NO124107B - - Google Patents
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- NO124107B NO124107B NO249668A NO249668A NO124107B NO 124107 B NO124107 B NO 124107B NO 249668 A NO249668 A NO 249668A NO 249668 A NO249668 A NO 249668A NO 124107 B NO124107 B NO 124107B
- Authority
- NO
- Norway
- Prior art keywords
- reaction
- acetic acid
- acetaldehyde
- ethylene
- treatment
- Prior art date
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 101
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 45
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Fremgangsmåte til fremstilling av vinylacetat. Process for the production of vinyl acetate.
Det er kjent å fremstille vinylacetat ved omsetning av It is known to produce vinyl acetate by reacting
etylen, eddiksyre og oksygen ved temperaturer fra 50 til 300°C og vanlig eller forhøyet trykk i nærvær av en elementær edelmetallholdig katalysator (tysk patent nr. 1.185.601!). ethylene, acetic acid and oxygen at temperatures from 50 to 300°C and normal or elevated pressure in the presence of an elemental noble metal catalyst (German patent no. 1,185,601!).
Ved den kjente fremgangsmåte kreves som råstoffer etylen, eddiksyre og oksygen. Fremgangsmåten kan gjengis ved likningen: In the known method, ethylene, acetic acid and oxygen are required as raw materials. The procedure can be reproduced by the equation:
Oppfinnelsen vedrører en fremgangsmåte til fremstilling The invention relates to a method for production
av vinylacetat ved omsetning av etylen med eddiksyre og oksygen i nærvær av en elementær edelmetallholdig katalysator ved 50 til 300°C of vinyl acetate by reaction of ethylene with acetic acid and oxygen in the presence of an elemental noble metal catalyst at 50 to 300°C
og vanlig eller forhøyet trykk, idet fremgangsmåten er karakterisert ved at man skiller reaksjonsproduktet i en gassfase og en flytende fase, oppvarmer den kondenserte del helt eller delvis i flytende fase ved 100 til 300°C, og oksyderer det derved dannede acetaldehyd til eddiksyre og tilbakefører denne i reaksjonen. and normal or elevated pressure, the method being characterized by separating the reaction product into a gas phase and a liquid phase, heating the condensed part wholly or partly in the liquid phase at 100 to 300°C, and oxidizing the acetaldehyde formed thereby to acetic acid and returning this in the reaction.
Fremgangsmåten ifølge oppfinnelsen kan gjengis ved følgende likning: The method according to the invention can be reproduced by the following equation:
De kondenserte deler anvendes ved fremgangsmåten ifølge oppfinnelsen normalt uten noen ytterligere behandling i etterbehandlingen, hvor det ved omsetning av vinylacetat med det i de kondenserte deler inneholdte vann oppstår acetaldehyd og eddiksyre. For sterkt å unngå dannelsen av polymere er det fordelaktig å fjerne i de konden- • serte deler oppløst oksygen før etterbehandlingen. Vanligvis er det tilstrekkelig trykkløst å avspenne de kondenserte deler før etterbehandlingen. Herved blir oppløst etylen fritt og medtar dessuten oppløste spor oksygen. Man kan videre til .de kondenserte deler, før etterbehandlingen sette mindre vannmengder. The condensed parts are used in the method according to the invention normally without any further treatment in the post-treatment, where upon reaction of vinyl acetate with the water contained in the condensed parts, acetaldehyde and acetic acid are produced. To strongly avoid the formation of polymers, it is advantageous to remove dissolved oxygen in the • condensed parts before finishing. It is usually sufficient to depressurize the condensed parts before finishing. Hereby, dissolved ethylene is free and also includes dissolved traces of oxygen. You can further add smaller amounts of water to the condensed parts before finishing.
Vinylacetatets omsetningsgrad til acetaldehyd retter seg etter betingelsene som temperatur, trykk og oppholdstid. Temperaturene ligger ved 100-300°C, fortrinnsvis ved 150-250°C. De anvendte trykk ligger fortrinnsvis under 50 atmosfærer og de midlere oppholdstider under 2 timer. The conversion rate of the vinyl acetate to acetaldehyde depends on the conditions such as temperature, pressure and residence time. The temperatures are at 100-300°C, preferably at 150-250°C. The pressures used are preferably below 50 atmospheres and the average residence times below 2 hours.
For å få de for oksydasjonen til eddiksyre nødvendige acetaldehydmengder, kan man enten anvende de samlede kondenserte deler i etterbehandlingen og velge slike betingelser at bare en del av tilstedeværende vinylacetat omsettes til acetaldehyd, eller man kan bare anvende en del av de kondenserte deler i etterbehandlingen og velge betingelsene således at praktisk talt hele vinylacetatet omsettes til acetaldehyd. In order to obtain the amounts of acetaldehyde required for the oxidation to acetic acid, one can either use the total condensed parts in the post-treatment and choose such conditions that only a part of the vinyl acetate present is converted to acetaldehyde, or one can only use a part of the condensed parts in the post-treatment and choose the conditions so that practically all of the vinyl acetate is converted to acetaldehyde.
Man kan gjennomføre de kondenserte delers etterbehandling i reaktorer under betingelser hvor praktisk talt hele reaksjonsrommet er fylt med væske. Eksempelvis kan man innpumpe det flytende produkt nederst i et loddrettstående oppvarmet trykkrør og utta reaksjonsproduktet øverst ved en trykkholdeventil og avspenne. Trykkholde-ventilen innstilles således at ved reaksjonstemperaturen foreligger reaksjonsproduktet i flytende fase. It is possible to carry out the after-treatment of the condensed parts in reactors under conditions where practically the entire reaction space is filled with liquid. For example, the liquid product can be pumped in at the bottom of a vertical heated pressure pipe and the reaction product can be taken out at the top via a pressure holding valve and released. The pressure holding valve is set so that at the reaction temperature the reaction product is in liquid phase.
Man kan imidlertid også gjennomføre kondenserte delers etterbehandling i reaktorer også under betingelser hvor bare en del av produktene foreligger i flytende fase. Eksempelvis kan man bringe de kondenserte deler i fordamperen av en destillasjonsk<p>lbe til de ønskede betingelser med hensyn til trykk, temperatur og oppholdstid for de flytende deler og utta de ved etterbehandlingen dannede acet-aldehyder i ren eller anriket form ved kolonnens hode. Tilløpsstedet for det anvendte produkt kan være ved forskjellige steder på kolonnen, også kan sumpprodukt tilbakeføres på forskjellige steder til kolonnen. Man kan videre innføre produkter av forskjellig sammensetning, som fremkommer under den destillative opparbeidelse i det samlede anlegg på egnede steder inn i reaktoren for etterbehandling. However, it is also possible to carry out the after-treatment of condensed parts in reactors also under conditions where only part of the products are in the liquid phase. For example, one can bring the condensed parts in the evaporator of a distillation flask to the desired conditions with regard to pressure, temperature and residence time for the liquid parts and extract the acet-aldehydes formed during the post-treatment in pure or enriched form at the head of the column. The inflow point for the used product can be at different places on the column, and sump product can also be returned to the column at different places. It is also possible to introduce products of different composition, which appear during the distillative work-up in the overall plant, at suitable places into the reactor for finishing.
For omsetningen av acetaldehyd til eddiksyre kan man eksempelvis adskille det ved etterbehandlingen dannede acetaldehyd destillativt og oksydere i nærvær av eddiksyre med oksygen, idet man fra kretsløpseddiksyren på forhånd adskiller det dannede vinylacetat. Denne oksydasjon kan man fortrinnsvis gjennomføre i loddrette, med kjøleslange utstyrte rør. For å akselerere reaksjonen kan man arbeide i nærvær av katalysatorer, som eksempelvis acetater av mangan, kobolt, krom, som fortrinnsvis er oppløst i eddiksyren. Man arbeider hensikts-messig ved svakt forhøyet trykk således at man i de med eddiksyre fylte rør nedentil innfører acetaldehyd og tilsetter det nødvendige oksygen i forskjellige høyder av røret. Man kan gjennomføre oksydasjonen også utelukkende i nærvær av eddiksyren, som har dannet seg av acetaldehydets oksydasjon. Den ved oksydasjonen nydannede eddiksyre adskiller man fra den katalysatorholdige oppløsning, fortrinnsvis ved destillasjon. Man kan gjennomføre denne destillasjon i kombina-sjon med fremstillingen av vinylacetat i en fordamper, hvorigjennom det føres den overveiende av etylen bestående kretsløpsgass av vinyl-acetatfrembringelsen; ved denne senkning av partialtrykket lettes vesentlig eddiksyrens fordampning. Den i fordampningsresiduet tilbake-blivende katalysator fører man tilbake i reaktoren for acetaldehydets oksydasjon. Man kan gjennomføre acetaldehydets oksydasjon med oksygen også i gassfase i nærvær av fast anordnede katalysatorer, idet man fortrinnsvis fører eddiksyren i dampform i kretsløp. For the conversion of acetaldehyde to acetic acid, for example, the acetaldehyde formed during the post-treatment can be separated by distillation and oxidized in the presence of acetic acid with oxygen, separating the vinyl acetate formed from the circulating acetic acid in advance. This oxidation can preferably be carried out in vertical pipes equipped with cooling hoses. To accelerate the reaction, one can work in the presence of catalysts, such as, for example, acetates of manganese, cobalt, chromium, which are preferably dissolved in the acetic acid. It is expedient to work at a slightly elevated pressure so that acetaldehyde is introduced into the tubes filled with acetic acid at the bottom and the necessary oxygen is added at different heights of the tube. The oxidation can also be carried out exclusively in the presence of the acetic acid, which has formed from the oxidation of the acetaldehyde. The acetic acid newly formed by the oxidation is separated from the catalyst-containing solution, preferably by distillation. This distillation can be carried out in combination with the production of vinyl acetate in an evaporator, through which the circuit gas consisting mainly of ethylene from the production of vinyl acetate is passed; this lowering of the partial pressure greatly facilitates the evaporation of the acetic acid. The catalyst remaining in the evaporation residue is fed back into the reactor for the oxidation of the acetaldehyde. The oxidation of acetaldehyde with oxygen can also be carried out in the gas phase in the presence of fixed catalysts, the acetic acid being preferably circulated in vapor form.
De etter etterbehandlingen dannede reaksjonsprodukter The reaction products formed after the post-treatment
kan opparbeides destillativt. Herved blir det fra råstoffene etylen og oksygen fremstilte vinylacetat isolert. Likeledes gjenvinnes den ved vinylacetatfremstillingen ikke omsatte eddiksyre og den ved etterbehandlingen dannede eddiksyre og kan tilbakeføres i omsetningen med can be worked up by distillation. In this way, the vinyl acetate produced from the raw materials ethylene and oxygen is isolated. Likewise, the acetic acid not converted during the production of vinyl acetate and the acetic acid formed during the post-treatment are recovered and can be returned to the turnover with
etylen. ethylene.
Fremgangsmåten ifølge oppfinnelsen skal i det følgende beskrives ved hjelp av noen eksempler. The method according to the invention will be described in the following with the help of some examples.
Eksempel 1. Example 1.
I et reaksjonsrør av 25 mm indre diameter og 2 m lengde befinner det seg 950 ml av en fast anordnet katalysator bestående av kiselsyrekuler av 3-4 mm diameter, inneholdende pr. liter 3,3 g palladium, 1,5 g gull og 30 g kaliumacetat. Gjennom dette reaksjonsrør føres det pr. time ved l64°C og 5 ato 560 g etylen, 64 g oksygen og 5"40 g eddiksyre, som utvinnes i løpet av fremgangsmåten. Reaksjonsproduktet avkjøles under trykk til 20°C og den derved dannede flytende fase avspennes til 0 ato. Det fremkommer pr. time 626 g flytende fase trykkløst. Den flytende fase har følgende sammensetning i vektprosent: 24,0 vinylacetat, 6,2 vann og 79,8 eddiksyre. Den flytende fase føres ved 25 ato og 196°C gjennom et tomt rør av 500 ml innhold, avkjøles deretter og avspennes trykkløst i en kontinuerlig destillasjonskolonne. Ved kolonnens hode fjernes pr. time 42 g acetaldehyd. Acetaldehydet føres gassformet gjennom et loddrettstående, med kjøleslange utstyrt rør, hvori det befinner seg eddiksyre, hvori det er oppløst 0,1 vektprosent manganacetat. Dessuten innføres oksygen fordelt på forskjellige høyder av røret. Gjennom 1 liter eddiksyre føres det pr. time 42 g acetaldehyd og 40 g oksygen. Trykket i reaksjonsrommet holdes på 3 atmosfærer og temperaturen innstilles ved kjøling til 60°C. Den dannede eddiksyre, hvorav 54$ av den anvendte fåes 42 g acetaldehyd, adskilles destillativt fra katalysatoroppløsningen. In a reaction tube of 25 mm internal diameter and 2 m length, there is 950 ml of a fixed catalyst consisting of silicic acid spheres of 3-4 mm diameter, containing per liter 3.3 g palladium, 1.5 g gold and 30 g potassium acetate. Through this reaction tube, per hour at 164°C and 5 ato 560 g of ethylene, 64 g of oxygen and 5"40 g of acetic acid, which are recovered during the process. The reaction product is cooled under pressure to 20°C and the resulting liquid phase is depressurized to 0 ato. It appears per hour 626 g liquid phase depressurized. The liquid phase has the following composition in weight percent: 24.0 vinyl acetate, 6.2 water and 79.8 acetic acid. The liquid phase is passed at 25 ato and 196°C through an empty tube of 500 ml content, is then cooled and depressurized in a continuous distillation column. At the head of the column, 42 g of acetaldehyde are removed per hour. The acetaldehyde is passed in gaseous form through a vertical pipe equipped with a cooling hose, in which is acetic acid, in which 0.1 percent by weight is dissolved manganese acetate. In addition, oxygen is introduced distributed at different heights of the tube. Through 1 liter of acetic acid, 42 g of acetaldehyde and 40 g of oxygen are passed per hour. The pressure in the reaction chamber is kept at 3 atmospheres and the temperature is set at keel ing to 60°C. The acetic acid formed, of which 54% of the used yield 42 g of acetaldehyde, is separated by distillation from the catalyst solution.
Fra destillasjonskolonnens sump, hvori det ved hodet uttas acetaldehyd, utvinnes ved destillativ opparbeidelse pr. time 67 g vinylacetat og 486 g eddiksyre. From the sump of the distillation column, in which acetaldehyde is withdrawn at the head, is extracted by distillative processing per hour 67 g vinyl acetate and 486 g acetic acid.
Denne eddiksyre forenes med den fra acetaldehydets oksydasjon fremstilte eddiksyre og gir de 540 g eddiksyre som - som nevnt ovenfor - anvendes pr. time i reaktoren for fremstillingen av vinylacetat et . This acetic acid is combined with the acetic acid produced from the oxidation of the acetaldehyde and gives the 540 g of acetic acid which - as mentioned above - is used per hour in the reactor for the production of vinyl acetate et .
Over den samlede prosess dannes av 56 g etylen ved omsetning med oksygen uten tilførsel av ny eddiksyre pr. time 67 g vinylacetat, dvs. 77$ av det teoretiske tilsvarende reaksjonen Over the overall process, 56 g of ethylene is formed by reaction with oxygen without the addition of new acetic acid per hour 67 g of vinyl acetate, i.e. 77$ of the theoretical corresponding reaction
Eksempel 2. Example 2.
I en trykkdestillasjonskolonne, hvis beholder kjøres ved et væskeinnhold på 1 liter, innpumpes pr. time 1 kg av en blanding av 24,1 vektprosent vinylacetat, 8,7 vektprosent vann og 67,2 vektprosent eddiksyre. Kolonnens sump oppvarmes til en temperatur på 184°C. Det innstiller seg i kolonnen et trykk på 7,5 ato. Ved kolonnens hode uttas pr. time 66 g acetaldehyd. Ved sumpen uttas pr. time 933 g av en blanding av 12,0 vektprosent vinylacetat, 6,3 vektprosent vann og 81,7 vektprosent eddiksyre. In a pressure distillation column, whose container is run at a liquid content of 1 litre, pumped in per hour 1 kg of a mixture of 24.1 weight percent vinyl acetate, 8.7 weight percent water and 67.2 weight percent acetic acid. The sump of the column is heated to a temperature of 184°C. A pressure of 7.5 ato is established in the column. At the head of the column, per hour 66 g acetaldehyde. At the swamp, per hour 933 g of a mixture of 12.0 weight percent vinyl acetate, 6.3 weight percent water and 81.7 weight percent acetic acid.
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF52854A DE1283226B (en) | 1967-07-04 | 1967-07-04 | Process for the production of vinyl acetate |
Publications (1)
Publication Number | Publication Date |
---|---|
NO124107B true NO124107B (en) | 1972-03-06 |
Family
ID=7105792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO249668A NO124107B (en) | 1967-07-04 | 1968-06-24 |
Country Status (9)
Country | Link |
---|---|
AT (1) | AT277954B (en) |
BE (1) | BE717624A (en) |
CH (1) | CH498079A (en) |
DE (1) | DE1283226B (en) |
ES (1) | ES355701A1 (en) |
GB (1) | GB1216018A (en) |
NL (1) | NL6809413A (en) |
NO (1) | NO124107B (en) |
SE (1) | SE337587B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3313072A1 (en) * | 1982-07-17 | 1984-01-19 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING A HYDROLYZABLE TITANYL SULFATE SOLUTION |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1010548A (en) * | 1963-11-09 | 1965-11-17 | Distillers Co Yeast Ltd | Improvements in or relating to the production of unsaturated organic esters |
DE1216290B (en) * | 1964-06-05 | 1966-05-12 | Hoechst Ag | Process for the production of vinyl acetate |
-
1967
- 1967-07-04 DE DEF52854A patent/DE1283226B/en active Pending
-
1968
- 1968-05-24 CH CH769068A patent/CH498079A/en not_active IP Right Cessation
- 1968-05-28 GB GB2539068A patent/GB1216018A/en not_active Expired
- 1968-06-07 AT AT544768A patent/AT277954B/en not_active IP Right Cessation
- 1968-06-24 NO NO249668A patent/NO124107B/no unknown
- 1968-07-01 SE SE903868A patent/SE337587B/xx unknown
- 1968-07-03 NL NL6809413A patent/NL6809413A/xx unknown
- 1968-07-03 ES ES355701A patent/ES355701A1/en not_active Expired
- 1968-07-04 BE BE717624D patent/BE717624A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
DE1283226B (en) | 1968-11-21 |
NL6809413A (en) | 1969-01-07 |
CH498079A (en) | 1970-10-31 |
ES355701A1 (en) | 1970-04-16 |
SE337587B (en) | 1971-08-16 |
BE717624A (en) | 1969-01-06 |
AT277954B (en) | 1970-01-12 |
GB1216018A (en) | 1970-12-16 |
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