JPS58164687A - Preparation of pitch with optical anisotropy - Google Patents

Abstract

PURPOSE:To prepare the titled pitch producing carbonaceous material with high strength and high elastic modulus, by stopping thermal reaction of carbonaceous heavy oil used as raw material for pitch production in the early stage, removing heavy pitch segment by settling treatment and then performing thermal reaction. CONSTITUTION:Carbonaceous heavy oil used as raw material for pitch production is subjected to thermal reaction at 370-460 deg.C in a circulated inert gas. The reaction is suspended at a point where the resultant pitch contains 5-50% optically anisotropic phase (AP) in spherical for, 2-20wt% quinoline-insolubles and 5-40wt% substance insoluble in quinoline but soluble in benzene and has an overall softening point of below 200 deg.C. The pitch is then subjected to settling treatment at 200-400 deg.C and, after separation of segments containing a large amount of phases with high specific gravity, the remaining pitch is subjected to polycondensation reaction by thermal decomposition and removal of low-molecular substances at 300-420 deg.C until the isotropic phase (IP) content is reduced to 0-20%, to obtain a pitch having an AP content of 80% or higher, an IP content of 20% or lower, a quinoline-insoluble content of 70wt% or lower and a softening point of 230-350 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes charcoal monofine and T? The method for producing optically anisotropic carbon bulky pitch J/C8 is suitable for producing other longitudinal materials, including ridge materials.

In terms of energy saving and 1-segment miI costs, voyage g!
Shin, a lightweight, high-strength, low-fist, high-performance bare-legged paddle made of elastic composite material, which is essential for automobiles and other applications.
Or high strength, which is pressure molded and used for lumberjacks.
There is a strong demand for highly densified molded carbon materials.

However, there is no sufficient disclosure regarding the composition and structure of optically anisotropic pitch suitable for the production of high-performance carbon fibers.
The relationship between the physical properties of carbonaceous pitch materials and their composition and structure has so far been unclear, and this woodcutter has developed techniques that can stably control and obtain fully satisfactory physical properties on an industrial scale. 1#I has not yet been completed.

Conventionally, the pitch of light that is shown, for example, the buttocks.
Shoda 9-/91 koku issue, same sog de 48 issue, same! ;0
-//The optically anisotropic pitch described in the No. The part #1 corresponds to the quinoline-soluble content (or the biridine-insoluble content), and when the AP part approaches 100-, the softening point increases significantly, and the spinning temperature reaches around 00℃ or higher. Therefore, in these production methods, the content of APiS is set to 90% or less, and riSO
The spinning temperature k is suppressed to ~7091 to prevent thermal decomposition and thermal polymerization.
A method of suppressing the temperature to a level that does not occur in 1ii11 is adopted.

However, a mixture of such a pitch composition a1^P and a considerable amount of optically isotropic fiber (hereinafter abbreviated as IP) has a non-uniform pitch of To9 and yarn breakage during spinning. Ta-4, 5-5, and delicate fibers have uneven thickness, and mamogi fibers have a low strength k.

In addition, in the pitch material disclosed in the article No. 9-143q, K can be seen where AP is essentially ioo's, but this is because the chemical structure of the pitch molecule has been specified. It is a special pitch, which is formed by simple heating of expensive pure substances such as Kuriron, 7-enanthrene, and tetrapenzophene-7, and has a good pitch of 69 and a relatively uniform structural molecular weight. However, KFi, which is produced from common mixed raw materials, has a very high softening point.

On the other hand, the pitch as a raw material for producing Gaku S* soap described in No. 53-7jt3.3 has a similar softening point and spinning temperature k, and is therefore easy to spin, but it contains ^PO. The ratio is unknown, and the raw material hydrocarbon X is polycondensed using a Lewis catalyst such as aluminum chloride, and the composition and structure of the pitch is special. The strength and modulus of elasticity are small. 1"6. □ (further,
The pitch material disclosed in the Patent Publication No. S is a homogeneous pitch consisting of AP of actual purchase/θ0-, but the manufacturing method is still an isotropic pitch that only undergoes a thermal reaction from beginning to end. It is a method that carefully controls and systematically performs pyrolysis and polymerization by adding
The softening point of these conventional pitch materials is about 330°C or higher, and when the spinning temperature reaches 370°C to 00°C or higher, it becomes difficult to light up at this 11°C range. It is still difficult to spin pitch like 111-A.

In addition, Tokukai Sho S Da Ibo Dako No. 7-tiyss-s
g Kozari issue, IIIIss-i3ogoq issue, 5s-
idaqOg7, and the same! ; 6-! ; The pitch material disclosed in 7ZA No. 11 is obtained by extracting the component t-, which mostly forms AP, by performing a vegetative extraction on isotropic pitch or pitch containing a small amount of 8Ptt. Since it is produced by melting, an optically anisotropic pitch with a narrow molecular weight distribution and a small quinoline age content is produced. However, as shown in the manufacturing method and data shown above, in general, a narrow pitch with a softening point is obtained, and the spinning temperature is qθ01I.
Since it becomes C Kinpaddy, it is thought that Kagabata will still be involved in industrially spinning such pitch in a stable manner. Furthermore, these manufacturing methods have the disadvantage that they require expensive and complicated operations such as a filtration step using one filter, solvent removal, and one bath agent recovery machine because they include a port agent release step.

As mentioned above, the iov'
Homogeneous optically anisotropic pitch containing AP in the s is expensive and generally has a low softening point, resulting in stable and good spinning. On the other hand, pitches with a low softening point4 are non-uniform except those manufactured from special raw materials and have a special composition and structure69, and spinning is similarly problematic, resulting in poor quality. carbon fiber. It is a waste to manufacture.

WilPft et al. described a rounded optically anisotropic pitch composition for producing high-performance carbon fibers.
As a result, the optical lateral pitch is 7 pitches with uniform molecular orientation, but 2
In reality, there are a variety of things mixed together.

Among them, those with low softening points and suitable for producing homogeneous carbon fibers have a specific chemical structure and composition, that is, in optically anisotropic pitch, 0 component, i.e., n-heptane soluble component, and ^ component. That is, it was discovered that the compositions and molecular weights of the components insoluble in n-hebutane and soluble in penzene were extremely overlapping. A method for producing such an optically anisotropic pitch has been completed and has already been filed as Japanese Patent Application No. 1985-11-27-7.

In general, when heavy hydrocarbon bulk oil or so-called tar, which is a pitch raw material obtained from the petroleum industry and six chemical industries, is subjected to a thermoheavy reaction at 310 to 60°C, the amount of produced ^P increases. hand.

1. The softening point of the entire pitch and the viscosity of the entire pitch that decreases at one time are large. In the vicinity of λptoo%, the softening point and viscosity of the resin are extremely low, and molding is often difficult.

The causes of this phenomenon include -K, which is caused by AP generated at the beginning of the thermal reaction remaining in the reaction system for a long time;
This can occur if polycondensation progresses excessively, and another reason is that the AP produced at the beginning of the thermal reaction is generally composed of substances that have a much higher softening point than the AP produced later. Find the benevolence that lies in you.

Based on this knowledge, the present inventors included a step of settling the pitch in a second-fist state at the point when AP is partially generated during the thermal massification process, and separating and extracting only the AP portion as a lower layer. It has been discovered that this method can provide an optically anisotropic pitch with a much lower softening point and a sufficiently high ^P concentration than in a method that thoroughly heats the material, and has already filed a patent application. −? ? The application was filed as No. 64cA. #
To further explain the method, the raw material for pitch production is pyrolyzed and polycondensed, and when the AP in the polycondensate reaches a specific amount, it is left to stand, and a high degree of AP is accumulated in the deposited layer. .

Pitch area where upper layer low density IP occupies most of the area
It is characterized by being separated from 1.

The inventors continue to demonstrate that such low softening point, high A
We conducted further detailed research on the manufacturing method of optically anisotropic pitch that has both a high P content and excellent homogeneity, and obtained the following findings.

Isothermal thermogravimetry of the pitch*St was carried out at different times, each settling, and approximately 10 AP separated into the lower layer.
Softening point of 0% pitch.

Show the results on the hospital map. Looking at the attached diagram, nine tracks 11N, indicated by the code 0, indicate the thermal massing reaction time and the thermal settling lower layer A.
This shows the relationship between the softening point of P and the softening point, which initially decreases as time passes during the thermal reaction, but increases after one hour.

On the other hand, im* indicated by the symbol M indicates the relationship between the thermal massing reaction time and the yield of thermally settled lower layer AP.
It is shown that the yield of the lower layer ^P increases with the elapse of the thermal] k-forming reaction time. Furthermore, if the thermogravidation reaction is carried out for about 2 hours and 30 minutes or more, the separation due to settling will occur.
It was also found that c.

From the above results, it was found that the initial 8P could be reduced by carrying out the thermal heavyization reaction time, separating and removing the initial OAP by settling, and reheating the upper layer, or by further thermal settling. It has been found that it is possible to obtain an optically anisotropic pitch having a softening point one order lower than that without removing AP.

In addition, in addition to thermal settling, methods for removing AP generated at the initial stage of the thermal deterioration reaction described above include solvent extraction and heating and pressure filtration, but these methods are both expensive and practical. The present inventors believe that the heating settling method is the most superior, inexpensive and 111! I thought it was an IgL method.

In addition, at the early stage of becoming heavy, the softening point of the entire pitch yarn and the viscosity 1 at settling tm* are very low, low settling temperature wrinkles and short settling tm*.
During the IJ song, it is possible to easily settle the saponified material at the beginning of the heat-improving reaction process 6.

In addition, during the initial stage of thermal M'x conversion, JI of solid particles that are mixed in the raw material for pitch manufacturing from the beginning in some cases can be removed by a method that removes the initially generated precipitation. Since carbonaceous materials, molecular weight carbonaceous materials, and non-rich high molecular weight quinolinous components that are likely to be formed in the initial stage are removed, the resulting optical It also has the advantage that the quality of the anisotropic pitch becomes more stable.

The present invention is based on the above-mentioned discoveries, and the main object of the present invention is to develop a carbon material with an optically anisotropic phase pitch suitable for producing carbon materials with ^9M wrinkles and -modulus of elasticity, particularly carbon fibers. Therefore, it is possible to provide a method for producing optically anisotropic carbonaceous pitch having a low softening point.

Another object of the present invention is to produce highly oriented and uniform optically anisotropic carbon fibers with eddy strength*5iIIIi elastic modulus & wood especially for producing carbon fibers. The purpose of the present invention is to provide a method for producing quality pitch.
,.

Another object of the present invention is to provide spinnable fibers that can be spun at a temperature sufficiently lower than the temperature required for thermal decomposition in order to produce carbon fibers with a modulus of elasticity of more than 1 Ilb. It is an object of the present invention to provide a method for producing a good optically anisotropic YII & award pitch.

Another object of the present invention is to produce a high-quality optically anisotropic pitch that is stable when the properties of the raw material change, thereby uniformly producing high quality charcoal wood IF+. It is an object of the present invention to provide a method for manufacturing optically anisotropic JR Mokami pitch that can be produced.

The above and other objects of the present invention are to abort at an early stage the thermal conversion of pitch material for pinch manufacturing, to divide the pitch into two parts by subjecting it to a thermal settling process, and to -F The thin pitch part of the skin is removed by precipitation, and then subjected to a suitable treatment machine including a heat direct chemical treatment. .

Next, the string and rectangle analysis method used to explain the present invention will be explained.

The “optically anisotropic phase (AP)” of the pitch used in this specification
) The meaning of the candy called J and '□ is not necessarily the same as that in academia, and fC is unified in various technical documents. ,
Cedar oil is one of the pinch constituents, and when a cross section of a pitch lump solidified in the vicinity of rich temperatures is polished and observed under crossed nicols with reflective polarized light, the K material or crossed nicols are rotated. The part where glitter is observed, that is, the pitch part that is optically anisotropic;
It is called. A clear boundary is established between AP and IP, and objects such as dust and air bubbles that are neither AP nor IP can be clearly identified.

Compared to IP, AP is mainly composed of molecules with a chemical structure that is more flat than that of polyfractionated aromatic ring metal, and is aggregated and associated in the form of stacked planes. It is thought to be in a liquid crystal state. Therefore, when this is pressed through a thin spinneret and spun, the molecular planes are aligned nearly parallel to the fiber axis.1 The fiber made from this optically anisotropic pitch has high elasticity. It becomes K to show. Also, one amount of AP or IP is examined and photographed under polarized orthogonal nicols to establish the opposite specimen occupied by the AP or IPO portion, so this represents the body &11 in terms of contribution. .

However, the difference in specific gravity between AP and IP is o, vsie at room temperature.
Since there are 4 cycles, it can be considered that, approximately, arrogance and weight superiority are equal to y using these average values.

In addition, "optical anisotropic pitch" means that AP is 100- or
Or, in Honjo Hosobara, it is expressed as a pitch in which the IP occupies the majority and is included in the AP in the form of a spherical body or irregularly shaped islands.

Regarding the homogeneity of the pitch, in the present invention, the antistatic result of the IP content in the above i is sufficiently small in VC, and solid particles (particle size of lμ or more) cannot be actually detected in the pitch cross section by reflective adhesive observation.
Is there really no foaming caused by volatile matter after melt spinning?
Since it shows excellent homogeneity in actual melt spinning, it is possible to use such a material with a practically uniform optical anisotropic pitch.

IP'f: In the case of a pitch containing more than 20p, or even if the IP is less than 0- but the dimension of the IP furrowed in the AP is large, it is difficult to use a highly viscous AP. Since it is a clear two-phase mixture with 1P of low viscosity, it is possible to spin a true pitch mixture with a high viscosity, a high degree of yarn breakage, high speed spinning, and a sufficiently thin St. Carbon fibers with a thin thickness cannot be obtained, and the fiber thickness also varies, resulting in a failure to obtain high-performance carbon fibers. Furthermore, during bath melt spinning, if pitch neutralizes infusible solid particles or low molecular weight volatile substances, it goes without saying that spinnability will be inhibited, and the spun pitch fibers will contain air bubbles and solid foreign matter. Contains and causes defects.

In this book, the softening point of pitch refers to the solid-liquid transition temperature of pitch lft-, but it can be calculated as the peak temperature of the latent heat O absorption and release of pitch III using a differential scanning calorimeter needle. be measured. This temperature is different from that measured by other methods such as the ring-and-all method and the micro-melting point method for pitch samples when dried at 10°C. The term "low softening point" in this book refers to a softening point in the range of λ30 to 320°5. In addition, there is a close relationship between the pitch of the spinning machine and the temperature of the maple part (Fi), and there are differences depending on the pitch, but when spinning with a fi-rich spinnability, the softening point is generally between 0 and /θ0. When spinning is carried out at temperatures as low as ℃, it exhibits a viscosity of 9 ml. Therefore, 30℃
For higher softening points, thermal decomposition occurs at 3gθ℃
Needless to say, since the temperature is higher than that, the generation of decomposition gas and the formation of infusible materials impairs the susceptibility, and the spun pitch M also contains air bubbles and deformed foreign matter, causing defects. It causes On the other hand, in the case of a low softening point of 230℃ or less,
It is undesirable that the unsaponification process requires long-term treatment at low temperatures or complicated and expensive treatment.

To explain the method of solvent extraction analysis of pitch and the names of the separated components in this book, powdered pitch is put into a cylindrical filter containing an average pore size of 7 μm - using a Soxhlet extractor to transfer it to n-! To n- obtained by hot extraction for 20 hours with men,',,.

The soluble component of butane is then dissolved with benzene. ,#,,ゎ,Ka1.46□4n--2,23□,
1111@ (JIS K-, 1e
The benzene-insoluble and quinoline-soluble components obtained by separation using 2S), so-called β-resin, are referred to as 8 components, and the quinoline bath component is referred to as component C. Such separation of constituent components can be carried out, for example, by the method described in Journal of the Japan Petroleum Institute, Vol. 0 (1), p. 5 (/q7) K.

Regarding the extraction analysis method of C component, in addition to this, ASTM,
D-co 3/Zaichi 76 @<7! Method of extracting at i℃)
There are methods such as , boiling quinoline/method (method of extracting with boiling quinoline), boiling viridi/ta (Soxhlet extraction using pyridine), etc., but the inventors have conducted a comparative IIR study on pitch samples of pitch. As a result, JIS monoline method, A
It has been found that the STM method and the Butto-pyridi method give almost equal data, but the boiling quinoline method gives lower insoluble data of 1 to 10% compared to these.

``Thermal settling'' as used in this book is sufficient to maintain the pitch in a bath-molten state and cause the 8P or other infusible substances, which are the phases with high specific gravity, to settle in the direction of gravity. At a certain temperature and with little turbulence, it is said that a large number of dense phases with a large specific gravity are piled up in the direction of attraction. Therefore, methods such as standing still with a small flow, thermal centrifugation, and hydrocyclone methods are also included.

Next, a method for producing an optically anisotropic pitch according to the present invention will be explained in more detail.

The feature of the method of the present invention is that in the process of heat-containing homogenization of pitch starting materials and total production or increased concentration of the components forming ^P81', a) Pitch that satisfies certain characteristics (vsb)
Through a simple and low-cost process called thermal settling,
No heat! C) This lower layer portion is removed by sedimentation, which is included as a phase with a high specific gravity in the pitch in the early stage of conversion, and is not desirable to be mixed into the product pitch. ) It is used as a starting material for the 1r-order pitch containing a large amount of the upper phase with low specific gravity, and is further subjected to post-treatments such as thermogravimetry.

That is, one pitch of carbonaceous oil obtained from the petroleum or coal industry as a starting material for pitch is used for one pitch of so-called tar.
However, it is possible to use a more preferable raw material.
3! 296, etc.

In other words, it is a carbon-6111 oil whose main components have boiling points in the range of 15O-, t0oC, and has an aromatic oil content of %n-hebutane (mW) and an aromatic content of the resin content. Carbon fraction is 0
．． Oil or boiling point with a number average molecular weight of 6 or more and a number average molecular weight of /, 000 or less! A tar-like substance containing undesirable components as produced components of ftto℃ or higher, with an aromatic oil component and a resin component each having an aromatic carbon fraction of 0.7 or more, and a number average molecular weight of i, ooo or less. It is.

The pitch starting material of Tosai et al. is subjected to thermal reaction (rotation and decomposition products) at 370''C to SOO℃, preferably 3gO℃ to 30℃. When it devolatilizes, the ^P phase is generated and increases, resulting in the final e (optically anisotropic pitch is desired, but in order to obtain a pitch of better quality and stable quality, T. improved optical anisotropy. As a method for producing sexual pitch, the method 1' of the present invention involves a thermal mIMization reaction step with 7C''ri, which is first cut to 71'' at an early stage, resulting in a characteristic kingship called IJ song.
I The timing for thermal settling is such that the pitch contains a small portion of quinoline-soluble matter and benzene-insoluble matter, the softening point of the pitch has not yet reached a high level, and two phases with different specific gravities are present in the molten state. This is when the state is such that it contains

Furthermore, to be more specific, the quinolinoleic content is approximately
2Q wt%, quinoline-soluble and benzene-insoluble components are approximately! -Contains U OwtlG and has a softening point of 200℃
Below is the relative specific gravity in the pitch in the molten state at about 100 degrees Celsius higher than its softening point? A big phase! ;
-! ; should be subjected to vitunaic thermal settling of properties such as Owt'lk included.

The pitch at this stage has its characteristics as described above.

It is not necessary to strictly control within a narrow range H, but 1ItI
mentioned.

Starting glands can be obtained under a wide range of conditions with mild heat conversion, and it is also possible to obtain them directly from other processes.

The bits that should be subjected to this heat settling are too excessively I[/Nized and contain quinoline.

Alternatively, if the benzene insoluble content is excessively larger than the above range, it is undesirable because a lot of lower layer pitch is discarded during thermal settling, which ultimately reduces the yield of the product.
Also, if the softening point is lower than about -00℃, use heat selling. It is not desirable because it involves summer and long waiting times.

In addition, on the other hand, the cram school is not made heavy enough, and the
Or, if the benzene insoluble matter is smaller than the above range, and the formation of a phase with a larger ratio of 1 in the pitch is too small, the separation and removal of the lower layer during thermal settling may be insufficient, or the lower layer may be As a result, the object of the present invention cannot be sufficiently coupled with VC in many cases.

Next K, charcoal tiir pitch starting qIIJ quality i as mentioned above
The IJ phase is produced in a temperature range where thermal reactions such as thermal decomposition and thermal combination are sufficiently gradual, and where the pitch system has sufficient fluidity. It is in a molten state containing properties, and the editing takes place in the f region. More specifically, although it depends on the softening point and viscosity of the pitch to be applied, a 11FK range of -00°C to 00°C is used. Also, mackerel root can be eaten with the addition of % zhuji or linkayu.

There is no particular need for this, and it is possible to settle using the car force settling effect in the molten state of the 1i contact pitch and the 1jr.
There is ilkt.

When using an fIAf tube at <100°C or higher in this process, the yarn may be disturbed by foaming and evaporation due to thermal decomposition products.
In addition, since this process is carried out with little or no fluidity of the liquid phase, if the salinity is too high, there is a risk of caulking (settling @ Ume no Kinho table (2)), which is not preferable. . Also.

At a temperature lower than θ0°C, sufficient fluidity can be obtained even if the softening point of the pitch used in the settling process is considerably lower than 200°C. Therefore, either a long s'111 time period or no phase separation occurs at all.

I@r is generated when it is difficult to extract the lower layer.

In the settling step, the purpose is to be delayed by maintaining the temperature at the above-mentioned temperature for a period of time without performing full-scale separation, but for the purpose of performing quadruple separation. , or for the purpose of making the fIAm distribution uniform throughout the system,
It goes without saying that there may be waves that do not help the tX and 1klIr of the sinking phase.

In addition, in the thermal settling step, the purpose is to separate and extract the phase with a higher specific gravity, and to remove the large turbulence of the phase with a higher specific gravity in the pitch.

There is no need to completely remove the lower layer, and there is no need to completely remove the lower layer.

That is, generally after the thermal settling, the lower pigeon meeting w,
Even in the upper layer of pitch, a small portion of a heavier phase remains, but it does not have a big impact on the final product of the original pitch. In the IJ song, the larger the contraction of the phase with a larger ratio in the lower layer, the better, but 70 to 90 wtfb power is sufficient, and - above him - middle IL fu. The survival rate of phases with a higher specific gravity than that of the filtrate is small.

preferably 5% to 301 before settling. If you can do it yourself, you can accomplish your goal 1sttt.

1 of the pitches to be subjected to the thermal settling process described above.
- Regarding the light weight method: 1. Although the present invention is not particularly limited, various carbonaceous monomer oils or so-called tars or pitches manufactured by Petroleum Industries or Sekishin Industries, which are raw materials for pitch production, may be used as raw materials for pitch production. @A preferable method is to add heat treatment to the armpit heat 1 and heat it to 111°C.

That is, for one thing, JIfi materials for pitch manufacturing are approximately 37
11 (heating in the range of θ°C to 60°C, preferably 00°C to 1730°C, during which time a small gas is passed over the pitch liquid surface, and a low molecular weight gas is bubbled into the pitch phase). While promoting the devolatilization of the substance, it causes a thermal reaction, and as a result, the remaining pitch contains AP spherical bodies S% to SO% and quinoline bath in the range of 2wt% to θWt. .

At the point when the softening point of the entire F1# K pitch is still below 200°C, the vl thermal iris conversion reaction is stopped, and it is removed from the boiling tank and heated to the next thermal stage). .

In the case of ζV, it is preferable that the settling step be carried out at a temperature in the range H of SO to θ0°C.

Another improved method for producing pitch for IJ song application is to use a raw material warehouse for pitch production, from 370°C to 60"C1, preferably q0
It is heated to a salinity in the range of 0°C to 30°C to cause a thermal reaction, but no inert gas is passed during this time.

Rather, it is carried out in a sealed system or under high pressure, without forcing the steamer to be removed, but by encouraging the reflux of the IN fuel and cracked oil (σ). To explain more specifically, when the raw carp is passed through a pressure-resistant thermal reaction vessel and heated to the above-mentioned salinity, thermal decomposition of low molecular weight/4: due to acid compounds, etc. Pressure increases, but pressure! Continuing the reaction meeting, the quinoline content of the produced pitch is l wt% ~
/ Q wt- range and benzene soluble content is 6o w
This is a method in which the thermal reaction process is stopped at a residence time such that the temperature reaches ts or higher and the softening point does not reach 750°C or higher, and the material is removed from the pinch reaction chamber and transferred to the next thermal settling process. In addition, a similar method is used at °C and normal pressure, or does not promote devolatilization.

Rather, most of the raw materials or low molecular weight substances that arrive are refluxed to the reaction system at the bottom of the kettle and subjected to a thermal reaction at the above-mentioned reaction temperature.
Quinoline bath content of generated pitch, 2wt%~/Q wt
H, penzen soluble content 6Q wt H or higher, soft point 750
Regarding the pressure in the above-mentioned closed system method, which is a method that costs less than K11llll, pressure does not have a direct effect on promoting the reaction, but is a decomposition product, or
In order to suppress the devolatilization of unreacted raw materials out of the system, [
Although the pressure may be increased, it is preferable that the pressure is as small as possible, so if the reaction mf is around 130℃,
It is preferable to use III pressure -1 for ex, 2.

In the pitch pottery making process before undergoing thermal settling, the liquid phase must be thoroughly stirred or stirred so that the two phases generated during the process do not clearly separate, and the temperature distribution during the reaction is not uneven. Needless to say, it must be made to flow.

The characteristics of the method for producing IJ songs with pitches of 4r and 4r are the pitches 1, Q, and 4r of IJ songs. Because it contains more low molecular weight substances, the heat and snow settling process can be completed at a lower rate. Ding, that is, /! ;0℃～DaOO℃.

More preferably, by using a temperature of 100° C. to 330° C., the purpose can be achieved under easy-to-operate conditions without any thermal reaction.

Next, the post-processing process of "the pitch portion containing many phases with lower specific gravity" obtained as a result of the above-mentioned thermal settling process will be explained in detail.

The post-processing process is in the pitch ^P#! The frequency increases, and
If the softening At is not increased too much, %V
Although adding 1 cllj is not enough, according to research by the Ministry of the Invention and others, it has been found that the method described in the first section is particularly preferable.

The method for year 7 is the above-mentioned heat treatment.
phase with a smaller ratio of 1 than 300°C
Once within the range of ~q-0℃, only the heat] IIjillization is performed,! This is a method in which the thermal atomization step is continued until the IP in the I-retention pitch becomes 20% or less.

, 1 In other words, the process of making the cabin is heated
・Medium V of "pitch part that includes many encounters with small Jri specific gravity"
C is already included incorrectly. The main part is the II1 stitch of the 1 pitch component to form ^P', and in addition there are some parts.

Since the pitch component for strongly forming ^P1r is generated by Iv11 C-shaped reaction, one method is 3SO℃~10℃, preferably 370℃~
At a temperature of 20°C, the lighter pitch after thermal settling is subjected to a thermal reaction mainly consisting of pyrolysis and thermal polycondensation reaction, during which time an inert gasket reaction system VcfIL is passed through, or the lighter pitch is processed under reduced pressure. A part of the components is converted into 11-substance fractions, and some of them are deposited outside the reaction yarn, gradually becoming 1-1
By converting to 1I, the AP shadow forming part becomes 1 km long, and finally the A2 part becomes more than gθ-, and the softening point becomes 230℃ ~
Entering the range of 320℃, quinoline cure is 70wt96
When the pitch is below, preferably less than J Owtfb, preferably less than II Owt16.

Another thermal m* conversion method is a method in which the reaction process is divided into a thermochemical reaction process and a vapor deposition process with less thermal reaction.

That is, *vl, 3'lO<0>C to 0<0>C in the lighter pitch part after thermal settling.

Preferably, at a temperature of 390°C to qθ0°C, the desired pitch is subjected to thermal decomposition, thermal polycondensation, and a thermochemical reaction mainly under reflux conditions that do not promote devolatilization. t-, 300°C to 370°C, preferably 3-0
By subjecting it to a slow thermal decomposition polycondensation reaction in the temperature range of ℃ to 350℃ and removal of low molecular weight substances by reduced pressure or inert gas flow, the APs content is gOs or more and the softening point is
It falls within the range of 230℃ to 3℃, and the quinoline bath content is 7
This is a method of achieving a pitch of θwt% or less, preferably sowt% or less, and more preferably ltQwt- or less.

According to the method, pitches with various characteristics can be made by combining the temperature and residence time of the thermochemical reaction process and the conditions and residence time of the devolatilization operation, but devolatilization is promoted at the same time. It is characterized by the fact that it is possible to operate the process stably under a sufficiently wide range of conditions compared to conventional methods, that it can be processed in a continuous process or a slow process, and that it has a high product yield.

As one of the improvements to this method.

Thermal reaction steps at 370°C to 20°C are omitted.

It is also possible to condense and increase the AP in vituna by suppressing thermochemical reactions as much as possible and performing only low-temperature heat treatment under reduced pressure or inert gas flow in a low-temperature region. That is, after thermal settling, the light pitch is boiled for a long time at a temperature of 3θ0°C to J70°C, more preferably 300°C to 330°C, under reduced pressure or under a flow of inert gas, so that the already contained 3 is dissolved. Of^
By VC, the P-forming components are slowly thermally decomposed and X-condensed, while the excess low molecular weight components are distilled out.

Contains ^p1rgO% or more, and has a softening point of 230°C to 320°C
℃ range left, S, and quinoline solubility tII Q
It is possible to produce a pitch coat containing no more than wt%.

This method has the advantage that the processing steps 11C and 11-C take a long time, but are characterized in that the operations are simple.

(11) During these heat enrichment steps, it is preferable to provide necessary and sufficient stirring or liquid phase flow to uniformly heat the vituna or to separate the phases. Needless to say.

The inert gas used in the above explanation is 400℃ 1r
Ch N2 * Ar @ steam, etc., which is a gas that does not have a significant chemical reaction with the pitch @ quality at II degree after II (h
/'2 or low molecular weight hydrocarbons are practical.

In the 10th post-treatment method for the lighter pitch portion obtained in the thermal settling step, the lighter pitch portion obtained in the thermal settling step described above, and in the thermal refining step described above.
However, the heat-heavy process was cut off midway through, and the pitch k
nbitsuya) IJ song offering.

In this case, the method below is to take out the "phase with higher specific gravity? The pitch part that contains a lot" and make it into a product.

That is, the above-mentioned method and Atsuzaka range are used in the thermograviding step, but only by doing so, ^Pkgθ% (A, softening point 230°C ~ 30°C, quinoline □11- insoluble content t70 □- Rather than ll1lIl11 with the following, heat, 19 J! In the middle of the pickling process, the AP of the pitch is 20% ~ 70.7
7. . 1.1. hot water. . ,~3Q%(Dゎ1.i 1su,
The quinoline solubility is less than 20 wt%, preferably 20 wt%.
t(lk or less), the quinoline resin contains 23 wts or more, preferably 30 wts or more of the benzene-insoluble fraction, and the softening point of the entire pitch is 250°C or less, and the thermal Next, that pitch't,,3
At a temperature within the range of 30°C to qθθ°C.

AP'4 which is 10 larger than the lower layer! After combining the sedimentation and extracting the pitch from the bottom layer # of AP, the AP content of the pigeon is separated and extracted from the pitch part, which is mostly composed of IP, and t″L is extracted. As is, or if necessary, with further finishing, it contains AP of at least 100%, has a softening point in the range of 130°C to 300°C, and has an optical difference of less than 100% quinolinous solubles. It is designed to have a directional pitch of 1rIlII.

According to this method, F! , compared to the above-mentioned post-treatment method using only the thermal m* chemical phase, it has a higher ^P content and a lower softening point 1, and provides carbon fibers and graphite III fibers with excellent spinnability and good physical properties. Optically anisotropic carbonaceous pitch can be produced.

[Heat in this method] Commonly used in the heating process - vertical.

The reaction powder, flow method, stirring, etc. may be exactly the same as those mentioned above, and only the residence time is known.

The reheat settling method in this method may be exactly the same as the first stage heat settling described above.

It's a different kind of Q, and it's full of anger. That is, in this case V
Crf, the viscosity of the entire system is kept sufficiently low because the pitch becomes quite electric and then the thermal settling VC decreases.

The spherical kmai of AP goes to the lower layer while promoting the APh body maturation chamber.
3.30°C to μ0 in order to bring down the lumpy body
0°C m degrees'r should be used. Generally at this stage,
When IIf is used at a temperature of 320° C. or lower, 6, the coalescence and separation of AP to the lower layer becomes steep.

At gA degrees above 70°C, there are cases in which AP separation occurs in a short time of several minutes, but generally the mvit time is longer than that, and severe heat [accompanied by the reaction] occurs. Since it becomes M-red, the pitch of the product softens and rises, which is undesirable.

Below, we will show examples and comparative examples to further explain the present invention.
(Let me know.

East Example 1 A pitchke starting material containing AP Ainikura in the form of spherical bodies with a diameter or fJ of 100μ or less and having a softening point of about 2096 ibg''c was used.The quinoline solubility content of this pitch is 9 wts, and the content of quinoline-soluble and benzene-insoluble components is Fi (10,/wt-).

Collect this starting material pitch kJOOgr and! ; 0
0 mg cylindrical glass I11! The yongmei was placed in a Matsufuru furnace in a nitrogen atmosphere at 360°C for an hour, and after cooling for 1V, the glass container was broken, and the relatively brittle and glossy Nippi pitch in the lower layer (36 g) was partially removed from the upper layer. pitch of about 21,
I got 0ttrk.

The pitch of the lower layer was an optically anisotropic pitch consisting of the ^P phase of ioo*, but the pitch of the quinoline bath was
It contained 6 wt% and had a softening point of 29g''C.This pitch was 1ra pitch and leaf.

The upper layer pitch is ^P of a spherical body with an IIL diameter of about 1Oμ or less.
The majority of the ios contained in the IP is vituna, and at the IF temperature temperature, the content of quinoline-soluble components is 2 wt %, and the shoulder percentage of quinoline-soluble and benzene-insoluble components is 25% by weight. , l, wt it was a whisper.

This upper layer pitch is 200tlrlr, internal volume is 500ml
in a stainless steel reaction vessel at 40°C for an hour.

VII! When the reaction was carried out while blowing the cable gas onto the pitch liquid level in the reaction vessel at a flow rate of 4 mL/ml, approximately 9
With a 3-P content, a softening point of 273°C, and a quinoline soluble J! -7vtt'lk *An optically anisotropic Pf/Sbgr containing 21A of quinoline-soluble and benzene-insoluble components and 0vtt% remained. This pitch yb pitch and Kanopu.

Next, when the above-mentioned 1-pitch and b-pitch t and 0.5-inch diameter nozzles were filled into a spinning machine and t'' LIPF was evaluated, it was found that -pinch cannot be spun at all at a spinning temperature of 370°C or lower. It was possible to spin the yarn at a rapid rate of extrusion of 300 ml and 1 ml at 200 mHg gas pressure at a temperature of 3 g θ°C.

b pitch is Yoitoon r) Prefecture FjLJS! ``C, extrude at a pressure of about 1000 m/rnl, spin at a take-up speed of 50(1) m/rnln, and press the M key for yarn breakage not more than once every 30 minutes. Ta.

Next, 200 pieces of pitch fibers were prepared from the pitch of the Japanese cypress in the upper part.
2 hours in an oxygen stream at 0°C and then 30 minutes in a molten stream at 0°C, then 50 minutes in argon gum.
℃/mln heating up to /S00''c,
It was immediately left to cool to obtain klt: fiber. The diameter sound of these two kinds of carbon fiber samples was measured and the tensile strength was measured. i
&, Sum 1 tensile modulus of elasticity, calculate the average value, and evaluate.
The average diameter of the carbon fiber obtained from a pitch is /llμ, the average stiffness is /A GPa, and the average elasticity is /, 1IX10
GPa, and the one obtained from b pitch has an average diameter of 1 g
, 7μ, average strength is ko 1, QPa% average elastic modulus ko, 3x
It was 102GPa.

Comparative Example 1 The same starting material as in Example 1, 00g, with an internal volume of 5oo
When the reaction was carried out in a stainless steel reaction vessel at 1,700°C for an hour while blowing nitrogen gas into the pitch liquid level in the reaction vessel at an amount of 1/ml, the ^P content was approximately 9S. An optically anisotropic pitch with . This pitch has a quinoline solubility of A/-/w
The amount of tss insoluble in quinoline and soluble in quinoline is 23,
The softening point reached 330° C., making it impossible to spin with the same spinning device as in Example 1.

Example 300 gr of the same starting material as in Example/ was settled in the same manner as in Example/, and the upper layer Pitzchiko 00 gr was heated in a stainless steel reaction vessel with an internal volume of 5 oou at AOO"C for 1 hour, and nitrogen gas was added to it. While circulating at /mln, it was subjected to thermogravimetry to obtain an intermediate pitch of /Af, 4(gr).

This pitch has a softening point of 111 min i) L q , 5 wt 9G Pennyang ° insoluble and quinoline soluble matter s s , ;t wt-, and contains about 5 P spheres. It was something. Next, this pitch was filled into a 200g glass cylindrical container and subjected to settling treatment again at 3gθ°C for 2 hours, and it was observed that the pitch was separated into an upper layer and a lower layer, and this lower layer pitch was about 22g. When its properties were examined, it was found that 99- was AP, had a quinoline solubility of 33.3 mm, and had a softening point of JII 4T. It was possible to spin for a long time without yarn breakage.

Comparative Example: 200 gr of the same starting material as in Example 1 was subjected to tI in a stainless steel reaction vessel with an inner volume of
Temporarily at 0.degree. C., the mixture was thermally agglomerated while flowing nitrogen gas at a rate of 1/ml to obtain an intermediate pitch of 31;1r. This intermediate pitch has a softening point of 22 degrees Celsius, contains approximately 100% of AP microspheres, and has: 1. 23.0 vtt* of quinoline-insoluble components; 30%/wt% of quinoline-soluble and benzene-insoluble components. It contained.

/00 gr of this intermediate pitch was collected, filled into a -〇〇u glass cylindrical container, and heated at 3gθ℃ for 2 hours) +
After 37gr treatment, it was observed that the pitch was separated into upper and lower two layers, and in this case, the lower layer pitch was about 2gr.
obtained, and when its properties are investigated, 1oos is mostly A.
P, has a softening point kogi, °C, and has a quinoline soluble content +
)? It contained #, U wt%, quinoline-soluble and benzene-insoluble matter of /, II wt'$. When this pitch was spun using the same spinning method as in Example, the optimum spinning temperature Fi3 was 0°C, but there were a lot of breakages.

Reference Example A pick-shaped material obtained from a petroleum catalytic cracking process is subjected to drop-free distillation under reduced pressure and has a boiling point of 1 ISO °C or higher converted to normal pressure as a starting material. 20e of this is collected and the internal volume is 5 g
Nitrogen gas 301/rri in a stainless steel reaction vessel.
The starting material of Example 1 was prepared by heat treatment at 30° C. for 5 hours under continuous flow. 1
Example 3 Same starting material tar as in the reference example, 400g, internal volume/e
The mixture was filled into a stainless steel autoclave, and after purging with nitrogen gas, the temperature was raised and heat-treated at 30° C. for 3 hours. At this time, the pressure is approximately S'Qp while removing cracked gas from the leak pulp.
/ tvm2. After the reaction, the reactor was cooled to 500C, the pressure was lowered, stirring was stopped at 230°C, and the reactor was allowed to stand for 30 minutes, after which it was cooled, the lid was opened, and the contents were decanted out at 750°C.

A slurry-like pitch remains on the walls, etc. and the bottom, and the outflow pitch is approximately S 2 gr, and its softening point is 700°C.
The following contained quinoline solubles, lIwtl, and benzene solubles g A wt91.

This 1700 gr was transferred to a stainless steel reactor at 360°C and nitrogen gas was introduced at 6e/min.
After being distributed, the remaining pitch was treated for about S hours to obtain 752 liters of residual pitch. This pitch had a softening point of 22/℃, contained about 100 grams of AP, had a quinoline-soluble content of 9 g, and was soluble in quinoline and benzene. It contained insoluble matter, IIwt.Next, this pitch/00 gr.

When the mixture was filled into a 200 m glass cylindrical container and allowed to settle at 3 g O°C for 1 hour, clear separation of upper and lower layers was observed, and a pitch of 211 gr was obtained as the lower layer. This pitch has a softening point of 241"C, ^P30, g
The pitch was wt%2, and this pitch was spun at 350°C f! using the same spinning method as in Example 1. degree,
It was possible to easily spin the yarn for more than 30 minutes without yarn breakage.

The same starting material tar as in Example and Reference Example was collected,
! A reflux tube was attached to a 00g stainless steel reactor, and a thermal reaction was carried out at SO 0 C for 3 hours without nitrogen gas flow, and 233g of residual pitch was obtained. This pitch #'i is a heterogeneous pitch that contains a small amount of slurry-like solid matter at SO℃, has a softening point of 92℃, and has a quinoline solubility of 4'*2 wt5! This pitch, which had a quinoline-soluble content and a benzene-insoluble content of 30.2 wt-, was heated in a cold apparatus for 30 minutes at SO℃, and the supernatant layer was collected by decantation, and this was transferred to a 5ooWu stainless steel reaction chamber. In the chamber, remove the reflux tube and add nitrogen gas 6#/mi.
Heat treatment was performed at 330° C. for 10 hours under a flow of n. Examining the residual pitch, ^P is about 9716, the quinoline-soluble content is 9 wt%, the quinoline-soluble and benzene-insoluble content is 'IO, 7 wt%, and the softening point is 7 wt%.
It was a pitch of 'C,

[Brief explanation of the drawing]

The attached figure is a graph showing the change in the yield of the thermally settled lower layer AP and the change in the softening point (■) with the elapse of the heat-settling reaction time. α...Settling separable region, β...Settling non-separable region. heat! Buying reaction time old r) →

Claims (1)

[Scope of Claims] (1) A method for producing optically anisotropic carbonaceous pitch, which includes a step of thermally treating a vertical grain heavy oil feedstock for pitch production, in which the thermally heavyizing is performed at an initial stage. After discontinuing the process, the pitch raw material is subjected to a settling process in which it is heated at a temperature in the range of 00 to 300°C and kept in a molten state, so that it contains a large amount of phase with a large ratio of separation. Remove the pitch part,
The remaining part of the pitch is subjected to a flexible process including a heat-heavy process.
A method for producing the optically anisotropic R woody pitch using IVi mold. (2) The raw material for pitch production is approximately 370-60
A thermal reaction is carried out while passing an inert gas at a temperature in the range of 50 to 50°C, and the pitch produced is an optically anisotropic phase, an AP spherical body 5-
soss, quinoline soluble content ~Xwt%, quinoline soluble and benzene soluble content, 1 to 90 wt%, and when the softening l of the entire pitch produced is 100°C or less, Il! The method according to claim (1)11, characterized in that the thermal reaction is stopped and settling is performed. +31 Approximately 370-da60 N grade for 1m pitch manufacturing
A thermal reaction is carried out at a temperature in the range of °C, and the pitch produced is quinoli/insoluble matter-~/OwtlG, penzen insoluble matter A.
At the point when the pitch contains Owtl1 or more and the softening point of the entire pitch is 750°C or less, the thermothermal reaction is terminated9.
The method described in Section (1) of Patent No. 11, characterized in that the method is transferred to a settling process. (4) The method according to claim e) or (8), wherein the thermal reaction is carried out at a temperature of 7'COk. +51 @Claims 8 of claims (2) to (4) characterized in that the powder used for producing pinches is heavy hydrocarbon oil, tar, or pitch produced as a by-product in the petroleum or coal industry.
1. The method described in either/product of Jjl. +61 Set III/Ko SO~q00℃
The claimed yoke TI, which is carried out at a temperature of 1 within the range of ! A (2)
) Also, the method described in item (4). (71) The settling knee is carried out at a temperature of a concave circle of 00 to aso C. (3) The method according to (4). (8) The post-treatment is 300 - 0 ° C. The process is continued until the optically isotropic phase and the IP content are within the range of 0 to 20 ms. Claims Nos. (1), (2), ~(
51, (7) IJ/method currently described. (9) The above-mentioned post-treatment is carried out at a temperature within the range of 300°C to 20°C, the AP of the produced pitch is 20-'10-, and the quinoline soluble content is 0. fwt%, a thermograviding process that is continued until the quinoline-soluble and benzene-insoluble content is at least cojwt% and the softening point of the wrinkle pitch is 25θ°C or less, )30~da000CC)N in the song The first process is carried out under high temperature. containing 7%
The method according to any one of clauses 11 to (6) of the patent claim, in which the heat distributing irises are treated as an image. and quinoline-soluble and benzene-free J Q wt- or more, the method of claim 8 Xie (9) Kiei Seki. The method described in Claim No. 81 (81, 91) is characterized in that the process is carried out at a temperature of 350 to 1 θ° C. The heat-heavy process in 37O to 9.
A step of accelerating the thermochemical reaction at a temperature in the range of 20°C, followed by a gradual heating of the thermochemical reaction at a temperature of 300°C to 300°C. 370
111iFff#fl, including a step carried out at a temperature within the range of °C under reduced pressure or under the flow of an inert gas. The heaviness step is carried out at a temperature within the range of 300 to 370°C where the thermochemical reaction is sufficiently slow, under reduced pressure or under the passage of an inert gas. 1), (81, (9)) or the method described in -.
1a41 The optically anisotropic carbonaceous pitch is 2
It has a softening point within the range of 30 to 320°C, and contains an AP of go- or more, an easy P1 of less than co-oqb, and a quinoline soluble content of less than or equal to Q wt-. (Method i according to any one of Items 11 to 2) Cod The method according to claim A4, wherein the quinoline solubility is not more than jg Q wH1. , Claim !!11 (method according to claim 19).