FI71336C - FOERFARANDE FOER OMVANDLING AV CELLULOSAHALTIGA UTGAONGSMATERIAL TILL KOKSARTAT BRAENSLE ELLER BRAENSLESUSPENSION - Google Patents

Description

ANNOUNCEMENT '.

• $ 81? ™ UTLÄGGNINGSSKRIFT / iOO Ό C (45) Tr [~ s; · c ·} -1 '”- ·· -; '' ·; 'S ί ^ ^ (51) Kv.lk. * / Lnt.CI. * C 10 L 9/08 // C 10 B 53/02 (21) Pttenttlhakemu * - Patentanöknlng 781 462 (22) Hakemlspllvi - Ansöknlngsdag 09.05.78 (FI) (23) Alkup & lvl— Glltighetsdag 09.05-78 (41) Has become public - Bllvit offentllg 08.03.79

National Board of Patents and Registration. date of hearing. -

Patent and registration authorities Ansökan utlagd och utl.skriften published 09.09.86 (86) Kv. application - Int. ansökan (32) (33) (31) Privilege claimed — Begärd priority 07 · 09 · 77 USA (US) 8313 ^ 3 (71) (72) Edward Koppelman, kk2k Bergamo Drive, Encino, California 91316, USA (US) ( 7 * 0 Oy Koi ster Ab (5 **) Method for converting cellulosic feedstocks into coke-like fuel or fuel suspension - Förfarande för omvandling av cellulosahaltiga utgängsmateria 1 account kokartat bränsle eller bränslesuspens ion (6l)

The present application is a supplementary patent application to Finnish patent application No. 771,990 (patent 61202). The said Finnish application 771 990 describes a process for refining lignite-type coal species, including lignite, lignite and chip bituminous coal, to convert them to a more suitable form for use as a solid fuel, resulting in heat conversion by producing a refined carbonaceous product that is stable and resistant to erosion. higher in calorific value, approaching the value of bituminous coal. As a result of such a method, large stocks of lignite-type coal are converted into useful fuel, which represents a potential solution to the current energy crisis.

2 71336

In addition to large stocks of lignite-type coal, large quantities of cellulosic-type materials are produced each year, as well as naturally occurring materials such as peat, as well as timber from sawmilling and agricultural waste available in a form unsuitable for efficient commercial use. Cellulosic waste materials such as sawdust, bark, wood waste, twigs and wood chips from wood treatment as well as various agricultural waste materials such as cotton mill stalks and the like have hitherto posed a waste management problem. Similarly, there has long been a need for a method of converting such cellulosic materials into valuable fuel products, not only providing a potential solution to fuel shortages and the current energy crisis, but also eliminating the cost of disposing of such wastes.

In addition to the problems mentioned above, in the U.S., federal and state regulations enacted by the Environmental Protection Agency (EPÄ) as well as the State of California have set relatively strict limits on the amount of sulfur in heating oils that can be burned in public facilities to generate electricity and steam. Current Environmental Protection Agency regulations allow a maximum sulfur content of 0.7% by weight in heating oil, while the state of California has enacted regulations that limit the maximum sulfur content to 0.3% in certain areas. In order to comply with these regulations, it has hitherto been necessary to mix heating oils with a relatively high sulfur content with low-sulfur heating oils imported from abroad in order to obtain a mixture with a permitted sulfur content. The purchase price of such foreign low-sulfur heating oils not only makes this practice more expensive, but also increases dependence on foreign oil suppliers. The above problem is solved in the context of the present invention by providing an extremely low sulfur and low ash coke product which, after grinding, can be mixed with high sulfur heating oils to provide a suspension that meets the requirements for sulfur content regulations.

3,71336

The invention thus relates to a process for the thermal conversion of cellulosic feedstocks, such as peat, agricultural waste, forestry waste and mixtures thereof, into coke-like fuel or fuel suspension under pressure. The process is characterized in that the second cellulosic feedstock is fed to an autoclave and heated to a temperature of about 400-680 ° C at a pressure of at least about 6900 kPa for a time such that moisture and at least some of the volatile organic constituents change into the gas phase and change chemical structure. partially thermally and its chemical composition changes, after which the solid product thus obtained is cooled and the processed solid coke product is recovered and possibly comminuted to a particle size of less than 0.33 mm and suspended in liquid fuel in an amount of about 1 to 50% by weight based on the weight of the suspension.

According to one embodiment of the present invention, the autoclaved coke product is comminuted to a particle size of less than C, 33 mm and preferably to a particle size of less than 0.07 U mm, after which it is mixed with a high sulfur heating oil in an amount ranging from as low as about 1%. as high as about 50% by weight of the total weight of the mixture forming the suspension. The properties of the comminuted coke allow the formation of stable suspensions without the addition of any chemical suspending additive, and the low sulfur content, on the order of only about 0.1%, and the ash content of only about 1-4%, provide a satisfactory fuel mixture.

Additional advantages and advantages of the present invention will become apparent upon reading the description of the preferred embodiments in connection with the accompanying drawings and examples.

The drawing comprises a schematic flow diagram of the process steps in connection with a preferred embodiment of the present invention.

The sequence of the different steps of the process according to the invention is schematically illustrated in the flow chart in the drawing. As shown, the cellulosic feedstock, or a mixture of different cellulosic feedstocks, is subjected to a pretreatment step in which the feedstock is subjected to ...

"71336 is subjected to a suitable cutting, grinding and screening treatment to obtain a feed mass of the desired particle size, after which the comminuted feed material is fed to a high temperature and high pressure reactor to be subjected to high temperature The gaseous by-products are removed from the reactor and taken to a condenser from which the condensable phase is collected as condensate, while the substantially non-condensable phase is recovered as a by-product fuel gas which can be advantageously recycled to the reactor process and power generation. from the reaction zone to a cooling zone where it is cooled to a lower temperature where it can be introduced into the atmosphere n, without ignition or other adverse effects. From the cooling zone, the solid reaction product or coke product is transferred to storage. According to a preferred embodiment of the present invention, the coke product is transferred from storage to a grinding and comminution step where the coke product is further ground to the desired size, making it suitable for use as a comminuted solid fuel compatible with the furnace type and burner design used. It is also possible that a portion of the comminuted coke product may be transferred from the grinder to a mixer where it is mixed with the fuel oil fed to form a suspension containing a controlled amount of comminuted wood coke as a suspension. The resulting fuel oil and dual suspension product are transferred from the mixer to the product warehouse.

According to the flow chart, the feed material may comprise any variety of cellulosic material or mixtures thereof, including waste cellulosic materials obtained from sawing steps and agricultural waste. For example, naturally occurring cellulosic materials such as peat can be used as well as waste cellulosic materials such as sawdust, bark, wood waste, twigs and chips from log treatment and sawing steps, as well as various agricultural waste materials such as cotton mills, corn husks and the like.

The feed material is optionally introduced, prior to transfer to the autoclave, to a pretreatment step, which may include the step of subjecting the material to a preparative treatment to extract excess water to reduce residual moisture to a level that facilitates treatment, as well as reducing moisture in the next reaction step. Since substantially all of the moisture in the feedstock is removed in the autoclaving step, such a pretreatment step is not usually necessary for most agricultural and wood processing waste materials. The pretreatment step may further comprise introducing the feed material into a suitable cutting or comminution step, where its particle size, depending on the nature of the feed material, is reduced to a size that facilitates handling and processing. The step of grinding may further comprise suitable grading or screening steps to separate the oversized particles for recirculation through the cutting device.

The feed material is introduced, with or without the optional pretreatment step, then to the feed end of the reactor, where it is subjected to a temperature of at least about 100 ° C and at least n.

A pressure of 6,900 kPa for a controlled period of time to bring about a controlled change in its chemical structure by heat, and to change its moisture and some of its volatile organic compounds as well as its heat transfer products in a gas phase In which is removed from the reactor and preferably passed through a condenser to separate and recover the phase contains valuable chemical by-product components. The substantially non-condensable gas phase removed from the condenser can be advantageously used as a gaseous fuel to heat the reactor and generate additional power to operate the process and the excess is available for commercial sale.

Although at least about 400 ° C temperatures are required during the autoclave reaction, temperatures of about 5 <+ 0 ° C are preferred due to the increased rate of evaporation of the feed material and thermal change of the structure to produce a higher solid carbon value, thus providing a shorter autoclave processing time and improved efficiency. reading. The temperature of the autoclave reaction may reach as high as about 680 ° C, but temperatures above this level are usually undesirable due to an excessive amount of non-condensable gases in the solid refined coke product. Particularly satisfactory results have been obtained using temperatures in the range of about 5U0 -n. 650 ° C at pressures in the range of about 6 9ΡΠ to 70 700 kPa. The maximum pressure used can be as high as about 27,770 kPa. In general, pressures above 22,700 kPa are undesirable due to the increased manufacturing cost of pressure vessels that can withstand pressures of this magnitude, and because no significant benefit is achieved at such elevated pressures in addition to those achieved at lower pressures of about 20,700 kPa. pressure level.

The processing time of the feed material in the autoclave varies depending on the specific temperature-pressure time ratio controlled by its parameters, as shown below, to achieve substantially complete evaporation of moisture content and evaporation of a few volatile organic ingredients and controlled change in the structure of the cellulosic feed material.

The change in structure by heat is not fully understood, but is believed to consist of two or more simultaneous chemical reactions that occur between the pyrolysis products and the gases present within the cellular structure of the cellulosic feedstock. The net effect of these conversion reactions is changes in chemical properties, resulting in an increase in the carbon / hydrogen ratio and a decrease in the sulfur and oxygen content as measured by the final analysis of the coke product. During the autoclaving phase, there is also a controlled change in the chemical structure and / or decomposition by heat, together with the development of new gaseous components which also enter the gas phase.

The required treatment time in the reactor decreases as the temperature and pressure in the autoclave increase; and conversely, increased processing time is required when lower order temperatures and pressures are used. Generally, treatment times ranging from 7,71336 to 15 hours at temperatures of about M-80 to about 650 ° C and pressures of about 6,900 to 20,700 kPa are sufficient. Advantageous results are also obtained with certain materials using temperatures and pressures close to the upper limit of the allowable ranges, using treatment times as low as about five minutes, while treatment times longer than one hour may also be used. In general, treatment times of more than about one hour do not provide a more significant benefit compared to treatment times of about 15 minutes -n. one hour, and the resulting reduced production and efficiency of the process, together with such excessive processing times, are undesirable from an economic point of view.

The pressurization of the contents of the autoclave can be suitably carried out by controlling the filling amount of the cellulosic feedstock relative to the internal volume of the autoclave and considering the moisture content of the filling so that when heated to elevated temperature, Additional pressurization of the autoclave can be achieved, if desired, by introducing pressurized non-oxidizing or reducing gases into the autoclave, as well as pressurized steam.

At the end of the autoclave step, according to an embodiment of the present invention, the autoclave is allowed to cool by cooling with air or using a cooling liquid such as water to a temperature lower than that at which the solid coke product converted to autoclave can be introduced into the air without adverse effects. Normally, cooling the autoclave to less than 150 ° C is sufficient. Cooling of the autoclave near or below 100 ° C in the presence of a gas phase is generally not desirable due to condensation of the gaseous aqueous phase which wets the coke product, increasing its moisture content and correspondingly lowering its calorific value. Preferably, the cooling step is performed after the gas phase has been removed to prevent condensation and precipitation of volatile organic substances, including relatively heavy hydrocarbon fractions and tars, on the surface and pores of the coke structure.

s 71336

The refined coke product is generally opaque black in appearance and has a porous structure and a residual moisture content in the range of about 1 to about 5% by weight.

According to a preferred embodiment of the invention, the remaining high pressure in the autoclave at the end of the autoclave operation stage is discharged at the operating temperature of the autoclave, and the hydrocarbon particles are recovered by condensation, and the organic non-condensable gaseous parts are recovered as by-product fuel. In this situation, only a small amount of volatile organic matter precipitates in the coke product. However, the coke product thus prepared is characterized by a thermally modified structure which gives it an improved calorific value.

It is also contemplated that a two-stage autoclave and coating step may be performed in which the gas phase released from the autoclave at the same temperature is passed to another autoclave chamber where the feedstock to be treated is used as a coolant to condense tar and oils in the gas phase.

The cooled solid coke product is transferred from the cooling zone according to the flow chart to a coke product depot from which it can be packed and transported in containers or in bulk, or alternatively further processed by subjecting it to suitable cutting or grinding treatment to break up average particle size range. The magnitude of the comminution of the coke product will vary depending on its intended use and the particular type of burner used to effect its combustion as a comminuted solid fuel. For example, if the coke product is used in burner models of the type used to burn pulverized coal and fuels of that type, particle sizes less than about 0.297 mm and less than n.

200 U.S. sieve sizes (0.074 mm loop). Alternatively, if the coke product is used in an automatic furnace feeder, larger particle sizes can be satisfactorily used.

Regardless of the particle size, the coke product forms a valuable solid fuel and can be used directly in that form 9,71336 or as a blend with other conventional fuels. The coke product is characterized by its very low sulfur content, usually less than about 1% by weight, and more usually about 0.2% by weight as low as 0.06% by weight of sulfur. In addition, the coke product is still characterized by its very low ash content, usually less than about 5% by weight as low as about 1% or less by weight. For example, certain feed materials consisting of agricultural waste, such as cotton stalks, give a coke product with up to 20% ash and less than 1% sulfur. Typically, the calorific value of the coke product is in the range of 27,300 to 37,200 kJ / kg.

Due to the extremely low sulfur and ash content of the coke product, it can be advantageously used in blends with other high sulfur fuels to produce the resulting fuel blend with a substantially lower average sulfur content as permitted by the Environmental Protection Agency and other state and local regulations. Although the comminuted coke product can be advantageously mixed with comminuted solid fuels, such as various bituminous and anthracite coals, particularly advantageous results are obtained by mixing it with fuel oils to produce a suspension of as little as 1% up to 50% by weight of coke. The maximum amount of coke combined with liquid fuel oil is determined taking into account the increase in viscosity of the mixture as the concentration of comminuted coke increases. In general, the upper limit of the coke concentration is the level at which the viscosity is sufficient to allow the mixture to be pumped, and at which the mixture is sufficiently distributed through existing types of commercial burner nozzles. Although alloy strengths containing as little as 1% by weight of coke are conceivable, such low levels do not significantly increase the benefit of incorporating low sulfur and ash coke products, instead of at least about 25 to about 50%. % by weight concentrations are preferred. At a level of about 50% by weight, the average sulfur content of the mixture is approximately half that of spent fuel, which allows the use of various high sulfur fuel oils to produce acceptable 10 71 3 36 fuel blends that comply with the Environmental Protection Agency and state and local sulfur regulations.

It has been found that mixtures of comminuted coke with a particle size of less than 0.105 mm and preferably with a particle size of 80% less than 0.074 mm give a relatively stable mixture at concentrations as high as 50% coke and 50% fuel oil, without the need to add substantial amounts of suspending additives to form a stable mixture. Usually, no suspending additives are required when using such a coke product, whereas in the case of conventional bitumens and anthracite coal / oil mixtures, such additives are necessary. Accordingly, the present invention provides a substantially simplified method of preparing the mixture and reducing the cost of the final mixture.

To further illustrate the process of this invention, the following specific examples are provided. It is to be understood that the examples are for illustrative purposes and are not intended to limit the scope of the invention.

Example 1

A cellulosic feed material comprising 59.5 g of a mixture of dry oak and spruce is fed to the test reactor together with 23.4 g of water. The wood to be fed has a cross section of 2 ....

1.6 - 3.2 cm pieces of wood with a nominal length of 20 cm.

The test reactor system comprises a cylindrical chamber of stainless steel with an inner diameter of 34.8 mm and a length of 3 cm of 30 cm, giving a total volume of 292 cm. The reactor is equipped with a connecting line to a water-cooled condenser and a water-displacing gas collector. A 35,000 kPa pressure gauge is connected to the reactor for continuous pressure monitoring, and a K-type thermocouple is placed in the opening in the reactor to continuously monitor the temperature. The system comprises a conical high pressure valve in the line between the reactor and the gas condenser to discharge the gas phase from the reactor in order to maintain the desired pressure in the reactor chamber.

After the reactor is filled and closed, it is placed in a horizontal position in the hot-sleeve furnace. After about five minutes, the reactor pressure is 10,350 kPa and the internal temperature indicated by the thermocouple is 295 ° C. At this point, the outlet valve is opened slightly and sufficient gas is introduced into the condensing system to keep the pressure in the reactor substantially constant at 10,350 kPa. During the next five minute period, or a total of 10 minutes after the reactor was placed in the muffle furnace, the temperature indicated by the thermocouple in the reactor is 555 ° C. The reactor is then removed from the furnace and allowed to cool to about 93 ° C.

The solid coke product, weighing about 18.9 g, is collected from the reaction. . . . . . Approximately 20 cm of liquid is collected from the 3 markets, 3a condenser;

The gas produced exceeds the capacity of the gas collection bottle, which has a volume of 7,800 cm. ·

Visual inspection of the solid coke product shows that it is black in color and has a "waffle-like" structure, which is for the most part similar to the original structure of the cellulosic pulpwood, and has the appearance of a coking liquid at several points. The original individual pieces of oak and spruce have deformed during the reaction process so that the recovered solid coke product is in the form of a single cylinder with a diameter smaller than that of the reaction chamber.

The recovered gas phase burns with a light blue flame typical of mixtures of hydrogen, carbon monoxide and methanol. The analysis of the solid product is as follows:

Moisture (wt%) 3.93

Volatile gases (% by weight 8.47 8.82

Ash (% by weight 1.09 L, 13

Solid carbon (% by weight) 86.5 90, 1 Calorific value, kJ / kg 35 500 37 000 12 71 336

Chemical analysis C (% by weight) 88.8 92, 4 H (% by weight) 2.06 2.14 S (% by weight) 0.12 0.12 N (% by weight) 0.18 0.19 O (% by weight) 3.82 4.02

Example 2 A 100 g charge of Canadian shpagnum peat is added to a test reactor system as previously described in connection with Example 1 equipped with a steam-cooled and water-cooled condenser. Analysis of the feed material shows a moisture content of about 75% by weight.

After filling, the reactor is placed in a horizontal position in a hot sleeve furnace as previously described in connection with Example 1, and after a period of 11 minutes the reactor pressure is 11,400 kPa and the internal temperature indicated by the thermocouple is 375 ° C. At this point, the outlet valve is slightly opened and sufficient gas is released from the reactor through the condenser system to maintain the pressure substantially constant at 10,350 kPa. After a further 23 minutes of additional heating period, or 34 minutes after the reactor was placed in the sleeve furnace, the reactor temperature is 542 ° C. The reactor is then removed from the furnace and a high pressure valve is opened to remove the entire gas phase until there is ambient pressure in the reactor chamber. The valve is then closed and the reactor is allowed to cool to ambient temperature.

At the end of the test, the steam-cooled condenser contains 74 g of liquid, while the water-cooled condenser contains 5 g of liquid, and 4.25 liters of non-condensable gas are obtained from the gas collector. There is 5.99 g of solid coke reaction product which, when visually tared, forms a brittle, black solid product which, on oxidation, gives 0.256 g of ash.

The analysis of the collected gas which, when ignited, burns with a blue flame is as follows:

Analysis of the collected gas

Ingredient Mole%

Hydrogen 4.96

Water 0.24

Oxygen 1.23

Hydrogen sulfide 0.00

Argon 0.11

Carbon dioxide 52.51

Methane 19.24

Ethane 2.13

Ethylene 0.12

Propane 0.29

Propylene 0.14

Isobutane 0.02 N-butane 0.05

Butene 0.03

Isopentane 0.01 N-pentane 0.01

Pentene 0.02

Hexane 0.00

Heptane 0.05

Benzene 0.38

Octane 0.00

Toluene 0.09

Nonane 0.00

Xylene 0.00

Nitrogen 14.44

Carbon monoxide 3.93 3 Calorific value kJ / m 3 400 71 336

Example 3 1 4

The experiment described in Example 2 is repeated using 173 g of the same peat as feed material and the same equipment. Eight minutes after the reactor has been placed in the sleeve furnace, the pressure is 10,350 kPa and the temperature in the reactor chamber is 230 ° C. After an additional treatment time of 21 minutes, or a total of 29 minutes after the start of the heating cycle, the temperature in the reactor is 540 ° C and the pressure is kept substantially constant at 10,350 kPa by allowing the gas phase into the condenser system.

3

A total of 58 cm of dark brown liquid is collected from the steam-cooled condenser, while 63 cm of yellow water is collected from the water-cooled condenser. A total of 11.2 liters of gas is collected from the gas collection system. A solid coke product similar to that obtained in Example 2, comprising 19.2 g, is recovered. Upon ignition, the gas is observed to burn with a blue flame identical to the flame in Example 2.

The recovered solid coke product contains 0.41% by weight of moisture and its approximate final composition (based on dry matter) is shown in the following table:

Analysis, peat feed material and coke product

Approximate ana- Peat feed material Solid coke product lysis by weight%

Volatile matter 77.5 6.34

Ash 1.22 4.40

Solid C 21.3 89.3

Higher calorific value kJ / kg 19,800 36,000

Final analysis% by weight 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 15 71 336

The solid coke product shows, on a moisture-free basis, clear evidence of an improvement in its calorific value of the order of magnitude of 66% over the feedstock and forms a high-quality, low ash and low sulfur solid fuel. The product, when subsequently ground to a particle size of about 0.074 mm, is ideally suited for blending with high sulfur fuel oils to provide a moderately low sulfur fuel oil suspension.

The fuel oil suspension is prepared using a finely ground coke product obtained from peat, mixing the same amounts of coke product and fuel oil with a sulfur content of 1%. A suspension of coke particles in the fuel oil is achieved by adding the comminuted coke material to the fuel oil while mixing with a finely divided mixer. The coke product is added to a concentration of about 40% by weight in the total mass.

The resulting fuel oil suspension has an average net sulfur content of 0.66%, making it suitable for use in public facilities to generate electricity and in accordance with the regulations of the Environmental Protection Agency on the maximum sulfur content. The resulting mass is still found to remain substantially stable with the solid coke particles remaining substantially uniformly suspended without additional suspension or dispersing additives.

Example 4

As a forest waste product, a typical feed material comprising pine and spruce bark, 51.76 g, is added to the reactor system previously described in Example 2. After seven minutes, the pressure reaches 10,350 kPa and gas is released to keep the pressure constant. The temperature in the reactor was 280 ° C. After an additional treatment time of 13 minutes, the temperature in the reactor was 530 ° C and the pressure is kept substantially constant at about 1 0 3 50 kPa by allowing the gas phase into the condenser system. 17.9 g of solid coke product are recovered. 15.8 g of liquid are recovered.

The product of the steam condenser comprises 5.3 ml of a yellow liquid on top of 0.6 ml of tar-like substance. The product of the water condenser ie 71336 comprises 10.5 ml of a clear liquid with a little oil. The liquids from both condensers are combined and 14.6 ml of water are separated. 0.254 g of tars soluble in hexane are recovered. 0.28 g of benzene-soluble tar is recovered. Approximately 9,000 cm of non-condensable gases are recovered. The composition and calorific value of the solid coke product and the composition of the non-condensable gas phase are shown in the following tables:

Solid product composition and calorific value

Solid produced (kg / kg fed)

Humidity 0.27%

Approximate analysis (moisture free)

Volatiles,% 11.04

Solid carbon,% 84.09

Ash,% 4.87

Final analysis (moisture free) C,% 88.58 H,% 2.71 S,% 0.06 N,% 1.36 O,% 2.42

Calorific value kJ / kg 35,500

Conversion of gas product Volume of gas produced liters / kg fed 180.4

Avg. molecular weight 31, 9 Calorific value 3 kJ / m 18 800

Composition mole percent (moisture free) H2 5.87% CHU 29.32% CO 7.55% C2-4.65% CO2 50.19%

Cg- 0.99% 17 71 336 C ^ - 0.47% C5 - 0.26% C6 - 0.40%

Example 5

The experiment using the reactor apparatus previously described in connection with Example 2 is repeated using 51.8 g of cellulose-containing feed material consisting of agricultural waste such as cotton straw and husks. The reactor pressure rose to 10,350 kPa within six minutes of being placed in the sleeve furnace, and the internal temperature of the reactor was 215 ° C. At this point, the valve is opened and the gas phase is released so that the reactor pressure remains substantially constant at about 10,350 kPa. After a further heating of 17 minutes, the temperature in the sleeve furnace is 540 ° C, with a total reaction time of 23 minutes, and the gas is continuously introduced to maintain a pressure of 10,350 kPa. After this time, the reactor is removed from the furnace and the pressure is reduced to ambient atmosphere. The total amount of gas recovered is 11,240 cm. The total amount of solid product is 16.1 g and the total amount of tar recovered is 0.6 g.

The composition and calorific value of the solid coke product and the composition of the non-condensable gas phase are shown in the following tables:

Solid product composition and calorific value

Solid produced (kg / kg fed)

Moisture percentage 1.58

Approximate analysis (moisture free)

Volatiles,% 17.45

Solid carbon,% 62.00

Ash,% 20.55

Final analysis (moisture free) C,% 72.28 H,% 2.62 S,% 0.69 N,% 1.20 O,% 2.66 Calorific value kJ / kg 26 700 18 71 336

Coalition of a gas product

Volume of gas produced liters / kg fed 217.0

Average molecular weight 29.2 Calorific value kJ / m3 20,000

Molar percentage of Coalition (moisture free) H 2 10.30% CH 2 34.44% CO 3.66% C2 4.01% CO2 44.97% C3 1.40% C4 0.87% C5 0.18%

Cg - 0.17%

Example 6 3

A batch comprising 60 g of wood chips and 15 cm of water is added to the experimental reactor. The experimental reactor system comprises a cylindrical chamber of stainless steel with a diameter of 31.6 3 mm and a length of 342 mm, with a volume of 255 cm. The reactor is equipped with a line connected to a water-cooled condenser and a water-displacing gas collector. A 34,500 kPa pressure gauge is connected to the reactor to continuously monitor the pressure, and a K-type thermocouple is installed in the orifice of the reactor system to continuously monitor the temperature. The system includes a conical tip high pressure valve and a gas condenser to mix the gas phase from the reactor to maintain the desired pressure in the reaction chamber.

After the reactor is filled and closed, it is placed in a horizontal position in a hot sleeve furnace. After a period of nine minutes, the reactor pressure is 12,100 kPa and the thermocouple temperature is 249 ° C. At this point, the reactor valve is slightly opened and sufficient gas is passed through the condenser system to maintain the pressure in the reactor substantially constant at 10,350 kPa. For the next 21 minutes, or a total of 30 minutes after the reactor was placed in the muffle furnace, the reactor temperature is 538 ° C, after which the reactor is removed from the furnace, the pressure is reduced to 104 kPa and the reactor is allowed to cool with air.

14.6 g of coke product and 11,200 cm @ 2 of non-condensable combustion gas are recovered, representing a total solids yield of 24%. The solid coke product is characterized by its coke-like appearance and its brittle porous structure. The recovered non-condensable fuel gas burns with a yellow-tipped flame.

The solid product is comminuted on a laboratory-sized ball mill for 10 minutes, then sieved through a 0.074 mm mesh screen. The fraction over 0.074 mm is ground for 10 minutes and sieved again. The fraction over 0.074 mm is comminuted for an additional five minutes, after which 12.75 g passed through a 0.149 mm sieve and 8.69 g through a 0.0074 mm sieve. 12.75 g of comminuted solid product is added to 8.52 g of Bunker C fuel oil to form a rigid paste containing 60% solids. Additional oil is added to the rigid paste until the voids appear to be filled. In this case, the composition contains 56% solids. Additional oil is added until the mixture is seen to flow at room temperature. This composition contained 52% solids.

Another batch of oil-on-solid mass is made from a similar wood solid coke product that was comminuted in a ball mill and screened through a 0.074 mm sieve. When this solid coke product is mixed with the same amount of Bunker C oil, the resulting mass is found to be a non-Newtonian liquid with a viscosity of 2C 500 cP at 93 °, measured on a Brookfield viscometer at 6 rpm and 12,100 cP at 60 k / min. min.

In the specific examples described above, the autoclave was a laboratory-scale batch-operated autoclave.

It should be noted that any type of autoclave known in the art that can withstand the high temperatures and pressures required to operate the process of this invention can also be used satisfactorily. It should also be noted that although the disclosure provided herein has primarily concerned batch-operated autoclaves, continuous autoclaves may also be used in the application of a process in which feed material is continuously introduced to the reactor inlet through a suitable pressure lock feeder or valve arrangement and coke product is continuously removed. from the cooling zone through a similar pressure lock feeder or valve arrangement.

While it will be apparent that the invention described herein is well designed to achieve the stated benefit and advantages, it will be appreciated that the invention may be modified, varied and altered without departing from the spirit thereof.

Claims (8)

A process for converting cellulosic starting materials, such as peat, agricultural waste, forest industry waste and mixtures thereof thermally under pressure into coke fuel or fuel suspension, characterized in that the cellulosic starting material is fed to an autoclave and heated to approx. . 400-680 ° C under a pressure of at least approx. 6900 kPa over such a period of time that the moisture and at least some of the volatile organic constituents contained in the material are converted to gas phase and the chemical structure of the material is partially thermally altered and its chemical composition changed, after which the solid product obtained is cooled and the refined solid coke product is collected and optionally finely divided to a particle size below 0.33 mm and suspended in a liquid fuel in an amount of approx. 1-50% by weight based on the weight of the pension. Process according to Claim 1, characterized in that the starting material is heated in an autoclave to a temperature of approx. 480-690 ° C. 3. A process according to claim 1, characterized in that the starting material is heated in an autoclave at a temperature of approx. 540-650 ° C. Process according to any of the preceding claims, characterized in that the heating is carried out under a pressure of approx. 6 900-22 800 kPa. Process according to any of the preceding claims, characterized in that the heating is carried out under a pressure of approx. 10 350-20 700 kPa. 6. A process according to any of the preceding claims, characterized in that the gas phase is removed from the autoclave, at least a portion of the customizable constituents containing the gas phase is extracted and the customizable portion and non-separable portion are recovered. Process according to any of the preceding claims, characterized in that the solid coke product is fine-tuned.