NO121605B - - Google Patents
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- NO121605B NO121605B NO16867267A NO16867267A NO121605B NO 121605 B NO121605 B NO 121605B NO 16867267 A NO16867267 A NO 16867267A NO 16867267 A NO16867267 A NO 16867267A NO 121605 B NO121605 B NO 121605B
- Authority
- NO
- Norway
- Prior art keywords
- catalyst
- palladium
- activity
- vinyl acetate
- noble metal
- Prior art date
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000007306 turnover Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Fremgangsmåte for kontinuerlig fremstilling av vinylacetat. Process for the continuous production of vinyl acetate.
Nærværende oppfinnelse vedrorer en forbedret fremgangsmåte for kontinuerlig fremstilling av vinylacetat på basis av eddiksyre og etylen. The present invention relates to an improved process for the continuous production of vinyl acetate based on acetic acid and ethylene.
Som bekjent oppnås vinylacetat ved at man leder en gassformet blanding av eddiksyre, etylen og molekulart oksygen ved en temperatur mellom 0 og 350° C, fortrinnsvis mellom 50 og 250°C, og et trykk mellom 1 og 70 atmosfærer, fortrinnsvis mellom 1 og 7 atmosfærer, over et eller flere edelmetaller fra platina-eller palladiumgruppen (gruppe VIII i det periodiske .system). Det katalytiske aktive edelmetall som kan være anbragt eller ikke anbragt på en bærer foreligger i metallform, men også som oksyd eller salt. Også blandinger av disse edelmetaller, deres salter eller oksyder kan tjene (se de britiske patenter 976 613 og 1 003<i+>99). As is known, vinyl acetate is obtained by passing a gaseous mixture of acetic acid, ethylene and molecular oxygen at a temperature between 0 and 350°C, preferably between 50 and 250°C, and a pressure between 1 and 70 atmospheres, preferably between 1 and 7 atmospheres, over one or more precious metals from the platinum or palladium group (group VIII in the periodic table). The catalytically active noble metal, which may or may not be placed on a carrier, exists in metallic form, but also as an oxide or salt. Also mixtures of these noble metals, their salts or oxides may serve (see British Patents 976,613 and 1,003<i+>99 ).
For foran nevnte esterfremstilling kommer med hensyn til den onskede selektive virkning, dvs. en hoy omsetning til vinylacetat og ved siden en lav omsetning til C02for anvendelse i stor målestokk en katalysator på basis av palladium i betraktning. En av en blanding av to eller flere katalysatorer bestående katalysatormasse, f.eks. en blanding av palladium på en bærer og et annet edelmetall på en bærer er på grunn av den lille selektivitet ikke egnet. For the above-mentioned ester production, a catalyst based on palladium is taken into account with regard to the desired selective effect, i.e. a high conversion to vinyl acetate and, on the other hand, a low conversion to C02 for use on a large scale. One of a mixture of two or more catalysts consisting of catalyst mass, e.g. a mixture of palladium on a support and another noble metal on a support is not suitable because of the low selectivity.
Anvendelse av en metallisk palladiumkatalysator, f.eks. en katalysator med 0,5 til 10 vekts$ Pd på bærer, oppviser dog den ulempe at den katalytiske virkning meget hurtig går tilbake. Det er nå blitt funnet at aktiviteten for en metallisk palladiumkatalysator forblir konstant i lengre tid eller også tiltar når katalysatoren er oppbygget på et bærerstoff, på hvilket sammen med palladiumet også en liten mengde av et eller flere andre edelmetaller fra gruppen platina, ruthenium eller rodium er anbragt, at vektsforholdet mellom palladium og det eller de andre edelmetaller ligger mellom 300 og 1 og 3 og 1. Et særlig gunstig vektsforhold ligger i området 20:1 og 5:1?og den i dette området opptredende aktivitet hevder seg nemlig i lengre tid under samtidig opprettholdelse av den onskede selektivitet, og er anvendelig for anvendelse i storteknisk målestokk. Use of a metallic palladium catalyst, e.g. a catalyst with 0.5 to 10% by weight of Pd on a support, however, exhibits the disadvantage that the catalytic effect very quickly reverses. It has now been found that the activity of a metallic palladium catalyst remains constant for a longer time or also increases when the catalyst is built up on a carrier substance, on which, together with the palladium, also a small amount of one or more other noble metals from the platinum, ruthenium or rhodium group is placed, that the weight ratio between palladium and the other precious metal(s) is between 300 and 1 and 3 and 1. A particularly favorable weight ratio lies in the area of 20:1 and 5:1? and the activity occurring in this area asserts itself for a longer time while simultaneously maintaining the desired selectivity, and is applicable for use on a large technical scale.
Katalysatorene fremstilles på vanlig måte ved impregnering av bærerstoffet med opplosning av palladiumkloridet og kloridene av det eller de andre edelmetaller, hvoretter massen torkes og derpå reduseres kloridene med en alkalisk hydrazinhydrat-opplosning til metall. The catalysts are produced in the usual way by impregnating the carrier material with a solution of the palladium chloride and the chlorides of the other noble metal(s), after which the mass is dried and the chlorides are then reduced to metal with an alkaline hydrazine hydrate solution.
Som bærer kommer de vanlige bærerstoffer som silicagel, aktivt kull, karborund, pimpesten, kiselgur eller molekularsikter i betraktning. As a carrier, the usual carrier substances such as silica gel, activated carbon, carborundum, pumice stone, diatomaceous earth or molecular sieves come into consideration.
Valget av temperaturen ved fremstillingen av vinylacetat be-tinges bl.a. av katalysatorens aktivitet, kontakttiden og trykk-et. Ved for lav temperatur synker omsetningsgraden til under den okonomisk tillatelige verdi, ved for hoye temperaturer overveier dannelsen av biproduktet CC>2 esterdannelsen. Alt etter foran nevnte betingelser ligger den optimale driftstemper-atur mellom 100 og 250°C. Heller ikke driftstrykket er kritisk; reaksjonen kan finne sted ved atmosfærisk trykk eller også ved trykk over og under atmosfæretrykk. En trykk-stigning har en gunstig innflytelse på reaksjonshastigheten, men forer imidlertid til hoyere investeringsomkostninger. The choice of the temperature for the production of vinyl acetate depends on, among other things, of the activity of the catalyst, the contact time and the pressure. At temperatures that are too low, the degree of conversion falls below the economically permissible value, at temperatures that are too high, the formation of the by-product CC>2 outweighs the ester formation. Depending on the conditions mentioned above, the optimum operating temperature is between 100 and 250°C. Nor is the operating pressure critical; the reaction can take place at atmospheric pressure or also at pressures above and below atmospheric pressure. An increase in pressure has a favorable influence on the reaction rate, but however leads to higher investment costs.
For etylen- og oksygenmengdene i reaksjonsblandingen velges fortrinnsvis stokiometriske forhold og da tilsvarende reaksjons-ligningen For the amounts of ethylene and oxygen in the reaction mixture, stoichiometric ratios are preferably chosen and then the corresponding reaction equation
Et overskudd av oksygen er ikke å anbefale, fordi dannelsen' av ennå flere biprodukter,fremfor alt imidlertid en sterk forbrenn-ing til CO2inntrer; en under den stokiometriske mengde liggende 02~andel kan ved innforing i storteknisk målestokk være nød-vendig for å unngå dannelsen av eksplosive gassblandinger. Syremengden kan med hensyn til etylenet likeledes være tilstede i stokiometrisk mengde, men det kan også velges en mengde som ligger noe eller litt over eller under den stokiometriske mengde. Det for reaksjonen nodvendige oksygen behover ikke å tilfores som hoykondensat-oksygen. Også luft eller med oksygen anriket luft er anvendelig. An excess of oxygen is not recommended, because the formation of even more by-products, above all, however, a strong combustion to CO2 occurs; an 02-proportion below the stoichiometric quantity may, when introduced on a large-scale technical scale, be necessary to avoid the formation of explosive gas mixtures. With respect to the ethylene, the amount of acid can likewise be present in a stoichiometric amount, but an amount that is somewhat or slightly above or below the stoichiometric amount can also be chosen. The oxygen required for the reaction does not need to be supplied as high condensate oxygen. Air or oxygen-enriched air can also be used.
Det har også vist seg at aktiviteten under opprettholdelse av den allerede bevirkede langtidsperiode for denne aktivitet, og den allerede oppnådde selektivitet vesentlig forbedres ved anvendelse av en katalysator hvis bærer stoff impregneres med opp- losninger av palladiumsalter og saltene av det eller de andre edelmetaller, hvilke salter etter torking underkastes en hydrolysebehandling og derpå reduseres. Denne hydrolysebehandling skjer fortrinnsvis ved koking av massen i en NaHCO^-opplosning. It has also been shown that the activity while maintaining the already effected long-term period for this activity, and the already achieved selectivity is significantly improved by using a catalyst whose carrier substance is impregnated with solutions of palladium salts and the salts of the other noble metal(s), which salts after drying are subjected to a hydrolysis treatment and then reduced. This hydrolysis treatment preferably takes place by boiling the mass in a NaHCO 3 solution.
Fordi den hoyere omdannelse i. en reaktor bevirker en okning av vinylacetatproduksjonen pr. reaktorvolum, og tidsenheten og til-setningen av platina eller annet edelmetall bare er bestemmende for opprettholdelse av palladiumaktiviteten betyr hydrolysen og den samtidige muliggjorte lille tilsetning av platina eller annet edelmetall en vesentlig reduksjon av de ved fremstillingen av vinylacetat med katalysator forbundne omkostninger. Because the higher conversion in a reactor causes an increase in vinyl acetate production per reactor volume, and the unit of time and the addition of platinum or other noble metal are only decisive for maintaining the palladium activity, the hydrolysis and the simultaneously enabled small addition of platinum or other noble metal means a significant reduction of the costs associated with the production of vinyl acetate with catalyst.
Oppfinnelsen forklares på basis av forsøksresultater. Disse resultater, såvel som vedkommende arbeidsbetingelser er satt sammen i en tabell. Forsokene Ia og Ila til Ile viser seg på anvendelse av uten hydrolyse av massen fremstilte katalysatorer, forsokene Illa til Ulf blir gjennomfbrt med katalysatorer, som er underkastet nevnte hydrolyse. The invention is explained on the basis of experimental results. These results, as well as the relevant working conditions, are compiled in a table. Experiments Ia and Ila to Ile are based on the use of catalysts prepared without hydrolysis of the mass, experiments Illa to Ulf are carried out with catalysts which have been subjected to said hydrolysis.
En sammenligning av forsøksresultatene viser: A comparison of the test results shows:
1. en katalysatormasse som bare inneholder Pd som aktiv komponent er på grunn av en hurtig tilbakegang av katalysator-aktiviteten ikke egnet for praksis (forsok Ia), 2. en katalysatormasse som bare inneholder Pt som virksom komponent er på grunn av den lille omsetning til vinylacetat med samtidig hoy omdannelse til CO2ikke egnet for praksis (forsok Ib), 3. ved en katalysatormasse, som uten Pd samtidig inneholder en viss mengde av et annet edelmetall fra platinagruppen, f.eks. Pt eller Rh, forblir begynnelsesaktiviteten tilnærmet opprettholdt (forsbk Ila og Ub, såvel Ila til Ulf), 1. a catalyst mass that only contains Pd as an active component is, due to a rapid decline in catalyst activity, not suitable for practice (experiment Ia), 2. a catalyst mass that only contains Pt as an active component is due to the small conversion to vinyl acetate with simultaneous high conversion to CO2 not suitable for practice (experiment Ib), 3. with a catalyst mass, which without Pd also contains a certain amount of another precious metal from the platinum group, e.g. Pt or Rh, the initial activity remains approximately maintained (eg Ila and Ub, as well as Ila to Ulf),
h. inneholder katalysatormassen i forhold til Pd en omtrent h. the catalyst mass in relation to Pd contains approx
like stor vektsmengde av et annet edelmetall, så er denne katalysator uegnet for praksis, fordi i dette tilfellet overveier omdannelse til CO^igjen sterk (forsok Ic) , 5. palladium og et annet edelmetall må sammen befinne seg på en bærer for å gi den onskede virkning - opprettholdelse av aktiviteten. En av en blanding av bærerstoff med palladium med platina bestående katalysatormasse viser ikke den onskede effekt (forsok Id), 6. begynnelsesaktiviteten for en katalysatormasse som foruten Pd samtidig inneholder en liten mengde av et annet edelmetall fra platinagruppen, f.eks. Pt eller Rh, og etter torkingen av den impregnerte masse, og for reduksjonen ble hydrolysert ved koking i en oppløsning forblir opprettholdt; det viser seg bestemt også at selve aktiviteten vesentlig forbedres. Man sammenligner her forsokene Ila og Illa, såvel Ub og Illb; ved forsokene Ille, Uld, Ule er foruten opprettholdelsen av begynnelsesaktiviteten likeledes å bemerke en hoy C^H^-omdannelse, som ved forsok Ille sågar en meget hoy verdi oppnådd. Forsok Ulf viser at også i tilfelle av et - med hensyn til an equal amount by weight of another noble metal, then this catalyst is unsuitable for practice, because in this case the conversion to CO^again strongly predominates (attempt Ic) , 5. palladium and another noble metal must together be on a support to give it desired effect - maintenance of the activity. One of a catalyst mass consisting of a mixture of palladium and platinum does not show the desired effect (experiment Id), 6. the initial activity of a catalyst mass which, in addition to Pd, also contains a small amount of another precious metal from the platinum group, e.g. Pt or Rh, and after the drying of the impregnated mass, and for the reduction was hydrolyzed by boiling in a solution remains maintained; it also clearly shows that the activity itself is significantly improved. One compares here the attempts Ila and Illa, as well as Ub and Illb; in experiments Ille, Uld, Ule, in addition to maintaining the initial activity, a high C^H^ conversion can also be noted, which in experiment Ille even achieved a very high value. Experiment Ulf shows that also in the case of a - with respect to
Pd - forholdsvis hbyt Pt-innhold ved en. ved hydrolyse fremstilt katalysator også gir en god omsetning. Pd - relatively high Pt content at a. catalyst produced by hydrolysis also gives a good turnover.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL6608559A NL6608559A (en) | 1966-06-21 | 1966-06-21 | |
| NL6706640A NL6706640A (en) | 1966-06-21 | 1967-05-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO121605B true NO121605B (en) | 1971-03-22 |
Family
ID=26644052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO16867267A NO121605B (en) | 1966-06-21 | 1967-06-20 |
Country Status (9)
| Country | Link |
|---|---|
| AT (1) | AT278731B (en) |
| BE (1) | BE700148A (en) |
| CH (1) | CH487829A (en) |
| DE (1) | DE1643077B2 (en) |
| ES (1) | ES342070A1 (en) |
| GB (1) | GB1154517A (en) |
| NL (2) | NL6608559A (en) |
| NO (1) | NO121605B (en) |
| SE (1) | SE307939B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5347046A (en) * | 1993-05-25 | 1994-09-13 | Engelhard Corporation | Catalyst and process for using same for the preparation of unsaturated carboxylic acid esters |
| US5576457A (en) * | 1995-05-23 | 1996-11-19 | Hoechst Celanese Corporation | Catalyst and procedure for preparation of vinyl acetate |
-
1966
- 1966-06-21 NL NL6608559A patent/NL6608559A/xx unknown
-
1967
- 1967-05-12 NL NL6706640A patent/NL6706640A/xx unknown
- 1967-06-16 CH CH856367A patent/CH487829A/en not_active IP Right Cessation
- 1967-06-19 GB GB2823967A patent/GB1154517A/en not_active Expired
- 1967-06-19 BE BE700148D patent/BE700148A/xx unknown
- 1967-06-20 ES ES342070A patent/ES342070A1/en not_active Expired
- 1967-06-20 AT AT573567A patent/AT278731B/en not_active IP Right Cessation
- 1967-06-20 SE SE877267A patent/SE307939B/xx unknown
- 1967-06-20 NO NO16867267A patent/NO121605B/no unknown
- 1967-06-21 DE DE1967ST027032 patent/DE1643077B2/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB1154517A (en) | 1969-06-11 |
| DE1643077A1 (en) | 1971-05-13 |
| ES342070A1 (en) | 1968-10-16 |
| NL6706640A (en) | 1968-11-13 |
| SE307939B (en) | 1969-01-27 |
| DE1643077B2 (en) | 1976-08-19 |
| BE700148A (en) | 1967-12-19 |
| NL6608559A (en) | 1967-12-22 |
| CH487829A (en) | 1970-03-31 |
| AT278731B (en) | 1970-02-10 |
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