JPS6317089B2 - - Google Patents
Info
- Publication number
- JPS6317089B2 JPS6317089B2 JP53152985A JP15298578A JPS6317089B2 JP S6317089 B2 JPS6317089 B2 JP S6317089B2 JP 53152985 A JP53152985 A JP 53152985A JP 15298578 A JP15298578 A JP 15298578A JP S6317089 B2 JPS6317089 B2 JP S6317089B2
- Authority
- JP
- Japan
- Prior art keywords
- terephthalic acid
- reaction vessel
- glycol
- pressure
- suspended phase
- 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 description 14
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000000376 reactant Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/0025—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by an ascending fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
本発明はテレフタル酸の乾燥粉体を反応容器に
充てんする方法に関する。さらに詳細には本発明
はグリコールを有する反応容器にテレフタル酸の
乾燥粉体を添加する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of filling a reaction vessel with dry powder of terephthalic acid. More particularly, the present invention relates to a method of adding dry powder of terephthalic acid to a reaction vessel containing a glycol.
グリコールとテレフタル酸からポリエチレンテ
レフタレートを製造する場合、これら成分は１対
１のモル比で使用するか、または、エーテル生成
の様な副反応をできるだけ最小にし、しかも、未
使用グリコールの回収の必要性をできるだけ避け
る様なモル比で使用することが望ましい。回分方
法の場合、グリコールとテレフタル酸との予備混
合ペーストを反応容器にポンプ輸送するか、また
はあらかじめ秤量された反応化合物を大気圧にお
いて部分的に冷却された反応容器に添加すること
によつて、テレフタル酸を反応容器に充てんでき
る。 When producing polyethylene terephthalate from glycol and terephthalic acid, these components are used in a 1:1 molar ratio, or side reactions such as ether formation are minimized as much as possible, and the need for recovery of unused glycol is avoided. It is desirable to use a molar ratio that avoids as much as possible. In the case of a batch process, by pumping a premixed paste of glycol and terephthalic acid into the reaction vessel or by adding preweighed reactants to a partially cooled reaction vessel at atmospheric pressure. Terephthalic acid can be charged into the reaction vessel.
原料物質を反応容器に充てん後、該反応容器は
エステル化反応に必要な圧力および温度にまで加
圧および加熱することができる。 After charging the raw material to the reaction vessel, the reaction vessel can be pressurized and heated to the pressure and temperature necessary for the esterification reaction.
連続方法の場合、反応化合物を反応容器中に連
続的に計量充てんする一方で、該エステル化反応
容器を高温高圧に維持しなければならない。この
様な操作は一般に、加圧反応容器中にグリコール
とテレフタル酸とから成るペーストをポンプ輸送
することができるスラリーポンプを使用すること
によつて行なわれる。この方法はグリコール対テ
レフタル酸の比が低い場合、該ペーストの粘度が
極めて高いという事実によつて限定される。温グ
リコールを含有し、しかも加圧されている反応容
器にテレフタル酸を添加することにともなう問題
は従来技術によつては十分に解決されていない。 In the case of a continuous process, the esterification reaction vessel must be maintained at high temperature and pressure while the reactants are continuously metered into the reaction vessel. Such operations are generally carried out using a slurry pump capable of pumping a paste of glycol and terephthalic acid into a pressurized reaction vessel. This method is limited by the fact that when the ratio of glycol to terephthalic acid is low, the viscosity of the paste is very high. The problems associated with adding terephthalic acid to a pressurized reaction vessel containing warm glycol have not been satisfactorily solved by the prior art.
本発明によれば、グリコールおよびテレフタル
酸は別々にエステル化反応容器に添加できる。本
発明によれば、テレフタル酸の乾燥粉体をその懸
濁相を形成するのに十分な圧力に加圧されている
チツ素の様な不活性ガスと接触、混合して、テレ
フタル酸のガス中懸濁相を形成し、そしてこの懸
濁相を加圧下でエステル化反応容器に計量充てん
する。グリコールはエステル化反応容器中でグリ
コールとテレフタル酸との所望の比率をもたらす
のに適正な量で反応容器中に別個にポンプ輸送さ
れる。 According to the invention, glycol and terephthalic acid can be added separately to the esterification reaction vessel. According to the present invention, a dry powder of terephthalic acid is contacted and mixed with an inert gas, such as nitrogen, pressurized to a pressure sufficient to form a suspended phase of the terephthalic acid powder. A medium suspended phase is formed and this suspended phase is metered into the esterification reaction vessel under pressure. The glycol is separately pumped into the reaction vessel in an amount appropriate to provide the desired ratio of glycol to terephthalic acid in the esterification reaction vessel.
通常、反応容器は加圧状態に維持され、そし
て、エステル化反応は約250〜約270℃の範囲内の
温度で実施される。 Typically, the reaction vessel is maintained under pressure and the esterification reaction is conducted at a temperature within the range of about 250 to about 270°C.
系中の出発原料の流れを示す添付図面を参照し
ながら本発明を以下の実施例によつてさらに詳細
に説明する。図において、テレフタル酸粉体は貯
蔵タンク（図示されていない。）から中間ホツパ
ー１に送られ、ここからさらに二重バルブ系２お
よび３を通つて計量タンク４に給送される。計量
タンク４には、該タンク４の底部から一定の距離
をもつて離間された多孔ダイヤフラム５が配設さ
れている。貯蔵タンク（図示されていない。）か
らのチツ素ガスは導管６および起動バルブ７を通
して多孔ダイヤフラム５の下部の方から計量タン
ク４の底部に導入される。テレフタル酸粉体はダ
イヤフラム５の全面からその孔１５を通つて噴出
して来るチツ素ガスと接触し、混合、分散されて
懸濁相を形成する。チツ素ガスは約80psigの圧力
に加圧されている。この圧力はダイヤフラム５を
通過し、テレフタル酸とチツ素ガスとの懸濁相を
形成するのに十分なほどの高さの圧力である。こ
の圧力において、チツ素ガスはその中にその１ポ
ンド（454ｇ）に相当する容量当りテレフタル酸
粉体を65ポンド（約30Kg）程度の量まで懸濁させ
ることができる。懸濁相は導管８および排出バル
ブ９を通してエステル化反応容器１０に導入され
る。エステル化反応容器１０は分離カラム１１、
凝縮器１２、および撹拌機１３を装備している。
導管８は図示のように反応容器１０においてその
器壁と撹拌機１３の軸とのほぼ中間に、導管８の
先端が導入されるエチレングリコールの液面の上
方に来るように配置されている。テレフタル酸が
エステル化反応容器に導入されるに応じて、グリ
コールとテレフタル酸との所望の比率をもたらす
のに適当な量でエチレングリコール１６を貯蔵タ
ンク（図示されていない。）から導管１４を通し
て反応容器にポンプ輸送する。ポンプ輸送し、そ
して撹拌機１３を作動させてこのエチレングリコ
ールを撹拌する。導管８を通つて反応容器に導入
されたテレフタル酸懸濁相は攪拌されているエチ
レングリコールの液面に接触するとそのテレフタ
ル酸粉体は速やかにエチレングリコールに混入さ
れ、反応混合物を形成する。エステル化反応容器
１０を70psigの圧力および約270℃の温度に維持
する。過剰なチツ素ガスはカラム１１を通してエ
ステル化反応容器１０から抜気される。連続操作
の場合、低分子量重合体はエステル化反応容器に
充てんされたテレフタル酸およびグリコールの量
と大体等しい量でエステル化反応容器１０から連
続的に除去される。 The invention will be explained in more detail by means of the following examples, with reference to the accompanying drawings showing the flow of starting materials through the system. In the figure, terephthalic acid powder is conveyed from a storage tank (not shown) to an intermediate hopper 1 from which it is further fed to a metering tank 4 through a double valve system 2 and 3. The metering tank 4 is provided with a porous diaphragm 5 spaced a certain distance from the bottom of the tank 4 . Ni gas from a storage tank (not shown) is introduced into the bottom of the metering tank 4 through a conduit 6 and an activation valve 7 towards the bottom of the porous diaphragm 5. The terephthalic acid powder comes into contact with the nitrogen gas ejected from the entire surface of the diaphragm 5 through the holes 15, and is mixed and dispersed to form a suspended phase. The nitrogen gas is pressurized to approximately 80 psig. This pressure is high enough to pass through the diaphragm 5 and form a suspended phase of terephthalic acid and nitrogen gas. At this pressure, the nitrogen gas can suspend up to 65 pounds of terephthalic acid powder per pound of nitrogen gas. The suspended phase is introduced into the esterification reaction vessel 10 through conduit 8 and discharge valve 9. The esterification reaction vessel 10 includes a separation column 11,
It is equipped with a condenser 12 and a stirrer 13.
As shown, the conduit 8 is arranged in the reaction vessel 10 approximately midway between the vessel wall and the shaft of the stirrer 13, such that the tip of the conduit 8 is above the liquid level of the ethylene glycol introduced. As terephthalic acid is introduced into the esterification reaction vessel, ethylene glycol 16 is reacted through conduit 14 from a storage tank (not shown) in an amount appropriate to provide the desired ratio of glycol to terephthalic acid. Pump into container. Pump and stirrer 13 is activated to stir the ethylene glycol. When the terephthalic acid suspended phase introduced into the reaction vessel through conduit 8 comes into contact with the stirred ethylene glycol liquid surface, the terephthalic acid powder is rapidly mixed into the ethylene glycol to form a reaction mixture. The esterification reaction vessel 10 is maintained at a pressure of 70 psig and a temperature of about 270°C. Excess nitrogen gas is vented from the esterification reaction vessel 10 through the column 11. In continuous operation, low molecular weight polymer is continuously removed from the esterification reactor vessel 10 in an amount approximately equal to the amount of terephthalic acid and glycol charged to the esterification reactor vessel.
以上説明した様に本発明によれば乾燥テレフタ
ル酸粉体を高温および高圧に保たれた反応容器に
充てんすることができ、しかも、テレフタル酸を
連続的に充てんできる。エステル化反応は好まし
くは約1.05対１〜1.7対１の範囲内のグリコール
対テレフタル酸の低比率でグリコールおよびテレ
フタル酸を用いて行なわれる。１対１よりも低い
比率でも本発明の反応系を使用することによつて
申し分なく充てんできる。 As explained above, according to the present invention, dry terephthalic acid powder can be filled into a reaction vessel maintained at high temperature and pressure, and moreover, terephthalic acid can be continuously filled. The esterification reaction is preferably carried out using glycol and terephthalic acid at a low ratio of glycol to terephthalic acid within the range of about 1.05:1 to 1.7:1. Even ratios lower than 1:1 can be filled satisfactorily using the reaction system of the present invention.
本発明の方法によれば従来技術の方法よりも優
れた利点がいくつももたらされる。グリコールお
よびテレフタル酸はいかなる比率ででも反応容器
に充てんできる。さらに、反応容器は乾燥テレフ
タル酸を充てんしながらのままでも高温および高
圧に維持できる。所望ならば、２個以上の計量タ
ンクを使用し、テレフタル酸の連続充てんを確保
することもできる。反応化合物、特にグリコール
は反応容器に充てんする前に所望の温度にまで予
備加熱することができる。こうすることによつて
反応時間を短縮できる。 The method of the present invention provides a number of advantages over prior art methods. Glycol and terephthalic acid can be charged to the reaction vessel in any ratio. Furthermore, the reaction vessel can be maintained at high temperature and pressure while still being filled with dry terephthalic acid. If desired, more than one metering tank can be used to ensure continuous filling of terephthalic acid. The reactant compounds, especially glycols, can be preheated to the desired temperature before filling the reaction vessel. By doing so, the reaction time can be shortened.
本発明の方法によつてテレフタル酸を反応容器
に充てんすることは正確であり、しかも再現性が
ある。グリコール対テレフタル酸を低比率で使用
した場合、極めて粘性であり、そのため、反応容
器、特に加圧状態の反応容器に搬送するのが容易
でないスラリーまたはペーストを生成する必要は
全くない。 Filling a reaction vessel with terephthalic acid by the method of the invention is accurate and reproducible. If a low ratio of glycol to terephthalic acid is used, there is no need to produce a slurry or paste that is very viscous and therefore not easy to transport into a reaction vessel, especially a reaction vessel under pressure.
本発明を説明する目的のために特定の代表的実
施例ならびに細部を示したが、本発明の精神また
は範囲を逸脱することなく各種の変更および修正
がなし得ることは当業者には明らかである。 Although certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention. .
第１図は本発明の方法を具体化した一例を示す
模式図である。
１……中間ホツパー、２，３……バルブ、４…
…計量タンク、５……多孔ダイヤフラム、６，
８，１１，１４……導管、７，９……バルブ、１
０……反応容器、１２……凝縮器、１３……撹拌
機。
FIG. 1 is a schematic diagram showing an example of the method of the present invention. 1... Intermediate hopper, 2, 3... Valve, 4...
...Measuring tank, 5...Porous diaphragm, 6,
8, 11, 14... Conduit, 7, 9... Valve, 1
0... Reaction vessel, 12... Condenser, 13... Stirrer.
Claims (1)
に導入されている、該テレフタル酸粉体を懸濁さ
せるのに十分な圧力に加圧されている不活性ガス
と接触、混合してテレフタル酸のガス中懸濁相を
形成し、そして該懸濁相を前記圧力よりも低い圧
力に維持されている反応容器に導入することを特
徴とする加圧下に保たれている反応容器にテレフ
タル酸を充てんする方法。 ２ 反応容器が高温度のグリコールを含有してい
る特許請求の範囲第１項に記載の方法。 ３ テレフタル酸懸濁相を連続的に反応容器に充
てんする特許請求の範囲第１項に記載の方法。 ４ 不活性ガスが窒素である特許請求の範囲第１
項記載の方法。 ５ テレフタル酸の乾燥粉体をガス中懸濁相とし
て反応容器に１：１〜1.7：１の範囲のグリコー
ル対テレフタル酸モル比を与えるような量で導入
する特許請求の範囲第２項記載の方法。[Scope of Claims] 1. A dry powder of terephthalic acid is introduced into the container, and an inert gas pressurized to a pressure sufficient to suspend the terephthalic acid powder is introduced into the container. maintained under pressure, characterized by contacting and mixing to form a suspended phase of terephthalic acid in gas, and introducing said suspended phase into a reaction vessel maintained at a pressure lower than said pressure. A method of filling a reaction vessel with terephthalic acid. 2. The method according to claim 1, wherein the reaction vessel contains glycol at high temperature. 3. The method according to claim 1, wherein the terephthalic acid suspended phase is continuously filled into a reaction vessel. 4 Claim 1 in which the inert gas is nitrogen
The method described in section. 5. A dry powder of terephthalic acid is introduced into the reaction vessel as a suspended phase in a gas in an amount so as to give a glycol to terephthalic acid molar ratio in the range of 1:1 to 1.7:1. Method.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86133377A | 1977-12-16 | 1977-12-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5490138A JPS5490138A (en) | 1979-07-17 |
| JPS6317089B2 true JPS6317089B2 (en) | 1988-04-12 |
Family
ID=25335519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15298578A Granted JPS5490138A (en) | 1977-12-16 | 1978-12-11 | Method of charging terephthalic acid to reactor |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5490138A (en) |
| BR (1) | BR7808100A (en) |
| CA (1) | CA1115446A (en) |
| DE (1) | DE2850951A1 (en) |
| FR (1) | FR2411631A1 (en) |
| GB (1) | GB2010294B (en) |
| IT (1) | IT1111091B (en) |
| NL (1) | NL188096C (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0958857A1 (en) * | 1998-05-14 | 1999-11-24 | Bp Chemicals S.N.C. | Process for the introduction of a catalyst into a gas phase polymerisation reaction |
| US6906164B2 (en) | 2000-12-07 | 2005-06-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
| PT1453883E (en) | 2000-12-07 | 2013-03-04 | Grupo Petrotemex Sa De Cv | Low cost polyester process using a pipe reactor |
| US7943094B2 (en) | 2006-12-07 | 2011-05-17 | Grupo Petrotemex, S.A. De C.V. | Polyester production system employing horizontally elongated esterification vessel |
| US7649109B2 (en) | 2006-12-07 | 2010-01-19 | Eastman Chemical Company | Polyester production system employing recirculation of hot alcohol to esterification zone |
| US7863477B2 (en) | 2007-03-08 | 2011-01-04 | Eastman Chemical Company | Polyester production system employing hot paste to esterification zone |
| US7872089B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Multi-level tubular reactor with internal tray |
| US7858730B2 (en) | 2007-07-12 | 2010-12-28 | Eastman Chemical Company | Multi-level tubular reactor with dual headers |
| US7829653B2 (en) | 2007-07-12 | 2010-11-09 | Eastman Chemical Company | Horizontal trayed reactor |
| US7842777B2 (en) | 2007-07-12 | 2010-11-30 | Eastman Chemical Company | Sloped tubular reactor with divided flow |
| US7868130B2 (en) | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Multi-level tubular reactor with vertically spaced segments |
| US7847053B2 (en) | 2007-07-12 | 2010-12-07 | Eastman Chemical Company | Multi-level tubular reactor with oppositely extending segments |
| US7872090B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Reactor system with optimized heating and phase separation |
| US7868129B2 (en) | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Sloped tubular reactor with spaced sequential trays |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3393944A (en) * | 1966-10-25 | 1968-07-23 | Petrocarb Inc | Method for pneumatically injecting solid particles into a high pressure zone |
| US4020049A (en) * | 1967-09-14 | 1977-04-26 | The Goodyear Tire & Rubber Company | Process for preparing polyester resin |
| DE1667010C3 (en) * | 1967-12-23 | 1975-10-09 | Dynamit Nobel Ag, 5210 Troisdorf | Method and device for the reliable filling of oxidation-sensitive materials |
| NL7016364A (en) * | 1970-10-21 | 1972-04-25 | ||
| ES419510A1 (en) * | 1972-12-15 | 1976-04-16 | Huels Chemische Werke Ag | Process for the esterification of terephthalic acid in the gas phase |
| US4018671A (en) * | 1975-01-14 | 1977-04-19 | Marathon Oil Company | Intermittent catalyst addition system |
-
1978
- 1978-10-03 CA CA312,576A patent/CA1115446A/en not_active Expired
- 1978-11-08 GB GB7843627A patent/GB2010294B/en not_active Expired
- 1978-11-24 DE DE19782850951 patent/DE2850951A1/en active Granted
- 1978-12-11 BR BR7808100A patent/BR7808100A/en unknown
- 1978-12-11 NL NLAANVRAGE7812037,A patent/NL188096C/en not_active IP Right Cessation
- 1978-12-11 JP JP15298578A patent/JPS5490138A/en active Granted
- 1978-12-12 IT IT52265/78A patent/IT1111091B/en active
- 1978-12-13 FR FR7835040A patent/FR2411631A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7812037A (en) | 1979-06-19 |
| BR7808100A (en) | 1979-08-07 |
| NL188096B (en) | 1991-11-01 |
| DE2850951C2 (en) | 1989-04-20 |
| NL188096C (en) | 1992-04-01 |
| GB2010294B (en) | 1982-08-11 |
| FR2411631A1 (en) | 1979-07-13 |
| GB2010294A (en) | 1979-06-27 |
| IT1111091B (en) | 1986-01-13 |
| IT7852265A0 (en) | 1978-12-12 |
| CA1115446A (en) | 1981-12-29 |
| FR2411631B1 (en) | 1982-04-30 |
| DE2850951A1 (en) | 1979-06-21 |
| JPS5490138A (en) | 1979-07-17 |
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