SE185252C1

SE185252C1 -

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Publication number: SE185252C1
Authority: SE
Publication date: 1963-01-01

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Uppfinnare: W C van Zijil Langhout, P van't Spijker och GJ F Stijntjes Prioritet begird frdn den 21 oktober 1960 (Nederldnderna) Uppfinningen avser ett satt for katalytisk selektiv hydrering av Mita, dien-haltiga krackade kolvateolj or. Inventors: W C van Zijil Langhout, P van't Spijker and GJ F Stijntjes Priority requested from 21 October 1960 (The Netherlands) The invention relates to a method for catalytically selective hydrogenation of Mita, diene-containing cracked hydrocarbon oils.

Med latta krackade kolvateoli or avses kolvateoljor med en slutkokpunkt (ASTM) av hogst 375° C. Lightly cracked hydrocarbon oils are hydrocarbon oils with a final boiling point (ASTM) of up to 375 ° C.

Det är redan kfint att dien-lhaltig krackad bensin och andra latta krackade kolvateoljor kunna selektivt hydreras genom att foras Over en lamplig hydreringskatalysator i narvaro av vale. It is already known that diene-containing cracked gasoline and other lightly cracked hydrocarbon oils can be selectively hydrogenated by passing over a suitable hydrogenation catalyst in the presence of vale.

Sarskilt lampliga ls.atalysatorer aro de som innehalla nickel anbragt pa en barare (t. ex. A1203 eller ett material innehallande A1203, BaSO4, BaCO3 etc.). Dessa katalysatorer ha foretradesvis sulferats fore anvandningen. Particularly suitable laser catalysts are those containing nickel applied to a carrier (eg Al 2 O 3 or a material containing Al 2 O 3, BaSO 4, BaCO 3, etc.). These catalysts have preferably been sulphated before use.

Vid dessa selektiva hydreringar hydreras dienerna (som aven kunna vara av cyklopentadien-typ) till motsvarande alkener (cykloalkener). Avlagsnandet av alkadiener och liknande foreningar Or nodvandigt i manga fall, enar i narvaro av dessa mycket reaktiva omattade foreningar de latta krackade kolvateoljorna aro ytterligt instabila och foljaktligen olampliga for anvandande exerapelvis som motorbransle-komponent. Sadana mycket reaktiva foreningar forekomma I relativt stora mangder i bensiner och fotogener erhallna genom mycket drastisk termisk kraekfling. In these selective hydrogenations, the dienes (which may also be of the cyclopentadiene type) are hydrogenated to the corresponding alkenes (cycloalkenes). The removal of alkadienes and the like compounds is necessary in many cases, in the presence of these highly reactive unsaturated compounds the slightly cracked hydrocarbon oils are extremely unstable and consequently unsuitable for use, for example, as a motor fuel component. Such highly reactive compounds occur in relatively large amounts in gasolines and kerosene obtained by very drastic thermal cracking.

Vad betraffar driftsbetingelserna kan namnas, att vid dessa selektiva hydreringsprocesser temperaturer anvandas, som i allmanhet aro lagre an de vilka forekomma vid full standiga hydrerings-, hydrodesulfureringsoch liknande processer. Vid selektiv hydrering overstiger temperaturen joke 280° C och vanligtvis joke 200° C. Foretradesvis ligger temperaturen inom omradet 70-1° C. As far as the operating conditions are concerned, it can be mentioned that in these selective hydrogenation processes temperatures are used, which are generally lower than those which occur in complete hydrogenation, hydrodesulfurization and similar processes. In selective hydration, the temperature joke usually exceeds 280 ° C and usually joke 200 ° C. Preferably the temperature is in the range 70-1 ° C.

I de fiesta fall overstiga trycken joke 100 kg/cm2 abs. och ligga I allmauhet inom omrklet -80 kg/cm2 abs. Mangden WHOA utgangsmaterial ligger vanligtvis Mom omradet 0,5-5 kg vatskeformigt utgangsmaterial per timme per liter katalysator och foretradesvis mom omradet 1-3 kg/h/l, samtidigt som forhallandet mellan mangden vatehaltig gas och totala mangden kolvateolj a vanligen ligger Mom. ontradet 50-300 n 1/kg. In most cases, the pressure joke exceeds 100 kg / cm2 abs. and lie in general within the range -80 kg / cm2 abs. The amount of WHOA starting material is usually Mom in the range of 0.5-5 kg of liquid starting material per hour per liter of catalyst and preferably in the range of 1-3 kg / h / l, while the ratio between the amount of aqueous gas and the total amount of hydrocarbon oil is usually Mom. ontradet 50-300 n 1 / kg.

Om onskvart kan en del av den behandlade oljan fa cirkulera och/eller en lamplig utspadningsolj a (kylolja) tillsattas. Blandning med den for hydrering avsedda olj an kan ske fore den forsta (eller enda) katalysatorbadden och/eller vid en eller flera punkter melIan katalysatorbaddarna (om flera an en badd anvandas). If desired, some of the treated oil may circulate and / or a suitable diluent oil a (cooling oil) may be added. Mixing with the oil intended for hydrogenation can take place before the first (or only) catalyst bath and / or at one or more points between the catalyst baths (if several baths are used).

Reaktionsbetingelserna aro foretradesvis sa valda, att den for raffinering avsedda olj an atminstone delvis forblir flytande under reaktionen, namligen till minst 50 vikts%. The reaction conditions are preferably chosen so that the oil intended for refining remains at least partially liquid during the reaction, namely to at least 50% by weight.

I praktiken utgores den anvanda gasen av en vatehaltig gasblandning. Den bor foretradesvis innehalla Over 60 volym% vate. I allmanhet aro vatehaltiga gaser erhallna exempelvis vid katalytisk reforminp av bensinfraktioner mycket Det har nu emellertid befunnits, att vid se- 2— — lektiv hydrering vissa vatehaltiga gaser, som med fardel kunna anvandas vid brukliga fullstaridiga hydrerings- och hydrodesulfureringsprocesser, medfora mycket Skadliga fenomen, som icke intraffa med andra vatehaltiga gaser, namligen en. Wining av svavelhalten hos oljan och en mycket brant minskning av katalysatorns aktivitet. In practice, the gas used consists of an aqueous gas mixture. It should preferably contain Over 60% by volume of water. In general, however, hydrogen-containing gases obtained, for example, in the catalytic reforming of gasoline fractions, have been found to be very harmful. which do not occur with other aqueous gases, namely a. Wining of the sulfur content of the oil and a very steep decrease in the activity of the catalyst.

Narmare undersokning liar visat, att dessa icke onskvarda fenomen hero pa en alltfor hog koncentration av svavelvate i reaktionsblandningen och icke uppkomma om man tillser, att mangden svavelvate i reaktionsblandningen ãr tillrackligt liten. Closer examination has shown that these undesirable phenomena are due to an excessively high concentration of hydrogen sulphide in the reaction mixture and do not arise if it is ensured that the amount of hydrogen sulphide in the reaction mixture is sufficiently small.

Uppfimiingen. avser dad& ett satt for katalytisk selektiv hydrering av latta, dien-haltiga krackade kolvateoljor vid temperaturer understigande 280° C och i narvaro av en vatehaltig gas och kannetecknas darav, att totala mangden svavelvate, som är narvarande I de till reaktionszonen forda strommarna, icke overstiger 0,1 kg per 1000 kg kolvaten, i strommarna. The invention. refers to the catalytic selective hydrogenation of light, diene-containing cracked hydrocarbon oils at temperatures below 280 ° C and in the presence of an aqueous gas and can be characterized in that the total amount of hydrogen sulfide present in the streams leading to the reaction zone does not exceed 0.1 kg per 1000 kg of hydrocarbons, in the streams.

Denna mangd svavelvate averstiger foretradesvis icke 0,01 kg per 1000 kg kolvaten. This amount of sulfur water preferably does not exceed 0.01 kg per 1000 kg of hydrocarbons.

Om vid forfarandet enligt uppfinningen komponenterna i reaktionsblandningen (farsk gas, cirkulerande gas, farsk olja, eventuell cirkulerande olja, eventuell utspadningsolja etc.) icke kunna valjas sa, att H2S-halten hos blandningen blir tillrackligt lag, bar H2S avlagsnas fran reaktionsblandningen eller frail en eller flera av de strommar, varav den är sammansatt. If in the process of the invention the components of the reaction mixture (fresh gas, circulating gas, fresh oil, any circulating oil, any diluent oil, etc.) can not be selected so that the H2S content of the mixture becomes sufficiently low, H2S should be removed from the reaction mixture or or several of the streams of which it is composed.

Detta kan ske pa i och for sig kith satt, t.ex. genom absorption av HS i en vattenlosning av ett eller flera fosfater, NaOH, KOH eller en organisk amin. Denna behandling foretages lampligen med den farska vatehaltiga gasen, som vanligtvis uteres av overskottsgas frail en. katalytisk »reforminp-anlaggning, enar i de fiesta fall derma strom är rikast pa svavelvate. This can be done in and of itself kith set, e.g. by absorption of HS in an aqueous solution of one or more phosphates, NaOH, KOH or an organic amine. This treatment is suitably carried out with the fresh aqueous gas, which is usually excreted in excess gas. catalytic »reforminp plant, in most cases this stream is richest in sulfur water.

Efter behandlingen med en sadan absorberande vatska tvattas den. strain, lean vilken H2S helt eller delvis avlagsnats, foretradesvis med vatten far avlagsnande av eventuellt medrivna droppar av absorptionsvatska, under vilken behandling namnda strain mattas med vatten. Detta innebar icke flagon _nackdel, da det visat sig, att aven om H2S skadligt paverkar processen till och med i relativt lag koncentration, vattenanga icke liar flagon sadan inverkan, varfor torkning icke erfordras. After treatment with such an absorbent liquid, it is washed. strain, lean in which H2S has been completely or partially removed, preferably with water is removed from any entrained drops of absorption liquid, during which treatment said strain is matte with water. This did not entail a flake disadvantage, as it was found that although H2S adversely affects the process even at a relatively low concentration, water vapor does not suffer from such a flaking effect, so drying is not required.

Del ãr anmarkningsvart och overraskande, att de ovannamnda skadliga verkningarna av H2S (och detta galler sarskilt minskningen i aktivitet) forekomma aven has katalysatorer, som sulfiderats fore anvandningen, t. ex. hos nickelkatalysatorer anbragta pa en barare, som fore anvandningen som katalysator f8r selektiv hydrering sulfiderats med H2S eller svavelhaltiga kolvateoljor. It is remarkably black and surprising that the above-mentioned harmful effects of H2S (and this is especially true of the reduction in activity) also occur in catalysts which have been sulphided before use, e.g. in nickel catalysts applied to a carrier which, before use as a catalyst for selective hydrogenation, has been sulphided with H2S or sulfur-containing hydrocarbon oils.

Forfarandet enligt uppfinningen är sarskilt betydelsefnllt vid den selektiva hydreringen av de bensiner (och fotogener), som erhallas som biprodukt vid framstallningen av gasformiga alkener (sarskilt eten och propen) ge- nom drastisk termisk krackningkolvate- olja. Dessa krackningsreaktioner utforas vanligtvis pa sa salt, att Over 50 vikt% av utgangskolvateoljan omvandlas till foreningar med 4 eller farre kolatomer i molekylen. Den vid denna krackning hildade biprodukten utgores av en bensin, som vanligen innehaller Over 30 och ofta aver 60 vikt% aromatiska foreningar och en betydande mangd alkener med ett relativt Mgt oktantal. F81j aktligen ha sadana bensiner hoga oktantal. Det innebar aven en fordel, att i de fiesta fall dessa bensiner are praktiskt taget fria frail svavel, dvs_ ha en halt av svavelforeningar (raknade sorn elementart svavel) avsevart under 0,1 vikts%. The process of the invention is particularly important in the selective hydrogenation of the gasolines (and photogens) obtained as a by-product in the production of gaseous alkenes (especially ethylene and propylene) by drastic thermal cracking hydrocarbon oil. These cracking reactions are usually carried out on such a salt that more than 50% by weight of the starting hydrocarbon oil is converted to compounds having 4 or fewer carbon atoms in the molecule. The by-product obtained during this cracking consists of a petrol, which usually contains more than 30% and often contains 60% by weight of aromatic compounds and a significant amount of alkenes with a relatively high octane number. F81j actually have such gasoline high octane number. It also meant an advantage that in most cases these gasolines are practically free of sulfur, i.e. have a content of sulfur compounds (shaved elemental sulfur) considerably below 0.1% by weight.

Emellertid innehalla dessa bensiner avsevarda mangder starkt reaktiva fareningar, sasom diener (daribland sadana av cyklopentadientyp), alkyner och foreningar av styrentyp, och det ãr ofta mycket onskvart att avlagsna dessa starkt reaktiva foreningar genom selektiv hydrering, da pa grund av narvaron av desamma bensinerna aro ytterligt instabila och foljaktligen olampliga exempelvis som komponent i ett motorbransle Det kan namnas, att den drastiska termiska kraekningen fOr framstallning av lagre alkener foretradesvis foretages i rorugnar °eh i narvaro av vattenanga. Denna vattenangkrackning sker vanligtvis vid temperaturer mom omradet c:a 550-900° C, foretradesvis 750-800° C, och heist vid ett tryck understigande ca 5 atm. abs. I allmanhet anvandas 0,1-10 viktsdelar vattenanga per viktsdel av utgangsmaterialet. Den namnda mycket drastiska krackningen kan emellertid aven ske pa andra satt, t. ex. genom att sammanfora utgangsmaterialet med ett mycket starkt upphettat finfordelat fast material, sasom sand, eller med ett mycket starkt upphettat smalt salt. However, these gasolines contain significant amounts of highly reactive compounds, such as dienes (including cyclopentadiene-type ones), alkynes and styrene-type compounds, and it is often highly undesirable to remove these highly reactive compounds by selective hydrogenation, as due to the presence of extremely unstable and consequently unsuitable, for example, as a component of a motor fuel. This water vapor cracking usually occurs at temperatures in the range of about 550-900 ° C, preferably 750-800 ° C, and is raised at a pressure below about 5 atm. abs. Generally, 0.1-10 parts by weight of water vapor are used per part by weight of the starting material. However, the said very drastic cracking can also occur in other ways, e.g. by combining the starting material with a very strongly heated finely divided solid material, such as sand, or with a very strongly heated narrow salt.

Sasom utgangsprodukt for dessa drastiska termiska krackningar anvandas faretradesvis lagkokande kolvateoljor, som aro relativt rika pa alifatiska kolvaten. Foljaktligen aro direktdestillerade bensinfraktioner mycket lampliga. As a starting product for these drastic thermal cracks, low-boiling hydrocarbon oils, which are relatively rich in aliphatic hydrocarbons, are used. Consequently, directly distilled gasoline fractions are very suitable.

Andra kolvateblandningar an de ovan angivna besinerna och fotogenerna kunna avenledes selektivt hydreras enligt uppfinningen,. t. ex. diolefiner innehallande hogre kokandeolefiniska fraktioner (t. ex. hogre kokande. olefinfraktioner rika pa C14—C18-olefiner) erhallna vid krackning av hogkokande kolvate- • fraktioner. Other carbonate mixtures of the above-mentioned besins and photogens can also be selectively hydrogenated according to the invention. e.g. diolefins containing higher boiling olefinic fractions (eg higher boiling olefin fractions rich in C14-C18 olefins) obtained by cracking high boiling hydrocarbon fractions.

Exempel Utgangsmaterialet utgjordes av en bensia erhallen som biprodukt vid framstallning av eten och propen genom vattenangkrackning — —a av en direktdestillerad kolvateolja med en slutkokpunkt av 230° C. Nananda bensin var fri Iran nafteniska kolvaten och inneholl 11 vikts% diener, 10 vikts% alkener, 36 vikts% aromatiska kolvaten och 43 vikts% mattade kolvaten. Example The starting material consisted of a benzene obtained as a by-product in the production of ethylene and propylene by water-cracking - aa of a directly distilled hydrocarbon oil with a final boiling point of 230 ° C. , 36% by weight of aromatic hydrocarbons and 43% by weight of matte hydrocarbons.

De &riga egenskaperna hos bensinen voro: kokpunktsomrade 41-180° C (ASTM), bromtal 55 g/100 g (McIlhineys metod), maleinhydridtal 110 mg/g (Ellis och Jones metod), svavelhalt 15 viktsdelar per 1 million viktsdelar bensin (dpm). Till foljd av den hOga dienhalten var bensinen mycket instabil. The other properties of the gasoline were: boiling point range 41-180 ° C (ASTM), bromine number 55 g / 100 g (McIlhiney method), maleic anhydride number 110 mg / g (Ellis and Jones method), sulfur content 15 parts by weight per 1 million parts by weight of gasoline (ppm ). Due to the high diene content, the petrol was very unstable.

Bensinen fordes over en katalysator tillsammans med rent Tate vid en temperatur av 100-110° C, ett tryck av 40 atm abs. saint i en mangd av 1 kg/h/l. Vatemangden uppgick till 170 nl/kg bensin. Den anvanda katalysatorn utgjordes av en nickelkatalysator anbragt pa aluminiumoxid (10 % Ni), sulfiderad med en direktdestillerad nafta (0,05 % svavel). The gasoline was passed over a catalyst along with pure Tate at a temperature of 100-110 ° C, a pressure of 40 atm abs. saint in an amount of 1 kg / h / l. The amount of water amounted to 170 nl / kg of petrol. The catalyst used consisted of a nickel catalyst applied to alumina (10% Ni), sulphided with a directly distilled naphtha (0.05% sulfur).

Produkten hade ett bromtal av 38 g/100 och ett maleinanhydridtal av 1,0 mg/g, vilket visade att hydreringen var ratt selektiv. Svavelhalten uppgick till 15 dpm. Da forsoket fortsattes under 825 timmar, forblevo maleinanhydridtalet och bromtalet konstanta inom felgranserna for observationen. The product had a bromine number of 38 g / 100 and a maleic anhydride number of 1.0 mg / g, which showed that the hydrogenation was steering selective. The sulfur content was 15 ppm. When the experiment was continued for 825 hours, the maleic anhydride number and the bromine number remained constant within the error limits of the observation.

Valet ersattes darefter med en vate-svavelvate-blandning innehallande 0,7 volym% H2S. Ovriga betingelser hallos omsorgsfullt oforandrade. Totala halten av H2S i de till reaktorn forda strOmmarna uppgick nu till 1,82 kg per 1000 kg bensin. Bromtalet och maleinanhydridtalet hos reaktionsprodukten steg nastan genast till 51g/100, g och 108 mg/g, vilket visar att det praktiskt taget icke forekom flagon ytterligare hydrering. Reaktionsprodukten befriad frau H2S inneh011 515 dpm svavel. The sample was then replaced with a cotton-sulfur cotton mixture containing 0.7% by volume of H 2 S. Other conditions are kept carefully unchanged. The total content of H2S in the streams fed to the reactor now amounted to 1.82 kg per 1000 kg of petrol. The bromine number and maleic anhydride number of the reaction product rose almost immediately to 51 g / 100 g and 108 mg / g, indicating that there was virtually no further hydrogenation of the flake. The reaction product liberated from H2S contained 515 ppm of sulfur.

Efter atergang till den ursprungliga H2Sfria gasen aterhamtade sig katalysatorn Pangsamt. Efter 100 timmar uppgick bromtalet hos produkten till 45 g/100 g och maleinanhydridtalet till 4,7 mg/g. Detta visar, att aktiviteten och selektiviteten praktiskt taget Merging° till den ursprungliga goda nivan. Svavelhalten uppgick Ater till 15 dpm. After returning to the original H2-free gas, the catalyst recovered slowly. After 100 hours, the bromine content of the product was 45 g / 100 g and the maleic anhydride number was 4.7 mg / g. This shows that the activity and selectivity are practically Merging ° to the original good level. The sulfur content of Ater was 15 ppm.

I ett f8ljande f8rsok (ovriga betingelser voro of orandrade) anvandes vale innehallande 0,002 volym% II2S. Totala halten av H2S i reaktionsblandningen uppgiek (Tailor till 0.0052 kg/1000 kg bensin. Maleinanhydridtalet var ursprungligen 1,0 kg/g och bromtalet 35 g/100 g. Efter 60 timmar hade de stigit till 1,6 mg/g resp. 40 g/100 g, vilket visar, att det forekom en minskning i aktivitet, som var ringa och vanligtvis alltjamt acceptabel. Svavelhalten hos produkten var ursprungligen 15 dpin och efter 60 timmar 17 dpm. In a subsequent experiment (other conditions were unchanged), vale containing 0.002% by volume of II2S was used. The total content of H2S in the reaction mixture was (Tailor to 0.0052 kg / 1000 kg of petrol. The maleic anhydride number was originally 1.0 kg / g and the bromine number 35 g / 100 g. After 60 hours they had risen to 1.6 mg / g and 40, respectively. g / 100 g, which shows that there was a decrease in activity, which was small and usually still acceptable.The sulfur content of the product was originally 15 dpin and after 60 hours 17 ppm.

I ett annat forsok (betingelserna i 8vrigt oforandrade) anvandes en gas innehallande 0,008 volym% H2S, medan aterstoden utgjordes av vale. Totala halten av H2S i reaktionsblandningen uppgick an till 0,02 kg/1000 kg bensin. In another experiment (the conditions were otherwise unchanged) a gas containing 0.008% by volume of H 2 S was used, while the residue consisted of vale. The total content of H2S in the reaction mixture was 0.02 kg / 1000 kg of petrol.

Maleinanhydridtalet uppgick ursprungligen till 1,0 mg/g och bromtalet till 35 g/100 g. Efter 60 timmar hade maleinanhydridtalet smaningom stigit till 3,0 mg/g, medan bromtalet var 41 g/100 g, vilket visar, att en H2Shalt av 0,02 kg/1000 kg bensin vanligtvis praktiskt resulterar i en icke Onskvard snabb minskning av katalysatoraktiviteten. Svavelhalten hos produkten uppgick ursprungligen. till 15 dpm och efter 60 timmar 21 dpm. The maleic anhydride number was initially 1.0 mg / g and the bromine number was 35 g / 100 g. After 60 hours the maleic anhydride number had gradually risen to 3.0 mg / g, while the bromine number was 41 g / 100 g, 0.02 kg / 1000 kg of gasoline usually practically results in a non-Onskvard rapid decrease in catalyst activity. The sulfur content of the product was originally. to 15 ppm and after 60 hours 21 ppm.

Claims

Patent Application:

1. Set for catalytic selective hydrogenation of light, diene-containing hydrocarbon oils at temperatures below 280 ° C and in the presence of aqueous gas, characterized in that the total amount of hydrogen sulfide in the streams fed to the reaction zone does not exceed 0.1 kg per 1000 kg of carbohydrates in these strains.

2. A kit according to claim 1, characterized in that the total amount of sulfur water in the streams fed to the reaction zone does not exceed 0.01 kg per 1000 kg of hydrocarbons in these stream streams.

3. A kit according to claim 1 or 2, characterized in that the aqueous gas from a catalytic reforming plant is used as the aqueous gas, which gas is completely or substantially completely liberated from hydrogen sulphide.

Salt according to any one of the preceding claims, characterized in that the selective hydrogenation is carried out at temperatures not exceeding 200 ° C.

5. sat according to any air patent claim, characterized in that the selective hydrogenation is carried out at temperatures in the range 70-150 ° C.

6. according to some of the foregoing patent claims, characterized in that the selective hydrogenation is carried out at a pressure not exceeding 100 kg / cin2 abs.

7. Set according to some of the preceding patent claims, characterized in that the selective hydrogenation is carried out at a pressure not exceeding 10-80 kg / cm 2 abs.

8. According to some of the preceding patent claims, it may be characterized by the fact that the ratio between the amount of aqueous gas and the total amount of hydrocarbon oil is in the range of 50-300 n 1 / kg.

9. According to some of the foregoing patent claims, characterized in that the oil intended for refining remains at least partially liquid during the reaction.

10. sat according to some of the preceding patent claims, characterized by the fact that the oil intended for refining consists of a petrol12. Selectively hydrated hydrocarbon oils are obtained as a product of drastically cracked pal palate some of the preceding patent claims of vertebrate oils for the production of the aforementioned Ott. ground gaseous alkenes.

11. Safi according to claim 10, can - Request publications: characterized in that the gasoline intended for refining is one obtained by drastic