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EP 0 366 138 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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03.08.1994 Bulletin 1994/31 |
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Date of filing: 26.10.1989 |
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International Patent Classification (IPC)5: C10G 1/00 |
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Process for manufacturing fuel from ligno-cellulose material
Verfahren zur Aufbereitung von Brennstoff aus Lignozellulose-Material
Procédé de préparation de combustible à partir de matières lignocellulosiques
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Designated Contracting States: |
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DE ES FR GB IT NL SE |
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Priority: |
27.10.1988 EP 88117948
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Date of publication of application: |
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02.05.1990 Bulletin 1990/18 |
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Proprietor: Strouth, Baron Howard Steven |
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Marbella(Malaga) (ES) |
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Inventors: |
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- Jelks J.W.
Sand Springs
Oklahoma (US)
- Strouth, Baron Howard Steven
Marbella (Malaga) (ES)
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Representative: Riederer Freiherr von Paar zu Schönau, Anton et al |
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Van der Werth, Lederer & Riederer
Postfach 2664 84010 Landshut 84010 Landshut (DE) |
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References cited: :
EP-A- 0 105 937 BE-A- 349 622
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EP-A- 0 204 354 GB-A- 407 992
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Remarks: |
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The file contains technical information submitted after the application was filed
and not included in this specification |
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| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
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[0001] The invention relates to a process as stated in the prior art portion of claim 1.
[0002] A process comprising the steps of reacting the ligno-cellulose material with sulfur
dioxide and water under heat and pressure by introducing steam; mixing the reacted
material from the first step with an alkaline solution to dissolve the reacted lignin;
and washing the material from the second step to remove the dissolved lignin from
the rest of the mixture, is known from EP-B 105 937 by the applicant. It had been
known for quite some time (US-A 4 053 645) to increase the digestability of cellulosic
material by converting it to a sugar and saccharine compound which can be used for
feeding animals. This compound, also, can be fermented and distilled, leading to alcohol
which can be used as fuel. This can be carried out in a self-contained process. Fermentation,
however, is a batch-process and usually requires 12 to 24 hours, depending upon the
type of cellulose derived from the raw material. Thus, this fermentation step considerably
limits the productivity of the prior art process. Further, the distillation for separating
the different alcohol and ether compounds requires a lot of energy and causes high
expenses.
[0003] Other attempts to gain fuel from biomass use pyrolyzis of the biomass and then in
a next step the pyrolyzis products are chemically condensed, i.e. subjected to a chemical
reaction involving union between molecules, possibly at the same time eliminating
simple molecules, to form new more complex compounds of greater molecular weight which
are intended to at least partially be used as fuel. The achievable yield, however,
is rather modest while the energy consumption for keeping the process going is rather
high.
[0004] Cracking in its broadest sense has already been contemplated also for biomass products
(BE-A 349 622 = DE-A 567 330) but without practical utilization.
[0005] It is also known (EP-A 0 204 354) to manufacture fuel from ligno-cellulose material
having a particle size of less than 3 mm, which is slurried with water and subjected
to pressure and heat of at least 300°C, whereupon the solids are separated from the
liquid and the liquid is further separated into aqueous and non-aqueous liquids, the
latter ones consisting to a major part of useful hydrocarbon-containing products with
reduced oxygen content.
[0006] The invention aims to enhance the productivity limits and to save costs, working
time and energy consumption. This is achieved by the invention characterized in the
claims. By the process of the invention, fermentation is eliminated and a high yield
is gained, and it is also possible to eliminate distillation.
[0007] According to the invention as characterized in claim 1, cracking is carried out,
and particularly not only on the basis of the cellulose material but also on the basis
of the lignin contained in the biomass, the process comprising the steps of pyrolyzing
the ligno-cellulose material so as to crack it and obtain gaseous pyrolyzis products,
and carrying out a catalytic condensation reaction of the pyrolyzis products to result
in a series of compounds from which such usables as fuel are separated. No energy
being gained from the lignin content of the biomass, it is desired to work with minimum
energy consumption and maximum yield, which is obtained by the measure that before
pyrolyzing, the ligno-cellulose material is pulverized, and that pyrolyzation and
the catalytic reaction take place in one same high-temperature reaction zone, into
which the pulverized material is transported to be mixed with catalyst powder. By
having dry materials to be processed, the heating energy is much less, and by getting
the places of pyrolization and catalytic reaction as close together as possible, a
maximum yield is obtained.
[0008] The subjects of claims 2 and 3 serve to obtain a very suitable fine-grain powder
as defined in claim 4, the particular digestion step leading to a very brittle wood
material which can easily be ground. The chemical treatment of the biomass is preferably
as described in another context in US-PS 4 053 645.
[0009] According to claim 5, the pulverized biomass is transported into contact with the
catalyst by means of a fluid stream which preferably is superheated steam which proves
the cheapest while at the same time heating the reaction zone.
[0010] The process can be carried out for increased energy saving in the manner as defined
in claim 9, using immediately part of the product which part might be less suitable
as fuel, for the system heating. Further, it is possible to re-cycle part of the product
so as to support transport and reaction.
[0011] The drawing shows schematic arrangements of process steps and of apparatuses which
may be employed in practising the invention.
Fig. 1 in a schematic diagram shows an arrangement for cracking powdered biomass which
for pre-processing has been separated into a lignin and into a cellulose path; and
Fig. 2 shows a schematic diagram for reacting pulverized biomass which had been pre-processed
un-separated.
[0012] In Fig. 1, first and second globe rotary digesters 10 and 12 are shown. While only
two digesters are shown, it is possible to use only a single digester or any number
of digesters for the purposes of this invention. The use of more than one digester,
however, is preferred since the reaction which takes place within each of the digesters
is a batch process. By using a plurality of digesters the procedure can be carried
out as a continuous process. Each of the globe rotary digesters 10, 12 is an apparatus
which is used to subject the contents to heat and pressure while the contents is being
mixed. Any device which accomplishes these results would be within the scope of the
invention, whether carried out as a batch process or a continuous process.
[0013] A ligno-cellulose material cut into small pieces is deposited in digester 10 to substantially
fill the digester, however leaving sufficient room so that the material will mix as
the digester rotates. The chosen ligno-cellulose may be any type of wood, straw, bagasse,
nut hulls, seed hulls, etc. The woody material is first chopped or ground into particles.
The size of the particles should be not more than approximately 7 mm (1/4") but may
be as fine as desired. The size of the particles is not important except that it is
apparent that the smaller the particles the more expeditious will be the subsequent
reaction. Thus the particle size is a matter of engineering trade-off between the
cost of reducing the ligno-cellulose material to smaller sizes versus the time utilized
in the steps of reaction.
[0014] After the ligno-cellulose material (hereinafter called wood) is deposited in digester
10, water and sulfur dioxide are added. The water is added at a ratio of approximately
40% by weight of water to the dry weight of the wood. Sulfur dioxide is added in form
of a gas at a ratio by weight of ½ to 6% of the dry weight of the wood. The quantity
of sulfur dioxide is predicated upon the percentage of lignin compared to cellulose
contained in the wood. The quantity of lignin is less when cottonwood species is used
as a raw material, compared to greater percentage when oak or pine are used as raw
material with the quantity of sulfur dioxide adjusted, accordingly. After the wood,
sulfur dioxide and water have been added, the contents of the digester 10 are pressurized
by the introduction of steam. Sufficient steam is introduced to bring the temperature
of the reaction mixture to between 44°C and 200°C, a range between 49°C and 200°C
being preferred, and at a pressure of between 2463 and 15750 hPa (35 and 225 psi).
The mixture is cooked at this pressure and temperature for a period of 40 minutes
to 1 hour. However, the duration is determined by the particulate size of the wood
raw material and the characteristics of the material.
[0015] After a cooking cycle is completed in digester 10, a valve 14 is opened to allow
steam to escape to the atmosphere. After the digester has been depressurized, the
loading door is opened and the contents discharge onto a digester pump pit 16. After
the digester is emptied, it is refilled with wood type material, water, and sulfur
dioxide and the process is repeated. By use of the second digester 12 it can be seen
that one digester may be in the process of being emptied and refilled while the other
digester is in the cooking cycle so that reacted raw material is deposited into the
digester pump pit 16 on a more frequent basis. By the use of a greater number of digesters
the input can be even more frequent so that the digester pump pit 16 always contains
a quantity of reacted material for subsequent processing on a continuous basis.
[0016] The reacted material in digester pit 16 is in the form of a slurry and, if necessary,
additional water may be added to the pit to maintain the slurry as a pumpable mixture.
The digester pump pit includes stirring apparatus 18 to make sure the reacted material
does settle out and is retained as a pumpable slurry.
[0017] By means of a pump 20 the slurry is conducted to a mixing box 22 where the mixture
is mixed with an alkaline solution from line 24. The source of the alkaline solution
which is conducted through line 24 can be that a combustible fuel is made for burning
in a boiler to produce at least part of the necessary heat from the dissolved lignin,
and that waste heat from the cracking reaction chamber is collected to produce hot
steam, the ash resulting from burning being used to provide the alkaline solution
to dissolve the modified lignin.
[0018] The reaction of the wood in digesters 10 and 12 is such that the sulfur dioxide in
the presence of water reacts with the lignin content of the wood to enhance the solubility
of the lignin content without destroying the carbohydrate content. Lignin is a fairly
complex organic material, varying somewhat from one plant species to another and the
exact reaction with sulfur dioxide is not precisely known; however, it has been experimentally
verified that the reaction of the sulfur dioxide and wood produces a solution wherein
when mixed with an alkaline solution the lignin is dissolved.
[0019] The processed mixture and alkaline solution flows out of mixing box 22 through line
26 into a vacuum washer 28 for separating lignin and cellulose materials. This apparatus
is a known type of equipment utilized in the chemical processing industry, and particularly
in the paper making industry. Therefore, it is well understood by practitioners in
the art and will not be described in detail. Suffice it to say that in a vacuum washer
a cylinder is equipped which is rotated in the solution. The interior of the cylinder
is impressed with a vacuum. Water is sprayed onto the cylinder from above the solution
to wash away the dissolved matter, the cellulose material, being fibrous in nature,
forms a mat on the cylinder. The fresh water utilized to wash the lignin content from
the matted cellulose is supplied by line 30. The vacuum required by the washer 28
may be supplied by a vacuum pump or by means of, as illustrated, a barometric leg
32 which communicates with an overflow box 34. The dissolved lignin is carried out
of the overflow box 34 by a line 36 while the cellulose is rolled off the vacuum forming
cylinder into a receiving box 38. This matted material is still in a slurry form and
is carried by a pump 40 into a second mixing box 42 where the cellulosic material
is mixed with water from line 30. The washing procedure is repeated in a second vacuum
washer 44 having a barometric leg 46 and overflow box 48 by which the overflow liquid
content is carried away from the vacuum washer. The matted cellulose content is rolled
off the cylinder into a receiving box 50. The content of receiving box 50 is properly
washed material which has more than 95% of the original lignin content removed. It
is passed on via a line 52.
[0020] While the use of vacuum washers 28 and 44 has been illustrated herein, it is understood
that alternate washing procedures can be used in practice of the invention and that
the particular means of washing the reacted ligno-cellulose material mixed with an
alkaline solution is not a critical element in the practice of the invention and that
other known washing systems may be employed. The essence of the washing step is simply
to separate the dissolved lignin content from the cellulose material.
[0021] The materials needed in the process include sulfur dioxide, a metal iron catalyst
from that group of metals having a valence of 3, an alkaline solution, water, heat
and steam, produced by the process itself.
[0022] The lignin solution from overflow box 48 is taken by line 90 to line 36.
[0023] The lignin solutions from overflow boxes 34 and 44 are carried by line 36 to a set
of multi-effect evaporators 98, 100, and 102. The number of such evaporators may be
varied. The purpose of the evaporators is to evaporate the water content from the
dissolved liquid solution. To obtain the heat necessary for the evaporation step,
steam is applied from a line 104 to a heat exchanger 106 in evaporator 102. Steam
from evaporator 102 is passed by line 108 to a heat exchanger 110 in evaporator 100.
In like manner, steam from evaporator 100 is passed by line 112 to a heat exchanger
114 in evaporator 98. The condensate from evaporator 98 is passed by line 116 into
evaporator 100. The condensate from evaporator 100 is passed by line 118 into evaporator
102. The condensate from evaporator 102 is passed by line 120 into a dryer 202. The
lignin content of the solution from the overflow box 34 will normally be of about
20% solids, more or less, and the balance liquid. This solution will be concentrated
so that the ligning content passing from the multi-effective evaporators in line 120
will be about 55% more or less.
[0024] Steam from a boiler 96 passing out through steam line 126 is conveyed to a turbine
generator 130 to produce electrical energy. The turbine is preferably of the bleeder
type which generates electricity and provides process steam by bleeding it from an
intermediate point in the turbine at line 104. This process steam is partly carried
by a line 134 to the globe rotary digesters 10 and 12 and partly by line 104 to the
multi-effect evaporator 102. Spent steam from the multi-effect evaporators may be
collected by apparatus not shown and condensed to provide the water which is reused
for input into the globe digesters 10, 12, the mixing box 42, and to spray water on
the washers 28 and 44.
[0025] The material supplied through line 52 is a cellulosic slurry which contains high
sugar and saccarine values, approximately 95% of the original lignin having been eliminated.
This slurry from receiving box 50 is supplied by a pump 201 to the dryer 202 which
also receives the concentrated lignin solution from line 120 and receives heating
steam from the turbine 130 via line 104. In the dryer 202, the already more or less
concentrated slurry material is fully dried and sent via a line 203 to a pulverizer
204 where it is pulverized to a very fine dry powder, sufficiently fine to pass a
screen with 150 µm passages (a 100-mesh screen).
[0026] The pulverized material is transported to a cracker/reformer 205 wherein, in a same
reaction zone, the powder is cracked by pyrolyzation and is reformed by condensation.
In the cracker/reformer 205, the powdered biomass is introduced into a hot environment,
i.e. in a catalyst bed being fluidized by a carrying gas which preferably is superheated
steam which is cheapest to arrange, or is an inert gas which may be cold or warm up
to 110 to 160°C, which is a temperature well below the temperature where pyrolyzis
starts. The fluidized bed of the catalyst has a much higher temperature, the carrier
gas thereof - of the same kind as the transporting carrier gas for the biomass - being
revolved by a blower pump 206 and in this cycle being heated by a heater 207.
[0027] The biomass powder entering the reaction zone is heated and pyrolyzis takes place,
resulting in fragmented molecules which enter the catalyst immediately and chemically
condense in contact therewith to form mainly liquid materials satisfactory for use
as gasoline fuel or to be blended with gasoline. The catalyst is a zeolite type catalyst,
i.e. ZSM-5. The reaction products of the cracking and reforming process are transported
via a line 143 to a separation column 145. The separation column breaks down the cracked
materials into various fractions. The material enters as a mixture of hot vapours
the column and therein rises through the bubble caps and condenses on different trays.
The lighter fractions do not condense until they reach the cooler trays, i.e. the
more up trays. The heavier fractions condense on the lower trays. Among the lighter
fractions are those which can be used as fuel. If desired, some heavier fractions
including tar can be re-cycled via a line 148 to the cracker/reformer 205. The reaction
also results in some waste gas and in the separation column 145, some non-condensable
gas is formed. This waste gas from the cracker/reformer 205 is transported via a line
208 to a fuel gas storage 209 also acting as a blender, as it further receives fuel
gas from outside by a line 210. Part of this gas is recirculated to the cracker/reformer
205, and part of it as well as the non-condensable gas from the column 145 is transported
via a line 212 or 213, respectively, to the boiler 96 which also has a supply 214
of combustion air, for heating and thus generating process steam.
[0028] By combining the pyrolyzis and the chemical condensation in the same reaction zone,
a considerably high yield is obtained in this step, leading generally to methyl-benzenes
and to a small decree to by-products such as coke, carbon oxides and water. If on
the other hand the pyrolyzed biomass would have been allowed to cool before condensation,
the resulting large molecules would also be reformed to the desired compounds, but
would shed water and carbon to a higher decree which would lower the yield of the
desired compounds.
[0029] Fig. 2 shows a variant of the process. The biomass, i.e. saw dust, chips etc., is
mixed in a mixer 301 with a reaction solution coming via a line 302 and a pump 303
from a mix tank 304 which is supplied by water, reactant and activator as described
somewhat later. The mixture of biomass and solution is supplied by a line 307 to a
wet chip storage and cooking tank 308 where it is subjected to boiling temperature
and from there to a dryer 309 which is combined with a furnace 310 for delivering
heat for drying. After careful drying, the bone-dry, brittle biomass is transported,
via a blower 311 and a separator 313, to a dry chip storage 314 and from there, via
a feeder 315, to a mill 316 grinding the dry chips to a fine powder similarly to be
specified as in the description of Fig. 1. The powder passes again a separator 320,
a storage 321, a powder feeder 322 and then, transported by a carrier gas stream 323,
enters cracker/reformer 325 combined with a catalyst bed heater 326. The output of
the cracker/reformer 325 passes a cooler 327 and then is supplied via a line 328 to
separation column 330 from which the different final products are extracted and stored
in storage tanks, a tank 331 for light, a tank 332 for medium and a tank 333 for heavy
hydrocarbons. Tar products are re-cycled to the cracker/reformer 325 via a line 335
for renewed processing.
[0030] Of some interest is the preparation of the biomass before cooking and drying. It
is carried out in a manner similar to what has been described in US-A 4053645 (Jelks).
The reactant and activator comprise an oxydizing acid like nitric acid (HNO₃), a non-oxidizing
acid such as sulfuric, phosphoric, hydrochloric or acetic acid and a trivalent metal
such as iron which has the function of a catalyst. Nitric acid which serves to deliver
some required oxygen is requested in an amount of approximately 2 to 30 grams per
kg of dry weight of the biomass. The materials are cooked, if necessary under pressure,
with the effect of attacking the lignin-cellulose bond and downgrading and saturating
the cellulose, and then are carefully dried resulting in a very brittle material which
can easily be ground to the required fine powder, demanding only rather low grinding
energy. Careful drying will help to circumvent the application of pressure during
digestion in the cooking step. The moderate energy consumption for grinding and for
the pyrolyzis of the dry material, together with the high yield of the locally combined
pyrolyzis and condensation, or in other words, cracking and reforming steps, makes
the present process very economic.
[0031] While the invention, as above indicated, has been described in certain detail, it
is understood that the invention is not limited to the embodiments set forth herein
but is to be limited by the scope of the attached claims, including the full range
of equivalency to which each element thereof is entitled.
1. Process for manufacturing fuel from ligno-cellulose material, to be carried out by
the steps of pyrolyzing the ligno-cellulose material so as to crack it and obtain
pyrolyzis products, and carrying out a catalytic condensation reaction of the pyrolyzis
products to result in a series of compounds from which usable fuels are separated,
characterized in that before pyrolyzing, the ligno-cellulose material is pulverized to a grain size of
less than 150 µm (corresponding to less than 100 mesh), and that pyrolyzation and
the catalytic reaction take place in one same high-temperature reaction zone, into
which the pulverized material is transported to be mixed with the catalyst which is
of zeolite type.
2. Process according to claim 1, characterized in that the ligno-cellulose material,
before being pulverized, is subjected to digestion by subjecting the material to heat
and pressure in presence of water and sulfur dioxide while it is being mixed.
3. Process according to claim 1, characterized in that the ligno-cellulose material,
for digestion by subjecting the material to heat and pressure in presence of water
and sulfur dioxide while it is being mixed and for pulverization, is saturated by
a treatment with an acid with a trivalent metal ion under heat and pressure so as
to attack the lignin cellulose bond and downgrade the cellulose, and then is dried
and ground.
4. Process according to claim 1, characterized in that the lignocellulose material, for
digestion by subjecting the material to heat and pressure in presence of water and
sulfur dioxide while it is being mixed, is saturated by a treatment with an acid with
a trivalent metal ion, the saturated cellulose material being dried under conditions
using dry air at a temperature under 100°C, so as to attack the lignin-cellulose bond
and downgrade the cellulose for grinding.
5. Process according to any of claims 1 to 4, characterized in that the pulverized material
and the catalyst powder are transported into a reaction chamber by a fluidized stream.
6. Process according to any of claims 1 to 4, characterized in that the reaction zone
is a fluid bed carrying the catalyst powder, the pulverzied material being blown to
this zone by a fluidized stream.
7. Process according to claims 5 or 6, characterized in that the fluidized stream consists
of superheated steam.
8. Process according to claims 5 or 6, characterized in that the fluidized stream consists
of an inert gas having a temperature which is lower than that required to pyrolyze
the biomass.
9. Process according to any of claims 1 to 8, characterized in that the lignin material
and the cellulose material are separated for processing, and are re-combined at least
before the cracking step.
10. Process according to claim 8, characterized in that a combustible fuel is made for
burning in a boiler (96) to produce at least part of the necessary heat from the dissolved
lignin, and that waste heat from the cracking reaction chamber is collected to produce
hot steam.
11. Process according to claim 10, characterized in that ash resulting from burning is
used to provide an alkaline solution to dissolve modified lignin.
12. Process according to any of claims 1 to 11, characterized in that separation is carried
out by feeding the chemical product output into a separation column.
13. Process according to any of claims 1 to 12, characterized in that the temperature
in the reaction zone is 250°C to 600° C.
1. Verfahren zum Herstellen von Treibstoff aus Lignozellulose-Material, das durchzuführen
ist durch die Schritte des Pyrolysierens des Lignozellulose-Materials so, daß dieses
gekrackt wird und Pyrolyse-Produkte erhalten werden, und des Durchführens einer katalytischen
Kondensationsreaktion der Pyrolyseprodukte zum Erhalten einer Reihe von Verbindungen,
aus denen verwendbare Treibstoffe separiert werden, dadurch gekennzeichnet, daß man
vor dem Pyrolysieren das Lignozellulose-Material zu einer Korngröße von weniger als
150 µm (entsprechend weniger als 100 mesh) pulverisiert und daß die Pyrolisierung
und die katalytische Reaktion in einer und derselben Hochtemperatur-Reaktionszone
stattfinden, in die man das pulverisierte Material transportiert, so daß es mit dem
Katalysator gemischt wird, der von der Zeolit-Art ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Lignozellulose-Material,
bevor es pulverisiert wird, dem Aufschließen unterwirft, indem man das Material Hitze
und Druck in Anwesenheit von Wasser und Schwefeldioxid unterwirft, während man es
mischt.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Lignozellulose-Material
für das Aufschließen durch die Behandlung des Materials unter Hitze und Druck in Anwesenheit
von Wasser und Schwefeldioxid, während man es mischt, und für die Pulverisierung saturiert,
und zwar durch eine Behandlung mit einer Säure mit einem dreiwertigen Metallion unter
Hitze und Druck, wodurch die Lignin-Zellulose-Bindung angegriffen wird und die Zellulose
degradiert wird, und man es dann trocknet und mahlt.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Lignozellulose-Material
für das Aufschließen durch die Behandlung des Materials unter Hitze und Druck in Anwesenheit
von Wasser und Schwefeldioxid, während man es mischt, saturiert, und zwar durch eine
Behandlung mit einer Säure mit einem dreiwertigen Metallion, wobei das saturierte
Zellulose-Material unter Bedingungen der Verwendung von trockener Luft bei einer Temperatur
unter 100°C getrocknet wird, wodurch die Lignin-Zellulose-Bindung angegriffen wird
und die Zellulose zum Mahlen degradiert wird.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man das pulverisierte
Material und das Katalysatorpulver durch einen fluidisierten Strom in eine Reaktionskammer
transportiert.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Reaktionszone
ein das Katalysatorpulver tragendes Fließbett ist und daß man das pulverisierte Material
durch einen fluidisierten Strom in diese Zone bläst.
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß der fluidisierte Strom
aus überhitztem Wasserdampf besteht.
8. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß der fluidisierte Strom
aus einem inerten Gas mit einer Temperatur, die unter der für die Pyrolyse der Biomasse
erforderlichen Temperatur liegt, besteht.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Lignin-Material
und das Zellulose-Material für die Verarbeitung getrennt werden und spätestens vor
dem Schritt des Krackens wieder kombiniert werden.
10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß zum Brennen in einem Heizkessel
(96) ein brennbarer Brennstoff zum Erzeugen von wenigstens einem Teil der erforderlichen
Wärme aus dem aufgelösten Lignin hergestellt wird und daß Abfallwärme aus der Krack-Reaktionskammer
zur Erzeugung von Heißdampf gesammelt wird.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man die aus dem Verbrennen
resultierende Asche dazu verwendet, eine Alkali-Lösung zu schaffen, um modifiziertes
Lignin aufzulösen.
12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß man eine
Separierung durchführt, indem man den Ausgangsstrom der chemischen Produkte eine Separier-Kolonne
einspeist.
13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Temperatur
in der Reaktionszone 250°C bis 600°C beträgt.
1. Procédé de préparation de combustible à partir de matière ligno-cellulosique, à effectuer
par les étapes de pyrolyse de la matière ligno-cellulosique de manière à la craquer
et à obtenir des produits de pyrolyse, et de mise en oeuvre d'une réaction de condensation
catalytique des produits de pyrolyse pour former une série de composés desquels on
sépare des combustibles utilisables, caractérisé en ce que, avant pyrolyse, la matière
ligno-cellulosique est pulvérisée à une granulométrie de moins de 150 µm (correspondant
à moins de 100 mesh) et que la pyrolyse et la réaction catalytique ont lieu dans une
même zone de réaction de température élevée dans laquelle la matière pulvérisée est
transportée pour être mélangée avec un catalyseur qui est du type zéolithe.
2. Procédé selon la revendication 1, caractérisé en ce que la matière ligno-cellulosique,
avant d'être pulvérisée, est soumise à une digestion en soumettant la matière à de
la chaleur et de la pression en présence d'eau et d'anhydride sulfureux tout en étant
mélangée.
3. Procédé selon la revendication 1, caractérisé en ce que la matière ligno-cellulosique,
pour la digestion en soumettant la matière à de la chaleur et de la pression en présence
d'eau et d'anhydride sulfureux tout en la mélangeant et pour la pulvérisation, est
saturée par un traitement par un acide avec un ion de métal trivalent sous chaleur
et pression de façon à attaquer la liaison lignine-cellulose et dégrader la cellulose,
puis elle est séchée et broyée.
4. Procédé selon la revendication 1, caractérisé en ce que la matière ligno-cellulosique,
pour la digestion en soumettant la matière à de la chaleur et de la pression en présence
d'eau et d'anhydride sulfureux tout en la mélangeant, est saturée par un traitement
par un acide avec un ion de métal trivalent, la matière cellulosique saturée étant
séchée dans des conditions d'utilisation d'air sec à une température inférieure à
100°C, de façon à attaquer la liaison lignine-cellulose et à dégrader la cellulose
pour le broyage.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérise en ce que la
matière pulvérisée et la poudre de catalyseur sont transportées dans une chambre de
réaction par un courant fluidisé.
6. Procédé selon l'une quelconque des revendications 1 à 4, caractérise en ce que la
zone de réaction est un lit fluide portant la poudre de catalyseur, la matière pulvérisée
étant insufflée dans cette zone par un courant fluidisé.
7. Procédé selon l'une ou l'autre des revendications 5 et 6, caractérisé en ce que le
courant fluidisé consiste en vapeur d'eau surchauffée.
8. Procédé selon l'une ou l'autre des revendications 5 et 6, caractérisé en ce que le
courant fluidisé consiste en un gaz inerte ayant une température qui est inférieure
à celle nécessaire pour pyrolyser la biomasse.
9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que la lignine et
la cellulose sont séparées pour le traitement, et sont recombinées au moins avant
l'étape de craquage.
10. Procédé selon la revendication 8, caractérisé en ce qu'on prépare un combustible pour
la combustion dans une chaudière (96) pour produire au moins une partie de la chaleur
nécessaire à partir de la lignine dissoute et que la chaleur évacuée de la chambre
de réaction de craquage est recueillie pour produire de la vapeur d'eau chaude.
11. Procédé selon la revendication 10, caractérisé en ce qu'on utilise les cendres résultant
de la combustion pour fournir une solution alcaline pour dissoudre la lignine modifiée.
12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la
séparation est effectuée en introduisant les produits chimiques sortants dans une
colonne de séparation.
13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que la
température dans la zone de réaction est de 250°C à 600°C.