JPH042576B2 - - Google Patents
Info
- Publication number
- JPH042576B2 JPH042576B2 JP1188818A JP18881889A JPH042576B2 JP H042576 B2 JPH042576 B2 JP H042576B2 JP 1188818 A JP1188818 A JP 1188818A JP 18881889 A JP18881889 A JP 18881889A JP H042576 B2 JPH042576 B2 JP H042576B2
- Authority
- JP
- Japan
- Prior art keywords
- butene
- reaction
- isobutylene
- sbb
- catalyst
- 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 - Lifetime
Links
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 53
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 24
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 17
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000006384 oligomerization reaction Methods 0.000 description 8
- -1 C 4 hydrocarbon Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000013638 trimer 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明は、イソブチレンと１−ブテンおよび／
または２−ブテンとを含むC4炭化水素混合物か
ら１−ブテンおよび／または２−ブテンを回収す
る方法に関する。
〔従来の技術〕
イソブチレン（もしくはイソブテン）のオリゴ
マー、例えば、２量体乃至５量体に相当する炭素
数８乃至20の炭化水素は多くの分野で利用されて
いる。例えば、２量体（DIB）は、オキソ化によ
るノニルアルコールやｐ−オクチルフエノールの
製造やガソリンの添加剤などに用いられている。
３量体（TIB）および４量体は、それ自体化学原
料として使用されるが、水添されたものがイソパ
ラフイン無臭溶剤として、また湿式コピーの溶剤
や高圧ポリエチレン製造用溶媒としても使用され
ている。
イソブチレンのオリゴマーを製造する場合に
は、通常、ナフサ等の石油留分の熱分解によるオ
レフイン製造の際に副生するブタン及びブテンの
各異性体を含むC4炭化水素混合物（SBBと称す）
を原料とし、これを各種触媒の存在下に接触的に
反応させることが行われている。触媒としては、
従来、例えば、H2SO4、H3PO4のような鉱酸や、
固体酸触媒として強酸性イオン交換樹脂や各種酸
化物触媒が数多く提案されている。しかし、これ
ら従来の触媒を用いる反応は、SBBからオリゴ
マーをつくることが主体であり、その時イソブチ
レンのみならず共存する１−ブテンや２−ブテン
も同様にオリゴマー化され、また１−ブテンが２
−ブテンに異性化する場合も多く、原料中に共存
する１−ブテンの転化率を低く押える工夫をした
ものはない。
特開昭54−92901の如くイソブチレンと１−ブ
テンまたは２−ブテンの共２量化に関するものも
あり、SBBを用いたオリゴマー化反応では、ｎ
−ブテンもオリゴマー化することが避けがたく、
さらにこれら従来の触媒では、１−ブテンが２−
ブテンへ大幅に異性化するのが普通である。特開
昭51−8201のように、１−ブテンを２−ブテンへ
異性化させた後オリゴマー化反応させ、オリゴマ
ーに消費されるｎ−ブテンの総量を減らす工夫が
されている例もある。これは、１−ブテンの方が
２−ブテンよりはるかに容易にオリゴマー化され
やすいことを示しており、それだけオリゴマー化
反応で、１−ブテンを変化させないで温存するこ
とが難しいことを示している。また、従来の触媒
の例では、１−ブテンについて、何も言及してい
ないものも多い。
〔発明が解決しようとする課題〕
ところが、１−ブテンの利用に関して、高密度
ポリエチレンのコモノマーあるいは最近注目を集
めている低圧法低密度ポリエチレン用コモノマー
としての用途が開け、その需要が急増する傾向に
ある。この１−ブテン確保の方法として、SBB
中のイソブチレンをオリゴマーとして除き、１−
ブテンを濃縮して分離する工程が考えられるが、
先に説明した従来の触媒では、いずれも１−ブテ
ンが異性化して２−ブテンになつたり、オリゴマ
ー化されて失われたりするので、１−ブテンが効
率よく濃縮されない点が、“１−ブテン確保”と
いう立場から考えると致命的欠点となつていた。
本発明者らは、上記欠点を解決するため、
SBBのオリゴマー化反応において、イソブチレ
ン転化率が高く、１−ブテン転化率の低い触媒に
ついて検討を行つた結果、本発明に到達したもの
である。
〔課題を解決するための手段〕
本発明によれば、上記課題を解決するため、活
性白土または酸性白土を空気中にて200〜600℃の
温度で焼成処理して得た触媒の存在下に、50〜
150℃の温度において、イソブチレンと１−ブテ
ンよび／または２−ブテンとを含むC4炭化水素
混合物中のイソブチレンを選択的に反応させ、次
いで除去精製することを特徴とする、C4炭化水
素混合物からの１−ブテンおよび／または２−ブ
テンの回収方法が提供される。
本発明に使用される触媒は、一般的には、イソ
ブチレンのオリゴマー化触媒の固体酸触媒の範囲
に含まれるものであるが、これら触媒の活性条件
を細かく検討した結果、従来の触媒にない特性を
引き出すことに成功したものである。
即ち、本発明者らは、活性白土又は酸性白土を
空気中で、一般には200〜600℃の温度で１〜10時
間、望ましくは400〜500℃の温度で３〜５時間焼
成処理したものを触媒として用いたときに、優れ
たイソブチレン転化率とオリゴマー収率が得られ
ると共に、１−ブテンの転化率を極めて低く抑え
ることができることを見出したものである。
オリゴマー化の反応条件としては特に制限はな
いが、通常、反応温度は50〜150℃、望ましくは
70〜100℃、圧力は５〜40Kg／cm2であり、原則的
には原料として用いるSBBが反応条件下に液状
を保つに必要な圧力であればよい。また、反応時
間は他の反応条件にもより一概には規定し得ない
が、１〜４時間程度が適当と言える。
溶媒については必ずしも必要はないが、ｎ−ヘ
キサン等の飽和炭化水素系の溶媒を用いた場合に
は１−ブテンの転化率を抑制する効果がある。
尚、原料中の水分が多いときは触媒の活性が十分
に発揮されないため、SBB中の水分を200ppm、
好ましくは10ppm以下とするのがよい。原料
SBB中に含有される少量のジエン類およびアセ
チレン類については前処理せず、そのままでも反
応に供することができる。
イソブチレンのオリゴマー化は、反応原料とな
るSBBに、触媒が１〜30wt％、望ましくは15〜
20wt％程度になるように添加し、連続式または
回分式にて反応させる。回分式では、スラリー状
での反応となる。反応終了後、オリゴマーと触媒
をを濾別し、必要に応じてさらに精製することに
より、１−ブテン／２−ブテンが高濃度で回収さ
れる。尚、１−ブテンと２−ブテンとは、所望に
より、蒸留により分離刷ることができる。
工業的には流通法での実施が望ましく、また実
施は十分可能で、何ら困難な点はない。
〔実施例〕
以下実施例により、本発明をさらに説明する。
尚、実施例では回分式反応器を用いて行つた結果
を示したが、本発明の実施にあたり、連続式を採
用することもできることはいうまでもない。
実施例 １
酸性白土（水沢化学株式会社製）をマツフル炉
中にて大気解放下に450℃で4.5hrs焼成処理し、
冷却して得られた触媒20.0ｇを、事前に洗浄し、
N2置換したオートクレーブに入れる。SBBをオ
ートクレーブに60.4ｇ導入し、N2で約２Kg／cm2
に加圧してから、オートクレーブを90℃で4hrs撹
拌しながら反応させた。１時間毎に液相からサン
プリングして、ガス分析を行つた。
反応終了後、オートクレーブを冷却して、反応
液が室温程度になつてから、バルブを開き、未反
応ガスをドライアイス−メタノールトラツプに通
し、SBB量をはかる。
オートクレーブを開け、（触媒＋オリゴマー）
を取り出し、仕込み触媒量を差し引いて、オリゴ
マー量とした。組成はGCにて分析定量した。
SBBガス組成は、トラツプ中の液体SBBを全
量、テドラーバツクにガス化させて良くかきまぜ
てからGC分析を行つて得た。１時間毎および４
時間後の結果は次の通りであつた。
[Industrial Application Field] The present invention relates to isobutylene, 1-butene and/or
The present invention relates to a method for recovering 1-butene and/or 2-butene from a C 4 hydrocarbon mixture containing or 2-butene. [Prior Art] Isobutylene (or isobutene) oligomers, such as hydrocarbons having 8 to 20 carbon atoms corresponding to dimers or pentamers, are used in many fields. For example, the dimer (DIB) is used in the production of nonyl alcohol and p-octylphenol through oxation, and as an additive for gasoline.
Trimers (TIB) and tetramers are themselves used as chemical raw materials, but their hydrogenated versions are also used as isoparaffin odorless solvents, wet copying solvents, and high-pressure polyethylene manufacturing solvents. There is. When producing isobutylene oligomers, a C4 hydrocarbon mixture (referred to as SBB) containing butane and butene isomers, which are by-produced during the production of olefins by thermal decomposition of petroleum fractions such as naphtha, is usually used.
is used as a raw material and catalytically reacted in the presence of various catalysts. As a catalyst,
Conventionally, mineral acids such as H 2 SO 4 , H 3 PO 4 ,
Many strong acid ion exchange resins and various oxide catalysts have been proposed as solid acid catalysts. However, in the reactions using these conventional catalysts, the main purpose is to create oligomers from SBB, and at that time, not only isobutylene but also coexisting 1-butene and 2-butene are oligomerized, and 1-butene is converted into 2-butene.
-Butene is often isomerized, and there is no method that has been devised to keep the conversion rate of 1-butene coexisting in the raw material low. There is also a study on co-dimerization of isobutylene and 1-butene or 2-butene, such as JP-A No. 54-92901, and in the oligomerization reaction using SBB, n
- Butenes also inevitably undergo oligomerization;
Furthermore, in these conventional catalysts, 1-butene is
Significant isomerization to butenes is common. In some cases, as in JP-A-51-8201, an attempt has been made to reduce the total amount of n-butene consumed by oligomers by isomerizing 1-butene to 2-butene and then subjecting it to an oligomerization reaction. This indicates that 1-butene is much more easily oligomerized than 2-butene, and this indicates that it is difficult to preserve 1-butene without being changed in the oligomerization reaction. . Moreover, many examples of conventional catalysts do not mention anything about 1-butene. [Problem to be solved by the invention] However, the use of 1-butene as a comonomer for high-density polyethylene or as a comonomer for low-pressure low-density polyethylene, which has been attracting attention recently, has opened up, and the demand for it is rapidly increasing. be. As a method of securing this 1-butene, SBB
The isobutylene inside is removed as an oligomer, and 1-
A process of concentrating and separating butene can be considered, but
With the conventional catalysts described above, 1-butene is either isomerized to 2-butene or oligomerized and lost, so 1-butene cannot be efficiently concentrated. This was a fatal flaw when considered from the standpoint of "security." In order to solve the above drawbacks, the present inventors
In the oligomerization reaction of SBB, the present invention was arrived at as a result of studies on catalysts with a high isobutylene conversion rate and a low 1-butene conversion rate. [Means for Solving the Problems] According to the present invention, in order to solve the above problems, activated clay or acid clay is heated in the presence of a catalyst obtained by firing activated clay or acid clay in air at a temperature of 200 to 600°C. , 50～
A C 4 hydrocarbon mixture, characterized in that isobutylene in the C 4 hydrocarbon mixture containing isobutylene and 1-butene and/or 2-butene is selectively reacted at a temperature of 150 ° C., and then removed and purified. A method for recovering 1-butene and/or 2-butene from The catalysts used in the present invention are generally included in the solid acid catalyst range of isobutylene oligomerization catalysts, but as a result of detailed study of the activation conditions of these catalysts, we found that they have characteristics that conventional catalysts do not have. It was successfully brought out. That is, the present inventors fired activated clay or acid clay in air, generally at a temperature of 200 to 600°C for 1 to 10 hours, preferably at a temperature of 400 to 500°C for 3 to 5 hours. It has been discovered that when used as a catalyst, excellent isobutylene conversion and oligomer yield can be obtained, and 1-butene conversion can be kept extremely low. There are no particular restrictions on the reaction conditions for oligomerization, but the reaction temperature is usually 50 to 150°C, preferably
The temperature is 70 to 100° C. and the pressure is 5 to 40 Kg/cm 2 .In principle, the pressure may be sufficient as long as the SBB used as a raw material remains in a liquid state under the reaction conditions. Further, although the reaction time cannot be absolutely defined depending on other reaction conditions, it can be said that about 1 to 4 hours is appropriate. Although the solvent is not necessarily required, when a saturated hydrocarbon solvent such as n-hexane is used, it has the effect of suppressing the conversion rate of 1-butene.
In addition, when there is a lot of moisture in the raw material, the activity of the catalyst will not be fully demonstrated, so the moisture in SBB should be reduced to 200ppm,
The content is preferably 10 ppm or less. material
A small amount of dienes and acetylenes contained in SBB can be subjected to the reaction as they are without pretreatment. In the oligomerization of isobutylene, 1 to 30 wt% of catalyst is added to SBB, which is the reaction raw material, preferably 15 to 30 wt%.
It is added to about 20wt% and reacted continuously or batchwise. In the batch method, the reaction takes place in the form of a slurry. After the reaction is completed, the oligomer and catalyst are filtered off, and 1-butene/2-butene is recovered at a high concentration by further purification if necessary. Note that 1-butene and 2-butene can be separated by distillation, if desired. Industrially, it is desirable to implement the method using the distribution method, and it is fully possible to implement, without any difficulty. [Example] The present invention will be further explained below with reference to Examples.
Although the Examples show the results obtained using a batch reactor, it goes without saying that a continuous reactor can also be employed in carrying out the present invention. Example 1 Acid clay (manufactured by Mizusawa Chemical Co., Ltd.) was fired in a Matsufuru furnace at 450°C for 4.5 hours under open air.
20.0g of the catalyst obtained by cooling was washed in advance,
Place in an autoclave with 2 N atmosphere. 60.4g of SBB was introduced into the autoclave, and about 2Kg/ cm2 was added with N2.
After pressurizing the autoclave to 90°C, the reaction was carried out with stirring for 4 hours. Samples were taken from the liquid phase every hour for gas analysis. After the reaction is completed, the autoclave is cooled, and after the reaction solution reaches room temperature, the valve is opened, the unreacted gas is passed through a dry ice-methanol trap, and the amount of SBB is measured. Open the autoclave and (catalyst + oligomer)
was taken out and the amount of catalyst charged was subtracted to obtain the amount of oligomer. The composition was analyzed and quantified using GC. The SBB gas composition was obtained by gasifying the entire amount of liquid SBB in the trap into a Tedler bag, stirring well, and performing GC analysis. hourly and 4
The results after hours were as follows.
【表】
実施例 ２
SBB仕込量63.5ｇ、反応温度70℃とした他は全
て実施例１と同様にして反応を行つた。結果は次
の通りである。[Table] Example 2 The reaction was carried out in the same manner as in Example 1, except that the amount of SBB charged was 63.5 g and the reaction temperature was 70°C. The results are as follows.
【表】
実施例 ３
SBB仕込量23.1ｇ、触媒（実施例１と同じ処理
をした酸性白土）使用量15.02ｇとした他は全て
実施例１と同様にして反応を行つた。経過は以下
の通りである。[Table] Example 3 The reaction was carried out in the same manner as in Example 1, except that the amount of SBB charged was 23.1 g and the amount of catalyst (acid clay treated in the same manner as in Example 1) was 15.02 g. The progress is as follows.
本発明の方法によれば、C4炭化水素混合物中
のイソブチレンを選択的に除去して、１−ブテ
ン／２−ブテンを高濃度で回収することができ
る。
According to the method of the present invention, it is possible to selectively remove isobutylene in a C4 hydrocarbon mixture and recover 1-butene/2-butene at a high concentration.
Claims (1)
600℃の温度で焼成処理して得た触媒の存在下に、
50〜150℃の温度において、イソブチレンと１−
ブテンおよび／または２−ブテンとを含むC4炭
化水素混合物中のイソブチレンを選択的に反応さ
せ、次いで除去精製することを特徴とする、C4
炭化水素混合物からの１−ブテンおよび／または
２−ブテンの回収方法。1 Activated clay or acid clay in the air at 200~
In the presence of a catalyst obtained by calcination at a temperature of 600℃,
At temperatures between 50 and 150°C, isobutylene and 1-
A method of selectively reacting isobutylene in a C4 hydrocarbon mixture containing butene and/or 2-butene, and then removing and purifying the C4
A method for recovering 1-butene and/or 2-butene from a hydrocarbon mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1188818A JPH0242029A (en) | 1989-07-24 | 1989-07-24 | Method for recovering 1-butene/2-butene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1188818A JPH0242029A (en) | 1989-07-24 | 1989-07-24 | Method for recovering 1-butene/2-butene |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56033811A Division JPS57149232A (en) | 1981-03-11 | 1981-03-11 | Preparation of isobutene oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0242029A JPH0242029A (en) | 1990-02-13 |
| JPH042576B2 true JPH042576B2 (en) | 1992-01-20 |
Family
ID=16230355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1188818A Granted JPH0242029A (en) | 1989-07-24 | 1989-07-24 | Method for recovering 1-butene/2-butene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0242029A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101439229B1 (en) * | 2013-03-28 | 2014-10-30 | 주식회사 동원테크 | Apparatus for making inner trim for automobile by vacuum and injection molding and method for manufacturing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2458028A1 (en) | 2001-08-22 | 2003-03-06 | Shell Internationale Research Maatschappij B.V. | Purification of titania |
-
1989
- 1989-07-24 JP JP1188818A patent/JPH0242029A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101439229B1 (en) * | 2013-03-28 | 2014-10-30 | 주식회사 동원테크 | Apparatus for making inner trim for automobile by vacuum and injection molding and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0242029A (en) | 1990-02-13 |
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