SE440914B - PROCEDURE FOR MANUFACTURING COKS WITH CELLULOSAM MATERIAL BASIS - Google Patents

Description

7806112-4 In addition to large amounts of household waste with lignite carbon occurs each year large quantities of cellulose-type materials, both of natural stroke, e.g. peat, as waste material from woodworking industry as well as agricultural waste and these materials are present in a form, which is unsuitable for efficient use as a commercial fuel. Cellulose-containing materials such as sawdust, needles, wood wood chips, branches and the like from tree felling as well as various kinds of waste from agriculture, e.g. different kinds of stems have so far entailed a major waste problem. It has thus been a long time coming a need for a process for the conversion of such cellulose compounds valuable fuel products in order not only to contribute an important solution to fuel shortages and the energy problems of our time without also to reduce the costs associated with the disposal of such waste materials.

In addition to these problems, the authorities have come up with a lot strict rules for limiting the sulfur content of fuel oils, such as incinerated for the purpose of generating electricity and steam power. Thus applies in the USA that the sulfur content in fuel oils may not exceed 0.7%, while in the state of California the maximum content is 0.3% sulfur applies in certain areas. For compliance with these regulations hitherto it has been necessary to desulphurize fuel oils or to import fuel oils with a low sulfur content, in order to stay within permissible limits. The costs of acquiring low-sulfur however, oils are very high, to which is added some uncertainty depending on the political conditions in the production states. These problems have been eliminated by the present invention, by The coke-like product with a very low sulfur content is obtained and low ash content, and this product can be comminuted and mixed with fuel oils with a high sulfur content, whereby a liquid suspension, which meets the requirements for the low sulfur content table.

: QQRSWWÜ 7806112-4 The advantages of the invention are achieved by a method, which is characterized in that the cellulosic starting material is fed into an autoclave, that this material is heated in an the claw to a temperature between 399 and 677 ° C and a pressure at least 7 x 105 Pa for a sufficient time to produce one conversion of moisture and at least some of the starting material volatile organic constituents of a gas phase and a thermal partial restructuring of the chemical structure of the material and a change in its chemical composition in order to achieve a solid reaction product and that the reaction product obtained then cooled and recovered as a processed solid coke-like product. Other features of the invention appear from the subclaims.

The accompanying drawing schematically shows a flow chart for the process steps according to a suitable embodiment of the invention ningen.

The procedural steps included in the procedure according to the invention is schematically illustrated in the flow chart of the drawing.

In the manner shown, cellulosic material or a mixture of the like is introduced in a pretreatment step, where the fed material is exposed appropriate tearing, disintegration and sieving, so as to obtain a suitable supply of material of the desired particle size, after the atomized material is introduced into a high temperature reactor temperature and high pressure, in which the material is exposed to heat and pressure to remove the moisture content of the material and volatile organic constituents and thermally decomposable products for the formation of a gas phase and to further provide a controlled thermal return. building up the chemical structure of the fed carbonaceous material terialet. The gaseous by-products are removed from the reactor and fed into a condenser, where the condensable gas is recovered as a condenser densat, while recovering the substantially uncondensable phase as a by-product in the form of combustible gas, which is suitably recycled i i ropa QUAUT * 7806112-4 for use in the process and generation of extra force. Reactive tmmwmwmnn fi mwfånæw fi muwmiræuwnwienwh zone, where it is cooled to a lower temperature, at which it can be in contact with the atmosphere without ignition or other disadvantages 'like effects. From the cooling zone, the solid reaction product is transferred. or the coke-like product to a storage room. According to a suitable embodiment of the invention, the coke product is transferred from the stock of a decomposition or malphase, where the coke product further pulverized to the desired size and made suitable for use as a solid particulate fuel, which is suitable for the special type of oven or burner oven, where it is to come to use. It should also be noted that part of the fine-tuning the divided coke product can be transferred from the grinding device to a mixed where the product is mixed with fuel oil to form a liquid shaped suspension, which contains a predetermined proportion of the distributed charcoal in the suspension. The fuel oil thus obtained and the coke suspension is transferred from the mixer to a storage the duct.

.According to the flow chart, the input material may include many different cellulosic materials or mixtures thereof, e.g. cellular loose waste material from forest management and waste from agriculture. For example, one can satisfactorily use in naturally occurring cellulosic materials, e.g. peat, as well as cellular loose waste materials, e.g. sawdust, bark, wood shavings, twigs and wood chips from timber handling and saws as well as various waste materials agricultural materials, such as plant stalks, nutshells, chaff and similar nande.

The fed material can before introduction into the autoclave possibly undergoing a pre-treatment, which may include a removal excess water to reduce the residual moisture content of the to a level that facilitates handling, as well as to reduce the amount of moisture that must be removed subsequently pQÜR QÜÅÜW 7806112-4 the reaction step. Since essentially all the moisture in the input the material has been removed during the treatment in the autoclave, is one such pretreatment is usually not necessary for most waste materials from agriculture and forestry. The pretreatment may further comprise one decomposition, e.g. tearing of the fed material, so that its particle size is reduced depending on the type of material a value, which facilitates handling and processing. Decomposition may also include appropriate division or screening for removal of excessive particles, which can be subjected to renewal decomposition.

The starting material is fed with or without pre-treatment thereafter to the inlet end of a reactor, where the material is subjected to a temperature of at least 400 ° C and a pressure of at least 7. 105 Pa for a predetermined time for controlled thermal restructuring material for the purpose of effecting a conversion of as well as some of its volatile organic constituents as well as a thermal conversion of the products therein to gas phase, which is discharged from the reactor and is conveniently passed through a condenser for separation and recovery of the condensable phase, which contains valuable chemical by-product ingredients. The essentially uncon- condensable gas phase is diverted from the condenser and can advantageously be used used as gaseous fuel for heating the reactor and for generating extra force for carrying out the process, wherein the surplus energy becomes available for sale on the market. Although temperatures of at least about 400 ° C are desirable during the autoclave treatment, temperatures are about 53700 att preferred due to the increased degree of evaporation and thermal restructuring of the starting material in order to achieve higher fixed carbon value, thus enabling shorter residence times in auto- the clef and the improved efficiency of the process is obtained. Tempera- the rate of the autoclave reaction can be increased up to 64806 and temperatures above this value are usually less desirable due to of an excessive ratio of non-condensable gases to solid prepared coke product. Particularly satisfactory results have pooR QUALITY ___ 7806112-4 obtained using temperatures between 537 and 64806 at pressure_from approx. 7. 105 - 21. 105 Pa. The maximum useful the pressure can be as high as about 23.1. 105 Pa. Press this value is usually less than desirable due to increased production costs for the pressure vessels, which must be able to withstand pressure of this size, and the lack of any noticeable advantage at such high pressure in addition to those obtained at the lower pressure levels of approx 21 _ 106 Pa.

The residence time of the starting material in the autoclave can vary depending on the particular relationship between temperature, pressure and time, which is controlled by the parameters to be specified below to achieve substantially complete evaporation of the moisture content and stripping of some of the volatile organic constituents and a controlled thermal restructuring of the cellulosic the starting material.

The thermal restructuring is not fully explored, however it should consist of two or more simultaneous chemical reactions, which occurs between the pyrolysis products and the gases present in the interior of the cellular structure of the cellulosic starting material rialet. The end effect of these restructuring reactions is changes in the chemical properties, resulting in an increase in hydrocarbon ratio, as well as a reduction in the sulfur and oxygen content during the measurement in the final analysis of the coke product. During autoclave the action also involves a controlled degree of thermal restructuring and / or degradation of the chemical structure accompanied by an ring of additional gas components, which are also introduced into the gas phase.

The required residence time in the reactor decreases when the temperature temperature and pressure increase in the autoclave, while prolonged holding time is required, when using lower temperatures and pressures.

Usually the residence time should be between about 15 minutes and 1 hour at temperatures between about 482 and 648 ° C at pressures between about 7. 105 and 21. 105 Pa. Beneficial results are also obtained with some material using temperature and pressure in the upper range of the permissible values using such a short residence time as about 5 min, even if residence times exceeding 1 hour can also come to use. Usually provides the use of the residence time * 7806112-4 in more than 1 hour no significant benefits other than those obtained read at residence times of about 15 minutes to 1 hour and the through reduced the capacity and efficiency of the procedure at use of such long residence times becomes less desirable economic reasons.

The establishment of pressure in the interior of the autoclave is carried out preferably under the control of the amount of cellulose fed starting material in relation to the internal volume of the autoclave in view on the moisture content of the fed material, so that when heated of this to the higher temperature the formation of the gas phase, which consists of superheated steam and volatile organic compounds, causes a pressure increase in the autoclave within the desired pressure range. If desired additional pressure can be achieved in the autoclave by introducing non oxidizing or reducing gases under pressure in the interior of the the clavicle as well as of steam under pressure.

At the end of the treatment in the autoclave, according to an form of the invention the autoclaves are cooled either by means of cooling or using a coolant, e.g. cold water, to a temperature lower than that at which it is present in the autoclave worked solid coke product can be brought into contact with air without adverse effects. Usually it is appropriate with a cooling off the autoclave to a temperature below about 15000. A cooling in the the claw to near 10000 or lower in the presence of the gas phase is usually less desirable due to the condensation of the gas water phase, which moistens the coke product and increases its moisture content. content and thus lowers its calorific value. Conveniently, cooling after the gas phase has been diverted, in order to prevent them volatile organic constituents, including relatively heavy ones hydrocarbon fractions and tar, to be condensed and precipitated on the surfaces and in the interior of pores in the coke structure.

The processed coke product usually has a matte-black finish. vision and porous structure and a residual moisture content between about 1 and 5 weight percent. pOOR QUPJ-ÄTY. 7806ll2 ~ 4 According to a suitable embodiment of the method according to the invention after completion of processing in the autoclave remaining overpressure in the autoclave at the operating temperature of the autoclave, and hydrocarbons the constituents are recovered by condensation and the organic inconsistencies Densitable gaseous constituents are recovered as a by-product in form of combustible gas. In this mode only one minor is affected amount of the precipitated volatile organic constituents on the coke similar product. The coke-like product thus prepared is nevertheless characterized by a thermally transformed structure with improved calorific value.

It should also be noted that a coating procedure in two steps can be performed in an autoclave, the gas phase being released from the autoclave, when it is still at a high temperature, is transferred to a second autoclave chamber, in which the fed material, which to be processed, used as a coolant for condensation of tar and oil in the gas phase.

The cooled, solid, coke-like product is transferred from the cooling zone in accordance with the flow chart to a repository for this product, from which it can be packaged and sold in containers or in loose form or further treated by being subjected to an appropriate disintegration or grinding. For breakdown of any agglomerates, which may be formed during autoclaving, as well as for further decomposition of the product into the desired average particle size. The degree of decomposition of the coke similar product varies depending on the intended use and the special burner construction, which will be used for the combustion of the fuel as a powdered solid fuel.

If the coke-like product is to be used in combustion drug constructions, e.g. of the kind used for incineration of pulverized coal and similar fuels, it is appropriate that use a particle size lower than about 0.295 mm mesh size and suitable I? C) ç? E & çëåjzåäálgfärs 7806112-4 less than about 0.074 mm mesh size. About the coke-like product may be used in an automatic furnace firing equipment a larger particle size can be used with satisfactory positive results.

Regardless of the particle size, the coke product is a valuable fully solid fuel and can be used directly in such form, or in admixture with other common fuels. The coke product is characterized by the fact that it has a very low sulfur content, usually less than 1% by weight and in fact mostly between about 0.2 and 0.06% by weight cent sulfur. In addition, the coke product is characterized by very low ash content, usually less than about 5% and down to about 1% or less.

Some agricultural waste products, e.g. stalks, gives one coke product with up to 20% ash and less than 1% sulfur. Like one examples can be mentioned that the coke product has a calorific value in the area menar »aa 25.6. 106 and 34.9. 105 a / kg.

Due to the extremely low sulfur and ash content of the coke similar product, it can be advantageously used for mixing in high sulfur fuels for the production of a fuel mixture with significantly lower average sulfur content and in accordance with permissible values according to official regulations and local regulations looks. Although the finely divided coke product can be mixed with advantage with powdered solid fuels, e.g. different types of bituminous coal and anthracite, very advantageous results can be obtained in mixing with fuel oils for the purpose of producing a liquid suspension, which contains 1 - 50% by weight of coke. The maximum amount of coke, which can be incorporated into the fuel oil, determined taking into account it increased the viscosity of the suspension as the concentration of powdered coke is increased. Usually, the upper limit for coke the concentration at the limit at which a suspension is required viscosity to be pumpable and what viscosity allows atomization of the suspension in the different types of 7806112-4 league burner nozzles. Although suspension concentrations with such low content which about 1% by weight of coke is very well conceivable, should be so low concentrations do not significantly improve the benefits that can be achieved by the addition of low-sulfur and low-ash ash containing coke products and usually the concentration should be at least about 25-50 weight percent be preferred. At concentrations of about 50 wt. cents will be the average sulfur content of the suspension mixture about half the concentration in the fuel used and this enables the use of many different high sulfur fuel oils for the production of acceptable fuel oil suspensions mixtures; which meet the requirements of state and municipal stämmel $ er.het regarding the sulfur content.

It has been shown that a mixture of finely divided coke with a grain size lower than about 0.104 mm mesh size and preferably a article size, where 80% is less than about 0.074 mm mesh size, gives a relatively stable suspension at concentrations as high as 50% coke and 50% fuel oil, without the need to use any larger ones amounts of additional additives to make the suspension mixture stable. Usually no additional suspending agents are required for ordinary bituminous carbon and anthracite containing suspensions mixtures. Consequently, significant simplification is obtained at the formation of suspension and a reduction in its costs the final mixture by means of the present invention.

In the following, the invention will be further explained by means of some specific examples. These examples are for reference only illustrate the invention and not to limit it.

Pooa QUALITY 7806112-4 11 Example 1 A ceïiuiosahaïtigt starting material, containing 59.5 g of a mixture of oak and pine (dry wood) was placed in a test reactor together with 23.4 g of water. The wood had the shape of a rectangular , chips approx. 6 x 12 mm with a nominal length of approx. 20 cm.

The test reactor system consisted of a cylindrical chamber of stainless steel. free standing with an inner diameter of 35 mm and a length of about 30 cm, viiket gives a totaï voïym of 295 cm3. The reactor is equipped with a conductor, which is connected to a water-cooled condenser and a water-cooled condenser displacing gas coefficient. A pressure gauge of 35 x 105 Pa is used connected to the reactor for continuous pressure monitoring and a K-type mokors are encapsulated in a käiïa in the reactor for continuousïig temperature monitoring. The system includes a conical, pointed height pressure valves in the line between the reactor and the gas condenser in purpose allowing the gas phase to escape from the reactor to maintain it desired pressure in the reactor chamber Once the reactor has been fed and closed, it is placed on the horizon. teiit ïäge in a hot muffle oven. After 5 minutes, the pressure reached the reactor to 10.5 x 105 Pa, and as indicated by the thermocouple the temperature went to 295 ° C. At this point, the opening the valve slightly and a sufficient amount of gas was drained from the condenser to keep the pressure in the reactor substantially constant at , 5 x 105 Pa. During the next five-minute period e11er in total , ..__._____, ________ aa oss * fi ofšïf fi í 7806112-4 12 minutes after placing the reactor in the muffle furnace the temperature in the reactor as indicated by the thermocouple to 55506.

The reactor was then removed from the furnace and allowed to cool to approx 95 ° C. _ A solid coke product weighing 18.9 g was obtained from the reactor and 20 cm 3 of liquid were obtained in the condenser. The gas produced was in excess in addition to the capacity of the collection bottle, which had a volume of 7800 cm3.

A visual inspection of the solid coke product showed that .this was black and had a honeycomb structure, which in a prominent way corresponded to the original structure of the cellulosic the starting material and the appearance of a coked liquid at several places. The original individual chips of oak and pine was added during the reaction, whereby the solid coke product was obtained in the form of a single cylinder with a diameter which was smaller than the the diameter of the drying chamber.

The recovered gas phase burned with a pale blue flame, which is typical for mixtures between hydrogen, carbon monoxide and methanol. An analysis of the solid product gave the following results. '7806112-4 13 Moisture by weight 3.93 Moisturizing substances weight percent 8.47 8.82 Ash weight percentage 1.09 1.13 Fixed ko1 weight percentage 86.5 90.1 calorific value .J / kg 33.3. 106 34.7. 106 Chemical analysis C weight percent 88.8 92.4 H weight percent 2.06 2.14 S weight percentage 0.12 0.12 N weight percent 0.18 0.19 0% by weight 3.82 4.02 _ _ v - .--. ___.......___._.___ POQR Q 7806112-4 14 Example 2 100 g of Canadian peat (spagnum peat) was placed in sample samples. tower in the manner described above and this reactor was equipped with a steam and water-cooled capacitor. An analysis of the starting material showed a moisture content of 75% by weight.

After feeding the reactor, it was placed in a horizontal position in a hot muffle oven as described above and after 11 minutes the reactor pressure increased to 11.6 x 105 Pa and the internal the temperature was indicated on the thermocouple to 26506. at this time the outlet valve was opened slightly and a sufficient amount of gas was drained from the reactor through the condenser system for the pressure to pass substantially constant at 10.5 x 105 Pa.

After a further 23 minutes of heating e11er totait 34 mi- minutes after the reactor had been placed in the socket furnace, amounted to the reactor temperature to 54,400. The reactor was then removed from the furnace and the high pressure valve were opened and the whole gas phase was allowed to flow out. ma, ti11s the reactor chamber reached atmospheric pressure. The valve was closed then and the reactor was allowed to cool to room temperature.

At the end of the experiment, the vapor-heated condenser was contained 74 g of liquid, while the water-cooled condenser contained 5 g liquid, and 4.25 liters of non-condensable gas were collected in the gas collector. The the solid product from the coke reaction comprised 6.99 g, as in visue11 survey was found to consist of a brittle black, solid product which on oxidation left 0.256 g of ash.

An analysis of the collected gas, which burned on ignition with blue eye, showed the following composition: íßßššfquamxmt 7806112-4 Analysis of recovered gas Uustånu§gg¿ HolprucenL Weight 4.9b v fl utun 0.21 » Acid 1.25 Sulfur hydrogen 0.00 Argon 0.11 Carbon dioxide 52.51 Methane 19.24 Ethane 2.13 Ethylene 0.12 Prdpan 0.29 Propylene 0.14 Isobutane 0.02 n ~ butane 0.05 Butane 0.03 Isopantane 0.01 n-Pantan 0.01 Puntan 0.02 Haxan 0.00 Haptan 0.05 Benzene 0.36 Uktan 0.00 ïoluen 0.09 Nonan 0.00 Xylene 0.00 Nitrogen 14.44 , Kulmonuxiu 3.95 BTU / Scï 0 299.1 mwwwwmwwíyvè POOR QÜÅLWYW ' 0 7806112-4 16 Example 3 The test described in Example 21 was repeated using use of 173 g of the same kind of peat and using ma equipment. The reactor pressure was 8 minutes, after that the reactor was placed in the muffle furnace to 10.5 x 105 Pa and the temperature clean in the reactor chamber amounted to 23200. After another 21 minutes residence time at this temperature or a total of 29 minutes after the start of the heating cycle, the temperature in the reactor increased to 54,000 and the pressure was maintained constant at 10.5 x 105 Pa by outflow of the gas phase to the condenser system.

A total of 58 cm3 of dark brown liquid was collected in the steam heated condenser, while 63 cm3 of yellow water collected in the water-cooled condenser. A total of 11.2 l of gas collected in the gas collection system. A solid coke product in a variety of 19.2 g and similar to that of Example 2 could be recovered. The gas burned after ignition with a blue flame in the same way as in the example 2.

The coke product obtained contained 0.41% by weight of moisture and has an approximate and final composition on a dry basis such as is shown in the following table. 7806112-4 17 Analysis, original peat material and coke product Approximate analysis Original peat- Solid coke- weight percent material product Volatile constituents 77.5 6.34 cAska 1.22 4.40 Solid carbon 21.3 89.3 Higher calorific value J / kg 20.3. 105 33.7. 105 Final analysis weight percent C 51.8 90.7 H 3.14 3.35 S 0.15 0.14 N 0.61 0.83 0 43.0 0.61 The solid coke product on a moisture-free base was a clear proof of that an improvement of the calorific value in relation to the input material the material of 66% and it consists of a low-sulfur solid fuel of high quality and with low ash content. The product is suitable for grinding to a particle size of about 0.074 mm mesh well for mixing with residual fuel oils with a high sulfur content for the production of a oil of suspension type and with moderately low sulfur content.

A fuel oil suspension was prepared using it finely ground coke product, which had been produced from peat by mixture of equal amounts by weight of the coke product and a residual ', fuel oil, which contained 1% sulfur. A suspension with the coke particles in fuel oil_erhblTs fi by adding the powdered coke p : Boa W * 7soa112-4 18 the product to fuel oil while stirring by means of a powerful mixer.

The coke product was added in such an amount as to obtain a concentration of about 40% by weight based on the entire suspension.

The fuel oil suspension thus obtained had an average net sulfur content of 0.66%, which made it suitable for use as a fuel in public facilities for the generation of electricity and in in accordance with the authorities' requirements with regard to the maximum sulfur content.

The resulting suspension has previously been found to remain substantially stable, the coke particles remaining substantially uniformly suspended. without the use of additional suspension and / or dispersion substances.

Example 4 A starting material of waste products from forestry and extensive conifer bark in an amount of 51.76 g is fed into a reactor of the kind described above according to Example 2. After seven minutes the pressure reached 10.5 x 105 Pa and the gas was diverted for the purpose of maintain constant pressure. The temperature in the reactor was 28300. After a residence time of another 13 minutes amounted the temperature in the reactor to 48200 and the pressure was mainly maintained constant at about 10.5 x 105 Pa by discharging gas to the con- densorn. A solid coke product was obtained in an amount of 17.9 g. 15.8 g of liquid were recovered. The vapor condensation product consisted of 5.3 ml of yellow liquid with 0.6 ml tar material at the surface. The water condensation product consisted of 10.5 ml clear liquid with traces of oil. The liquid from both the condensers were combined and 14.6 ml of water separated. 0.254 g of hexane-soluble tar was recovered and 0.28 g of benzene-soluble tar was extracted. Approximately 9000 cm3 of non-condensable gas was recovered.

The mixture and fuel value of the solid coke product and the composition of the non-condensable gas phase is shown in the following tables. 7806112-4 Solid product composition and fuel value Elevated solids (kg / kg feed) 0.346 Humidity percentage Approximate analysis (moisture-free) Moist substances,% Fast koï,% Ash,% S1ut1ig analysis (moisture free) C,% HRS, % S,% N,% 0,% Calorific value BTU / Ib J / RQ 0.27% 11,042 84.09% 4.87% 88.58% 2.71% 0.06% 1.36% 2.42% 33.2. 1o6 7806112-40 Composition of the gas product Voïym forward gas (1 kg amount fed) (SGF / tonne) Average moïvikt Calorific value (J / m3) (BTU / scF) San composition, mole percent (moisture free) H2 CH4 CO C2's C02 C3's C4's C5'S C5's Example 5 180.4 (5784) 31.9 18.8 _ 106 (as) , 87% 29.32% 7.55% 4.65% 50.19% 0.99% 0.47% 0.26% 0.40% An experiment in the reactor equipment described with Referring to Example 2, was repeated using 51.8 g ceiïulosahaitigt starting material, which consisted of iantbruksavfaïï i in the form of steaks from bomuïispiantor and fröskaï. Reactor pressure reached the value of 10.5 x 105 Pa within six minutes after application 7806112-4 21 in the muffeiugien at an internal reactor temperature of 21700. At this At that time, the valve was opened and the gas phase was allowed to escape, so that the reaction the tort pressure remained essentially constant at about 10.5 x 105 Pa.

After an additional 17 minutes of heating in the muffle furnace, the temperature the temperature to 541 ° C for a total reaction period of 23 minutes and gas was continuously allowed to leak out, so that the pressure was raised constantly at 10.5 x 105 Pa. At the end of this time period, the reactor was taken out from the furnace and the pressure is aviastas to 11 atmospheric pressures. The total the recovered gas amounted to 11240 cm3. Solid product increased to tait in an amount of 16.1 g and tar with 0.6 g.

The composition and calorific value of the solid coke product and the composition of the uncondensable gas phase are shown in the following tables: 7806112-4 22 The composition and fuel value of the solid product Solid product (kg / kg quantity fed) Fukthaït Approximate analysis (moisture free) Volatiles,% Fast koï,% Ash,% Silicone analysis (moisture free) C,% hrs S, N 0 b fi BQivQhQ IN Calorific value BTU / lb J / K9 0.310 1.58% l7.45% 62.00% , 55% 72.28% 2.62% 0.69% 1.20% 2.66% 11510 26.3. 106 gvaai " 23 Composition of gas produced Volume of gas produced (1 kg starting material) (SCF / ton) Average molecular weight Calorific value (J / mï) (BTU / SCF) Composition mole percent (moisture free) H2 CH4 CO C2'5 C02 C3'5 C4's C5'S C6 | S Example 6 7806112-4 217.0 (6966) 29.2 19.9. 106 (sams) , 30% 34,442 3.66% 4.01% 44.97% 1.40% 0.87% 0.18% 0.17% An amount of 60 g of wood chips and 15 cm 3 of water was placed in one experimental reactor. The test reactor system consisted of a cylindrical one stainless steel sleeves with a diameter of 31.75 mm and a length of 343 mm, giving a volume of 267 cm3. The reactor was provided with a pipe, which was connected to a water-cooled condenser and a water-displacing gas collector. A meter for pressure up to 35 x 105 Pa was connected to the reactor for continuous modern pressure monitoring and a type K thermal cross was connected in the source of the reactor system for continuous temperature monitoring. e * 'X reach) os » 420% 7806112-4 24 The system included a high pressure valve with a conical tip in the between the reactor and the gas condenser in order to allow the gas phase leak out of the reactor to maintain the desired the pressure in the reaction chamber.

Thereafter, the filled and closed reactor was placed in the horizon. tented position in a hot muffle furnace. After a time of nine minutes amounted the reactor pressure to 12.25 x 105 Pa and the temperature was, which was indicated on the thermocouple, to 24900. At this time the reactor valve was slightly and sufficient gas was released through the condenser system to maintain the pressure in the reactor substantially constant at 10.5 x 105 Pa. During the following 21 minutes, or after a total of 30 minutes, the reactor was placed in a muffle furnace with reactor temperature 54000, after which the reactor was removed from the furnace and the pressure were lowered to 0.105 x 105 Pa, after which the reactor got cold in the air.

A coke product was obtained in an amount of 14.6 g together with 11,200 cm3 of non-condensable combustible gas, which meant a total 24% solids recovery. The solid coke product was distinguished of a coke-like appearance and it had a brittle porous structure.

The recovered non-condensable fuel gas burned with a flame with yellow tip. IN The solid product was ground in a laboratory-sized ball mill for ten minutes and then sieved through a sieve with a mesh size of 0.074 mm. The fraction exceeding this mesh size was ground into ten minutes and re-aimed. The fraction which is still step 0.074 mm mesh size, ground for another five minutes, after 12.75 g passed through a mesh size of 0.147 mm and 8.69 g passed through a mesh width of 0.074 mm. 12.75 g ground solid product 7 was added to 8.52 g of Bunker C fuel oil to form a solid pasta, which contained 60% solid product. Additional oil was added to the solid paste, until the voids appeared to be filled. at this Poon Quamï 7806112-4 At the time, the mixture contained 56% solid product. Additional oil was added until the mixture was found to run at room temperature.

This mixture contained 52% solids.

A second batch of suspension on oil and solid was prepared of a similar solid coke product, which had been made of wood, which had been ground in a ball mill and sieved through a sieve of mesh size 0.074 mm. When this solid coke product was mixed with true weight Bunker C fuel oil, the resulting suspension was found to be a non-Newtonian liquid with a viscosity of 20500 cp at a temperature of 93,306 when measured in a Brookfield viscometer at 6 rpm and 12100 cp at 60 rpm.

In the specific examples above, the autoclave consisted of one laboratory scale model for a batch working autoclave with it ground material. It should be noted that autoclaves of any kind preferably known type in this technique can satisfactorily be used, if they can withstand the specified high temperatures and pressures required in the process of the invention.

It should be noted that although the description above in the first hand has focused on batch-working autoclaves, including continuous working autoclaves can be used for implementation of the process according to the invention, wherein the starting material normally fed at the inlet end of the reactor through a suitable pressure lock feeding device or valve and that the coke product is normally removed from the cooling zone of the reactor by a similar pressure lock supply device or valve. Although the device above has been described in conjunction with some embodiments which are well suited for achieving the stated parts and progress, can be implemented within the framework of subsequent requirements many modifications. fr: 2003 QÜNÅ to fl *

Claims (10)

7806112-4 26 P A T E N T K R A V 1. A process for converting cellulosic starting material to a solid usable fuel, characterized in that the cellulosic starting material is fed into an autoclave, that this material is heated in the autoclave to a temperature of 399 and 67 ° C. a pressure of at least 7 x 105 Pa for a sufficient time to effect a conversion of moisture and at least one of the moist organic constituents of the starting material into a gas phase and a thermal de-restructuring of the chemical structure of the material and a change in its chemical composition in order to provide a solid reaction product and the resulting reaction product is then cooled and evaporated as a worked-up solid coke-like product. 2. A method according to claim 1, characterized in that the heating of the starting material is carried out at a temperature of about 418 - 67700. 3. A method according to claim 1, characterized in that the heating of the starting material is carried out at a temperature of about 538 - 64900. 4. A method according to any one of the preceding claims, characterized in that the heating of the starting material is carried out at a pressure of a mean of 7 x 105 and 23.1 x 105 Pa. 5. A method according to any one of claims 1 - 3, characterized in that the heating of the starting material is carried out at a pressure of about 10.5 x 105 and 12 x 106 Pa. 6. A process according to any one of the preceding claims, characterized in that the gas phase is recovered from the autoclave and that at least one of the condensable constituents in the gas phase is extracted and that the extracted condensable dough and the remaining, non-condensable are recovered. deien. soon ouáišši * 7806112-4 27 A method according to any one of the preceding claims, characterized in that the recovered solid coke product is decomposed into the desired particle history. A method according to any one of the preceding claims, characterized in that the solid coke product is decomposed into a particle size less than about 0.295 mm mesh size, the finely divided coke product is mixed with fuel oil, whereby a fuel oil suspension is obtained in liquid form, which contains between 1 and 50% by weight of coke product based on the total weight of the mixture. 9. A method according to claim 8, characterized in that the solid coke product is decomposed so as to obtain particles with a size preferably less than 0.074 mm mesh size. 10. A method according to any one of the preceding claims, characterized in that the starting material consists of cellulosic material selected from the group consisting of peat, waste products from agriculture, waste products from forestry and mixtures thereof.