JPH02142891A - Production of raw material pitch for pitch or carbon microballoon - Google Patents
Production of raw material pitch for pitch or carbon microballoonInfo
- Publication number
- JPH02142891A JPH02142891A JP63296165A JP29616588A JPH02142891A JP H02142891 A JPH02142891 A JP H02142891A JP 63296165 A JP63296165 A JP 63296165A JP 29616588 A JP29616588 A JP 29616588A JP H02142891 A JPH02142891 A JP H02142891A
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- softening point
- quinoline
- raw material
- infusibility
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002994 raw material Substances 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000007664 blowing Methods 0.000 claims abstract description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000011295 pitch Substances 0.000 abstract description 83
- 238000005187 foaming Methods 0.000 abstract description 15
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 239000011271 tar pitch Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011339 hard pitch Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0048—Fibrous materials
- C04B20/0056—Hollow or porous fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ピッチないし炭素微小中空体を製造するため
の原料ピッチの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing raw material pitch for producing pitch or carbon micro hollow bodies.
〈従来の技術〉 炭素微小中空体は、耐熱性、耐薬品性、導電性。<Conventional technology> Carbon microhollow bodies are heat resistant, chemical resistant, and electrically conductive.
軽量性などの緒特性を生かして、電気炉等に用いられる
高温断熱材、原子炉用炉材、Ｎ−電性プラスデック用フ
ィラー、金属や無機物との複合材料。Taking advantage of its light weight and other properties, it is used as a high-temperature insulation material used in electric furnaces, reactor materials for nuclear reactors, fillers for N-electrode plus decks, and composite materials with metals and inorganic materials.
モールディングコンパウンド用フィラー等の多岐にわた
る用途に利用することができる。It can be used in a wide variety of applications, including as a filler for molding compounds.
通常、ピッチ類を原料として炭素微小中空体を得るには
、まず原料となるピッチを球状化する必要がある。ここ
で得られるピッチ中空体についても、そのまま塗料用の
増量材、低温断熱材、各種複合材の原料等に用いること
ができるが、用途が限られるため、前述したような優れ
た特性を発現するためには、さらに不融化、炭化処理を
施す必要がある。Normally, in order to obtain carbon microhollow bodies using pitch as a raw material, it is first necessary to spheroidize the raw pitch. The pitch hollow bodies obtained here can also be used as they are as extenders for paints, low-temperature insulation materials, raw materials for various composite materials, etc., but their uses are limited, so they cannot exhibit the excellent properties mentioned above. In order to achieve this, it is necessary to further perform infusibility and carbonization treatments.
しかし、通常市販されているピッチは軟化点が１００°
Ｃ程度と低いため、そのまま用いると発泡時にピッチ中
空体同士の融着が起こりやすく、さらに不融化処理の際
にも不融化が完了する前にピッチが軟化溶融してしまい
中空形状を維持することが困難であり、またキノリン不
溶分で示される）リーカーボン１石炭、コークス粉、メ
ソフェーズ等の不溶性、あるいは難溶性の不均質物質を
含んでいる□ために、発泡工程において不均一な発泡を
起こし、均質な製品を得ることができない。However, the softening point of commercially available pitch is 100°.
Since the pitch is as low as C, if used as is, pitch hollow bodies are likely to fuse together during foaming, and even during infusibility treatment, the pitch softens and melts before the infusibility is completed, causing the pitch to maintain its hollow shape. □Contains insoluble or poorly soluble heterogeneous substances such as coal, coke powder, mesophase, etc., which causes non-uniform foaming during the foaming process. , it is not possible to obtain a homogeneous product.
そこで、従来、ピッチ系炭素中空体を得る方法について
、いくつかの提案がなされているが、いずれもピッチを
中空化する方法についての提案であり、用いる原料ピッ
チの製造方法や性状について詳しく説明されたものはな
い。Therefore, several proposals have been made regarding methods for obtaining pitch-based carbon hollow bodies, but all of them are proposals for methods for hollowing pitch, and the manufacturing method and properties of the raw material pitch used have not been explained in detail. There's nothing left.
例えば、特公昭４９−３０２５３号公報では、軟化点１
００〜３５０°Ｃ，ニトロヘンゼン不溶分Ｏ〜２５％。For example, in Japanese Patent Publication No. 49-30253, a softening point of 1
00-350°C, nitrohenzene insoluble content O-25%.
Ｈ／Ｃ＝０．２〜１．０の高芳香族性硬ピツチを原料と
する提案がなされζいるが、低軟化点（１５０°Ｃ未満
）のピッチでは発泡処理後の空気酸化による不融化処理
に長時間を要し、工業的に製造するには適していない。Proposals have been made to use highly aromatic hard pitch with H/C = 0.2 to 1.0 as a raw material, but pitch with a low softening point (less than 150°C) becomes infusible due to air oxidation after foaming. It takes a long time to process and is not suitable for industrial production.
〈発明が解決しようとする課題〉
本発明の目的は以−ヒの問題点を考慮して、均質性、不
融化性に優れたピッチないし炭素微小中空体用の原料と
なるピッチの製造方法を提案するものである。<Problems to be Solved by the Invention> The purpose of the present invention is to provide a method for producing pitch that is excellent in homogeneity and infusibility or as a raw material for carbon microhollow bodies, taking into account the following problems. This is a proposal.
く課題を解決するための手段〉
本発明者らは、前記問題点を解決すべく鋭意検討した結
果、クールピッチ類に濾過、沈腎分離等を施して、キノ
リン不溶分（Ｑ ｌ ）を実質上除去して得られた精製
ピッチを原料として所定の熱処理を施すことにより、４
１れた均質性、不融化性を有する微小中空体用ピンチを
製造できることを見出し、本発明を完成するに至った。Means for Solving the Problems> As a result of intensive studies to solve the above problems, the present inventors subjected cool pitches to filtration, kidney precipitate separation, etc. to substantially remove the quinoline insoluble content (Q l ). By using the purified pitch obtained by removing the top as a raw material and subjecting it to a prescribed heat treatment, 4
The present inventors have discovered that it is possible to produce pinches for micro hollow bodies that have excellent homogeneity and infusibility, and have completed the present invention.
すなわち本発明は、実質的にキノリン不溶分を含まない
精製ピッチを準備し、次いで該精製ピンチに不活性ガス
を吹込みながら減圧下で３００〜３８０°Ｃの熱処理を
施し、軟化点が１５０〜２５０℃、ベンゼン不溶分が３
５〜５５重量％、かつキノリン不溶分が０．０１重量％
未満の光学的等方性ピッチになるように調製することを
特徴とするピッチ乃至炭素微小中空体用原料ピッチの製
造方法である。That is, in the present invention, a purified pitch containing substantially no quinoline insoluble matter is prepared, and then heat treatment is performed at 300 to 380°C under reduced pressure while blowing an inert gas into the purified pitch to obtain a softening point of 150 to 380°C. 250℃, benzene insoluble content is 3
5 to 55% by weight, and quinoline insoluble content is 0.01% by weight
This is a method for producing pitch or raw material pitch for carbon microhollow bodies, which is characterized in that the pitch is prepared to have an optically isotropic pitch of less than or equal to.
ここで、ヘンガン不溶分。キノリン不溶分は、日本工業
標準のタールピンチ試験方法により得られるものであり
、軟化点は６°（： ／ ｍａｎの昇温速度でピッチを
加熱しながら０．５ｍｍのノズルから圧）月Ｏｋｇ／Ｃ
ｌ１ｌの荷重で押し出した時に、ピッチがノズルから吐
出し始める温度のことである。Here, the insoluble matter. The quinoline insoluble content is obtained by the Japanese industrial standard tar pinch test method, and the softening point is 6° (pressure from a 0.5 mm nozzle while heating the pitch at a temperature increase rate of 0 kg/man). C
This is the temperature at which the pitch starts to be discharged from the nozzle when extruding with a load of 11 l.
〈作 用〉 以下、本発明について具体的に説明する。<For production> The present invention will be specifically explained below.
−Ｉｌｌｕに、コールクール類は石炭の高温乾留により
得られるため原料石炭由来の灰分等の無機質、フリーカ
ーボン及びわ〕状コークス等のキノリンネ溶の固形分を
数％含んでいる。このため、このようなタールをそのま
ま蒸留してピンチにすると、ピッチ中にこれら固形分が
残留し、球状化する時不均質な発泡を起ごし、欠陥とな
るため好ましくない。従ってこれらの固形分はあらかじ
め分離除去しておく必要があるが、この方法としては濾
過沈陵分離等、公知の方法が採用できる。In addition, since coal cours are obtained by high-temperature carbonization of coal, they contain several percent of inorganic substances such as ash derived from raw coal, free carbon, and quinoline-soluble solids such as warp coke. Therefore, if such tar is directly distilled into a pinch, these solid contents remain in the pitch, causing non-uniform foaming when spheroidizing, resulting in defects, which is not preferable. Therefore, it is necessary to separate and remove these solid contents in advance, and known methods such as filtration and sedimentation separation can be used for this purpose.
次に、精製されたタールピンチ類から軽質油分を蒸留し
て、キノリン不溶分を実質」１含まない精製ピッチを得
る。このようにして得られた精製ピッチは、固形物を含
まないため非常に均質なピ・ンチとなる。Next, light oil components are distilled from the purified tar pinches to obtain purified pitch substantially free of quinoline-insoluble components. The purified pitch obtained in this way does not contain any solid matter, so it becomes a very homogeneous pitch.
次に、ピッチの不融化性を向上さゼるために、熱処理を
施してピッチの軟化点を上昇させる必要があるが、一般
に熱処理を施してピンチの軟化点を高めようとすると、
ピッチを高温士で処理しなければならない。このため、
通常の処理方法ではピッチ中の重質成分が急速な重縮合
反応によりメソフェーズ化するためピッチ中に不均質な
Ｑ＋（キノリン不溶分）成分が生成する。このメソフェ
ーズは初期過程では微小球体として発生し、熱処理の進
行に伴い成長１合体を経てピンチ全体に広がりバルクメ
ソフェーズを経て最終的にはコークスとなるが光学的等
方性のピッチマトリックス中に光学的異方性のメソフェ
ーズが発生したピッチはメソフェーズが難溶性、不融性
を示すために均質性が悪い。従ってこのようなメソフェ
ーズの生成したピッチを原料として発泡を行うと不均質
な発泡を起こし、変形したピッチ中空体しか得ることが
できない。Next, in order to improve the infusibility of the pitch, it is necessary to perform heat treatment to raise the softening point of the pitch, but generally speaking, when heat treatment is applied to raise the softening point of the pitch,
The pitch must be treated with a high-temperature technician. For this reason,
In normal processing methods, the heavy components in the pitch undergo a rapid polycondensation reaction to form a mesophase, resulting in the formation of a heterogeneous Q+ (quinoline insoluble) component in the pitch. This mesophase is generated as microspheres in the initial process, and as the heat treatment progresses, it grows and coalesces and spreads over the entire pinch, passing through the bulk mesophase and finally becoming coke. The pitch in which an anisotropic mesophase is generated has poor homogeneity because the mesophase is poorly soluble and infusible. Therefore, when foaming is performed using pitch produced in such a mesophase as a raw material, non-uniform foaming occurs and only a deformed pitch hollow body can be obtained.
しかしながら、このメソフェーズの生成を抑えて軽度の
熱処理を行ったピッチでは、揮発性の軽質成分がピッチ
に残留するため、軟化点が十分に」二がらず発泡時、不
用（化時の融着の原因となりやすい。However, with pitch that has been lightly heat-treated to suppress the formation of mesophase, volatile light components remain in the pitch, so the softening point does not decrease sufficiently and is unnecessary during foaming. This is likely to be the cause.
本発明はこれらの問題に、＋＝Ｊ して、精製ピッチを
熱処理して微小中空体用ピンチを調製する際、熱処理温
度を高めて軟化点を−にげろのではなく、熱処理時にピ
ッチ中に不活性ガスを流通させながら減圧下でピンチ中
の揮発性軽質成分を除去することにより、メソフェーズ
の生成しない均質で、かつ高軟化点のピンチを製造づ−
るごとに成功した。The present invention solves these problems by heat-treating purified pitch to prepare pinches for micro hollow bodies. By removing the volatile light components in the pinch under reduced pressure while flowing an inert gas, a homogeneous pinch with a high softening point that does not generate mesophase can be produced.
I was successful every time.
ここで、熱処理温度を３００〜３８０°〔：としている
が、ごれＧよ３００°Ｃ，ｋ ｆ＋”Ａのｌ晶度では１
分に軟化点を高めるのは困テ１Ｆであり、また熱処理温
度が３８０°Ｃを超えると、メソフェーズの生成する確
立が高くなり均質なピンチの歩￥！Ｉりが低ト″づるか
らである。Here, the heat treatment temperature is set to 300 to 380° [:, but the dirt G is 300°C, and the l crystallinity of kf+”A is 1
It is difficult to raise the softening point to 1F, and if the heat treatment temperature exceeds 380°C, there is a high probability that mesophase will be generated, resulting in a homogeneous pinch layer! This is because the I resistance is low.
また、ごの熱処理時の真空度と不活性ガス流通量は任意
に選択するごとができるが、通常は比較的低温域で処理
する場合は真空度を下げ、不活性ガス流量を増大し、比
較的高温域で処理する場合は真空度は高めで、不４も１
テ１ガス流通甲を少なく設定するのが好ましい。In addition, the degree of vacuum and the flow rate of inert gas during heat treatment can be selected arbitrarily, but normally when processing at a relatively low temperature range, the degree of vacuum is lowered and the flow rate of inert gas is increased. When processing at a high temperature range, the degree of vacuum should be high, and
It is preferable to set the gas distribution A to a small value.
次に、熱処理の程度は得られるピッチが微小中空体用に
通した、ずなわらＪＩＳ規格に基づく１業分析（、Ｂｌ
、Ｑｌｌ、 〕１７−テスターによる軟化点、偏光顕微
鏡によるピンチ組織の観察により、ベンゼン不溶分（Ｂ
ｌ）が３５〜５５重型％、キノリン不溶分（Ｑｌ）が０
．０１重量％未ン１ｖｊ、軟化点が１５０〜２５０“Ｃ
１かつ全面光学的等方性の条（’Ｉを満足するように決
定される。Next, the degree of heat treatment is determined by an analysis based on the Zunawara JIS standard (Bl.
, Qll, ]17-By observing the softening point with a tester and the pinch structure with a polarizing microscope, the benzene insoluble matter (B
l) is 35-55% heavy type, quinoline insoluble content (Ql) is 0
．． 01% by weight less than 1vj, softening point 150~250"C
1 and the entire optically isotropic condition ('I).
すなわち、Ｂｌ＜３５％、軟化点＜１５０°Ｃの場合は
、いずれもピッチの重質化、揮発１ｆ１．軽質成分の除
去が十分に行われていないことを示しており、後工程の
発泡、不融化が困難となる。That is, when Bl<35% and softening point<150°C, pitch becomes heavier and volatilization 1f1. This indicates that light components are not sufficiently removed, making foaming and infusibility in subsequent steps difficult.
一方、Ｂｌ＞５５％、軟化点〉２５０°Ｃのピッチは、
粘度が高いため発泡温度を高くしなりればならず、その
結果ピッチの熱変質等が起こり均一・な発泡が困難とな
るため好ましくない。On the other hand, the pitch with Bl>55% and softening point>250°C is
Since the viscosity is high, the foaming temperature must be raised, which is not preferable because it causes thermal deterioration of the pitch and makes uniform foaming difficult.
さらに、Ｑｌ≧０．０１％ではピッチ中に超重質な難溶
性、不融性成分の存在が認められるため、ピンチは不均
質となり均一な発泡をすることが困難となる。Furthermore, when Ql≧0.01%, the existence of extremely heavy, poorly soluble and infusible components is recognized in the pitch, so the pinch becomes heterogeneous and it becomes difficult to foam uniformly.
また、偏光顕微鏡下、光学的異方性のメソフエズが観察
されたピンチは明らかに不均質物質が含まれるため不均
一な発泡を起こし、最終的には製品欠陥となる。In addition, pinches in which optically anisotropic mesophores were observed under a polarizing microscope clearly contain non-uniform substances, causing non-uniform foaming and ultimately resulting in product defects.
これらの理由から、微小中空体用ピンチの原料としては
、Ｂ ｌ ： ３５〜５５−Ｌ％、軟化点；１５０〜２
５０°Ｃ１Ｑ Ｉ ＜０．０１ｗｔ％、全面光学的等方
性のものに限定される。For these reasons, as raw materials for the pinch for micro hollow bodies, Bl: 35-55-L%, softening point: 150-2
Limited to 50° C1Q I <0.01wt% and optically isotropic over the entire surface.
〈実施例〉 以下、本発明を実施例により具体的に説明する。<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例
コールタール（Ｂ ｌ −２，４，Ｑ ＋ ＝ ０．２
）を濾過して精製クールを得た。ごのクールの分析値は
［３＋ −２，２％、 Ｑ ＋ ＜０．０１％であった
。次にこのタールを常圧蒸留（３６０“Ｃ）して、表１
に示す精製ピッチΔを得た。このピッチの分析値はＢ１
−１４６％、 Ｑ ｌ ＜０．０１％、軟化点９０°Ｃ
であった。Example coal tar (B l −2,4, Q + = 0.2
) was filtered to obtain purified cool. The analytical value of the coolant was [3+ -2.2%, Q + <0.01%. Next, this tar was distilled under atmospheric pressure (360"C), and Table 1
A purified pitch Δ shown in was obtained. The analysis value of this pitch is B1
-146%, Q l <0.01%, softening point 90°C
Met.
次に、この精製ピンチを表１に示ず熱処理温度２８０
３００ ３８０、４００’Ｃの各温度及び真空度ならび
に窒素ガス流量で熱処理して、各々硬ピツチＢＣ，Ｄ、
Ｅを調製した。得られたピッチの分析結果を表１にまと
めて示す。Next, this refining pinch is not shown in Table 1, and heat treatment temperature is 280.
After heat treatment at temperatures of 300, 380, and 400'C, vacuum degrees, and nitrogen gas flow rates, hard pitches BC, D, and
E was prepared. The results of the pitch analysis obtained are summarized in Table 1.
また、このうちり、 Ｅのピッチを研磨後、偏光顕微鏡
（２００倍）で写真撮影した結果をそれぞれ第１図（ａ
）、 （ｂ）に示した。ピッチＤは全面が光学的等方性
を示しているがピッチＥでは微小メソフェーズが発生し
ていることがわかる。In addition, after polishing the pitches of this part and E, the results of taking photographs with a polarizing microscope (200x magnification) are shown in Figure 1 (a).
) and (b). It can be seen that at pitch D, the entire surface exhibits optical isotropy, but at pitch E, a minute mesophase occurs.
次にこれらのピ・ンチＡ−Ｅにトルエンをピンチに対し
１０重量％になるように加えて耐圧容器に仕込み各りの
ピッチの軟化点の温度で２時間’ｆＡ拌混合して、含溶
剤ピッチＡ１〜Ｅｌを製造した。各ピッチの溶剤含有率
は表２に示′づ通りであった。Next, toluene was added to these pinches A-E so that the amount was 10% by weight based on the pinch, and the mixture was charged into a pressure-resistant container and stirred and mixed for 2 hours at the temperature of the softening point of each pitch. Pitches A1 to El were produced. The solvent content of each pitch was as shown in Table 2.
引き続き、これらのピッチをもとのピッチの軟化点＋６
０〜８０°Ｃの温度で溶融し、窒素圧５ｋｇ／Ｃｌｌ１
で加圧して気相中にスプレーすることにより、ピッチ微
小中空体を製造した。しかしながら、ピッチＡを原料と
したものはほとんどが中空体同士が融着したものであっ
た。またピッチ１３を原料としたものにも一部融着した
ものが見られた。本発明を満足するピッチＣ及びＤは均
一で融着の殆どない微小中空球状体が得られた。Continue to increase the softening point of these pitches by +6
Melts at a temperature of 0 to 80°C, nitrogen pressure 5kg/Cl1
Pitch micro hollow bodies were manufactured by spraying into the gas phase under pressure. However, most of those made from Pitch A were hollow bodies fused together. In addition, some fusion was observed in products made from Pitch 13 as a raw material. Pitches C and D satisfying the present invention were uniform, and micro hollow spheres with almost no fusion were obtained.
さらにこれらの微小中空体のうち、融着したＡｌを除い
た８１〜Ｅ１について不融化、炭化処理を行った。Further, among these micro hollow bodies, 81 to E1 excluding the fused Al were subjected to infusibility and carbonization treatment.
不融化条件は空気流通下で１５０’Ｃまで３０分かけて
昇温し１５０°Ｃから３００°Ｃまで３時間かけて昇温
することにより行った。次に、炭化は不融化後、空気を
アルゴンに切り換え３００〜１０００°Ｃまで４時間か
けて昇温後、１０００°Ｃで１時間保持することにより
行ったところ、Ｂ１では融着したがＣＩ、Ｄｌでは粒径
約２００〜７００μｍの均一な炭素微小中空体を製造す
ることができた。またＥｌは粒径が２００ｐｍ〜２ｍｍ
にばらつき、均一なものが得られなかった。また球状化
率は５０％以下であった。The infusibility was achieved by raising the temperature to 150'C over 30 minutes under air circulation, and then raising the temperature from 150°C to 300°C over 3 hours. Next, carbonization was carried out by switching the air to argon after making it infusible, raising the temperature from 300 to 1000°C over 4 hours, and then holding it at 1000°C for 1 hour. With Dl, it was possible to produce uniform carbon microhollow bodies with a particle size of about 200 to 700 μm. Also, El has a particle size of 200pm to 2mm.
It was not possible to obtain a uniform product. Moreover, the spheroidization rate was 50% or less.
次に、前述のコールクールを濾過しないで蒸留し、ピッ
チＩ？を得た。次いでこのピッチを３８０°Ｃの温度で
真空度１０ｍｍ１ｌＢ、窒素ガス流量０．１ｆｆｉ／飾
・ｋｇで熱処理し硬ピンチＧを得た。これらの分析値を
表１に示す。さらにこのピッチＧにトルエンをピッチに
対し１０重量％になるように加えて耐圧容器に仕込み、
ビッヂの軟化点の温度で２時間撹拌混合しピッチＧ１を
得た。ピッチＧ１の溶剤含有率は表２に示すとおりであ
る。Next, the aforementioned Coal Coeur is distilled without filtration and pitch I? I got it. Next, this pitch was heat-treated at a temperature of 380°C, a degree of vacuum of 10 mm, 11 B, and a nitrogen gas flow rate of 0.1 ffi/kg to obtain a hard pinch G. Table 1 shows these analytical values. Furthermore, toluene was added to this pitch G so that the amount was 10% by weight based on the pitch, and the mixture was placed in a pressure container.
Pitch G1 was obtained by stirring and mixing for 2 hours at a temperature of the softening point of pitch. The solvent content of pitch G1 is as shown in Table 2.
次に、含溶剤ピッチＧｌを、ピッチの軟化点＋６０〜８
０°Ｃの温度で溶融し、窒素圧５ｋｇ／ｃＪで加圧して
気相中にスプレーすることにより、ピッチ微小中空体Ｇ
２を製造した。この結果を表２に示す。Next, the solvent-containing pitch Gl was added to the pitch with a softening point of +60 to 8
Pitch micro hollow bodies G are melted at a temperature of 0°C and sprayed into the gas phase under a nitrogen pressure of 5 kg/cJ.
2 was manufactured. The results are shown in Table 2.
６２発泡状況はＥｌと同様に不均一であり、球状化率は
５０％以下であった。Similar to El, the foaming condition of No. 62 was non-uniform, and the spheroidization rate was less than 50%.
表１
表２
〈発明の効果〉
以上の実施例からもわかるように、本発明の方法により
精製されたピッチに不活性ガスを流通させながら減圧下
で所定の熱処理を行うことにより、均質で高軟化点のピ
ッチを得ることができ、このピッチはピッチないし炭素
微小中空体を製造するための原料ピッチとして、優れた
発泡性、不融化性を有している。Table 1 Table 2 <Effects of the Invention> As can be seen from the above examples, pitch refined by the method of the present invention is subjected to a prescribed heat treatment under reduced pressure while flowing an inert gas, resulting in a homogeneous and high-quality pitch. A pitch with a softening point can be obtained, and this pitch has excellent foamability and infusibility as a raw material pitch for producing pitch or carbon microhollow bodies.
第１図（ａ）は本発明のピッチＤ中の、（ｂ）はピッチ
Ｅ中の粒子の構造を示す、それぞれ偏光顕微鏡組織図で
ある。FIG. 1(a) is a polarizing microscopic structure diagram showing the structure of particles in pitch D and FIG. 1(b) is a structure of particles in pitch E of the present invention.
Claims (1)
、次いで該精製ピッチに不活性ガスを吹込みながら減圧
下で３００〜３８０℃の熱処理を施し、軟化点が１５０
〜２５０℃、ベンゼン不溶分が３５〜５５重量％、キノ
リン不溶分が０．０１重量％未満、かつ全面光学的等方
性になるように調製することを特徴とするピッチないし
炭素微小中空体用原料ピッチの製造方法。Purified pitch containing substantially no quinoline-insoluble matter is prepared, and then heat treated at 300 to 380°C under reduced pressure while blowing an inert gas into the purified pitch to achieve a softening point of 150.
~250°C, for pitch or carbon microhollow bodies prepared to have a benzene insoluble content of 35 to 55% by weight, a quinoline insoluble content of less than 0.01% by weight, and to be optically isotropic over the entire surface. A method for producing raw material pitch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63296165A JPH02142891A (en) | 1988-11-25 | 1988-11-25 | Production of raw material pitch for pitch or carbon microballoon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63296165A JPH02142891A (en) | 1988-11-25 | 1988-11-25 | Production of raw material pitch for pitch or carbon microballoon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02142891A true JPH02142891A (en) | 1990-05-31 |
Family
ID=17829999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63296165A Pending JPH02142891A (en) | 1988-11-25 | 1988-11-25 | Production of raw material pitch for pitch or carbon microballoon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02142891A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03206127A (en) * | 1989-12-28 | 1991-09-09 | Nkk Corp | Pitch composition |
| WO1999011585A1 (en) * | 1997-09-02 | 1999-03-11 | Lockheed Martin Energy Research Corporation | Pitch-based carbon foam and composites |
| WO1999061549A1 (en) * | 1998-05-22 | 1999-12-02 | Alliedsignal Inc. | Methods for making a pitch-based carbon foam |
| CN1076011C (en) * | 1998-01-13 | 2001-12-12 | 南通碳素厂 | Porous carbon material producing process |
| CN109250716A (en) * | 2018-12-05 | 2019-01-22 | 宁波设会物联网科技有限公司 | A kind of preparation method of asphaltic base hollow ball shape active carbon |
-
1988
- 1988-11-25 JP JP63296165A patent/JPH02142891A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03206127A (en) * | 1989-12-28 | 1991-09-09 | Nkk Corp | Pitch composition |
| WO1999011585A1 (en) * | 1997-09-02 | 1999-03-11 | Lockheed Martin Energy Research Corporation | Pitch-based carbon foam and composites |
| US6261485B1 (en) | 1997-09-02 | 2001-07-17 | Ut-Battelle, Llc | Pitch-based carbon foam and composites |
| US6387343B1 (en) | 1997-09-02 | 2002-05-14 | Ut-Battelle, Llc | Pitch-based carbon foam and composites |
| AU757545B2 (en) * | 1997-09-02 | 2003-02-27 | Ut-Battelle, Llc | Pitch-based carbon foam and composites |
| US6656443B2 (en) | 1997-09-02 | 2003-12-02 | Ut-Battelle, Llc | Pitch-based carbon foam and composites |
| US6663842B2 (en) | 1997-09-02 | 2003-12-16 | James W. Klett | Pitch-based carbon foam and composites |
| US6315974B1 (en) | 1997-11-14 | 2001-11-13 | Alliedsignal Inc. | Method for making a pitch-based foam |
| CN1076011C (en) * | 1998-01-13 | 2001-12-12 | 南通碳素厂 | Porous carbon material producing process |
| WO1999061549A1 (en) * | 1998-05-22 | 1999-12-02 | Alliedsignal Inc. | Methods for making a pitch-based carbon foam |
| CN109250716A (en) * | 2018-12-05 | 2019-01-22 | 宁波设会物联网科技有限公司 | A kind of preparation method of asphaltic base hollow ball shape active carbon |
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