JPS5823882A - Fine particulate carbonaceous spherule containing oil and its preparation - Google Patents

Abstract

PURPOSE:To obtain fine particulate pitch spherules, handleable in the same manner as a liquid, and convenient for transportation and storage effectively, by mixing and finely powdering a pitch, e.g. petroleum or coal, under specific conditions, and quenching the particulate pitch. CONSTITUTION:A pitch, e.g. petroleum or coal, as a raw material pitch is having a softening point of 60-220 deg.C and a fixed carbon content of 40-75wt% as a raw material pitch kept at 150-400 deg.C is mixed with a gas stream inert to the pitch at 200-300 deg.C under ordinary pressure -10kg/cm<2> and powdered. The mixture stream is then quenched at 70-400 deg.C to separate and recover the fine particulate pitch spherules and oil and give the aimed pitch spherules having an average diameter of 30-200mu. Preferably, the pitch spherules have an average diameter of 30-200mu, an oil content of 55-15wt%, a fixed carbon content of 45-85wt% and a softening point >=140 deg.C, in the spherical form under compression at ordinary temperature and 10kg/cm<2> without adhesion.

Description

[Detailed description of the invention]

The present invention relates to fine pitch balls and raw coke balls, and more specifically, the present invention relates to fine pitch balls and raw coke balls. It can be handled in the same way as fluids, and can be transported and stored! Concerning iK convenient granules, pitch balls and raw coke balls. In general, the distinction between pitch and raw coke is based on their composition.Although it is difficult to be certain, this is not an exception, and pitch balls and raw coke balls are distinguished by their compositions such as fixed carbon value and hydrogen/carbon ratio. The above has properties that I favor, but in my case, the two can be clearly distinguished from each other based on the manufacturing method (decomposition, degree of sludge of heavy metals), and differences in physical and chemical properties. Therefore, hereinafter, in the present invention, 1: will be referred to as a pitch ball and a raw ball. Pitches can be obtained in large quantities from J611, such as petroleum 1 coal, and from J611, such as petroleum-based heavy oil (work oil), such as Shimaho Bucess, Tarnando, and Oil Sea Tsubasa. There are also pitches that can be obtained such as coal carbonization, coal carbonization, and coal drying, as well as bicemen and asphalt 1. Some of these pitches are used for various purposes such as binder pitch for electrodes, binder pitch for iron and its false binder pitch, electrode coke, carbonaceous and coke etc. solid fuel, etc.
C.
-ru. However, these pitches are difficult to handle during transportation and storage 11 because they are viscous liquids, or they become sticky when the temperature rises even though they are solid, as is known from natural bitemens or asphalts. Therefore, it cannot be said that it is still being used effectively. The pitch spheres and raw coke spheres of the present invention eliminate the above-mentioned drawbacks of these pitches and provide new pitch and raw coke crystals that can be handled in the same way as adhesive bodies. Yes, these "pitch balls and raw gas balls, which are easy to transport and store, are very effective in solving the problem of fm in various types of heavy oil boots, which are considered important in 11th century." It is something. That is, the crude oil that is currently produced and obtained tends to be heavier, while the requirements for petroleum steel are in the realm of lighter crude oil. I! As a result, there is an urgent need to increase the number of processing units needed to lighten and improve the quality of heavy oil. The heavy oil obtained from these processes is also subject to treatment processes to make it lighter and improve its quality. In the heavy oil processing process for lighter oil and higher quality

[Inevitably, carbonaceous residues are generated, and in the current 4) 11 heavy oil processing systems, there is a large amount of effort required to handle and utilize these carbonaceous residues. For example, representative examples of the four processes for producing heavy petroleum oil include delayed tsuka, &recap buying cess, 7)-)' tsuka, and 7-shiko car. In Delayed Tomi-★-, the #M:1-x in the E1m moat in the coater drum is grown by the Sesebutteguses, and this is periodically crushed by hydraulic or mechanical methods to form lumps [4! In order to discharge the coke, some work is required to take out the bottle, and the coke product also contains water, making it inconvenient to transport and store, and there are also problems in using it as fuel. On the other hand, Erica Busses is a patch Busses, but the residue is pitch and C
Therefore, the pitch is taken out continuously, and the pitch is cooled with a flaker to form a III shape, and is layered as a binder for steel. Although this method makes it possible to take out the residue in a pitch-like manner, it is still somewhat inconvenient in terms of transportation and static conditions.
There is a c@ world. In Fluid Tsuker, the generated residue is obtained as IL grains, but because the processing conditions are relatively high temperature, the combustibility of coke is not very good, and its value as a working material is low. 7th life Shibu-★-
In this case, the residual coke grains were subsequently converted to t'JI gas. Although gas is convenient for transportation, it is inconvenient for static conditions, and furthermore, this gas has a low curly content and has limited usefulness as a fuel. The inventors of the present invention have developed a system in which the carbonaceous residue that inevitably grows in heavy oil processing booths is continuously extracted using pitch.
The pitch J of the fine particles that meet by treating the liquid like a fluid
9. If raw coke or raw coke is made clear, transportation and storage will be convenient.9. Moreover, there are many rolls that can be used as fuel as is, and if necessary, it can be converted into an effect m1clx, and I! Tsute. 1l1111, the charcoal quality of heavy oil that leaves many problems! I! Thinking that it would be able to greatly contribute to the use of casings, and as a result of intensive research, we have developed a pitch ball and raw J- I ended up offering Kusu balls. The pitch ball of the present invention is II! It is thin and at least has a front side. Since it has been hardened by being exposed to KIA once and does not cause adhesion in late summer, the sled assembly behaves like a fluid. Therefore, handling, transportation, and 1 PJI have a container of 4111.6 In addition, this pitch ball contains virtually no moisture, and many rolled metals have a small amount of moisture, so they can be handled without being crushed. As a special fuel, it can be burned in a general-purpose burner by adjusting its properties, and by adjusting the oil content (volatile content) contained in the pitch ball, its combustibility can be improved. It also has the advantage of being adjustable. Furthermore, as will be described in detail later, if this pitch ball is thermally decomposed using a fluidized bed or the like, part of the oil contained in the pitch is decomposed and lightened and can be separated, while the remainder is The raw coke is heated and becomes raw coke, and since it is a raw coke ball with pores, it can be used as a fuel in kilns, etc., and it can be easily gasified, so it can be used as fuel or hydrogen. It becomes useful as a raw material for gas production. It is no wonder that the raw coke of the present invention has a softening point of 60~!ffi@1 since the raw coke is made of spheroid particles with a viscosity of 1 IJll, so it is difficult to handle, transport, and store it as a job. :, 5
Itr carbon 4o ~ 75 vtjg using a raw material pitch that looks like an island, ■ atomization and spheroidization of this pitch and 0
Oil content is released from this spherical pitch, or if necessary, it is obtained by mild surface conversion of the pitch ball or washing with a solvent, etc., and the average particle of this pitch ball is m<s*s weight) is 30~200U 411! ! rh~15vt! l! , 1IjHI
till (JIgAM1$12) is 45~$1vtj
(g) It is shown that the particles have a softening point of 140° C. or higher and are substantially non-adhesive and can maintain the deposited layer under the pressure ring of (a). - The spear has a softening point of 140 or less, or - Nitrogen carbon is 41! For rolls of less than VT, it is rated 1 in terms of adhesiveness and strength.
Does not exhibit sufficient properties to withstand normal transportation and storage. In addition, the relatives indicated by the values of oil content, fixed carbon, etc. in pitch IIK with and are the average values of the particles. In comparison, the chain content in the center is large (all! carbon value is low ~), and it may be an uneven stratification, so to speak, where an epidermis exists. The force can be obtained by disassembling the above pitch ball, reducing the heavy oil content contained in the pitch 31 by weight, and then removing the heavy oil. A pitch with a softening point of 60 to 220°C and a constant carbon content of 40 to 75 wt% is used as a raw material, 1. This pitch is atomized and spheroidized, and the oil content is extracted from this spherical pitch. or
Mild pitch ball 1 if necessary! ! Both oxidation and solvents, etc.
Washing and ■ Heat content is 2 S ~ 4 vt%, iii
The particles have a constant carbon of 75 to 11wt1ll and a pore volume larger than that of O,OS'. This rolling metal has constant carbon of 75 vtjl! The following windings have side holes and have the required strength of 4: I
It is difficult to obtain a square sphere, and it is inconvenient that a winding metal with a carbon value of *@vt arc has poor combustibility and cannot be used as fuel. In addition, although this raw soybean is comparable to pitch sphere in terms of its composition as indicated by the value of carbon content, %l11tF carbon, etc., and its average particle size, it is more susceptible to thermal decomposition and heavy content than pitch sphere. Those with a high degree of advanced pukes have a thermal decomposition weight of 1 to 41.
The difference between the pitch ball and the Mei 1FK is that the light oil produced in this process evaporates from inside the particle, resulting in particles with pores. axis, the average value of the raw coke ball during the above pitch grinding@(SO
The range of weight (lI) is 30-200trl. If the particle size is less than 30 Kuhns, mutual agglomeration of particles is likely to occur in the IflK flow state Ilc, and if the particle size is 200 Kuhns or more, the smoothness is poor when flowing with gas. m*L for operations such as transportation, storage, or fluidization.
<No. The raw materials used in the production of the pitch balls and raw coke balls of this plant include petroleum pyrolysis products, heavy 111k (
III residue oil) processing boothes (for example: L9 turnip w-k
x, 8D Mpuse> (8o1v*nt aeasph
Coal-based pitch steel produced from stones such as natural bicemen and asphalt (altig)), coal-based pitch steels such as coal thuds, , and other various pitches with a softening point of 60 to 22G"IC1
Preferably 100 to 18G”e, fixed longitudinal cable (J
I84M-8812) is used with a pitch of 40-75vt-. Softening point is 60℃ or less, or iI constant carbon is 4
01! The following cases are not suitable as raw materials for the pitch balls and raw coke balls of the present invention in terms of the softening point of the product pitch balls and the hardness of the raw coke balls. The pitch balls and raw coke balls of the present invention can be manufactured by various methods. For example, raw material pitch melted to a relatively low viscosity at 0150 to 400°C is mixed with an inert male having a higher temperature than the raw material pitch using a two-fluid nozzle or a high-pressure nozzle to atomize and remove some of the heavy weights in the raw material. Method of obtaining pitch balls by evaporating heavy oil and then cooling it in a suitable manner (in this case, heavy oil is recovered by evaporation), 0
The raw material pitch, which has been melted to a relatively low viscosity at 150 to 400°C, is mixed with an inert gas at a lower temperature than the raw material pitch to make it moldy and cooled. A method of accelerating the production of pitch spheres: ■ Pulverize solid pitch at room temperature in an appropriate manner, and introduce the finely powdered pitch into a scalpel at a temperature higher than the melting point of the raw pitch (singing point + about 20°C). By melting and spheroidizing and evaporating some of the heavy oil in the
After that, it is cooled in a suitable manner [method of obtaining pitch balls (in this case, heavy oil is recovered by MLC), etc., and inert gas is used to obtain pitch balls. A substantially inert gas having no chemical reactivity,
For example, fuel gas containing light hydrocarbons such as methane, etc., such as those emitted from Bouseme, etc. Manufacturing method■■■IC
and, if necessary, carry out appropriate modifications of their manufacturing methods, such as atomization, treatment of pitch balls separated from an inert gas, or pretreatment of pitch balls, etc. ■−
The surface of the particles is slightly heated to K11 by using a gas containing a chemical agent.
The pitch ball that has been chlorinated or separated from the O inert gas may be washed with a suitable solvent, for example, a light hydrocarbon solvent such as Soot, for example. If the softening point of the raw material pitch is 140°C or less in the 4HC■ method, the above treatment is required to make the softening point of the product pitch ball 140°C or higher. In addition, in the production method ■■, the viscosity of the heated and melted pitch is reduced to the extent necessary for atomization, but if necessary, a small amount of decomposition product oil, etc. may be added to reduce the viscosity. ,, (Also, the process pressure in method #C of above ■■0 is the same as the amount of inert 1s for the pitch ball [although it varies, it is generally in the range of normal pressure to 10 Jg/cs*''. Pressure When is lower than this range, the amount of strained active gas increases,
The equipment is also large #IVc [and is served without noise. On the other hand, if the pressure exceeds this range, particles will be generated, collisions between particles will increase, and adhesion between particles will occur, which is undesirable. (1~$2
A pitch ball that maintains its spherical shape without being magnetically attached can be obtained by oversizing at 0°C. In each of the above-mentioned methods ①@[F], the pitch ball and the gas flow can be separated by a mechanical method such as a knife fermentation method or a bag filter. Next, to produce a %41: Goks ball, the pitch ball obtained by the above method is heated to 40G-! It can be obtained by thermal decomposition under conditions of $20℃, normal pressure to 1 G kl/11". In this case, the oil contained in the pitch ball can be pyrolyzed and lightened to 11". Gadeden, !1I111 is processed by Jumonsha, and as the conversion to x-cus progresses, it is possible to obtain raw cortus spheres with pores due to the volatilization of @ quality oil. Below, the degree of decomposition is uniform,
If the temperature is higher than 20°C, the oil content and strength of the raw sukusu spheres will be poor and the layered structure may not be as spherical, which is undesirable. In addition, when producing only raw coke balls without charging pitch balls, adjust the atomization/spheroidization knee conditions and quenching temperature in the method described in ■■, and immediately heat the coke at a relatively high temperature. By transitioning to decomposition, it is also possible to heat-bound and make the material into clay. In order to more clearly show the moldiness of the pitch balls and raw coke balls of the present invention, the manufacturing method described in (1) above will be explained in more detail below in accordance with 1 and 7-- of the drawings. The method for producing the pitch balls of this invention is herein referred to as the first method, and the method for producing the raw coke balls of the present invention from the pitch balls is referred to as the second method. The No. 1 factory atomizes the heated wavy pitch to produce spherical pitch balls with hardened, non-adhesive surfaces, and also removes the heavy oil contained in the raw pitch. In Step 1 of recovering a portion, the raw material pitch is heated to 150 to 400'' or maintained at a temperature of 150 to 400'', and preferably has a viscosity of 30 mm or less. The high pressure pump 2 is used to send the atomizer 3 to the atomizer 3. At 2 G ON, the temperature is 800°C, preferably from 300 to 0.
The atomizer 3 is a contactor with a bench temperature of 4.0 and is preferably partially injected with a substantially inert gas relative to the pitch. Pitch is injected into a high-speed inert gas flow with a linear velocity of m/@ah through mx* number of internal pressure nozzles (e.g. swirl nozzles).In this case, the temperature of the raw pitch is 150-400°C. Generally, below 150℃, the viscosity is high and atomization is a national problem, and above 400℃, the pitch deteriorates due to heat, which is undesirable.
oo℃ is good, zo. If the temperature is below ℃, the evaporation rate of the oil will be uneven and a large amount of scalpel will be required, which is not economical. If it is above SOO℃, the evaporation rate will be too continuous (desirable liquid pitch balls cannot be obtained.
The amount of inert gas for the pitch ball is in the range of 0, z to 1s (weight ratio), usually 0.5 to 8s. In addition, in the process of liquid pitch, the high-velocity inert gas first forms fine pitch droplets, and heat transfer occurs from the high-temperature gas flow to the pitch droplets. El in the gas flow! As a result, the temperature of the mixed flow of pitch and inert gas decreases, and the temperature of the mixed metal falls within about 0 seconds for many windings.
The mixed stream is then quenched to between 5 and 475°C to solidify the pitch droplets and allow the gas to flow. In this case, heat recovery from the pitch ball and recovery of heavy oil such as gas #1 are also performed by appropriate methods. The important parameters in this atomizer 3 are the ratio of the temperature and supply amount of the inert gas to the temperature and supply amount of the raw material liquid pitch, injection and/or mixing conditions, residence time of the mixed flow, and Such as quenching temperature. These −
The knots determine the pitch ball's constant carbon content, the average content of grains, the distribution of oil in the pitch ball, the softening point (adhesion), etc. The pitch ball can also be rapidly cooled by, for example, injecting water or low-temperature gas into the mixed flow to bring the temperature of the mixed flow to 70 to 40°C. If the winding cooling degree is below 70°C, the evaporated spears and water vapor will condense and mix into the spool crystal! It is undesirable that temperatures above 400'C cause thermal decomposition of the pitch spheres and secondary agglomeration and adhesion between particles.Furthermore, the pitch spheres can also be cooled using a multi-stage fluidized bed 5. In other words, in order to separate the pitch ball from the gas flow,
For example, the pitch ball that has passed through the tank 4 and entered the multistage fluidized bed 5 is introduced into the fluidized bed at room temperature to 1°C. It is directly or indirectly heat exchanged with a suitable inert gas of usually 5''' 100 C1l/see, preferably 10 to 60-4.℃, cooled and crushed at a temperature of room temperature to 10 G'IC. Also, a moving bed may be used instead of the multi-stage fluidized bed.The gas stream separated from the pitch spheres is cooled by passing through a suitable heat exchanger 8 and a cooler 10, and the gas that was present in the gas stream is cooled. The oil is distilled in the distillation column 12. The heat recovered in the heat exchange IIs and the multi-stage fluidized bed 5 is used to heat the inert scalpel in the illustrated example to improve thermal efficiency. The collected pitch balls are virtually non-adhesive and can be used as special fuel products that are difficult to handle, transport, and store. The oil content is used as fuel oil after undergoing 4611 such as desulfurization.The second step is to produce whole coke balls as required, and this step is performed from the fine pitch balls obtained from the first step. This is a process in which a relatively light oil is harvested through thermal decomposition, while the remaining particles are turned into a raw material with pores.The pitch ball obtained from the Tateichi process differs depending on the conditions of the knee. is fixed carbon 45~I!!r%fi, 5
! j ~15 vtl I) Nlk content, IP':) Fine particles with virtually no fliKm adhesion. The pitch spheres of the product obtained in the first step or the pitch spheres extracted at an appropriate temperature in the Kiichi process are supplied to 6 to the fluidized bed pyrolysis 11 in which coke particles are flowing.
IkIIk state. 'Thermal decomposition temperature is 400 N52
0"C1 pressure 7)st normal pressure I G kl/m", the average transit time for pyrolysis is within 1 minute to 2 hours.・. In addition, the coke particles used in this fluidized bed are
Product coke particles obtained at Tate Niko 1 are used.
3 - In the process of this second step, the pitch spheres become all coke spheres due to the polycondensation reaction occurring in parallel with thermal decomposition, and these raw = -tas spheres have a high amount of fixed carbon in the raw pitch spheres. In addition, due to the polycondensation reaction in the decomposition step, the strength is also high, and some have pores. Since the whole coke spheres coming out of the first-layer pyrolysis II Haruka are at a high temperature, they are cooled while recovering heat, for example, in a multi-stage fluidized bed 7, and become raw soot spheres as a product. In addition, using the above multi-stage flow 1 crane, preferably 7-〇-40g+/s@c 0
In the illustrated example, heat recovery from the multi-stage fluidized bed 1 is performed by heat exchange with low-temperature inert gas, so by guiding this inert gas to the heater 9 and using it, the efficiency of heat utilization is improved. be able to. is cooled through a heat exchanger 8 and a cooler 10 together with the inert gas used in the slight softener, and is then sent to a distillation column 12.
The oil is recovered. The separated and recovered light oil undergoes treatments such as desulfurization, and the zero cracked gas that becomes the product may be processed in the distillation column 12 together with the inert gas of the atomizer, as shown in the figure, but only the light oil is obtained. For this purpose, a separate distillation column may be provided for separation. is 25-4 vrt%, fixed carbon is 75-9@vt pores! These particles are difficult to handle, transport, and store, and are used as solid fuels and carbon materials, but because they are porous, they can be easily gasified, and can also be used as raw materials for gas fuel and hydrogen gas production. Are suitable. The ratio of the amount of pitch balls produced in the first process and the total coke balls □ produced in the second process 1 is the same for each! i butt) (C
1) It is possible for ε to change appropriately depending on k. Next, the present invention will be further illustrated by examples. This example is an example of a manufacturing method for a more complete understanding of the present invention, and does not define all manufacturing methods or uses of the pitch balls and whole coke balls of the present invention. Example 1 The raw material pitch used in Example 1 was obtained by thermally decomposing vacuum residual oil, and its properties were as shown in Table 1. Cjl1 table] Heat the raw material pitch to 310"e 31 G"e
Km viscosity 100cp) at a flow rate of 30”l/hr, 4
The mixture was atomized by being injected from a nozzle into a nitrogen gas stream heated to 00°C. The flow rate of nitrogen gas was 77"I/hr. The atomization device had a maximum diameter of 5 mm, an inner diameter of 151 w, and a length of 2,500 m.
ll Contact snow receiver, 4 nozzles of 0.3■φ are installed just before the tie, and the raw material pitch is injected from the nozzles so that there is an inward flow (angle 45°) to the flow of nitrogen gas. Ru. The nozzle pressure in jetting with J[family pitch is approximately 15
It was 0 jg/-. By injection of pitch into nitrogen gas, the mixed gas flow is approximately 35
Although the temperature decreased to 0"ck, water of 2S"C was further injected at the outlet of the contacting device to about 15 by/br "t" to rapidly cool it to about to'c. The pitch spheres were separated and the pitch spheres were obtained.The residence time for atomization (heat transfer and evaporation) was 2 apc.The average particle diameter of the product pitch spheres was approximately 8 degrees ( 40N
The particles had a softening point of 90° C. or more, and the particles could maintain their spherical shape under compression of 10 kI/- at room temperature. The properties of the pitch ball were similar to those of No. 211. The pitch spheres were ejected at a rate of about 26.4 jv/hr, and the yield based on the raw pitch was about 88 wtl. On the other hand, the nitrogen gas stream that was separated from the pitch ball was cooled down in a cooler and collected in an oily state. [jK oil is a heavy oil containing about 30% of 1 min with a boiling point of 540° C. or higher, and the yield based on the raw material pitch was about 12 W scratches. Example-1-B - The pitch ball obtained in Example-1-B was used as a 26.4JIF raw material. Using a fluidized bed reactor with an inner diameter of 210 mm and an effective height of 1000 mm, pitch balls at 80°C were used. First, 1 ml of oxidation J12! shown on the front page was preliminarily carried out for about 2 hours using 2.OIm''/hr of air at about 100°C containing 3 vol of ozone-QF, and then nitrogen gas at 600°C was added. Blow in with 6" Ar and gradually raise the temperature to 450 degrees.
℃ and then thermal decomposition was carried out. Pyrolysis conditions I
t. The reaction temperature was 450° C., the pressure was 0.3·“l/a”, and the reaction time was 0.97 hours. The tower velocity of nitrogen gas in the fluidized bed was 0.13□@C. After the summer, the nitrogen gas was switched to 40°C and cooled, and raw Zugs bulbs at 6S°C were obtained as products. Raw product: - Couscous balls are grains! ! The particles with a particle size of 40 to 150 particles were particles with a particle size of 80 particles, and their properties were as shown in Table 3. - [Table 3] The yield of raw = - Tussu is 197 k1g, the yield is 74.6 vtl for the pitch sphere, it fi B, 7 vtjG ``e b ivy @ pyrolysis for the raw material pitch The decomposed male that came out was cooled to 40'C in a coo-two, and the cracked oil and C, and the following cracked gas were separated.The cracked oil was about 214vt% of the raw material pitch ball &9, and the cracked gas was S, The properties of the Ovtl 0 cracked oil were as shown in Table 4. [Table 4] Example 2 The raw material pitch used in Example 2 was obtained by thermally decomposing vacuum residual oil. The properties of the pitch were as shown in No. S@. [Table 5] This JI pitch was maintained at 320°C and
The viscosity is 200 cp) 30 jv/hr #
) 1 weight was injected by a nozzle into an inert gas stream heated to 600″e.The flow rate of the inert gas was 28 k
g/hr and the gas composition was like Rattan 61R. The mold IIjLf device is a Bench & Lee II*m device with a maximum diameter of sO■φ and a 15-φ length of 150G, and four 0.3-φ nozzles. The inert gas is injected from this nozzle at a diagonal line (angle 4s@) to the inert gas stream. The nozzle pressure applied to the injection of raw material pitch is: I
00 kl/'os''. By injecting pitch into the inert knife, the 81 knife flow was approximately 4
1! l:, but the sit water was further reduced to 11jv/hr.
It was fired at the opening of the event, and the temperature electrified to about 300 degrees Celsius. The residence time required for anification (heat transfer/evaporation) was approximately 0.15 seconds. The mixed stream is separated into pitch balls and males using a knife separator, and then the pitch balls are brought into contact (cooled) with a 40°C inert gas introduced into the bottom of the fluidized bed in a multi-stage fluidized bed chamber. However, the φ component pitch sphere obtained as a product at 65℃ has an average particle size of about 100μ (sO ~ 150μ is 90μ), a softening point of soo℃ or more, and a particle size of 10III/
It maintained delamination under compression of 100 g, and its properties were as shown in Table 7. [Table 7] Pitch 3I was milled at 25.5 l/hr, and the yield based on the raw pitch was 8 S vt%. On the other hand, the gas stream separated by the pitch ball and the pump is cooled by a heat exchanger and a cooler, and is separated into water, condensed water, and off-gas in a distillation column, and the off-gas is circulated.
The mixture was passed through a heater as an inert gas to form atomized MiI gas, and a portion was used as a cooling gas for a multi-stage fluidized bed cooler 2.-. The oil separated in the distillation column was a heavy oil with a boiling point of 540"C or higher containing about sO, and the yield was about 1 sWts. Example-2-B Example-2-M A pitch ball was made using the same method as above using the same raw materials as above, and the pitch ball was extracted from the second stage of a multi-layer cooler, which was separated from the gas flow using a Naikoon (temperature 119℃), inside@ 210■, effective height 1,00
Using a 0111 111I fluidized bed pyrolyzer, 2
! ! , pyrolyzed at $1111/hr. @The maximum decomposition temperature was 450°C, the pressure was 0.3 Jv/w'', and the time was a, s for Chiyunka Ojioka. Also, the fluidizing gas in the fluidized bed contained soo', the same gas used for atomization. The gas composition was shown in the exposure table of Example 2-5, and the column speed was 0.1 S/s@c. Raw coke obtained by pyrolysis The spheres are introduced into the bottom of a multi-stage fluidized bed cooler, brought into contact with an inert gas of 4 (1), cooled and discharged as a product at 65°C. 8 particles
The properties of the finely granulated raw coke balls were as shown in Table 8. On the other hand, the cracked gas coming out of the fluidized bed pyrolyzer is cooled in a heat exchanger and cooler separately from the inert gas that comes out of the atomizer and is separated from the pitch spheres in a Naikoon, and then sent to a distillation column.
The cracked oil, condensed water, and tower top gas were separated, and the tower top gas was circulated and used as an inert gas through a heating furnace, as a gas for atomization, or for cooling a multistage fluidized bed. The decomposition gas separated in the distillation column is approximately t for the original pitch pitch.
o vt%, and the cracked oil is about 15.6 vt-
Its properties were as shown in Table 9. The drawing shows the book G &Beak's III thesis,
The main parts of li are as follows. 1: Heat retention tank, 2: High pressure pump, 3! Contact atomizer, 4: T-tern separator, 5! Multistage fluidized bed (for rapid cooling), 6! Fluidized bed pyrolyzer, 7: Multistage fluidized bed (for cooling), 12
: Amendment to Distillation Column Procedures September 17, 1984 Director General of the Patent Office Shima 1) Indication of Tono Haruyuki Case 1978 Patent Application No. 121844 Title of Invention Case of a person amending fine oil-impregnated carbonaceous spheres and their manufacturing method Relationship of patent applicant name
Fuji Standard Research Co., Ltd. Agent - 1 Issuance of the declaratory document subject to amendment ← Applicant's column - Invention in the description → n ← Scope of claims - Detailed description of the invention column Contents of the amendment As shown in the attached sheet The description is amended as follows. t In the 9th line of page 26, the word ``Nitou'' is corrected to ``Kuto J.'' 2 The word ``μ'' in the 8th and 9th lines of the 30th page is corrected to ``Mita 4''. , 5. In the third line of page s2, after the word "so", add "ku". 4 In the 8th line of the same page, the word "μ" is corrected to "miturn".翫 On the 7th line from the bottom of the same page, it says r ky/mJ.
/'kJ.

Claims (1)

[Claims] - Average diameter (io-weight II) is So ~ 2004 oil, oil content is 5 s ~ 15 t, - 1 fixed carbon is 45 ~
15vtJ, softening point is 140℃ or higher, room temperature, 10K
Substantially non-adhesive pitch ball capable of retaining its spherical shape under compression of y/ax. -1 fixed carbon is 75~?
A raw coke ball that is 4wtj and has pores. (5) The raw material pitch is petroleum-based or coal-based pitch with a softening point of 60 to 220°C and a constant carbon of 40 to 7'5vt6%, while maintaining the pitch at a temperature of 150 to 400°C under normal pressure to 10%. Under a pressure of ky/a/, the mixture is atomized in a gas flow which is substantially inert to pitch and whose temperature ranges from 200 to -OS°C, and the atomization is reduced to 70 to 400 °C.
It consists of quenching to 'e' and separating the fine pitch balls from the oil, and the production of pitch balls with an average weight of 30-200 l is possible. 4. Pitch, which is a common material, is heated in a warm environment at a temperature of 200 to 800 °C, while maintaining its softening point of ゛・O ~ 1 °C. The pitch balls obtained in Step 1 are granulated, and the mixed flow is rapidly cooled to 70 to 400°C to separate the am pitch balls and oil. [Temperature 40G-5! ℃
, pressure, snow pressure ~10 keyaki/e1m", average residence time ~1 minute
The second step consists of pyrolysis and separation of fine raw coke balls and one quality cracked oil in two hours. A method for producing raw coke balls with an average particle size of go-zoo-rich.