JPS63210081A - Manufacture of carbonaceous granular heat insulator - Google Patents
Manufacture of carbonaceous granular heat insulatorInfo
- Publication number
- JPS63210081A JPS63210081A JP62042721A JP4272187A JPS63210081A JP S63210081 A JPS63210081 A JP S63210081A JP 62042721 A JP62042721 A JP 62042721A JP 4272187 A JP4272187 A JP 4272187A JP S63210081 A JPS63210081 A JP S63210081A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- pellets
- binder solution
- heat insulating
- specific gravity
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000012212 insulator Substances 0.000 title 1
- 239000006229 carbon black Substances 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000008188 pellet Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 11
- 239000011810 insulating material Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000012774 insulation material Substances 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 239000007771 core particle Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011361 granulated particle Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 101100295884 Aedes aegypti SGPRor7 gene Proteins 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920003261 Durez Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101150041122 Orco gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000009818 secondary granulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、非酸化性雰囲気の高温炉に使用する炭素質粒
状断熱材の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a carbonaceous granular heat insulating material used in a high temperature furnace in a non-oxidizing atmosphere.
炭素材は、非酸化性雰囲気中における高温安定性ならび
に化学的安定性が優れており、高温炉における耐火材や
断熱材として使用されている。Carbon materials have excellent high-temperature stability and chemical stability in non-oxidizing atmospheres, and are used as refractory materials and heat insulating materials in high-temperature furnaces.
炭素質断熱材としては、発泡樹脂を焼成炭化するもの、
炭素繊維のフェルトに樹脂を含浸して焼成炭化するもの
等が実用化されており、これらはいずれらフオーム状の
形態として存在する空隙の断熟作用を利用するものであ
る。しかし、原料が高価であり、また製造工程も複雑な
ために、コストが高くなり使用範囲が制限される欠点が
ある。As carbonaceous insulation materials, foamed resin is fired and carbonized,
Products in which carbon fiber felt is impregnated with resin and fired and carbonized have been put into practical use, and these methods utilize the ripening effect of voids that exist in a foam form. However, the raw materials are expensive and the manufacturing process is complicated, resulting in high costs and limited range of use.
カーボンブラックは、１０〜２００ｎｍの極めて微細な
球状の基本粒子が融着結合および二次的に凝集した鎖状
構造の凝集体から成り、凝集体内部には多くの空隙がｒ
ｔ在する。また、基本粒子は表面層やその近傍は炭素六
角網面を構成しているが、全体的には無定形炭素である
。したがって、カーボンブラック自体優れた断熱機能を
有しており、かつ安価であるので、例えば高温炉の断熱
充填材等として用いられている。Carbon black consists of aggregates with a chain structure in which extremely fine spherical basic particles of 10 to 200 nm are fused and aggregated, and there are many voids inside the aggregates.
t exists. Furthermore, although the surface layer and the vicinity of the basic particle form a hexagonal carbon network, the basic particle is amorphous carbon as a whole. Therefore, since carbon black itself has an excellent heat insulating function and is inexpensive, it is used, for example, as a heat insulating filler for high temperature furnaces.
しかし、カーボンブラックは微粉体状であり、充填ある
いは排出時等に飛散し易く、流動性も悪いノこめに取扱
いが極めて困難である。また、粉体カーボンブラックを
造粒したペレットら造粒強度か小さいために取扱い時に
磨損や破粒し易く、微粉化して飛散したり、流動性を悪
化させる等の問題がある。However, carbon black is in the form of a fine powder, easily scatters during filling or discharging, and has poor fluidity, making it extremely difficult to handle. Furthermore, since the granulation strength of the pellets obtained by granulating the powdered carbon black is low, the particles are easily abraded or broken during handling, and there are problems such as pulverization and scattering, and deterioration of fluidity.
本出願人は、カーボンブラックの断熱性能を保持すると
と乙に粒強度を増大さ仕て取扱いの容易な粒状断熱材の
製造方法として、カーボンブラックペレットに、熱硬化
性樹脂を有機溶媒に溶解した溶液を含浸し、加熱して有
機溶媒を揮散除去した後予備硬化し、必要に応じて更に
その表面を前記溶液で処理して加熱硬化した後焼成炭化
する方法を提案した（特願昭６２−１８１６５）。The present applicant has developed a method for producing a granular heat insulating material that retains the heat insulating performance of carbon black, increases grain strength, and is easy to handle. We proposed a method in which a solution is impregnated, heated to volatilize and remove the organic solvent, and then precured, and if necessary, the surface is further treated with the solution, heated and cured, and then fired and carbonized (Patent Application No. 1982- 18165).
〔発明が解決しようとする問題点り
ごの方法で得られる粒状断熱材は、カーボンブラック自
体の有する断熱性能を損なうことなく大きな粒強度をａ
しており、磨損や破粒し短いために取扱いが容易であり
、流動性ら優れたものであるが、工程が複雑となり製造
能率が悪いという問題がある。[Problems to be solved by the invention The granular heat insulating material obtained by Rigo's method has a large grain strength without impairing the heat insulating performance of carbon black itself.
It is easy to handle because it does not wear out or break, and has excellent fluidity, but it has the problem that the process is complicated and manufacturing efficiency is low.
本発明は、上記問題点を解消して優れた断熱性能を有す
るとと乙に粒強度の大きな炭素質粒状断熱材を、能率よ
く製造する方法を提供する乙のである。The present invention solves the above-mentioned problems and provides a method for efficiently producing carbonaceous granular heat insulating material having excellent heat insulation performance and high grain strength.
ずなわら本発明は、下記特性のカーボンブラックペレッ
トを炭化性成分を６機溶媒に溶解したバインダー溶液を
添加して再造粒した後加熱硬化し、次いで不活性雰囲気
中で焼成炭化することを特徴とする炭素質粒状断熱材の
製造方法である。Zunawara The present invention involves adding a binder solution in which carbonizable components are dissolved in six solvents to carbon black pellets having the following properties, re-granulating them, heating and hardening them, and then firing and carbonizing them in an inert atmosphere. This is a method for manufacturing a carbonaceous granular heat insulating material.
圧縮ＤＢＰ吸油ｆｆｌ ８０ｍ（１／ Ｉ ００ｇ
以上窒素吸着比表面積 ３５ｍ”７ｇ 以上真比重
関係値（Δｄ＝ｄ２） ０．１５０ 以下但し、真比
重関係値（Δｄ＝ｄ２）は、Δｄ＝ｄ２＝ｄ、−ｄ、で
定義され、（１，およびｄ、は夫々６５０℃および２６
００℃で熱処理したカーボンブラックの真比重値と４゛
る。Compressed DBP oil absorption ffl 80m (1/I 00g
Nitrogen adsorption specific surface area: 35m”7g True specific gravity relationship value (Δd=d2): 0.150 or less However, the true specific gravity relationship value (Δd=d2) is defined as Δd=d2=d, -d, and (1 , and d are 650°C and 26°C, respectively.
The true specific gravity value of carbon black heat-treated at 00°C is 4°.
カーボンブラック微粉体を造粒機に入れ、バインダー溶
液を加えて直接造粒すると、ペレット形成時に侵入した
バインダー溶液は、カーボンブラックの鎖状構造凝集体
内部にまで浸透するために加熱硬化時にも残留し易く、
そのまま炭化ずろ。When carbon black fine powder is placed in a granulator and directly granulated by adding a binder solution, the binder solution that entered during pellet formation penetrates into the chain structure aggregates of carbon black and remains even during heat curing. easy to do,
Just carbonize it.
その結果、カーボンブラック本来の断熱性能が損なわれ
る。As a result, the heat insulating performance inherent to carbon black is impaired.
本発明は、カーボンブラックの鎖状構造凝集体をはじめ
とする基本粒子特性と断熱性能との関係について詳細に
研究した結果、特定の基本粒子特性を１丁するカーボン
ブラックを用い、かつそのペレットをバインダー溶液で
再造粒して２次造粒粒子を形成した後加熱硬化、焼成炭
化処理ずろと断熱性能を劣化することなく大さな強度を
ｎずろ粒状体が得られろことを知見して完成したもので
ある。As a result of detailed research on the relationship between basic particle properties such as carbon black chain structure aggregates and heat insulation performance, the present invention uses carbon black that has one specific basic particle property, and its pellets. After re-granulating with a binder solution to form secondary granules, it was found that a granular material with great strength could be obtained without deteriorating heat-insulating performance by heating and hardening and firing and carbonizing the granules. It is completed.
微粉体状のカーボンブラックを、まず球状のペレットに
造粒ずろ。造粒は公知の方法によって行なうことができ
、例えば湿式法ではピンを表面に備えたシトフト等の強
制攪拌機構をもつ円筒管中にカーボンブラックを入れ、
シャフトを回転させて攪拌しながら適量の水を加えて造
粒する乙のであり、乾燥してペレットとする。また、乾
式法ではわずかな傾斜をもって緩やかに回転する円筒形
キルンを用い、その中にカーボンブラックを入れて転勤
造粒してペレットを形成ずろらのである。First, fine powder carbon black is granulated into spherical pellets. Granulation can be carried out by a known method. For example, in the wet method, carbon black is placed in a cylindrical tube equipped with a forced stirring mechanism such as a shaft with pins on the surface.
It is granulated by adding an appropriate amount of water while stirring by rotating the shaft, and then dried to form pellets. In the dry method, a cylindrical kiln that rotates slowly with a slight inclination is used, and carbon black is placed in the kiln and granulated in rotation to form pellets.
カーボンブラック微粉体は、ます造粒過程の初期におい
て鎖状構造凝集体が多数集合して造粒核粒子を形成し、
この造粒核粒子が合体してペレットに成長する。In carbon black fine powder, a large number of chain-like aggregates gather together to form granulation core particles at the early stage of the granulation process.
These granulation core particles coalesce and grow into pellets.
このカーボンブラックペレットを前記湿式造粒機に入れ
て、攪拌しながら所定量のバインダー溶液を添加して造
粒する。バインダー溶液としては熱硬化性樹脂、タール
、ピッチ等の炭化性成分を有機溶媒に溶解した溶液が用
いられる。熱硬化性樹脂としては炭化率の高いフェノー
ル系やフラン系の樹脂が好ましい。また、ａ機溶媒とし
ては、これらの炭化性成分を溶解する乙のであればよく
、アルコール、エーテル、アセトン、ベンゼン、トルエ
ン、キシレン、シクロヘキサン等任意のものを使用づ゛
ることかできる。なお、バインダー溶液の濃度や添加量
は、カーボンブラックの特性に応じて適宜設定する。The carbon black pellets are placed in the wet granulator and granulated by adding a predetermined amount of binder solution while stirring. As the binder solution, a solution in which a carbonizable component such as a thermosetting resin, tar, or pitch is dissolved in an organic solvent is used. As the thermosetting resin, phenol-based or furan-based resins having a high carbonization rate are preferred. Further, as the organic solvent, it is sufficient that it dissolves these carbonizable components, and any solvent such as alcohol, ether, acetone, benzene, toluene, xylene, cyclohexane, etc. can be used. Note that the concentration and amount of the binder solution to be added are appropriately set depending on the characteristics of carbon black.
カーボンブラックペレットを造粒機に入れて攪拌しなが
らバインダー溶液を添加すると、ペレットは破砕されつ
つバインダー溶液により再造粒されて球状の２次造粒粒
子を形成する。この場合、カーポンプダックペレットは
鎖状構造凝集体にまで破砕されることは少なく、造粒核
粒子らしくはそれらの集合した状態でバインダー溶液に
よって球状の２次造拉粒子に成長する。したがって、バ
インダー溶液は鎖状構造凝集体の空隙内部にまで浸透す
ることなく、造粒核粒子あるいはその集合体の表面に吸
着存在するに過ぎない。その結果、この２次造粒粒子を
加熱して溶媒成分を除去した後硬化および炭化処理した
場合に形成する炭化物は、鎖状構造凝集体の空隙部には
殆んど存在しないのでカーボンブラック本来の有する断
熱性能の劣化が防止されろ。また、この炭化物により粒
強度は粁しく増大する。なお、微粉体状のカーボンブラ
ックを直接バイングー溶液で造粒ずろ場合には、バイン
ダー溶液はカーボンブラック鎖状構造凝集体内部にまで
浸透するので、硬化および焼成炭化時にもそのまま残留
して炭化物を形成することになり、断熱性能は苦しく阻
害される。When carbon black pellets are placed in a granulator and a binder solution is added while stirring, the pellets are crushed and re-granulated by the binder solution to form spherical secondary granulated particles. In this case, the carpump duck pellets are rarely crushed into chain-like structure aggregates, and, like granulation core particles, the aggregated state grows into spherical secondary agglomerated particles by the binder solution. Therefore, the binder solution does not penetrate into the pores of the chain structure aggregates, but merely exists by adsorption on the surface of the granulation core particles or their aggregates. As a result, the carbide that is formed when the secondary granulated particles are heated to remove the solvent component and then cured and carbonized is not present in the voids of the chain structure aggregates, so it is essentially carbon black. Prevent the deterioration of the insulation performance of In addition, grain strength is significantly increased by this carbide. In addition, when fine powder carbon black is directly granulated with a binder solution, the binder solution penetrates into the carbon black chain structure aggregates, so it remains as it is during curing and firing carbonization, forming carbides. As a result, the insulation performance is severely impaired.
この場合、カーボンブラックの断熱性能は、カーボンブ
ラックの基本粒子特性と密接に関係し、断熱性能を高度
に保持するためには鎖状構造凝集体が大きく内部空隙が
多いこと、バインダー溶液が鎖状構造凝集体の内部空隙
に浸透し難いこと、また形成する造粒核粒子が相対的に
大きくて２次造粒粒子の成長に必要なバインダー溶液が
相対的に少量であること等が望ましい。ずなわらカーボ
ンブラックの基本粒子特性としては、高ストラクチャー
、高比表面が好ましいことになる。In this case, the thermal insulation performance of carbon black is closely related to the basic particle characteristics of carbon black, and in order to maintain a high level of thermal insulation performance, the chain structure aggregates must be large and have many internal voids, and the binder solution must have a chain structure. It is desirable that the binder solution is difficult to penetrate into the internal voids of the structural aggregate, that the granulated core particles to be formed are relatively large, and that a relatively small amount of the binder solution is required for the growth of the secondary granulated particles. The basic particle characteristics of Zunawara carbon black are preferably high structure and high specific surface.
本発明は、これらの観点から圧縮ＤＢＰ吸油量を８０ｍ
（／１００９以上、窒素吸着比表面積を３５ｍ”／ｙ以
上に設定するものである。圧縮ＤＢＰ吸油屯を８０ｍ（
１／ ｌ ００ｇ以上に設定することにより相対的に鎖
状構造凝集体が大きく、その内部空隙し多くなり、また
大きな造粒核粒子の形成も容易となるので、バインダー
溶液ら少ない量で２次造粒核拉子の成長が可能となる。From these viewpoints, the present invention improves the compressed DBP oil absorption to 80 m
(/1009 or more, the nitrogen adsorption specific surface area is set to 35 m"/y or more. The compressed DBP oil absorption tonne is set to 80 m"/y or more.
By setting the value to 1/l 00g or more, the chain structure aggregates are relatively large and have many internal voids, and it is also easy to form large granulation core particles, so a small amount of binder solution can be used for secondary The growth of granulation nuclei becomes possible.
窒素吸着比表面積を３５ｍ”／９以上に設定するのは、
カーボンブラックの基本粒子径が小さく、形成した造粒
核粒子中にバインダー溶液が浸透し難いためであり、そ
の結果２次造粒粒子の空隙の低下が防止される。Setting the nitrogen adsorption specific surface area to 35 m”/9 or more is
This is because the basic particle size of carbon black is small, making it difficult for the binder solution to penetrate into the formed granulated core particles, and as a result, reduction of the voids in the secondary granulated particles is prevented.
なお、圧縮Ｄ Ｂ Ｐ吸浦量および窒素吸着比表面積は
下記の測定方法によって得られる値である。In addition, the compression DBP absorption amount and the nitrogen adsorption specific surface area are values obtained by the following measurement method.
圧縮１） Ｂ Ｐ吸油量：
ＡＳｉ”Ｍ Ｄ３４９３−７９ “Ｃａｒｂｏｎ
ＢｌａｃｋＤｉｂｕｔｙｌ Ｐｂｔｈａｌａｔｅ
Ａｂｓｏｒｐｔｉｏｎ Ｎｕｍｂｅｒ ｏｒＣｏ
ｍｐｒｅｓｓｅｄ Ｓａｍｐｌｅ″による。Compression 1) BP oil absorption: ASi"MD3493-79"Carbon
Black Dibutyl Pbthalate
Absorption Number orCo
mpressed Sample''.
窒素吸着比表面積：
ＡＳｉ’Ｍ Ｄ３０３７−７８ ’ Ｓｔａｎｄａ
ｒｄＭｃｔｂｏｄｓ ｏｆ Ｔｅｓｔｉｎｇ Ｃａｒｂ
ｏｎ Ｂｌａｃｋ ５ｕｒｆａｃｅ Ａｒｅａｂｙ Ｎ
ｉｉＮｌｌｒｏ Ａｂｓｏｒｐｔｉｏｎ″ Ｍｅｔｈｏ
ｄ Ｂによる。Nitrogen adsorption specific surface area: ASi'M D3037-78' Standa
rdMctbods of Testing Carb
on Black 5 surface Area N
iiNllro Absorption”Metho
d By B.
また、真比重関係値Δｄ＝ｄ２は、下記定義に基づく値
であるが、この値はカーボンブラック基本粒子の内部構
造と密接に関係する。ずなわち、Δｄ＝ｄ２はカーボン
ブラックの生成過程における炭化度（黒鉛状炭素六角網
面構造）の進行程度に対応し、カーボンブラックの基本
粒子径が小さく、比表面積および圧縮Ｄ ［３１）吸油
量が相対的に大きい場合にはΔｄ＝ｄ２は小さい値とな
る。これはカーボンブラック基本粒子内部における無定
形炭素構造が高温処理した場合に、粒子内部で再配向し
難く、Ｆｕ ＭＵな黒鉛化形態をとるために粒子内部が
空洞化乃至スポンジ状のポーラス構造になるためと考え
られろ。Further, the true specific gravity relationship value Δd=d2 is a value based on the following definition, and this value is closely related to the internal structure of carbon black basic particles. In other words, Δd=d2 corresponds to the degree of progression of carbonization (graphitic carbon hexagonal network structure) during the production process of carbon black, and the basic particle size of carbon black is small, specific surface area and compression D [31] Oil absorption If the amount is relatively large, Δd=d2 will be a small value. This is because when the amorphous carbon structure inside basic carbon black particles is subjected to high-temperature treatment, it is difficult to reorient within the particles, and the inside of the particles becomes hollow or has a spongy porous structure because it takes a Fu MU graphitized form. It can be considered as a reason.
このΔｄ＝ｄ２を０．１５０以下に設定することにより
基本粒子内部のポーラス措造化が進行して断熱性能の向
上をはかることができる。By setting Δd=d2 to 0.150 or less, the inside of the basic particles becomes porous, and the heat insulation performance can be improved.
真比重関係値（Δｄ＝ｄ２）：
カーボンブラック試料を落し直付るつぼに採り６５０±
２５℃の温度で脱気処理を施した後“工業化学雑誌”第
６６巻、第１２号（１９６３）１７５８頁に掲載された
Ｂ法に準拠して測定した真比重値をｄ、とする。別に温
度２６００±５０℃で熱処理を施した後同様にして測定
した真比重値をｄ、とする。真比重関係値（Δｄ＝ｄ２
）は、Δｄ＝ｄ２＝ｄ、−ｄ。True specific gravity relationship value (Δd=d2): Drop a carbon black sample and take it into a crucible directly attached to it.650±
The true specific gravity value measured in accordance with method B published in "Industrial Chemistry Magazine" Vol. 66, No. 12 (1963), p. 1758 after degassing at a temperature of 25° C. is defined as d. Separately, the true specific gravity value measured in the same manner after heat treatment at a temperature of 2600±50° C. is defined as d. True specific gravity relation value (Δd=d2
) is Δd=d2=d, -d.
で定義した算出値である。This is the calculated value defined in .
このようにして得られた２次造粒粒子は、大気＋１ｊ
３００℃以下の温度で熱処理してバインダー溶液中の６
機溶媒を除去するとと乙に炭化性成分を硬化さＵｏる。The secondary granulated particles thus obtained are exposed to the atmosphere +1j
6 in the binder solution by heat treatment at a temperature below 300°C.
When the organic solvent is removed, the carbonizable components are hardened.
この場合、回転ドラム中に入れて回転転動しながら加熱
硬化すると整粒作用が促進されて真球状に近くなり、破
粒の防止もはかられるので取扱いの上からもａ刊である
。更に５００℃前後の温度に昇温すると炭化し難い成分
を除去４゜ることかできる。次いで、非酸化性雰囲気中
で１０００〜２０００℃に加熱して炭化性成分を焼成炭
化することにより、強固な炭素質粒状物が製造される。In this case, if the particles are placed in a rotating drum and heated and cured while being rotated and rolled, the granulation effect will be promoted and the particles will become close to perfect spheres, and breakage of the particles will be prevented. Further, by raising the temperature to around 500°C, components that are difficult to carbonize can be removed by 4°. Next, strong carbonaceous granules are produced by heating to 1000 to 2000° C. in a non-oxidizing atmosphere to burn and carbonize the carbonizable components.
本発明方法を適用４゛ることにより、形成した２次造粒
拉子は鎖状措造凝集体の空隙内部へのバインダー溶液の
浸透が巧みに阻止されろ。したがって、この２次造粒拉
子を焼成炭化−して得られる炭素質粒状物はカーボンブ
ラック本来の断熱性能を維持しつつ、粒強度の昔しい増
大化をはかることができろ。By applying the method of the present invention, the secondary granulation particles formed can effectively prevent the binder solution from penetrating into the voids of the chain-like aggregates. Therefore, the carbonaceous granules obtained by firing and carbonizing the secondary granules can maintain the heat insulating performance inherent to carbon black while increasing grain strength.
実施例１
各種特性のカーボンブラックペレットを用いて、バイン
ダー溶液を添加して造粒した。バインダー溶液はフェノ
ール樹脂（住友デュレズ（株）、Ｉ”Ｒ１６４７０）お
よびフラン樹脂（日立化成（株）、ヒタフランＶＦ３０
３）を、エタノールおよびエタノール／アセトン混合液
（ｌ対ＩＶｏ１．比）に、所定濃度に溶解して使用した
。Example 1 Carbon black pellets with various properties were used and granulated by adding a binder solution. The binder solution was a phenolic resin (Sumitomo Durez Co., Ltd., I"R16470) and a furan resin (Hitachi Chemical Co., Ltd., Hitafuran VF30).
3) was used after being dissolved in ethanol and an ethanol/acetone mixture (l:IVo1. ratio) to a predetermined concentration.
得られた２次造粒粒子は、大気中で１５０℃１１時間加
熱して溶媒を押故除去するとと乙に樹脂成分を予備硬化
した。次いで大気中２５０℃で１時間加熱硬化した後窒
素雰囲気中で２０００℃、３０分間焼成炭化した。この
ようにして得られた炭素質粒状断熱材の強度特性および
熱伝導率を測定した。なお、測定値は次の方法による値
を用いた。The obtained secondary granulated particles were heated in the atmosphere at 150° C. for 11 hours to remove the solvent and pre-cure the resin component. Next, it was heat-cured at 250°C in the air for 1 hour, and then fired and carbonized at 2000°C for 30 minutes in a nitrogen atmosphere. The strength characteristics and thermal conductivity of the carbonaceous granular heat insulating material thus obtained were measured. Note that the measured values were determined by the following method.
（１）粒強度； 粒径１ｚｔｔｔのサンプルを天秤上に
のＵｏ、上からピストンで荷重をかけて破粒時の荷重を
測定し、サンプル５０ケについての平均値。(1) Grain strength: A sample with a grain size of 1zttt was placed on a balance with a piston applied with a load from above, and the load at the time of grain breakage was measured, and the average value for 50 samples.
（２）アトリッション： １２５μ肩の篩上にサンプル
２５ｇを入れ、５分間振とうして１２５μ肩の篩を通過
したものを除去したのち、更に１５分間振とうして１２
５μｍの篩を通過したものの重量圧（ＡＳ１’Ｍ Ｉ）
４３２１１−８４に準拠）。(2) Attrition: Place 25g of sample on a 125μ shoulder sieve, shake for 5 minutes to remove what passed through the 125μ shoulder sieve, shake for another 15 minutes, and then shake for 12 minutes.
Weight pressure of the material passing through a 5μm sieve (AS1'M I)
43211-84).
（３）熱伝導率； 周囲を断熱材で囲んだ直径３０■、
高さ９０ＪＩＩＩの円筒部の下部に、熱伝導率既知の黒
鉛標準試料（直径３０ｘｘ、高さ３０．ＭＪりを装入し
、その」二にサンプルを装填（高さ３０ｉｍ）Ｌ、更に
その上部に前記黒鉛標準試料（直径３０ｍＲ。(3) Thermal conductivity; diameter 30cm surrounded by insulation material,
A graphite standard sample of known thermal conductivity (diameter 30xx, height 30.MJ) is loaded into the lower part of the cylindrical part with a height of 90 JIII, and a sample (height 30 mm) is loaded into the lower part of the cylindrical part (height: 30 mm). The graphite standard sample (diameter 30 mR).
高さ３０■）を装入し、下部に設けた熱源により加熱す
る。測定は、窒素雰囲気中で行ない、円筒部の黒鉛標準
試料およびサンプルの温度を測定して、定常状態におけ
ろ温度勾配から熱伝導率を算出した。30cm high) and heated by a heat source installed at the bottom. The measurements were carried out in a nitrogen atmosphere, and the temperatures of the graphite standard sample and sample in the cylindrical part were measured, and the thermal conductivity was calculated from the temperature gradient in a steady state.
これらの結果を表−１に示した。また、比較のために本
発明要件をはずれる特性を有４°るカーボンブラックペ
レットについてら同様に実施し、その結果を同表中に併
記した。These results are shown in Table-1. For comparison, the same test was carried out on carbon black pellets having characteristics outside the requirements of the present invention, and the results are also shown in the same table.
実施例２
実施例Ｉで得られたＲｕｎ Ｎｏ、 １およびＮｏ、３
の２次構造粒子を、回転ドラム（回転数１５ｒｐｍ、２
００℃、２時間）中で加熱硬化した後、窒素雰囲気中で
２０００℃、３０分間焼成炭化した場合の強度特性およ
び熱伝導率を表−２に示した。なお、この方法で得られ
た粒状物の形状は、実施例１で得られたものに比べて、
球状性がより優れたものであった。Example 2 Run No. 1 and No. 3 obtained in Example I
The secondary structure particles of
Table 2 shows the strength characteristics and thermal conductivity when the specimens were heat-cured at 00°C for 2 hours and then fired and carbonized at 2000°C for 30 minutes in a nitrogen atmosphere. Note that the shape of the granules obtained by this method is different from that obtained in Example 1.
The sphericity was better.
表−２
〔発明の効果〕
上記説明で明らかなように本発明により、カーボンブラ
ック本来の有する高度の断熱性能を保持しながら、粒強
度の著しく高い粒状断熱材を能率よく製造することが可
能となる。したがって、作業性の優れた粒状断熱材の工
業的大量生産に適する製造方法として極めてａ用である
。Table 2 [Effects of the Invention] As is clear from the above explanation, the present invention makes it possible to efficiently produce a granular heat insulating material with extremely high grain strength while maintaining the high level of heat insulating performance inherent to carbon black. Become. Therefore, it is extremely useful as a manufacturing method suitable for industrial mass production of granular heat insulating materials with excellent workability.
Claims (1)
分を有機溶媒に溶解したバインダー溶液を添加して再造
粒した後加熱硬化し、次いで不活性雰囲気中で焼成炭化
することを特徴とする炭素質粒状断熱材の製造方法。 圧縮ＤＢＰ吸油量 ８０ｍｌ／１００ｇ以上窒素吸着比
表面積 ３５ｍ＾２／ｇ以上 真比重関係値（Δｄ） ０．１５０以下 但し、真比重関係値（Δｄ）は、Δｄ＝ｄ＿２−ｄ＿１
で定義され、ｄ＿１およびｄ＿２は夫々６５０℃および
２６００℃で熱処理したカーボンブ ラックの真比重値とする。 ２、炭化性成分が熱硬化性樹脂、タールあるいはピッチ
である特許請求の範囲第１項記載の炭素質粒状断熱材の
製造方法。 ３、加熱硬化を回転ドラム中で行なう炭素質粒状断熱材
の製造方法。[Claims] 1. Adding a binder solution in which a carbonizable component is dissolved in an organic solvent to carbon black pellets having the following characteristics, re-granulating the pellets, heating and hardening the pellets, and then firing and carbonizing the pellets in an inert atmosphere. A method for producing a carbonaceous granular insulation material characterized by: Compressed DBP oil absorption 80ml/100g or more Nitrogen adsorption specific surface area 35m^2/g or more True specific gravity relationship value (Δd) 0.150 or less However, true specific gravity relationship value (Δd) is Δd=d_2-d_1
where d_1 and d_2 are the true specific gravity values of carbon black heat-treated at 650°C and 2600°C, respectively. 2. The method for producing a carbonaceous granular heat insulating material according to claim 1, wherein the carbonizable component is a thermosetting resin, tar, or pitch. 3. A method for producing a carbonaceous granular heat insulating material in which heat curing is performed in a rotating drum.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62042721A JPS63210081A (en) | 1987-02-27 | 1987-02-27 | Manufacture of carbonaceous granular heat insulator |
| US07/133,989 US4888215A (en) | 1987-01-30 | 1987-12-17 | Carbonaceous granular heat insulator and process for preparing the same |
| EP87311169A EP0276563B1 (en) | 1987-01-30 | 1987-12-18 | Carbonaceous granular heat insulator and process for preparing the same |
| DE8787311169T DE3778005D1 (en) | 1987-01-30 | 1987-12-18 | CARBONATED GRAINY HEAT ISOLATOR AND METHOD FOR THE PRODUCTION THEREOF. |
| US07/348,924 US5053278A (en) | 1987-01-30 | 1989-05-08 | Carbonaceous granular heat insulator and process for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62042721A JPS63210081A (en) | 1987-02-27 | 1987-02-27 | Manufacture of carbonaceous granular heat insulator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63210081A true JPS63210081A (en) | 1988-08-31 |
| JPH0466834B2 JPH0466834B2 (en) | 1992-10-26 |
Family
ID=12643931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62042721A Granted JPS63210081A (en) | 1987-01-30 | 1987-02-27 | Manufacture of carbonaceous granular heat insulator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210081A (en) |
-
1987
- 1987-02-27 JP JP62042721A patent/JPS63210081A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0466834B2 (en) | 1992-10-26 |
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