (d) Cooling the components 60formed in step (c), in order to obtain liquid bio-oil 120, wherein steps (b) and (c) areaccomplished by means of subjecting the carbonaceous, solid raw material to high- temperature steam 28 at a temperature within the interval of 400-700°C.

By means of the method, the resulting bio-oil obtained upon quenching will be up-graded in respect of both hydrogen content, and also in respect oxygen content, i.e. the oxygen content will be low.

In the inventive method, steps (b) and (c), i.e. the pyrolysis and the deoxygenation, respectively, can be carried out in the same reactor 30.

Also, steps (b) and (c) can be combined into one step, wherein the raw material is subjected to preheated high-temperature steam.

As opposed to the prior art, no intervening condensation or recovery step betweenthe pyrolysis step and the deoxygenation step is required, and steps (b) and (c) canbe combined into one step. Thus, upgraded, low oxygen content, hydrodeoxygen-ated bio-oil can be obtained in merely one step, in addition to the quenching step, that is.

Additionally, the use of high-temperature steam in the pyrolysis has been found toreduce the yield of char. The char produced from the inventive process using high-temperature steam has been found to exhibit a higher surface area and higher car-bon content, than char obtained from conventional pyrolysis. The char produced by the inventive process can therefore be used as e.g. an activated carbon precursor.

Also, by using steam, any co-produced synthesis gas during the process will not bediluted, as opposed to when e.g. Ng, or another inert gaseous component is beingused. According to the claimed process, only steam is required to be added. Thehydrogen enriched gas that is produced can thus be utilized for heat generation forproviding the necessary high-temperature steam of the inventive process, as well as raw material for chemical synthesis.

The bio-oil of the present invention generally comprises products containing low _7_ oxygen to carbon ratio (O:C) Which is essential for a good quality bio-oil. This Willenhance the production, as Well as the use of bio-oil as transport fuel substitute or/ and chemicals.

The present inventors have found the resulting bio-oil obtained by means of themethod to have a reduced content of soot, a reduced viscosity, enhanced storage-life, and a lighter colour, than conventionally obtained bio-oil. Accordingly, as op-posed to the prior art pyrolysis oil, Which is usually black and opaque, the bio-oil of the invention is typically yellow to broWn in colour, and essentially transparent.

Recently, the inventors found that step (c) of the above generic embodiment of themethod can be substantially enhanced by providing additional hydrogen radicals(H*) to the process, Which radicals can be readily generated, using electrical means 50, from the high-temperature steam present in the process, that is in steps (b) and (c).

The inventors have found that, at the relevant temperature, Water molecules (H20)of the preheated high-temperature steam Will to some extent dissociate into radicals(H* and OH*). This is presently believed to the main reason for the observed hydro-genation and oXygenation in the above article by Kantarelis et al. Especially the hy-drogen radicals (H*) are believed to effectively contribute to the deoxygenation ofoxygenated species in the pyrolysis gas by reacting With said oxygenated species.The type of deoxygenation of the invention can therefore be designated as hydrode-oxygenation (HDO).

According to the invention, the high-temperature steam consequently serves thedual purposes of both constituting a heat carrying agent, Which supplies the majorpart of the necessary heat for effecting pyrolysis, and also constituting a source ofhydrogen radicals, thus also supplying a reactive agent (H*) that Will serve to deoxy-genate oxygen containing species in the pyrolysis gas, Whereby the bio-oil, obtained upon quenching, Will be upgraded in this respect and exhibit a low oxygen content.

The provision of additional hydrogen radicals in the process Will therefore furtherimprove the quality of the resulting bio-oil, by virtue of additional deoxygenation and hydrogenation.

Accordingly, in a preferred embodiment of the method, additional hydrogen radicals(H*) are being generated and supplied to the method. The additional hydrogen radi-cals are being formed from the high-temperature steam in using electrical means.Oxygenates formed in pyrolysis step (b) are then brought into contact With the hy-drogen radicals thus formed. Thereby, deoxygenation of oxygenates contained in thepyrolysis gas Will be enhanced, and the quality of the resulting bio-oil further im- proved.

For large scale operations, the use of a hydrogen radical generator Will also serve tooffer effective means of controlling the process, in terms of desired extent of hydro- genation and deoxygenation.

In another aspect the present invention relates to a corresponding arrangement forcarrying out the above preferred inventive method comprising: a pyrolysis reactor30 With the capability of Withstanding temperatures in the range of 400-700°C,Which reactor exhibits an inlet for a carbonaceous, solid raw material 40, and aninlet for high-temperature steam 28 of a temperature Within the interval of 400-700°C; and quenching means 10 for cooling the pyrolysis gas 60 obtained in thepyrolysis reactor 30, Wherein the reactor further comprises electrical means 50 forproducing hydrogen radicals (H*) from the high-temperature steam Within the reac- tor.

In a preferred embodiment, the arrangement also comprises separation means 70,such as e.g. a cyclone, for removing char and solid residues from the pyrolysis gas before quenching.

In yet a preferred embodiment the quenching means 100 is also provided With elec-trical means 50 for producing hydrogen radicals (H*) from the high-temperature steam Within the quenching means.

In a preferred embodiment, an arrangement for carrying out the above generic in-ventive method comprises: a pyrolysis reactor 30 With the capability of Withstandingtemperatures in the range of 400-700°C, Which reactor exhibits an inlet for a car-bonaceous, solid raw material 40, and an inlet for high-temperature steam 28 of a temperature Within the interval of 400-700°C; and quenching means 100 for cooling _9_ the pyrolysis gas obtained in the pyrolysis reactor 30, wherein the arrangement fur-ther comprises separation means 70 for removing char and solid residues 80 fromthe pyrolysis gas 60 before quenching, so as to obtain clean pyrolysis gas 90, which then can be quenched in cooler 100 so as to form bio-oil 120.

Another objective is the online reforming of complex long chain hydrocarbons andcyclic hydrocarbons, formed from the carbonaceous, solid raw material fed into theprocess upon pyrolysis thereof, to enhance the hydrogenation of the produced bio- oil.

Another objective is the direct transformation of biomass, wastes and plastics tobio-oils in a one step process using the optimized hydrogenation process at con-trolled thermal fields. The extent of high temperatures is dictated by the composi- tion and characteristics of biomass, waste and plastics for effective hydrogenation.

Other objects and advantages of the present invention will become obvious to thereader and it is intended that these objects and advantages are within the scope of the present invention.

According to the embodiments of the present invention, biomass undergoes pyroly-sis producing liquid oil, value added products and gaseous fuel products. The term“liquid oil' as used herein means a liquid which is obtained upon quenching of thepyrolysis gases, which is in a liquid state at room temperature. The terms liquid oil, bio-oil and pyrolysis liquid have been used interchangeably herein.

The inventive method is carried out in continuous operation.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a general system flow diagram, wherein reference numeral 28 de-notes a high-temperature steam inlet, 30 denotes a pyrolysis reactor, 40 carbona-ceous feeding, 50 hydrogen radical generators, 60 pyrolysis gas generated from py- rolysis reactor, 70 a cyclone separator, 80 char and solid residues, 90 clean pyroly- _10- sis gas, 100 a Cooler, 110 syngas obtained from the process, and 120 denotes bio- oil obtained from the inventive process.

Figure 2 shows a pilot batch plant, which was used for carrying out the inventivemethod in batch mode operation on a pilot scale, wherein 1-4 denotes gas nozzles,5 air nozzle, 6 methane nozzle, 7 gas burner, 8 combustion chamber, 9 ceramichoneycomb, 10 cooling chamber, 11 lid, 12 online gravimetric measurement, 13cooling nitrogen nozzle, 14 perforated basket with sample, 15 flue gases, 16 sam-pling line, 17 gas washing bottle for liquid collection, 18 reaction chamber, 19 win-dow, 20 thermocouple for steam temperature measurement, 21 thermocouple forsample temperature measurement, 22 cooling bath of -15°C to -10°C, 23-26 coolingwater, and 27 denotes a gas chromatograph. The pilot batch plant is not an em- bodiment of the arrangement of the invention.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODI-MENTS THEREOF Introduction of high-temperature steam in biomass pyrolysis process results in alow oxygen content upgraded bio-oil with an O / C ratio less than 0.2. The introduc-tion of high-temperature steam allows the reforming and cracking of heavy bio-oilmolecules to lower molecular weight substances while the hydrogen radicals thatare present due to steam dissociation reactions are taking part in the hydrodeoxy-genation (HDO) of the primary oxygenated species resulting from the pyrolysis. Theinventive system includes a biomass pyrolysis reactor 30 working in the tempera-ture range of 400°C to 700°C, into which reactor high-temperature preheated steamof a temperature within the range of 400°C to 700°C is injected. The stream is notonly acting as a heating agent supplying the major part of the heat necessary forthe pyrolysis, but also acting as a hydrogen donor, providing reactive hydrogenwhich will react with oxygenates in the pyrolysis gas, and thereby reduce the oxy- gen:carbon in order to get rid of oxygen.The preferred working temperature range of the pyrolysis reactor, and also of thehigh-temperature steam being fed into the reactor, is within the interval of about 440°C to 600°C.

The heat required for the pyrolysis is mainly provided by the high-temperature _11- steam entering the reactor. However, additionally heating Will typically be requiredin order to maintain the temperature Within the pyrolysis reactor Within the rangeof 400-700°C. The additional heat can be provided by electrical heating of the reac-tor, and/ or by means of hot flue gases being passed into the pyrolysis reactor fromcombustion outside the reactor, such as e.g. from upstream generation of high-temperature steam. Such flue gases could enter the pyrolysis reactor together Withthe high-temperature steam, or via a separate inlet. Accordingly, the pyrolysis reac-tor may be provided With means for electrical heating thereof and/ or an inlet for hot flue gases.

In a preferred embodiment the pyrolysis reactor uses a fixed or fluidized bed, pref- erably a fluidized bed, to Which the carbonaceous raw material is being fed.

The pyrolysis reactor is preferably operating at essentially atmospheric pressure,since otherwise the bio-oil yield Will decrease. Also, for the same reason, the high-temperature steam is fed into the pyrolysis reactor preferably at about atmospheric pressure.

Preferably, the pyrolysis reactor is provided With electrical means for generating hy-drogen radicals from the high-temperature steam in the pyrolysis reactor. Hydrogenradicals can e.g. be generated by means of electrical discharge, such as electrodes,or plasma. The electrical discharge is preferably operating continuously during thepyrolysis. In the case of a fixed or fluidized bed, the electrical means (discharge or plasma) is preferably located in the freeboard of the bed.

Simultaneously the produced bio-oil during the pyrolysis process is cracked andreformed in the presence of steam to produce H2. Produced hydrogen can take placein hydrogenation reactions; in addition hydrogen radicals from the highly super-heated steam, and/ or from the electric spark, or plasma, can also take part in theHDO of the of the oxygenated species contained in the pyrolysis gas, so as to pro-duce an upgraded bio-oil. The hydrogen radicals are very reactive during thermal cracking. _12- Hydrogen radicals are hydrogen donors enhancing the online Upgrading of the pro-duced bio-oil. The above mentioned can be schematically depicted by the following scheme: CHO Lmß-Cflf x y z2 The above mentioned features result in a low oxygen content bio-oil, which is essen- tial for the stability and overall quality of the resulting bio-oil as a fuel.The co-produced gas is a hydrogen rich gas and therefore a valuable gas product.

The solid residue produced from the process exhibits enhanced surface characteris- tics that can enhance the exploitation of the material.

The pyrolysis vapors leaving the furnace are being passed trough a tube and arerapidly quenched. With reference to the pilot plant illustrated in Figure 2, this canbe accomplished using gas washing bottles at temperatures of -10°C down to -15°C,and a cooling bath. In large scale plants, the cooling temperature will typically beatmospheric or ambient. Condensable molecules are then obtained as a liquid, i.e. as bio-oil.

Having read the instant disclosure, optimum dimensional relationships for theparts of the invention, including variations in size, materials, shape, form, functionand manner of operation, assembly and use, will be readily apparent and obvious to one skilled in the art.

Therefore, the foregoing is considered as illustrative only of the principles of the in-vention. Further, since numerous modifications and changes will readily occur tothose skilled in the art, it is not desired to limit the invention to the exact construc-tion and operation shown and described, and accordingly, all suitable modificationsand equivalents may be resorted to, falling within the scope of the invention as de- fined in the appended claims. _13- In accordance with the present invention, and with reference to Fig. 1, there is pro-vided a process for converting carbonaceous materials to liquid. In a preferred em-bodiment the process comprises the following steps. Feeding preheated high-temperature steam 28 of a temperature Within the range of 400°C to 700°C, whichcan be generated by a regenerative system, an electrical heater, a boiler, or fromcombustion of hydrogen and oxygen. Feeding the carbonaceous, solid material 40into pyrolysis reactor 30. The reactor 30 is operating in the temperature of 400°C to700°C. The temperature of reactor 30 is maintained by an electric heater (notshown), or by hot flue gas combusted by biomass directly, or syngas 110 obtainedfrom the process, solid residue 80 generated from pyrolysis reactor 30. A hydrogenradical generator 50 is installed in the reactor 30. This generator produces hydro-gen radicals (H*), which are used as a hydrogen donor for the deoxygenation processof the pyrolysis gas. The stream of pyrolysis gas 60 generated from the pyrolysisreactor 30 passes through a cyclone separator 70. Here, solid residues 80 can beseparated from the pyrolysis gas stream 60. A clean pyrolysis gas stream 90 exitingcyclone 70 flows into a cooler 100. Here, most of the gas is cooled to produce a py-rolysis liquid (i.e. bio-oil) 120. The pyrolysis liquid can then can be collected fromthe process. A hydrogen radical generator 50 is also installed in the cooler 100 inorder to provide hydrogen radicals also at this location, enabling additional deoxy-genation reaction of the gaseous oxygenates and hydrogenation reaction of gaseous unsaturated compounds before being converted into a liquid state.

The following Example is provided for a better understanding of the features, as- pects, and advantages of the present invention.

EXAMPLE The principal steps of the inventive process were carried out in batch-wise operationmode on a pilot scale apparatus as shown in Fig. 2. The pilot scale apparatus isbased on a universal batch reactor, which reactor has been developed for a differentpurpose and has been described in more detail by Anna Ponzio, Sylvester Kalizs,Juliette Promelle, Wlodzimierz Blasiak, Susumo Mochida, Combustion of wood pel-lets in a high temperature and oxygen diluted environment, Proceedings from öth Hi-TACG conference 2005 , Essen 2005. The pilot scale plant shown in Figure 2 is not an arrangement according to the invention. _14- The experimental pilot scale rig shown in Figure 2 consists of a horizontal combus-tion chamber with an inner diameter about 0.1 m. High-temperature steam wasobtained as follows. Methane and air were fed via nozzles 5 and 6 to the gas burner7. As the fuel burns in the combustion chamber 8 the hot flue gases will heat theceramic honeycomb 9 and flow through the second part of the reactor 18 and to-wards the furnace's outlet 15. The rig is run in heating mode until the desired tem-perature of the honeycomb is reached. Once the proper temperature is reached, themethane feed is shut off and the experimental stage started. The proper feed gas (inthis case Ng) is set by adjusting the flow of steam and the resulting heating agent isfed through feed gas nozzles 1-4 and is heated by the hot honeycomb 9. The heatedagent temperature is measured by a thermocouple 20. A portion of a feedstock isattached to a piston as a thin bed in a basket 14 fabricated by metal net for thispurpose. The lid 11 with the piston and the feedstock sample is attached to the rig,with the feedstock sample in a small cooling chamber 10 where it is cooled by ni-trogen 13. The experiment starts when the sample on the piston is pushed downinto the reactor chamber 18 from above. Once the sample is in the chamber, thesample is visible through glass window 19. The temperature of the sample is meas-ured by a thermocouple 21. Thereafter, the basket is lifted from the chamber to thecooling chamber 10 in order to quench the reactions through cooling with nitrogen.The pyrolysis vapors leaving the furnace are passed a sampling line 16 and they arerapidly quenched by gas washing bottles 17 to temperatures of -10°C down to -15°C, using a cooling bath 22. Condensable molecules are obtained as a liquid. The gases are driven to GC analyzer 27.

Bamboo has been tested in above facility. The particle size of the bamboo was about200-500 um. The elemental analysis was performed using a Vario Micro ElementalAnalysis instrument. The alkali content and other metals that can be found in theash of the material were analyzed using a PE5300DV inductively coupled plasma spectrometer. _15- Table 1 Analysis of the raw material Moisture [%Wt] 1.87Cellulose [%Wt] 39.61Hemicellulose [%Wt] 17.53Lignin [%Wt] 22.61 Extraction mat- ter[%wt] 18.38 Ultimate Analysis C [% Wt] 47.98H [% Wt] 6.59O [% Wt] 42.875N [% Wt] 1.93Al [% Wt] 0.004Ca [% Wt] 0.044Fe [% Wt] 0.05K [% Wt] 0.417Mg [% Wt] 0.044Mn [% Wt] 0.01Na [% Wt] 0.042P [% Wt] 0.012Zn [% Wt] 0.002 The quality of the inventive bio-oil generated from bamboo via fast pyrolysis in pres-ence of steam Was assessed. The results show that the ratio H / C is 1.51, and the ratio of O /C is 0.16. Both values demonstrate a good quality of the resulting bio-oil.

The Water content in the resulting liquids Were around 30% and the liquids ob- tained Were fully miscible in Water.

The bio-oils obtained Were transparent, broWn liquids. _16- Elemental composition of bio-oi1 obtained from steam pyrolysis at 797 K (523.85°C) Component Content [%wt] High-TemperatureSteam Pyrolysis at797 K (523.85°C) (this study) C 74.449.55 O 16.01 During the pyrolysis process of bamboo, the yields of different productions at differ- ent temperature are given below. 797 2s ss 20(szass)ses 21 43 ss (s91.ss)

Claims (9)

1. A method of producing bio-oil from a carbonaceous, solid raw material (40)selected from waste materials and biomass, and mixtures thereof, comprising thesteps of:(a) providing a carbonaceous, solid raw material (40);(b) subjecting the carbonaceous, solid raw material to conditions effective foraccomplishing fast pyrolysis of said carbonaceous, solid raw material;(c) subjecting the oxygenates formed in step (b) to conditions effective for ac-complishing deoxygenation of said oxygenates; and(d) cooling the gaseous components formed in step (c), in order to obtain liquidbio-oil,wherein steps (b) and (c) are accomplished by means of subjecting the carbona-ceous, solid raw material to high-temperature steam at a temperature within the interval of 400-700°C.

2. The method of claim 1, wherein steps (b) and (c) are being carried out in the same reactor (30).

3. The method of claims 1 or 2, wherein there is no intervening condensation or recovery of pyrolysis liquid between steps (b) and (c).

4. The method of any one of claims 1-3, wherein the cooling step (d) is multi-staged.

5. The method of any one of claims 1-4, wherein step (c) is enhanced by the fol- lovving additional steps:(cl) generation of hydrogen radicals (H*) from the high-temperature steam beingused in steps (b) and (c) by active, electrical means (50); and(c2) contacting the oxygenates formed in step (b) to hydrogen radicals (H*) formed in step (cl).

6. The method of any one of claims 1-5, wherein an additional step (e) is in-cluded between steps (c) and (d), wherein solid material (80) is separated from thegaseous components (60) obtained from steps (b) and (c), before cooling of the gase- ous components (90) in step (d) to form bio-oil (120). _18-

7. An arrangement for carrying out the method of claim 1 comprising:a pyrolysis reactor (30) With the capability of Withstanding temperatures in therange of 400-700°C, said reactor being provided With an inlet for a carbona-ceous, solid raw material (40), and an inlet for high-temperature steam (28) of atemperature Within the interval of 400-700°C; andquenching means (100) for cooling the pyrolysis gas obtained in the pyrolysisreactor (30), Wherein the reactor (30) further comprises electrical means (50) for producing hy- drogen radicals (H*) from the high-temperature steam in the reactor.

8. The arrangement of claim 7, further comprising means (70) for separatingsolids from the pyrolysis gas (60) obtained from the pyrolysis reactor (30) before cooling thereof to form bio-oil (120).

9. An arrangement for carrying out the method of claim 1 comprising:a pyrolysis reactor (30) With the capability of Withstanding temperatures in therange of 400-700°C, said reactor being provided With an inlet for a carbona-ceous, solid raw material (40), and an inlet for high-temperature steam (28) of atemperature Within the interval of 400-700°C; andquenching means (100) for cooling the pyrolysis gas (60) obtained in the pyroly-sis reactor (30), Wherein the arrangement further comprises means (70) for separating solids (80) from the pyrolysis gas (60) obtained from the pyrolysis reactor (30) before cooling thereof into bio-oil.