JPS6365602B2 - - Google Patents
Info
- Publication number
- JPS6365602B2 JPS6365602B2 JP58178855A JP17885583A JPS6365602B2 JP S6365602 B2 JPS6365602 B2 JP S6365602B2 JP 58178855 A JP58178855 A JP 58178855A JP 17885583 A JP17885583 A JP 17885583A JP S6365602 B2 JPS6365602 B2 JP S6365602B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- expanded graphite
- sulfur
- treatment
- graphite
- 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.)
- Expired
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910002804 graphite Inorganic materials 0.000 claims description 28
- 239000010439 graphite Substances 0.000 claims description 28
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000005985 organic acids Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- -1 organic acid esters Chemical class 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 238000006477 desulfuration reaction Methods 0.000 description 12
- 230000023556 desulfurization Effects 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Description
【発明の詳細な説明】
(イ) 発明の技術分野
この発明は、たとえば弾性シール材に使用され
るような膨張黒鉛に関し、さらに詳しくは高耐食
性に富む膨張黒鉛の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Technical Field of the Invention The present invention relates to expanded graphite used, for example, in elastic sealing materials, and more particularly to a method for producing expanded graphite with high corrosion resistance.
(ロ) 発明の背景
通常使用されている膨張黒鉛の製造方法は、微
細に粉砕された黒鉛粒子を酸処理した後、水洗い
処理し、これを加熱して所定の膨張黒鉛を得てい
る。(B) Background of the Invention In the commonly used method for producing expanded graphite, finely ground graphite particles are treated with acid, washed with water, and then heated to obtain a desired expanded graphite.
しかしながら、このような製造方法にあつて
は、酸処理液の主体となる硫酸の熱分解生成物と
して硫黄および硫黄化合物等の硫黄系の不純物が
黒鉛中に3000〜5000PPm介入されることになり、
このようにして成形された膨張黒鉛をたとえばシ
ール材の素材として使用した場合、膨張黒鉛に介
入した硫黄系不純物がシール面間の金属材に対し
て腐食を誘起する原因となる。また膨張黒鉛を触
媒担体や電池の素材等に利用する場合にも、この
硫黄系の不純物が利用機能上の弊害を来たす原因
となるため、その用途についても制約を受けてい
た。 However, in such a manufacturing method, 3000 to 5000 PPm of sulfur-based impurities such as sulfur and sulfur compounds are interposed in graphite as thermal decomposition products of sulfuric acid, which is the main component of the acid treatment solution.
When the expanded graphite formed in this manner is used, for example, as a material for a sealing material, sulfur-based impurities in the expanded graphite cause corrosion of the metal material between the sealing surfaces. In addition, when expanded graphite is used as a catalyst carrier or a material for batteries, the sulfur-based impurities cause problems in terms of its functionality, so there are restrictions on its use.
そのため、硫黄系の不純物の介在を極力抑制す
ることが望まれるが、現状では商業上の見地から
硫酸を使用しない方法は実現されておらず、また
膨張黒鉛の脱硫処理に種々の試みがなされている
が、未だ廉価な脱硫手段は得られていないのが実
情である。 Therefore, it is desirable to suppress the presence of sulfur-based impurities as much as possible, but currently, from a commercial standpoint, a method that does not use sulfuric acid has not been realized, and various attempts have been made to desulfurize expanded graphite. However, the reality is that no inexpensive means of desulfurization has yet been obtained.
(ハ) 発明の目的
そこでこの発明者は、種々の脱硫手段を試みた
結果廉価で効率のよい脱硫方法を得ることができ
る膨張黒鉛の製造方法を見い出した。(c) Purpose of the Invention The inventor has tried various desulfurization methods and has discovered a method for producing expanded graphite that provides an inexpensive and efficient desulfurization method.
(ニ) 発明の要約
すなわち、この発明は黒鉛粒子を酸処理し、次
いで水洗い処理した後、加熱して成形する膨張黒
鉛を製造するに際して、酸処理液および水洗い水
のうち、少なくとも一方の処理液に、炭素、水
素、酸素の３元素からなる化合物の内、有機酸お
よび有機エステルより選ばれた少なくとも一種の
化合物を３〜30重量％添加し、この添加した処理
液で酸処理または水洗い処理を行なう膨張黒鉛の
製造方法であることを特徴とする。(D) Summary of the Invention That is, the present invention provides a method for producing expanded graphite in which graphite particles are treated with an acid, then washed with water, and then heated and molded. 3 to 30% by weight of at least one compound selected from organic acids and organic esters among compounds consisting of the three elements carbon, hydrogen, and oxygen is added, and the added treatment liquid is used for acid treatment or water washing treatment. The method is characterized in that it is a method for producing expanded graphite.
(ホ) 発明の効果
そしてこの発明によれば、処理液中に含まれる
有機酸ないしそのエステルの熱分野生成物が硫黄
と結合して硫黄を除去する作用をなすため、得ら
れた膨張黒鉛は化硫黄含有率の高品質の膨張黒鉛
となる。(e) Effects of the Invention According to the present invention, the thermal field product of the organic acid or its ester contained in the treatment liquid combines with sulfur and acts to remove sulfur, so that the obtained expanded graphite is This produces high quality expanded graphite with a high sulfur content.
したがつて、耐食性に優れ、しかも多目的の用
途に適用でき、種々の成形素材として極めて有益
に使用できる。 Therefore, it has excellent corrosion resistance, can be applied to a variety of purposes, and can be extremely usefully used as a variety of molding materials.
(ヘ) 発明の実施例
次に、この発明の一実施例に基づいて、この発
明の膨張黒鉛の製造方法を述べる。(F) Embodiment of the Invention Next, a method for producing expanded graphite of the present invention will be described based on an embodiment of the invention.
98％硫酸2500ｇと61％硝酸500ｇとの混酸処理
液に、５重量％のシユウ酸を添加した酸処理液
で、微細に粉砕された粒度60メツシユの黒鉛粒子
100ｇを約６時間酸処理（浸漬）し、次いで水洗
いした後、400度Ｃ以上の高温雰囲気中に保持し
て加熱したところ、約100倍程度にいも虫状形の
大きさに膨張成形された膨張黒鉛が得られた。 Graphite particles with a particle size of 60 mesh are finely ground using an acid treatment solution made by adding 5% by weight of oxalic acid to a mixed acid treatment solution of 2500g of 98% sulfuric acid and 500g of 61% nitric acid.
When 100g of the material was acid-treated (immersed) for about 6 hours, then washed with water, and heated in a high-temperature atmosphere of 400 degrees Celsius or higher, it was expanded and molded to about 100 times the size of a caterpillar. Expanded graphite was obtained.
上述のシユウ酸は、周知のごとく加熱すると、
二酸化炭素とギ酸に分解し、また濃硫酸を加えて
加熱すれば二酸化炭素と一酸化炭素と水に分解す
る性質を備えているため、上述の加熱時にあつて
は、黒鉛中に酸処理を経て硫黄と共存したシユウ
酸が分解し硫黄と結合し、H2S、SO2として硫黄
を除去する。これは、炭素、水素、酸素（Ｃ、
Ｈ、Ｏ）の３元素からなる化合物としての有機酸
が共加熱作用によつて、分解生成した活性水素、
一酸化炭素等黒鉛中に介入した硫黄および硫黄化
合物をH2S、SO2として除去するためである。 As is well known, when the above-mentioned oxalic acid is heated,
Because it has the property of decomposing into carbon dioxide and formic acid, and when heated with concentrated sulfuric acid, it decomposes into carbon dioxide, carbon monoxide, and water. Oxalic acid coexisting with sulfur decomposes and combines with sulfur, removing sulfur as H 2 S and SO 2 . This includes carbon, hydrogen, and oxygen (C,
Active hydrogen produced by decomposition of an organic acid as a compound consisting of three elements (H, O) by co-heating action,
This is to remove sulfur and sulfur compounds such as carbon monoxide that have intervened in graphite as H 2 S and SO 2 .
なお、ギ酸は加熱することにより二酸化炭素と
水素とに分解し、また濃硫酸を加えて加熱すれ
ば、一酸化炭素を発生する。 When heated, formic acid decomposes into carbon dioxide and hydrogen, and when concentrated sulfuric acid is added and heated, carbon monoxide is generated.
このように、有機酸は、脱硫効果に顕著な性質
を持つ。なお、Ｃ、Ｈ、Ｏの３元素からなる化合
物として、糖類等の等の炭水化物、アルコール類
等、もあり一定の脱硫作用がみられるが、特にシ
ユウ酸、ギ酸等の有機酸およびその有機酸エステ
ルは、脱硫効果が顕著で、取扱い面およびコスト
面からも適している。 Thus, organic acids have remarkable desulfurization effects. Compounds consisting of the three elements C, H, and O include carbohydrates such as saccharides, alcohols, etc., and have a certain degree of desulfurization effect, but especially organic acids such as oxalic acid and formic acid, and their organic acids. Esters have a remarkable desulfurization effect and are suitable from the viewpoint of handling and cost.
また、上述のシユウ酸の添加量は、混酸濃度等
によつて添加容量は異なるが、３重量％未満にな
ると脱硫能力が弱くな、また30重量％を越えると
酸処理に支障を来たすため、３〜30重量％が脱硫
効果を得るのに適している。 The amount of oxalic acid added above varies depending on the mixed acid concentration, etc., but if it is less than 3% by weight, the desulfurization ability will be weak, and if it exceeds 30% by weight, it will interfere with acid treatment. 3 to 30% by weight is suitable for obtaining a desulfurization effect.
なお、上述の脱硫処理は黒鉛粒子は膨張成形す
る加熱工程と共に行なえるため、新たな処理工程
を要することがなく、有機酸ないし有機酸エステ
ルを混酸処理液に添加する簡単な操作で効率のよ
い脱硫処理が行なえる。 Furthermore, since the desulfurization treatment described above can be carried out along with the heating process for expansion molding of graphite particles, no new treatment process is required, and the desulfurization treatment can be performed efficiently by simply adding an organic acid or organic acid ester to the mixed acid treatment solution. Desulfurization treatment can be performed.
このような膨張黒鉛の製造方法により、活性な
硫黄および硫黄化合物は気化して除去されるもの
であり、得られた膨張黒鉛中の硫黄含有率を測定
した結果、500PPm以下の低硫黄含有率の高品質
の膨張黒鉛であることが認められた。 With this method of manufacturing expanded graphite, active sulfur and sulfur compounds are removed by vaporization, and as a result of measuring the sulfur content in the expanded graphite obtained, it was found that the sulfur content was as low as 500 PPm or less. It was recognized that it was high quality expanded graphite.
なお、上述の一実施例においては有機酸（シユ
ウ酸）を混酸処理液に添加したが、これに限らず
水洗い水に有機酸ないしそのエステルを添加して
も、水洗い処理時に有機酸が黒鉛中に介入するた
め、その後の加熱工程時には同様の脱硫効果を得
ることができる。 In addition, in the above-mentioned example, an organic acid (oxalic acid) was added to the mixed acid treatment solution, but this is not the only option, and even if an organic acid or its ester is added to the washing water, the organic acid will not be present in the graphite during the washing process. Therefore, a similar desulfurization effect can be obtained during the subsequent heating process.
Claims (1)
後、加熱して膨張成形する膨張黒鉛の製造方法で
あつて、 前記酸処理液および水洗い水のうち少なくとも
一方の処理液に、有機酸、有機酸エステルより選
ばれた少なくとも一種の化合物を３〜30重量％添
加し、この添加した処理液で前記酸処理または水
洗い処理を行なうことを特徴とする膨張黒鉛の製
造方法。[Scope of Claims] 1. A method for producing expanded graphite, in which graphite particles are treated with an acid, then washed with water, and then heated to expand and mold, wherein at least one of the acid treatment liquid and the water washing water is added to the treatment liquid. A method for producing expanded graphite, comprising adding 3 to 30% by weight of at least one compound selected from organic acids, organic acid esters, and performing the acid treatment or water washing treatment with the added treatment liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58178855A JPS6071507A (en) | 1983-09-26 | 1983-09-26 | Manufacture of expanded graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58178855A JPS6071507A (en) | 1983-09-26 | 1983-09-26 | Manufacture of expanded graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6071507A JPS6071507A (en) | 1985-04-23 |
| JPS6365602B2 true JPS6365602B2 (en) | 1988-12-16 |
Family
ID=16055854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58178855A Granted JPS6071507A (en) | 1983-09-26 | 1983-09-26 | Manufacture of expanded graphite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6071507A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0662285B2 (en) * | 1988-09-22 | 1994-08-17 | 工業技術院長 | Method for producing elastic graphite body |
| JP2620606B2 (en) * | 1990-05-16 | 1997-06-18 | 東洋炭素株式会社 | High purity flexible expanded graphite sheet and method for producing the same |
| DE4117074A1 (en) * | 1991-05-25 | 1992-11-26 | Bayer Ag | METHOD FOR PRODUCING MOLDED BODIES |
| US5698088A (en) * | 1996-07-08 | 1997-12-16 | The Hong Kong University Of Science And Technology | Formic acid-graphite intercalation compound |
| KR100642923B1 (en) * | 2002-06-18 | 2006-11-03 | 도요탄소 가부시키가이샤 | High pure expanded graphite sheet having flexible bending ability and its manufacturing method, and the inner layer of crucible using the sheet |
-
1983
- 1983-09-26 JP JP58178855A patent/JPS6071507A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6071507A (en) | 1985-04-23 |
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