NO139858B - PROCEDURE FOR SELECTIVE HYDROGENATION OF DIOLEFIN HYDROCARBONS TO OLEFINE HYDROCARBONS - Google Patents
PROCEDURE FOR SELECTIVE HYDROGENATION OF DIOLEFIN HYDROCARBONS TO OLEFINE HYDROCARBONS Download PDFInfo
- Publication number
- NO139858B NO139858B NO3023/73A NO302373A NO139858B NO 139858 B NO139858 B NO 139858B NO 3023/73 A NO3023/73 A NO 3023/73A NO 302373 A NO302373 A NO 302373A NO 139858 B NO139858 B NO 139858B
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- Prior art keywords
- hydrocarbons
- diolefin
- amount
- hydrogenation
- catalyst
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- -1 DIOLEFIN HYDROCARBONS Chemical class 0.000 title claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003751 zinc Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
- C07C2527/25—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Den foreliggende oppfinnelse angår en fremgangsmåte for sele"ktiv hydrogenering av diolef inhydrokarboner til olefinhydrokarboner i nærvær av en palladiumbasert katalysator og i nærvær av et deaktiveringsmiddel for katalysatoren, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at det som deaktiveringsmiddel for katalysatoren anvendes sink i form av en vandig løsning av sinksalt som tilsettes hydrogeneringsblandingen i en mengde slik at vektforholdet mellom vannmengden i løsningen og sinksalt er fra 1 : 1 til 50 : 1, idet sinksalt anvendes i en mengde på 0,-01 - 5 vektprosent i forhold til diolefin-hydrokarbonet, og idet hydrogeneringen foretas ved moderate temperaturer på mellom 20 og 60°c og trykk på 1 - 50 atmosfærer og fortrinnsvis i nærvær av en aminforbindelse eller ammoniakk i en mengde som ikke over- The present invention relates to a method for the selective hydrogenation of diolefin hydrocarbons to olefin hydrocarbons in the presence of a palladium-based catalyst and in the presence of a deactivating agent for the catalyst, and the peculiarity of the method according to the invention is that zinc is used as deactivating agent for the catalyst in form of an aqueous solution of zinc salt which is added to the hydrogenation mixture in an amount such that the weight ratio between the amount of water in the solution and zinc salt is from 1 : 1 to 50 : 1, zinc salt being used in an amount of 0.01 - 5 percent by weight in relation to diolefin -hydrocarbon, and the hydrogenation is carried out at moderate temperatures of between 20 and 60°c and pressure of 1 - 50 atmospheres and preferably in the presence of an amine compound or ammonia in an amount that does not exceed
stiger 0,5 vektprosent i forhold til diolefinhydrokarbonet. rises 0.5 percent by weight in relation to the diolefin hydrocarbon.
Det er kjent at det er mulig å hydrogenere diolefinforbindelser It is known that it is possible to hydrogenate diolefin compounds
i nærvær av palladium-katalysatorer, men det oppnås en blanding av olefin- og mettede forbindelser med en ikke styrbar selektivitet til olefin-forbindelsexie. For å oppnå tilfreds-stillende resultater og for å hindre den etterfølgende hydrogenering av olefin-forbindelsen til mettet forbindelse har det vært foreslått en delvis deaktivering av palladiumkatalysatoren ved impregnering eller samutfelling med -salter av Pb, Zn, Hg, Cd, Th, Sn, etc. slik som vist i BRD utlegnings- in the presence of palladium catalysts, but a mixture of olefinic and saturated compounds is obtained with an uncontrollable selectivity to olefinic compounds. In order to achieve satisfactory results and to prevent the subsequent hydrogenation of the olefin compound to a saturated compound, a partial deactivation of the palladium catalyst by impregnation or coprecipitation with salts of Pb, Zn, Hg, Cd, Th, Sn, etc. as shown in the BRD layout
skrift nr. 1 181 700. document no. 1 181 700.
Metodene for impregnering eller samutfelling er vanskelige å gjennomføre i praksis på -grunn av at deaktiverings-betingelsene for katalysatoren (temperatur, konsentrasjon av deaktiverings-salt, driftstid) er meget kritiske, og å arbeide ved betingelser som skiller seg litt fra de optimale vil føre til at det oppnås katalysatorer som enten ikke er selektive eller som er full-stendig deaktiverte. The methods for impregnation or co-precipitation are difficult to carry out in practice because the deactivation conditions for the catalyst (temperature, concentration of deactivation salt, operating time) are very critical, and working under conditions that differ slightly from the optimum will lead to so that catalysts are obtained which are either not selective or which are completely deactivated.
Det er også kjent at for å oppnå katalysatorer med høy selektivitet er det nødvendig at impregneringen eller samutfellings-behandlingen utføres ved svært høye temperaturer, f.eks. .80 - 100°C, som på den annen side er spesielt uheldig med hensyn til katalysatorer som er utfelt på bærere. It is also known that in order to obtain catalysts with high selectivity it is necessary that the impregnation or co-precipitation treatment is carried out at very high temperatures, e.g. .80 - 100°C, which, on the other hand, is particularly unfortunate with regard to catalysts that are precipitated on supports.
Det er nå funnet at det er mulig å oppnå en selektivitet på It has now been found that it is possible to achieve a selectivity of
opp til 100 % ved hydrogenering av diolefinforbindelser til olefinforbindelser ved å gjennomføre hydrogeneringen ved moderat temperatur i området 20 - 60°c, og ved å anvende en „vani-i-g pallådiumkatalysator, som eventuelt kan være utfelt på kalsiumkarbonat eller bariumsulfat, og ved at det til reaksjonsblandingen tilsettes en vandig løsning av et sinksalt. Ved den foreliggende fremgangsmåte er det mulig å oppnå en selektivitet så høy som 100 % uten at det er nødvendig å underkaste palladiumkatalysatoren for varmeimpregnering eller samutfellings-behandling som er meget kostbar og vanskelig å gjennomføre. Sinkforbindelsen tilsettes fortrinnsvis kontinuerlig som en vandig løsning til hydrogeneringsblandingen. Foruten de nevnte praktiske og økonomiske fordeler gir den foreliggende fremgangsmåte en ytterligere forbedring ved at katalysatoren opprett-holder sin selektivitet over et lengere tidsrom enn for kjente deaktiverte katalysatorer. up to 100% when hydrogenating diolefin compounds to olefin compounds by carrying out the hydrogenation at a moderate temperature in the range of 20 - 60°c, and by using a standard palladium catalyst, which may optionally be precipitated on calcium carbonate or barium sulphate, and by an aqueous solution of a zinc salt is added to the reaction mixture. With the present method, it is possible to achieve a selectivity as high as 100% without it being necessary to subject the palladium catalyst to heat impregnation or co-precipitation treatment, which is very expensive and difficult to carry out. The zinc compound is preferably added continuously as an aqueous solution to the hydrogenation mixture. In addition to the aforementioned practical and economic advantages, the present method provides a further improvement in that the catalyst maintains its selectivity over a longer period of time than for known deactivated catalysts.
Innføring av material som skal hydrogeneres og sinksalt inn på katalysatoren kan utføres mange ganger i løpet av kontinuerlige forsøk og hele tiden ved oppnåelse av meget god selektivitet. Anionet av sinksaltet har ingen betydning med hensyn til selektiviteten, men det er foretrukket at saltet har høy oppløselig-het i vann. For å oppnå denne betingelse kan det benyttes et klorid, sulfat, nitrat, acetat og oksalat. Introduction of material to be hydrogenated and zinc salt onto the catalyst can be carried out many times in the course of continuous experiments and all the while achieving very good selectivity. The anion of the zinc salt has no significance with regard to the selectivity, but it is preferred that the salt has a high solubility in water. To achieve this condition, a chloride, sulphate, nitrate, acetate and oxalate can be used.
Mengden av salt kan variere fra 0,01 til 5 vektprosent, fortrinnsvis fra 0,01 til 2 vektprosent, med hensyn til diolefinforbindelsen. Den minimale vannmengde som er nødvendig for å oppnå et godt reaksjonsforløp er den som er tilstrekkelig til å oppløse sinksaltet under reaksjonsbetingelsene. Det er således nødvendig at vektforholdet mellom vann/sinksalt er på minst 1/1. The amount of salt may vary from 0.01 to 5% by weight, preferably from 0.01 to 2% by weight, with respect to the diolefin compound. The minimum amount of water necessary to achieve a good course of reaction is that which is sufficient to dissolve the zinc salt under the reaction conditions. It is therefore necessary that the weight ratio between water/zinc salt is at least 1/1.
På den annen side er det ikke ønskelig å benytte et vann/sinksalt-forhold større enn 50/1 for oppnåelse av en tilfreds stillende reaksjonshastighet. Ved fravær av vann vil hydrogeneringen av diolefin-forbindelsene ikke stoppe ved første trinn, dvs. ved dannelsen av olefin-forbindelser, men fort-sette videre og danne mettede forbindelser. On the other hand, it is not desirable to use a water/zinc salt ratio greater than 50/1 to achieve a satisfactory reaction rate. In the absence of water, the hydrogenation of the diolefin compounds will not stop at the first step, i.e. with the formation of olefin compounds, but will continue further and form saturated compounds.
Det er fordelaktig å tilsette en aminforbindelse som f.eks. ammoniakk til reaksjonsblandingen i mengder mindre enn 0,5 vektprosent med hensyn til diolefinforbindelsen. Større mengder, f.eks. 20 til 30 vektprosent, vil dog ikke ha negativ innvirkning på reaksjonen. It is advantageous to add an amine compound such as e.g. ammonia to the reaction mixture in amounts less than 0.5 weight percent with respect to the diolefin compound. Larger quantities, e.g. 20 to 30 percent by weight, however, will not have a negative impact on the reaction.
Den foreliggende fremgangsmåte kan anvendes i kontinuerlige eller ikke-kontinuerlige prosesser over et stort temperatur-område mellom 20 og 60°C, og ved trykk av 1 - 50 atmosfærer. The present method can be used in continuous or non-continuous processes over a large temperature range between 20 and 60°C, and at pressures of 1 - 50 atmospheres.
Det skal bemerkes at mengden av salt som skal tilsettes reak-sjons blandingen innen de ovennevnte områder avhenger av reaksjonshastigheten, dvs. av hydrogentrykket og temperaturen, men også av omrøringseffektiviteten. It should be noted that the amount of salt to be added to the reaction mixture within the above-mentioned ranges depends on the reaction rate, i.e. on the hydrogen pressure and temperature, but also on the stirring efficiency.
Ved den foreliggende fremgangsmåte stopper absorpsjonen av hydrogen fra reaksjonsblandingen etter at en av dobbelt-binding-ene er hydrogenert til en enkelt binding, og selv om reaksjonsblandingen blir værende ved reaksjonsbetingelsene i relativt lang tid så skjer det ikke noen ytterligere hydrogenering i vesentlig grad. In the present method, the absorption of hydrogen from the reaction mixture stops after one of the double bonds has been hydrogenated to a single bond, and even if the reaction mixture remains at the reaction conditions for a relatively long time, no further hydrogenation occurs to a significant extent.
De følgende eksempler illustrerer oppfinnelsen nærmere. The following examples illustrate the invention in more detail.
EKSEMPEL 1 EXAMPLE 1
Cyklopentadien hydrogeneres i nærvær av 2 vektprosent Pd-katalysator på CaCO^ som katalysatorbærer (5 % Pd) ved en temperatur av 30°C. O,2 % ammoniakkløsning, 0,2 % dihydrati-sert sinkacetat og 0,4 vektprosent vann føres inn i en auto-klav som holdes under omrøring ved hjelp av en rører bestående av en nul aksel for innbobling av hydrogen. Hydrogentrykket holdes på 5 kg/cm . Reaksjonsforløpet kontrolleres ved hjelp av gasskromatograferingsanalyser som utføres på prøver som tas ut med jevne mellomrom. Etter 90 minutter var det ikke lenger merkbar hydrogenabsorpsjon og selektiviteten til cyklopenten. Cyclopentadiene is hydrogenated in the presence of 2% by weight Pd catalyst on CaCO^ as catalyst support (5% Pd) at a temperature of 30°C. 0.2% ammonia solution, 0.2% dihydrated zinc acetate and 0.4% by weight water are introduced into an autoclave which is kept under stirring by means of a stirrer consisting of a zero shaft for bubbling in hydrogen. The hydrogen pressure is kept at 5 kg/cm. The course of the reaction is checked using gas chromatography analyzes which are carried out on samples taken at regular intervals. After 90 minutes, hydrogen absorption and the selectivity of the cyclopentene were no longer appreciable.
var 99,4. Utgangsforbindelsen cyklopéntadien var praktisk talt ikke tilstede. Etter ytterligere 90 minutter ved reaksjonsbetingelsene var selektiviteten høyere enn 99 %. was 99.4. The starting compound cyclopentadiene was practically not present. After a further 90 minutes at the reaction conditions, the selectivity was higher than 99%.
EKSEMPEL 2 EXAMPLE 2
Det benyttes samme metode som i eksempel 1, men vannmengden The same method as in example 1 is used, but the amount of water
var 1 %. Etter at utgangsforbindelsen cyklopentadien var borte var selektiviteten til cyklopenten i det oppnådde produkt 99,2 % og var praktisk talt konstant også etter en lang tid hvor produktet forble ved reaksjonsbetingelsene. was 1%. After the starting compound cyclopentadiene was gone, the selectivity of the cyclopentene in the product obtained was 99.2% and was practically constant even after a long time when the product remained at the reaction conditions.
EKSEMPEL 3 EXAMPLE 3
Det ble benyttet samme metode som i eksempel 1, men vann ble ikke tilsatt. Selektiviteten til cyklopenten, etter at dicyklo-pentadien var borte, var 89 %. Ved å holde produktet ved reaksjonsbetingelsene i 30 minutter sank selektiviteten til 74 på grunn av dannelsen av cyklopentan, og etter ytterligere 30 minutter var selektiviteten sunket til 60 %. The same method as in example 1 was used, but no water was added. The selectivity to the cyclopentene, after the dicyclopentadiene was gone, was 89%. By keeping the product at the reaction conditions for 30 minutes, the selectivity dropped to 74 due to the formation of cyclopentane, and after another 30 minutes, the selectivity had dropped to 60%.
EKSEMPLER 4 OG 5 EXAMPLES 4 AND 5
Isopren og pentadien underkastes hydrogenering ifølge metoden beskrevet i eksempel 1. Isoprene and pentadiene are subjected to hydrogenation according to the method described in example 1.
Etter total fjernelse av diolefinene ble det oppnådd blandinger av olefinisomerer ved selektiviteter på henholdsvis 99,1 og 98,7. After total removal of the diolefins, mixtures of olefin isomers were obtained at selectivities of 99.1 and 98.7 respectively.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT27492/72A IT963424B (en) | 1972-07-27 | 1972-07-27 | HYDROGENATION PROCESS OF DIOLEFIN HYDRO CARBONS TO OLEFINIC HYDROCARBONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO139858B true NO139858B (en) | 1979-02-12 |
| NO139858C NO139858C (en) | 1979-05-23 |
Family
ID=11221753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO3023/73A NO139858C (en) | 1972-07-27 | 1973-07-26 | PROCEDURE FOR SELECTIVE HYDROGENATION OF DIOLEFIN HYDROCARBONS TO OLEFINE HYDROCARBONS |
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|---|---|
| US (1) | US3857894A (en) |
| JP (1) | JPS5313602B2 (en) |
| AR (1) | AR227263A1 (en) |
| AT (1) | AT328417B (en) |
| AU (1) | AU477097B2 (en) |
| BE (1) | BE802721A (en) |
| BG (1) | BG21008A3 (en) |
| BR (1) | BR7305591D0 (en) |
| CA (1) | CA1046535A (en) |
| CH (1) | CH588428A5 (en) |
| CS (1) | CS176241B2 (en) |
| DD (1) | DD104500A5 (en) |
| DK (1) | DK136524B (en) |
| ES (1) | ES417524A1 (en) |
| FR (1) | FR2194672B1 (en) |
| GB (1) | GB1428287A (en) |
| HU (1) | HU172415B (en) |
| IE (1) | IE38478B1 (en) |
| IN (1) | IN139205B (en) |
| IT (1) | IT963424B (en) |
| LU (1) | LU68103A1 (en) |
| NL (1) | NL169724C (en) |
| NO (1) | NO139858C (en) |
| PL (1) | PL90383B1 (en) |
| RO (1) | RO70140A (en) |
| SE (1) | SE379533B (en) |
| TR (1) | TR17413A (en) |
| YU (1) | YU35092B (en) |
| ZA (1) | ZA734155B (en) |
| ZM (1) | ZM10573A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947510A (en) * | 1972-07-27 | 1976-03-30 | Snamprogetti S.P.A. | Hydrogenation of linear hydrocarbon diolefins to linear hydrocarbon olefins |
| US4167529A (en) * | 1977-11-11 | 1979-09-11 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene using Raney nickel catalyst and ammonium hydroxide in the reaction mixture |
| FI66019C (en) * | 1977-12-19 | 1984-08-10 | Unilever Nv | FOERFARANDE FOER SELEKTIV HYDRERING AV TRIGLYCERIDOLJA |
| US4570025A (en) * | 1985-06-14 | 1986-02-11 | Phillips Petroleum Company | Preparation of alkenes and cycloalkenes |
| DE3736557A1 (en) * | 1987-10-28 | 1989-05-11 | Sued Chemie Ag | CATALYST FOR THE SELECTIVE HYDROGENATION OF MULTIPLE UNSATURATED HYDROCARBONS |
| US6620982B1 (en) | 1998-10-07 | 2003-09-16 | Equistar Chemicals, Lp | Method of producing purified cyclopentane |
| CN106694010B (en) * | 2016-12-27 | 2018-08-28 | 重庆建峰工业集团有限公司 | A kind of catalyst and preparation method thereof for half Hydrogenation enol of alkynol |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2456633A (en) * | 1946-11-29 | 1948-12-21 | Universal Oil Prod Co | Catalyst preparation |
| US2728713A (en) * | 1952-09-25 | 1955-12-27 | Exxon Research Engineering Co | High activity reforming catalysts for use in the hydroforming of naphtha |
| FR1323307A (en) * | 1962-05-21 | 1963-04-05 | Basf Ag | Partial hydrogenation of cycloaliphatic compounds containing at least two olefinic double bonds |
| GB1086639A (en) * | 1963-10-29 | 1967-10-11 | Geigy Uk Ltd | Production of cyclododecene |
| CH462809A (en) * | 1964-06-03 | 1968-09-30 | Hoffmann La Roche | Use of organosulfur compounds to increase the selectivity of hydrogenation catalysts |
| US3408415A (en) * | 1965-09-20 | 1968-10-29 | Uniroyal Inc | Catalytic hydrogenation |
| US3418386A (en) * | 1966-07-05 | 1968-12-24 | Columbian Carbon | Hydrogenation of cyclooctadienes to cyclooctenes |
| US3433842A (en) * | 1967-04-12 | 1969-03-18 | Universal Oil Prod Co | Process for the hydrogenation of trans,cis-1,5-cyclodecadiene to ciscyclodecene |
| US3433843A (en) * | 1967-10-09 | 1969-03-18 | Universal Oil Prod Co | Selective hydrogenation of trans,cis-1,5-cyclodecadiene to cis-cyclodecene |
| DE2025411A1 (en) * | 1970-05-25 | 1971-12-09 |
-
1972
- 1972-07-27 IT IT27492/72A patent/IT963424B/en active
-
1973
- 1973-06-20 ZA ZA734155A patent/ZA734155B/en unknown
- 1973-06-26 YU YU1719/73A patent/YU35092B/en unknown
- 1973-06-26 ZM ZM105/73*UA patent/ZM10573A1/en unknown
- 1973-06-26 CS CS4591A patent/CS176241B2/cs unknown
- 1973-06-27 RO RO7375259A patent/RO70140A/en unknown
- 1973-06-28 AU AU57469/73A patent/AU477097B2/en not_active Expired
- 1973-07-05 JP JP7533473A patent/JPS5313602B2/ja not_active Expired
- 1973-07-05 TR TR17413A patent/TR17413A/en unknown
- 1973-07-16 IE IE1194/73A patent/IE38478B1/en unknown
- 1973-07-17 BG BG24125A patent/BG21008A3/xx unknown
- 1973-07-17 GB GB3408373A patent/GB1428287A/en not_active Expired
- 1973-07-18 IN IN1682/CAL/73A patent/IN139205B/en unknown
- 1973-07-18 CH CH1052073A patent/CH588428A5/xx not_active IP Right Cessation
- 1973-07-20 FR FR7326822A patent/FR2194672B1/fr not_active Expired
- 1973-07-24 ES ES417524A patent/ES417524A1/en not_active Expired
- 1973-07-24 BE BE133808A patent/BE802721A/en unknown
- 1973-07-24 US US00382055A patent/US3857894A/en not_active Expired - Lifetime
- 1973-07-25 BR BR5591/73A patent/BR7305591D0/en unknown
- 1973-07-25 DD DD172509A patent/DD104500A5/xx unknown
- 1973-07-26 PL PL1973164309A patent/PL90383B1/pl unknown
- 1973-07-26 CA CA177,367A patent/CA1046535A/en not_active Expired
- 1973-07-26 DK DK414073AA patent/DK136524B/en not_active IP Right Cessation
- 1973-07-26 SE SE7310415A patent/SE379533B/xx unknown
- 1973-07-26 HU HU73SA00002513A patent/HU172415B/en unknown
- 1973-07-26 AT AT658773A patent/AT328417B/en not_active IP Right Cessation
- 1973-07-26 NO NO3023/73A patent/NO139858C/en unknown
- 1973-07-26 LU LU68103A patent/LU68103A1/xx unknown
- 1973-07-26 NL NLAANVRAGE7310423,A patent/NL169724C/en not_active IP Right Cessation
- 1973-10-17 AR AR249129A patent/AR227263A1/en active
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