JPH04202144A - Production of dimethylnaphthalene - Google Patents
Production of dimethylnaphthaleneInfo
- Publication number
- JPH04202144A JPH04202144A JP2336274A JP33627490A JPH04202144A JP H04202144 A JPH04202144 A JP H04202144A JP 2336274 A JP2336274 A JP 2336274A JP 33627490 A JP33627490 A JP 33627490A JP H04202144 A JPH04202144 A JP H04202144A
- Authority
- JP
- Japan
- Prior art keywords
- pore diameter
- dimethyl
- dimethylnaphthalene
- solid acid
- methylnaphthalene
- 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
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011148 porous material Substances 0.000 claims abstract description 36
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011973 solid acid Substances 0.000 claims abstract description 12
- 239000012022 methylating agents Substances 0.000 claims abstract description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- LRQYSMQNJLZKPS-UHFFFAOYSA-N 2,7-dimethylnaphthalene Chemical compound C1=CC(C)=CC2=CC(C)=CC=C21 LRQYSMQNJLZKPS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005234 chemical deposition Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は２−メチルナフタリンをメチル化して高選択率
下に２．６−ジメチル（及び／または２．７−ジメチル
）ナフタリンを製造する方法に関するものである。２．
６−ジメチル（及び／または２．７−ジメチル）ナフタ
リンは、ポリエステルまたはポリアミドを製造するため
に使用されるナフタリン−２，６−ジカルボン酸及び／
または２．７−ジカルボン酸の出発原料として有用なも
のである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing 2,6-dimethyl (and/or 2,7-dimethyl)naphthalene with high selectivity by methylating 2-methylnaphthalene. It is related to. 2.
6-dimethyl (and/or 2,7-dimethyl) naphthalene is a naphthalene-2,6-dicarboxylic acid and/or used to produce polyesters or polyamides.
Alternatively, it is useful as a starting material for 2,7-dicarboxylic acid.
［従来の技術］
２−メチルナフタリンを原料とし、ゼオライト系の固体
酸触媒の存在下にメチル化剤を反応させて２．６−ジメ
チル（及び／または２．７−ジメチル）ナフタリンを製
造する技術は、それ自体公知（特開昭６３−２０１１３
５号公報）である。[Prior art] A technology for producing 2,6-dimethyl (and/or 2,7-dimethyl) naphthalene by using 2-methylnaphthalene as a raw material and reacting it with a methylating agent in the presence of a zeolite solid acid catalyst. is known per se (Japanese Patent Application Laid-Open No. 63-20113
Publication No. 5).
上記公知方法においては固体酸触媒として例えばゼオラ
イトＺＳＭ−５が用いられるが、ＺＳＭ−５の細孔径は
最大のもので５．５人程度とされており、その細孔構造
がメチル化に適していると記載されている。In the above known method, for example, zeolite ZSM-5 is used as the solid acid catalyst, but the maximum pore diameter of ZSM-5 is approximately 5.5 pores, and its pore structure is suitable for methylation. It is stated that there is.
［発明が解決しようとする課題］
分子の大きさは、Ｌｅｎａｒｄ−Ｊｏｎｅｓポテンシャ
ル関数から求められる速度論的直径（ｋｉｒｌｅＨｃｄ
ｉａｍｅｔｅｒ）や臨界分子直径、或は化学結合距離等
で定義することができるが、メチルナフタリンおよび２
．６−ジメチルナフタリンの場合、化学結合距離を基に
計算された分子径は第１図（ａ） 、 （ｂ）に示すＹ
軸方向に見て前者で６．１人、後者で６．２人であり、
前記ＺＳＭ−５の細孔径（５，５人）に比べやや大きい
ようである。その結果２−メチルナフタリンがＺＳＭ−
５の細孔内で反応する場合、細孔内での２−メチルナフ
タリンの拡散性が悪く、その為ジメチルナフタリンへの
転化率が低くなり、従フて当然に２．６−ジメチル（及
び／または２．７−ジメチル）ナフタリンの収率も低い
という問題があった。[Problem to be solved by the invention] The size of the molecule is determined by the kinetic diameter (kirleHcd) obtained from the Lenard-Jones potential function.
iameter), critical molecular diameter, or chemical bond distance, but methylnaphthalene and 2
．． In the case of 6-dimethylnaphthalene, the molecular diameter calculated based on the chemical bond distance is Y as shown in Figure 1 (a) and (b).
Looking in the axial direction, the former has 6.1 people and the latter has 6.2 people.
The pore size seems to be slightly larger than the pore size of ZSM-5 (5.5 people). As a result, 2-methylnaphthalene is ZSM-
When reacting within the pores of No. 5, the diffusivity of 2-methylnaphthalene within the pores is poor, resulting in a low conversion rate to dimethylnaphthalene, which naturally results in 2,6-dimethyl (and/or Another problem was that the yield of 2,7-dimethyl)naphthalene was also low.
本発明は上記の様な事情に着目してなされたものであっ
て、ジメチルナフタリンへの転化率を高めることのでき
る様な製造技声の確立を第１の目的とした。しかしなが
ら上言、己転化率を高めたとしても、メチル基を６位及
び／または７位に選択的に導入することができない場合
、即ち例えば４位、５位等への導入率が高い場合は、２
．６−ジメチル（及び／または２．７−ジメチル）ナフ
タリンの製造方法としては不適当と言わなければならな
い。そこで６位または７位への導入選択率の高い製造技
術を確立することを第２の目的とした。The present invention was made in view of the above-mentioned circumstances, and its first objective is to establish a production technique that can increase the conversion rate to dimethylnaphthalene. However, as mentioned above, even if the self-conversion rate is increased, if the methyl group cannot be selectively introduced into the 6-position and/or 7-position, for example, if the introduction rate into the 4-position, 5-position, etc. is high, ,2
．． It must be said that this method is inappropriate as a method for producing 6-dimethyl (and/or 2,7-dimethyl) naphthalene. Therefore, the second objective was to establish a manufacturing technology with a high selection rate for introduction into the 6th or 7th place.
［課題を解決するための手段コ
本発明は上記各目的を達成したものであって、固体酸触
媒として少なくとも入口細孔径平均が６．０〜６．５人
の多孔質固体酸触媒を用いてメチル化する点に要旨を有
するものである。[Means for Solving the Problems] The present invention achieves each of the above objects, and uses a porous solid acid catalyst having an average inlet pore diameter of at least 6.0 to 6.5 as the solid acid catalyst. The gist of this is that it is methylated.
［作用］
本発明は上記の様に２−メチルナフタリンからジメチル
体への転化率を高めると共に、特に２゜６−ジメチル体
または２，７−ジメチル体への選択率を高める手段とし
て入口細孔径平均が６．０〜６．５人の多孔質固体酸触
媒を用いる点にポイントを有するものである。[Function] As described above, the present invention improves the conversion rate of 2-methylnaphthalene to dimethyl form and, in particular, improves the inlet pore diameter as a means of increasing the selectivity to 2゜6-dimethyl form or 2,7-dimethyl form. The key point is that a porous solid acid catalyst having an average of 6.0 to 6.5 people is used.
即ち、入口細孔径を、原料である２−メチルナフタリン
及び目的とする２、６−ジメチル（及び／または２．７
−ジメチル）ナフタリン（それぞれ分子径６．２人／６
１人）が通過でき、目的としない他のジメチルナフタリ
ン等（例えば２．４−体、２．５一体及び２．８一体の
分子径は６．９人、１．５一体は７．７ 人）が通過し
にくい大きさに入口細孔径を制御することにより目的を
達成することができたものである。入口細孔径が小さ過
ぎると原料である２−メチルナフタリンが触媒細孔内に
進入しにくく、反応による転化率が低くなり、また大き
過ぎると反応転化率は向上するものの、２．６−ジメチ
ル（及び／または２，７−ジメチル）ナフタリンの選択
率が低下する。細孔径の制御は入口細孔径の制御を行な
えばよく、必ずしも触媒内部の細孔径まで制御する必要
はない。尚細孔径の測定は［日本化学会誌、４２０〜４
２３、（３）、’１９８９コに記載の方法に準じて行な
った。That is, the inlet pore diameter is adjusted between the raw material 2-methylnaphthalene and the target 2,6-dimethyl (and/or 2.7
-dimethyl) naphthalene (each molecular size 6.2 people/6
1 person) can pass through, and other dimethylnaphthalene, etc. that are not intended (for example, 2.4-body, 2.5-body, and 2.8-body have a molecular diameter of 6.9 people, and 1.5-body has a molecular diameter of 7.7 people). ) was able to achieve this goal by controlling the inlet pore diameter to a size that makes it difficult for the particles to pass through. If the inlet pore diameter is too small, it will be difficult for the raw material 2-methylnaphthalene to enter the catalyst pores, resulting in a low reaction conversion rate; if it is too large, the reaction conversion rate will improve, but 2,6-dimethyl ( and/or the selectivity of naphthalene (2,7-dimethyl) is reduced. The pore diameter may be controlled by controlling the entrance pore diameter, and it is not necessarily necessary to control the pore diameter inside the catalyst. The pore diameter is measured according to [Journal of the Chemical Society of Japan, 420-4
23, (3), '1989.
上記細孔径に制御する方法としては公知の方法より任意
に選択することができる。例えば、テトラメトキシシラ
ンの化学蒸着法（ＣＶＤ法）［日本化学会誌、４１０〜
４１９．（３）、１９８９及び日本化学会誌、４２０〜
４２３．（３）。The method for controlling the pore size described above can be arbitrarily selected from known methods. For example, the chemical vapor deposition method (CVD method) of tetramethoxysilane [Journal of the Chemical Society of Japan, 410-
419. (3), 1989 and Journal of the Chemical Society of Japan, 420-
423. (3).
１９８９等］やイオン交換法（特開昭６３−１４６８３
４等）等により実施することができる。アルキル化反応
の条件も特に制限されるものではなく、メタノール、ジ
メチルエーテル、トルエン等を用いた公知の方法を利用
することができる。1989, etc.] and ion exchange method (Japanese Patent Application Laid-Open No. 14683-1983)
4 etc.) etc. The conditions for the alkylation reaction are not particularly limited either, and known methods using methanol, dimethyl ether, toluene, etc. can be used.
以下実施例によって本発明を更に詳述するが、下記実施
例は本発明を制限するものではなく、前・後記の趣旨を
逸脱しない範囲で変更実施することは全て本発明の技術
範囲に包含される。The present invention will be explained in more detail with reference to examples below, but the following examples do not limit the present invention, and all modifications and implementations within the scope of the spirit of the preceding and later descriptions are included within the technical scope of the present invention. Ru.
［実施例］
実施例１
第２図に示される装置を用いて２−メチルナフタリンの
メチル化を実施した。[Example] Example 1 Methylation of 2-methylnaphthalene was carried out using the apparatus shown in FIG.
まず、ＣＶＤ法により入口細孔径を６．３人に制御した
Ｙ型ゼオライトを作成した。得られたゼオライト０．５
ｇと海砂１．５ｇをよく混合し、石英ガラスカラム７に
充填した後、アルゴンガス３０ｃｃ／ｍｉｎ、温度Ｂｏ
ｏ℃の条件下で十分に予備乾燥し焼成を行なった。メシ
チレン１００重量部に対しメタノール３０重量部及び２
−メチルナフタリン５０重量部を含んだ溶液０．０２０
ｃｃ／ｍｉｎ 、及びキャリアガスとしてアルゴンガス
３０ ｃｃ／ｍｉｎを温度４００℃の条件下に供給した
。１時間経過後にコールドトラップ５に回収されていた
反応液の分析を行なった。First, a Y-type zeolite with an inlet pore diameter controlled to 6.3 pores was created using the CVD method. Obtained zeolite 0.5
After mixing well with 1.5 g of sea sand and filling the quartz glass column 7, argon gas 30 cc/min and temperature Bo
It was sufficiently pre-dried and fired at 0°C. 30 parts by weight of methanol and 2 parts by weight for 100 parts by weight of mesitylene
-0.020 of a solution containing 50 parts by weight of methylnaphthalene
cc/min, and 30 cc/min of argon gas as a carrier gas were supplied at a temperature of 400°C. After one hour had passed, the reaction solution collected in the cold trap 5 was analyzed.
実施例２
細孔径が６．１人に制御されたモルデナイトを使用した
以外は実施例１と同様に処理した。Example 2 The same process as in Example 1 was carried out except that mordenite whose pore size was controlled to 6.1 pores was used.
比較例１
細孔径が制御されていないＹ型ゼオライト（細孔径７．
４人）を用いた以外は実施例１と同様に処理した。Comparative Example 1 Y-type zeolite with uncontrolled pore diameter (pore diameter 7.
The process was carried out in the same manner as in Example 1, except that 4 people) were used.
比較例２
細孔径が制御されていないＡ型ゼオライト（細孔径４，
２人）を用いた以外は実施例１と同様に処理した。Comparative Example 2 Type A zeolite with uncontrolled pore size (pore size 4,
The process was carried out in the same manner as in Example 1, except that 2 persons) were used.
上記実施例１．２及び比較例１．２の結果を第１表に示
す。The results of Example 1.2 and Comparative Example 1.2 are shown in Table 1.
第１表に示される様に実施例１及び２における２、６−
ジメチル及び２．７−シメチルナフタリンの選択率は８
０％以上であり、選択性が非常に優れていた。一方比較
例１は細孔径が大きく転化率は５１．１％と実施例より
優れていたが、選択率は３２．６％とかなり低かフた。2, 6- in Examples 1 and 2 as shown in Table 1.
The selectivity for dimethyl and 2,7-dimethylnaphthalene is 8
It was 0% or more, and the selectivity was very excellent. On the other hand, Comparative Example 1 had a large pore diameter and a conversion rate of 51.1%, which was superior to the examples, but the selectivity was quite low at 32.6%.
また比較例２は細孔径が小さい為反応がほとんど起こら
ず、選択率も低かフた。Furthermore, in Comparative Example 2, the pore diameter was small, so almost no reaction occurred, and the selectivity was low or even zero.
［発明の効果］
本発明は以上の様に構成されており、固体酸触媒の入口
細孔径を制御することによって、２．６−ジメチル及び
２．７−シメチルナフタリンを選択性良く製造すること
ができるようになった。[Effects of the Invention] The present invention is configured as described above, and can produce 2,6-dimethyl and 2,7-dimethylnaphthalene with good selectivity by controlling the inlet pore diameter of the solid acid catalyst. Now you can.
第１図（ａ） 、 （ｂ）は夫々２−メチルナフタリン
と２．６−シメチルナフタリンの分子径を示す図、第２
図は本発明の実施に用いられる反応装置の一例を示す図
である。
１・・・ポンプ ２・・・ヒータ３・・・グラ
スウール ４・・・触媒層５・・・コールドトラップFigures 1 (a) and (b) are diagrams showing the molecular diameters of 2-methylnaphthalene and 2,6-dimethylnaphthalene, respectively.
The figure is a diagram showing an example of a reaction apparatus used for carrying out the present invention. 1... Pump 2... Heater 3... Glass wool 4... Catalyst layer 5... Cold trap
Claims (1)
チル化剤を反応させてジメチルナフタリンを製造するに
当たり、固体酸触媒として少なくとも入口細孔径平均が
６．０〜６．５Åの多孔質固体酸触媒を用いて高選択率
下に２，６−ジメチル（及び／または２，７−ジメチル
）ナフタリンを製造することを特徴とするジメチルナフ
タリンの製造方法。In producing dimethylnaphthalene by reacting a methylating agent with 2-methylnaphthalene in the presence of a porous solid acid catalyst, a porous solid acid having an average inlet pore diameter of at least 6.0 to 6.5 Å is used as the solid acid catalyst. A method for producing dimethylnaphthalene, which comprises producing 2,6-dimethyl (and/or 2,7-dimethyl)naphthalene at high selectivity using a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2336274A JP2820792B2 (en) | 1990-11-29 | 1990-11-29 | Method for producing dimethylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2336274A JP2820792B2 (en) | 1990-11-29 | 1990-11-29 | Method for producing dimethylnaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04202144A true JPH04202144A (en) | 1992-07-22 |
| JP2820792B2 JP2820792B2 (en) | 1998-11-05 |
Family
ID=18297415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2336274A Expired - Fee Related JP2820792B2 (en) | 1990-11-29 | 1990-11-29 | Method for producing dimethylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2820792B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128711A (en) * | 2000-10-24 | 2002-05-09 | Nippon Steel Chem Co Ltd | Method of producing 2,6-dimethylnaphthalene |
| US6601594B2 (en) * | 1997-05-09 | 2003-08-05 | Semitool, Inc. | Apparatus and method for delivering a treatment liquid and ozone to treat the surface of a workpiece |
-
1990
- 1990-11-29 JP JP2336274A patent/JP2820792B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6601594B2 (en) * | 1997-05-09 | 2003-08-05 | Semitool, Inc. | Apparatus and method for delivering a treatment liquid and ozone to treat the surface of a workpiece |
| JP2002128711A (en) * | 2000-10-24 | 2002-05-09 | Nippon Steel Chem Co Ltd | Method of producing 2,6-dimethylnaphthalene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2820792B2 (en) | 1998-11-05 |
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Legal Events
| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |