SE446971B - PROCEDURE FOR THE PREPARATION OF A CARBON WHEAT MIXTURE BASED FROM A CARBON MONOXIDE AND WHEAT MIXTURE - Google Patents
PROCEDURE FOR THE PREPARATION OF A CARBON WHEAT MIXTURE BASED FROM A CARBON MONOXIDE AND WHEAT MIXTUREInfo
- Publication number
- SE446971B SE446971B SE8103437A SE8103437A SE446971B SE 446971 B SE446971 B SE 446971B SE 8103437 A SE8103437 A SE 8103437A SE 8103437 A SE8103437 A SE 8103437A SE 446971 B SE446971 B SE 446971B
- Authority
- SE
- Sweden
- Prior art keywords
- catalyst
- weight
- parts
- mixture
- conversion
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- 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
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
-
- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/86—Chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
446 971 med en kobolt- eller ruteniumhaltig monofunktionell kataly- sator med aktivitet med avseende på omvandlingen av en H2/CO- blandning till i huvudsak kolväten, med det förbehållet att, om tillflödet till det andra steget har ett molförhållande H2/CO av mindre än 1,5, vatten sätts till nämnda tillflöde och att i det andra steget man använder en kobolt- eller ru- teniumhaltig bifunktionell katalysator eller katalysatorkom- bination, som förutom att uppvisa aktivitet med avseende på omvandlingen av en H2/CO-blandning till i huvudsak kolväten även uppvisar aktivitet med avseende på omvandlingen av en H20/CO-blandning till en H2/C02-blandning. Detta förfarande icke endast möjliggör att man vid användning av ovannämnda höga volymhastighet R (nu baserad på det totala katalysator- systemet i det första och andra steget) uppnår en hög omvand- lingsgrad utan stabilitetsproblem utan även att den uppnådda omvandlingsgraden har ett högre värde än ovannämnda omvand- lingsgrad C. 446 971 with a cobalt- or ruthenium-containing monofunctional catalyst with activity with respect to the conversion of an H2 / CO mixture to essentially hydrocarbons, with the proviso that, if the inflow to the second stage has a molar ratio H2 / CO of less than 1.5, water is added to said feed and that in the second step a cobalt or ru- tenium-containing bifunctional catalyst or catalyst bination, which in addition to exhibiting activity with respect to the conversion of an H2 / CO mixture into essentially hydrocarbons also exhibits activity with respect to the conversion of a H 2 O / CO mixture to an H 2 / CO 2 mixture. This procedure not only enables the use of the above high volume rate R (now based on the total catalyst system in the first and second stages) achieves a high conversion degree of stability without stability problems but also that it achieved the degree of conversion has a higher value than the above-mentioned conversion degree C.
Föreliggande uppfinning avser därför ett förfarande för fram- ställning av en kolväteblandning, vid vilket en blandning av _kolmonoxid och väte med ett H2/CO-molförhållande av mindre än 1,0 i ett första steg bringas i kontakt med en Fe-haltig bi- funktionell katalysator eller katalysatorkombination, såsom har definierats ovan, och vid vilket i reaktionsprodukten i första steget närvarande kolmonoxid och väte, eventuellt till- sammans med andra komponenter i nämnda reaktionsprodukt, i ett andra steg bringas i kontakt med en kobolt- eller rute- niumhaltig bifunktionell katalysator, såsom definierats ovan, med det förbehållet, att om tillflödet till andra steget har ett H2/CO-molförhållande av mindre än 1,5, vatten sätts till nämnda tillflöde och att i det andra steget man använder en kobolt- eller ruteniumhaltig bifunktionell katalysator eller katalysatorkombination, såsom har definierats ovan.The present invention therefore relates to a process for producing position of a hydrocarbon mixture, in which a mixture of Carbon monoxide and hydrogen with an H2 / CO molar ratio of less than 1.0 in a first step is contacted with an Fe-containing bi- functional catalyst or catalyst combination, such as has been defined above, and in which in the reaction product in carbon monoxide and hydrogen present in the first stage, optionally together with other components of said reaction product, i a second step is brought into contact with a cobalt or router potassium-containing bifunctional catalyst, as defined above, with the proviso that if the influx to the second stage has an H2 / CO molar ratio of less than 1.5, water is added said inflow and that in the second step one uses one cobalt or ruthenium-containing bifunctional catalyst or catalyst combination, as defined above.
Vid förfarandet enligt uppfinningen är utgångsmaterialet en H,/CO-blandning med ett H2/CO-molförhållande av mindre än 2,3. Pylika E , .1_ . _ _ ._ _ ," 1 _ __“,1_p >_ C--o_=n:n1ng=r kan :eo :order framztaiaa; geia 446 971 ångförgasning av ett kolhaltigt material. Exempel på dylika material är lignit, antracit, koks, råmineralolja och frak- tioner därav, liksom oljor framställda ur tjärsand och bi- tuminös skiffer. Ångförgasning utförs företrädesvis vid en temperatur av 900-l500°C och vid ett tryck av 10-100 bar.In the process according to the invention, the starting material is one H, / CO mixture with an H2 / CO molar ratio of less than 2.3. Pylika E , .1_. _ _ ._ _, "1 _ __“, 1_p> _ C - o_ = n: n1ng = r kan: eo: order framztaiaa; geia 446 971 steam gasification of a carbonaceous material. Examples of such materials are lignite, anthracite, coke, crude mineral oil and fractional thereof, as well as oils obtained from tar sands and tuminous slate. Steam gasification is preferably performed at a temperature of 900-1500 ° C and at a pressure of 10-100 bar.
Vid förfarandet enligt uppfinningen har H2/C0-utgângsbland- ningen företrädesvis ett H2/CO-molförhållande av mer än 0,25.In the process of the invention, the H2 / CO starting mixture has preferably an H 2 / CO molar ratio of more than 0.25.
De Fe-haltiga bifunktionella katalysatorerna eller katalysa- torkombinationerna, som är lämpliga för användning i det första steget av förfarandet enligt uppfinningen, bör för- utom att uppvisa aktivitet med avseende på omvandlingen av en H2/CO-blandning till i huvudsak kolväten uppvisa aktivi- tet med avseende på omvandlingen av en H20/CO-blandning till en H2/C02-blandning. I det första steget av förfarandet an- vänds företrädesvis en bifunktionell katalysator framställd genom impregnering och innehållande järn på en bärare. Exem- pel på dylika katalysatorer är: a) katalysatorer innehållande 30-75 viktdelar järn och 5-40 viktdelar magnesium per 100 viktdelar aluminiumoxid och framställda genom impregnering av aluminiumoxidbärare med en eller flera vattenlösningar av salter av järn och man- nesium och därefter torkning av kompositionen, kalcinering därav vid en temperatur av 700-l200°C och reduktion därav.The Fe-containing bifunctional catalysts or catalysts the dryer combinations suitable for use therein the first step of the process according to the invention, except to show activity with respect to the conversion of an H2 / CO mixture to essentially hydrocarbons exhibit activity with respect to the conversion of an H 2 O / CO mixture to an H 2 / CO 2 mixture. In the first step of the procedure preferably a bifunctional catalyst prepared is used by impregnation and containing iron on a support. Eczema piles on such catalysts are: a) catalysts containing 30-75 parts by weight of iron and 5-40 parts by weight of magnesium per 100 parts by weight of alumina and prepared by impregnation of alumina supports with one or more aqueous solutions of salts of iron and nesium and then drying of the composition, calcination thereof at a temperature of 700-1200 ° C and reduction thereof.
Företrädesvis används dylika katalysatorer, som förutom 40-60 viktdelar järn och 7,5-30 viktdelar magnesium inne- håller 0,5-5 viktdelar koppar som reduktionspromotor och l-5 viktdelar kalium som selektivitetspromotor per 100 viktdelar aluminiumoxid och som har kalcinerats vid 750- ß5o°c och reducerats vid z5o-3so°c; b) katalysatorer innehållande 10-40 viktdelar järn och 0,25- l0 viktdelar krom per 100 viktdelar kiseldioxid och fram- ställda genom impregnering av en kiseldioxidbärare med en eller flera vattenlösningar av salter av järn och av krom, ffilii av iørknxno av kompositionen, kalcinering därav och 446 971 reduktion därav vid en temperatur av 350-75000. Företrä- desvis används sådana katalysatorer, som förutom 20-35 viktdelar järn och 0,5-5 viktdelar krom innehåller l-5 viktdelar kalium som selektivitetspromotor per 100 vikt- delar kiseldioxid och som har kalcinerats vid 350-700°C och reaueerats via 3so-soo°c. ”c Det första steget av förfarandet enligt uppfinningen kan med fördel utföras genom att tillflödet får passera en vertikalt anordnad reaktor i uppåtgående eller nedåtgående riktning, I vilken reaktor innehåller en stationär eller rörlig bädd av den Fe-haltiga bifunktionella katalysatorn eller katalysator- kombinationen. Det första steget kan exempelvis utföras genom drift i stationär bädd, bunkerflöde, kokande bädd eller flui- diserad bädd. Det första steget av förfarandet utförs företrä- desvis under följande betingelser: en temperatur av 200-350°C och i synnerhet 250-350°C, ett tryck av 10-70 bar och i syn- nerhet 20-50 bar och en volymhastighet av 500-5000 och i syn- nerhet 500-2500 Nl gas/liter katalysator/timme.Preferably, such catalysts are used, as in addition 40-60 parts by weight of iron and 7.5-30 parts by weight of magnesium contain holds 0.5-5 parts by weight of copper as a reduction promoter and 1-5 parts by weight of potassium as selectivity promoter per 100 parts by weight of alumina and which have been calcined at 750 δ 50 ° C and reduced at 50 ° C to 30 ° C; b) catalysts containing 10-40 parts by weight of iron and 0.25- 10 parts by weight of chromium per 100 parts by weight of silica and by impregnating a silica support with a or more aqueous solutions of salts of iron and of chromium, f fi lii of iørknxno of the composition, calcination thereof and 446 971 reduction thereof at a temperature of 350-75000. Preferred in addition, such catalysts are used, which in addition to 20-35 parts by weight of iron and 0.5-5 parts by weight of chromium contain 1-5 parts by weight of potassium as selectivity promoter per 100 parts of silica and which has been calcined at 350-700 ° C and reacted via 30-50 ° C. C The first step of the process according to the invention may involve advantage is carried out by allowing the inflow to pass one vertically arranged reactor in the upward or downward direction, I which reactor contains a stationary or moving bed of the Fe-containing bifunctional catalyst or catalyst the combination. The first step can be performed, for example, by operation in stationary bed, bunker flow, boiling bed or fluid dissected bed. The first step of the process is preferably performed under the following conditions: a temperature of 200-350 ° C and in particular 250-350 ° C, a pressure of 10-70 bar and in 20-50 bar and a volume speed of 500-5000 and in unit 500-2500 Nl gas / liter catalyst / hour.
Vid förfarandet enligt uppfinningen används i reaktionsproduk- ten från första steget närvarande kolmonoxid och väte som till- flöde till det andra steget. Förutom kolmonoxid och väte kan tillflödet till det andra steget innehålla ytterligare kompo- nenter från reaktionsprodukten från det första steget. Så exempelvis är det möjligt att som tillflöde till det andra steget använda C;-fraktionen eller C;-fraktionen från reak- tionsprodukten från det första steget och t.o.m. hela reak- tionsprodukten från det första steget. I det andra steget av förfarandet enligt uppfinningen är syftet att omvandla så stor mängd som möjligt av den i tillflödet till det andra steget närvarande kolmonoxiden till i huvudsak kolväten över en mono- funktionell kobolt- eller ruteniumhaltig katalysator med akti- vitet med avseende på denna reaktion. För detta ändamål måste H2/CO-molförhållandet i tillflödet till det andra steget vara minst 1,5 och företrädesvis 1,75-2,25. Om man använder en H2/CO-blandning med ett högt H2/CO-molförhållande som tillflö- 446 971 de till det första steget är det möjligt vid förfarandet en- ligt uppfinningen att erhålla en reaktionsprodukt från det första steget med ett H2/CO-molförhållande av minst 1,5, vil- ken blandning lämpligen som sådan kan omvandlas i det andra steget över nämnda katalysator.In the process of the invention used in reaction products carbon monoxide and hydrogen present from the first stage flow to the second stage. In addition to carbon monoxide and hydrogen can the inflow to the second stage contain additional components from the reaction product from the first step. So for example, it is possible to as an inflow to the other step using the C; fraction or the C; fraction from the reaction the product from the first step and t.o.m. whole reaction from the first stage. In the second step of the process of the invention is intended to convert so large as much as possible of it in the inflow to the second stage present carbon monoxide to essentially hydrocarbons over a mono- functional cobalt or ruthenium-containing catalyst with active with respect to this reaction. For this purpose must The H2 / CO molar ratio in the feed to the second stage is at least 1.5 and preferably 1.75-2.25. If you use one H2 / CO mixture with a high H2 / CO molar ratio which flows 446 971 to the first step, it is possible in the procedure according to the invention to obtain a reaction product therefrom first stage with an H2 / CO molar ratio of at least 1.5, which the mixture suitably as such can be converted into the other the step over said catalyst.
Om vid förfarandet enligt uppfinningen man från första steget erhåller en reaktionsprodukt med ett H2/CO-molförhållande av mindre än 1,5 bör vatten sättas till tillflödet till det and- ra steget och man bör i det andra steget använda en kobolt- eller ruteniumhaltig bifunktionell katalysator eller katalysa- torkombination, som förutom att uppvisa aktivitet med avseen- de på omvandlingen av en H2/CO-blandning till i huvudsak kol- väten även uppvisar aktivitet med avseende på omvandlingen av en H20/CO-blandning till en H2/C02-blandning.If in the process according to the invention one from the first step obtains a reaction product with an H2 / CO molar ratio of less than 1.5, water should be added to the inflow to the step one and in the second step a cobalt or ruthenium-containing bifunctional catalyst or catalyst dryer combination, which in addition to exhibiting activity with on the conversion of an H2 / CO mixture into essentially carbon hydrogen also exhibits activity with respect to the conversion of an H 2 O / CO mixture to an H 2 / CO 2 mixture.
Om vid förfarandet enligt uppfinningen tillflödet till det andra steget har ett H2/CO-molförhållande av mindre än l,5 används företrädesvis i det andra steget en bifunktionell ka- talysatorkombination bestående av två separata katalysatorer, vilka i det följande för enkelhetens skull betecknas kataly- sator A och katalysator B. Katalysator A är den kobolt- eller ruteniumhaltiga katalysatorn med aktivitet med avseende på om-' vandlingen av en H2/CO-blandning till i huvudsak kolväten och katalysator B är katalysatorn med aktivitet med avseende på omvandlingen av en H20/CO-blandning till en H2/C02-blandning.If in the process according to the invention the inflow to it the second stage has an H2 / CO molar ratio of less than 1.5 preferably used in the second step is a bifunctional talysator combination consisting of two separate catalysts, which for the sake of simplicity are hereinafter referred to as Catalyst A and Catalyst B. Catalyst A is the cobalt or the ruthenium-containing catalyst with activity with respect to the conversion of an H2 / CO mixture into mainly hydrocarbons and Catalyst B is the catalyst with activity with respect to the conversion of an H 2 O / CO mixture into an H 2 / CO 2 mixture.
Både vid användningen av en monofunktionell katalysator och vid användningen av en bifunktionell katalysatorkombination vid det andra steget av förfarandet enligt uppfinningen an- vänds företrädesvis som katalysator A en koboltkatalysator och i synnerhet en katalysator framställd genom impregnering och innehållande kobolt på en bärare. Med fördel används ka- talysatorer innehållande l0-40 viktdelar kobolt och 0,25-5 viktdelar zirkonium, titan eller krom och framställda genom impregnering av en kiseldioxidbärare med en eller flera vat- tenlösningar av salter av kobolt och zirkonium, titan eller krom, följt av torkning av kompositionen, kalcinering därav vid 35o-7oo°c och reduktion därav vid 2oo-35o°c. Katalysato- 446 971 rer innehållande koppar och zink och vari Cu/Zn-atomförhållan- det ligger mellan 0,25 och 4,0 är speciellt lämpliga som kata- lysator B. I de kobolt- eller ruteniumhaltiga bifunktionella katalysatorkombinationerna kan katalysatorerna A och B vara närvarande som en fysikalisk blandning. Om det andra steget av förfarandet utförs med användning av en stationär katalysa- torbädd är bädden företrädesvis uppbyggd av två eller flera alternerande skikt av partiklar av katalysator B resp. kata- lysator A. Vid förfarandet enligt uppfinningen kan vatten sät- tas till tillflödet till det andra steget och en bifunktionell katalysatorkombination kan användas i det andra steget, både i de fall,då reaktionsprodukten från det första steget har ett H2/CO-molförhållande av mindre än 1,5, och i de fall, då reak- tionsprodukten från det första steget redan har ett H2/CO- molförhållande av minst 1,5; det är emellertid önskvärt att tíllflödet, som bringas i kontakt med katalysator A i det and- ra steget, har ett högre H2/CO-molförhållande. Om vid förfaran- det enligt uppfinningen man väljer en utföringsform, där vat- ten sätts till tillflödet till det andra steget och en bifunk- tionell katalysatorkombination används i det andra steget, be- stäms den erforderliga mängden vatten i huvudsak av H2/C0-mol- förhållandet i tillflödet till det andra steget, aktiviteten av katalysatorkombinationen för omvandlingen av en H20/CO- blandning till en H2/C02-blandning och det önskade H2/CO-mol- förhållandet hos den produkt som bringas i kontakt med kata- lysator A.Both in the use of a monofunctional catalyst and when using a bifunctional catalyst combination in the second step of the process according to the invention preferably a cobalt catalyst is used as catalyst A and in particular a catalyst prepared by impregnation and containing cobalt on a support. Advantageously, talysators containing 10-40 parts by weight of cobalt and 0.25-5 parts by weight of zirconium, titanium or chromium and produced by impregnation of a silica support with one or more aqueous solutions of salts of cobalt and zirconium, titanium or chromium, followed by drying of the composition, calcination thereof at 35 ° -70 ° C and reduction thereof at 200-35 ° C. Catalytic 446 971 containing copper and zinc and wherein the Cu / Zn atomic ratio it is between 0.25 and 4.0 are particularly suitable as lysator B. In the cobalt- or ruthenium-containing bifunctional the catalyst combinations, catalysts A and B may be present as a physical mixture. About the second step of the process is carried out using a stationary catalyst dry bed, the bed is preferably made up of two or more alternating layers of particles of catalyst B resp. kata- lysator A. In the process of the invention, water can be added taken to the inflow to the second stage and a bifunctional catalyst combination can be used in the second step, both in cases where the reaction product from the first step has a H2 / CO molar ratio of less than 1.5, and in cases where the reaction the product from the first stage already has an H2 / CO molar ratio of at least 1.5; however, it is desirable that the feed stream, which is contacted with catalyst A in the second step, has a higher H2 / CO molar ratio. If in the proceedings According to the invention, an embodiment is chosen in which water is added to the inflow to the second stage and a by-function catalyst combination is used in the second step, the required amount of water is mainly composed of H2 / CO the relationship in the inflow to the second stage, the activity of the catalyst combination for the conversion of an H mixture to a H2 / CO2 mixture and the desired H2 / CO molar the ratio of the product brought into contact with the lysator A.
Det andra steget av förfarandet enligt uppfinningen kan med fördel utföras genom att man låter tillfödet passera en verti- kalt anordnad reaktor i uppâtgående eller nedåtgående riktning, vilken reaktor innehåller en stationär bädd av den monofunk- tionella katalysatorn eller av den bifunktionella katalysa- torn eller katalysatorkombinationen. Det andra steget av för- _ farandet kan även utföras genom användning av en suspension av katalysatorn eller katalysatorkombinationen i en kolväteolja.The second step of the method according to the invention can be included advantage is carried out by allowing the supply to pass a vertical cold-mounted reactor in the ascending or descending direction, which reactor contains a stationary bed of the monofunctional the catalyst or of the bifunctional catalyst tower or the catalyst combination. The second stage of the process can also be carried out by using a suspension of the catalyst or catalyst combination in a hydrocarbon oil.
Det andra steget av förfarandet utförs företrädesvis under föl- jande betingelser: en temperatur av l25-350°C, i synnerhet 446 971 175-275°C, och ett tryck av l-150 bar, i synnerhet 5-100 bar.The second step of the process is preferably carried out under the following conditions: a temperature of 125-350 ° C, in particular 446 971 175-275 ° C, and a pressure of 1-150 bar, in particular 5-100 bar.
Uppfinningen åskådliggörs närmare medelst följande utförings- exempel, vari temperaturangivelserna avser Celsiusgrader.The invention is further illustrated by the following embodiments. examples, in which the temperature indications refer to degrees Celsius.
Exemgel Följande katalysatorer användes: šatalysator l En Co/Zr/SiO2-katalysator innehållande 25 viktdelar kobolt och 1,8 viktdelar zirkonium per 100 viktdelar kiseldioxid och framställd genom impregnering av en kiseldioxidbärare med en vattenlösning innehållande ett kobolt- och ett zirkonium- salt, följt av torkning av kompositionen, kalcinering därav vid 500°C och reduktion därav vid 280°C.Exemgel The following catalysts were used: catalyst l A Co / Zr / SiO2 catalyst containing 25 parts by weight of cobalt and 1.8 parts by weight of zirconium per 100 parts by weight of silica and prepared by impregnating a silica support with an aqueous solution containing a cobalt and a zirconium salt, followed by drying of the composition, calcination thereof at 500 ° C and reduction thereof at 280 ° C.
Katalysator 2 En Fe/Mg/Cu/K/A1203-katalysator innehållande 50 viktdelar järn, 20 viktdelar magensium, 2,5 viktdelar koppar och 4 viktdelar kalium per 100 viktdelar aluminiumoxid och fram- ställd genom impregnering av en aluminiumoxidbärare med en vattenlösning innehållande ett järn-, magnesium-, koppar- och kaliumsalt, följt av torkning av kompositionen, kalcine- ring därav vid 80000 och reduktion därav vid 325°C.Catalyst 2 An Fe / Mg / Cu / K / Al 2 O 3 catalyst containing 50 parts by weight iron, 20 parts by weight of magnesium, 2.5 parts by weight of copper and 4 parts by weight of potassium per 100 parts by weight of alumina and set by impregnating an alumina support with a aqueous solution containing an iron, magnesium, copper and potassium salt, followed by drying of the composition, calcine- ring thereof at 80,000 and reduction thereof at 325 ° C.
Katalysator 3 En Cu/Zn/Al2O3-katalysator med ett Cu/Zn-atomförhållande av 0,55.Catalyst 3 A Cu / Zn / Al 2 O 3 catalyst with a Cu / Zn atomic ratio of 0.55.
Katalysatorblandning I Katalysatorblandning I består av ett skikt av katalysator 3 och ett skikt av katalysator l i ett volymförhâllande av 1:2.Catalyst mixture I Catalyst mixture I consists of a layer of catalyst 3 and a layer of catalyst 1 in a volume ratio of 1: 2.
Katalysatorerna l och 2 och katalysatorblandningen I testades 446 971 med avseende på framställningen av en kolväteblandning i ett eller två steg utgående från en H2/CO-blandning. Testet utför- des i en eller två reaktorer vardera innehållande 50 ml av en stationär katalysatorbädd. Fem försök utfördes. Försöken l och 3 utfördes i ett steg: de övriga försöken i två steg. I samt- liga försök användes en temperatur av 280°C i det första ste- get. I samtliga försök som utfördes i tvâ steg var temperatu- ren 230°C i det andra steget. I samtliga försök var trycket 30 bar och volymhastigheten, baserad på det totala katalysa- torsystemet, var 1000 Nl.l_l.h-1 des hela reaktionsprodukten från det första steget som till- flöde till det andra steget. I försök 4 användes C-fraktio- 4 nen av produkten från första steget som tillflöde till det _ Vid försöken 2 och 5 använ- andra steget. Resultaten av försöken återges i tabellen nedan. :n 446 971 .Hflwmfib wmfimmw :H wmnmwwmwwow :H w mmfimww mfimomfl Zwbmm wwfiwHKmm«OH M mwfimfiw wfimmwfl_ äw Em\OOlEOwmGfiäwHHmDmw w fiwwwmwmmmn fiwww mmfimfiw mfiwmmd Ww\nO|äOwmaHïwHHmDmm w wwomcwflmb mnwä mmfimflw wfimmmfl mmdmfi Nwo fiwäämflm mñwmfi mmfimfi wooo fiwäämflm mwwwfi Zcäämw vw wmfimwwmmwow mwwmw Wmfiwwwmmwofldwwdmdwäm H mbmfiw mfimfiwfi Zmbmm wwfimwwmwfiofi H wbmwm mfimümfi. Ev Swbmm nwwwmmfin mämwm wdmmmd_ Bw ^HH«mH WmfiwHMmmdoHv|w.r|w mmfimfi Nmo dwE5wHm mfiwmfi mmfimfi wooo flwäšwfim mfiwmfi 0E wmflwfi Nwo fiwääwfim mfiwwn wmfimw wooo fiwäšwfim mwwmfi 1 H .. w a Nå I ma» wo å ä 3 w ß m N N N Ho m Q o~m o_æ o.w m H.w N_N H.qw w~Hw H_ | H w I w w | | I HH» I mm om mu ao om wwCatalysts 1 and 2 and catalyst mixture I were tested 446 971 with respect to the preparation of a hydrocarbon mixture in a or two steps starting from an H2 / CO mixture. The test is performed in one or two reactors each containing 50 ml of one stationary catalyst bed. Five experiments were performed. Attempts l and 3 were performed in one step: the other experiments in two steps. In addition- experiments, a temperature of 280 ° C was used in the first get. In all experiments performed in two steps, the temperature was pure 230 ° C in the second step. In all experiments, the pressure was Bar and the volume rate, based on the total catalyst tor system, was 1000 Nl.l_l.h-1 the whole reaction product was removed from the first step flow to the second stage. In Experiment 4, the C-fraction was used. 4 the product from the first step as an inflow to it In experiments 2 and 5, second step. The results of the experiments are given in the table below. : n 446 971 .H fl wm fi b wm fi mmw: H wmnmwwmwwow: H w mm fi mww m fi mom fl Zwbmm ww fi wHKmm «OH M mw fi m fi w w fi mmw fl_ äw Em \ OOlEOwmG fi äwHHmDmw w fi wwwmwmmmn fi www mm fi m fi w m fi wmmd Ww \ nO | äOwmaHïwHHmDmm w wwomcw fl mb mnwä mm fi m fl w w fi mmm fl mmdm fi Nwo fi wääm fl m mñwm fi mm fi m fi wooo fi wääm fl m mwww fi Zcäämw vw wm fi mwwmmwow mwwmw Wm fi wwwmmwo fl dwwdmdwäm H mbm fi w m fi m fi w fi Zmbmm ww fi mwwmw fi o fi H wbmwm m fi müm fi. Ev Swbmm nwwwmm fi n mämwm wdmmmd_ Bw ^ HH «mH Wm fi wHMmmdoHv | w.r | w mm fi m fi Nmo dwE5wHm m fi wm fi mm fi m fi wooo fl wäšw fi m m fi wm fi 0E wm fl w fi Nwo fi wääw fi m m fi wwn wm fi mw wooo fi wäšw fi m mwwm fi 1 H .. w a Now I ma » wo å ä 3 w ß m N N N Ho m Q o ~ m o_æ o.w m H.w N_N H.qw w ~ Hw H_ | H w I w w | | I HH »I mm om mu ao om ww
Claims (10)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL8003215A NL8003215A (en) | 1980-06-03 | 1980-06-03 | PROCESS FOR PREPARING HYDROCARBONS. |
Publications (2)
Publication Number | Publication Date |
---|---|
SE8103437L SE8103437L (en) | 1981-12-04 |
SE446971B true SE446971B (en) | 1986-10-20 |
Family
ID=19835408
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SE8103437A SE446971B (en) | 1980-06-03 | 1981-06-01 | PROCEDURE FOR THE PREPARATION OF A CARBON WHEAT MIXTURE BASED FROM A CARBON MONOXIDE AND WHEAT MIXTURE |
Country Status (16)
Country | Link |
---|---|
JP (1) | JPS5724314A (en) |
AT (1) | AT371793B (en) |
AU (1) | AU539212B2 (en) |
BE (1) | BE888922A (en) |
BR (1) | BR8103445A (en) |
CA (1) | CA1152535A (en) |
DE (1) | DE3121752A1 (en) |
ES (1) | ES502652A0 (en) |
FR (1) | FR2483400A1 (en) |
GB (1) | GB2077754B (en) |
IN (1) | IN154191B (en) |
IT (1) | IT1136783B (en) |
NL (1) | NL8003215A (en) |
NZ (1) | NZ197260A (en) |
SE (1) | SE446971B (en) |
ZA (1) | ZA813658B (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8006484A (en) * | 1980-11-28 | 1982-06-16 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
NL8006751A (en) * | 1980-12-12 | 1982-07-01 | Shell Int Research | PROCESS FOR PREPARING OXYGEN-BASED ORGANIC COMPOUNDS AND PARAFFINIC HYDROCARBONS. |
CA1196617A (en) * | 1982-07-14 | 1985-11-12 | George E. Morris | Catalyst composition, method for its production and its use in the production of hydrocarbons from synthesis gas |
ATE32875T1 (en) * | 1982-11-22 | 1988-03-15 | Shell Int Research | PROCESS FOR THE PRODUCTION OF HYDROCARBONS. |
CA1234158A (en) * | 1983-11-15 | 1988-03-15 | Johannes K. Minderhoud | Process for the preparation of hydrocarbons |
CA1240708A (en) * | 1983-11-15 | 1988-08-16 | Johannes K. Minderhoud | Process for the preparation of hydrocarbons |
GB8330606D0 (en) * | 1983-11-16 | 1983-12-21 | Shell Int Research | Preparation of hydrocarbons and fuel gas |
NL8400609A (en) * | 1984-02-28 | 1985-09-16 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBONS. |
US4617283A (en) * | 1984-06-27 | 1986-10-14 | Union Carbide Corporation | Catalyst for converting synthesis gas to liquid motor fuels |
US4579830A (en) * | 1984-06-27 | 1986-04-01 | Union Carbide Corporation | Enhanced catalyst for converting synthesis gas to liquid motor fuels |
US4556645A (en) * | 1984-06-27 | 1985-12-03 | Union Carbide Corporation | Enhanced catalyst for conversion of syngas to liquid motor fuels |
CA1236454A (en) * | 1984-06-27 | 1988-05-10 | John J. Tsai | Monomeric cationic glycoside derivatives |
US4663355A (en) * | 1984-06-27 | 1987-05-05 | Union Carbide Corporation | Catalyst and process for converting synthesis gas to liquid motor fuels |
US4632941A (en) * | 1984-06-27 | 1986-12-30 | Union Carbide Corporation | Enhanced catalyst and process for converting synthesis gas to liquid motor fuels |
US4617320A (en) * | 1984-06-27 | 1986-10-14 | Union Carbide Corporation | Enhanced conversion of syngas to liquid motor fuels |
GB2243616A (en) * | 1990-05-04 | 1991-11-06 | Shell Int Research | Preparation of paraffinic and aromatic hydrocarbons |
US6331573B1 (en) * | 2000-02-29 | 2001-12-18 | Chevron U.S.A. Inc. | Increased liquid sensitivity during fischer-tropsch synthesis by olefin incorporation |
US20040133054A1 (en) * | 2002-12-06 | 2004-07-08 | Pelati Joseph E. | Dehydrogenation catalyst and process for preparing the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7704658A (en) * | 1977-04-28 | 1978-10-31 | Shell Int Research | PROCESS FOR THE PREPARATION OF HYDROCARBONS. |
NL190603C (en) * | 1979-07-13 | 1994-05-16 | Shell Int Research | Process for the preparation of iron-chromium catalysts and their use for the preparation of hydrocarbons. |
NL184214C (en) * | 1979-08-06 | 1989-05-16 | Shell Int Research | PROCESS FOR THE PREPARATION OF A HYDROCARBON MIXTURE FROM A MIXTURE CONTAINING CARBON MONOXIDE AND HYDROGEN WITH ONE HŸ2/CO MOL. CONTAINS LESS THAN 1.0 RATIO. |
-
1980
- 1980-06-03 NL NL8003215A patent/NL8003215A/en not_active Application Discontinuation
-
1981
- 1981-03-18 CA CA000373306A patent/CA1152535A/en not_active Expired
- 1981-03-26 IN IN331/CAL/81A patent/IN154191B/en unknown
- 1981-05-22 BE BE1/10229A patent/BE888922A/en not_active IP Right Cessation
- 1981-05-29 FR FR8110709A patent/FR2483400A1/en active Granted
- 1981-06-01 JP JP8258181A patent/JPS5724314A/en active Pending
- 1981-06-01 IT IT22074/81A patent/IT1136783B/en active
- 1981-06-01 AT AT0243881A patent/AT371793B/en not_active IP Right Cessation
- 1981-06-01 SE SE8103437A patent/SE446971B/en not_active IP Right Cessation
- 1981-06-01 BR BR8103445A patent/BR8103445A/en unknown
- 1981-06-01 ES ES502652A patent/ES502652A0/en active Granted
- 1981-06-01 DE DE19813121752 patent/DE3121752A1/en active Granted
- 1981-06-01 GB GB8116650A patent/GB2077754B/en not_active Expired
- 1981-06-01 AU AU71211/81A patent/AU539212B2/en not_active Ceased
- 1981-06-02 ZA ZA00813658A patent/ZA813658B/en unknown
- 1981-06-02 NZ NZ197260A patent/NZ197260A/en unknown
Also Published As
Publication number | Publication date |
---|---|
GB2077754B (en) | 1983-06-02 |
BR8103445A (en) | 1982-02-24 |
ATA243881A (en) | 1982-12-15 |
FR2483400A1 (en) | 1981-12-04 |
AU7121181A (en) | 1981-12-10 |
FR2483400B1 (en) | 1985-05-03 |
IT1136783B (en) | 1986-09-03 |
ZA813658B (en) | 1982-06-30 |
AU539212B2 (en) | 1984-09-13 |
DE3121752A1 (en) | 1982-01-28 |
NL8003215A (en) | 1982-01-04 |
IN154191B (en) | 1984-09-29 |
JPS5724314A (en) | 1982-02-08 |
ES8303269A1 (en) | 1983-02-01 |
NZ197260A (en) | 1983-11-18 |
AT371793B (en) | 1983-07-25 |
IT8122074A0 (en) | 1981-06-01 |
ES502652A0 (en) | 1983-02-01 |
GB2077754A (en) | 1981-12-23 |
SE8103437L (en) | 1981-12-04 |
DE3121752C2 (en) | 1989-06-01 |
CA1152535A (en) | 1983-08-23 |
BE888922A (en) | 1981-11-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
SE446971B (en) | PROCEDURE FOR THE PREPARATION OF A CARBON WHEAT MIXTURE BASED FROM A CARBON MONOXIDE AND WHEAT MIXTURE | |
EP0313375B1 (en) | Process and catalyst for converting synthesis gas to hydrocarbons | |
SA99200231B1 (en) | Gas conversion using hydrogen produced from synthesis gas to regenerate the catalyst and convert hydrocarbons | |
US4857559A (en) | Process for production of hydrocarbons | |
US6806296B2 (en) | Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide | |
JPS6166790A (en) | Synthesis of liquid hydrocarbon using ruthenium support catalyst | |
AU2003295625B2 (en) | Process for the preparation of linear alpha-olefins from synthesis gas over a cobalt catalyst | |
SA99200195B1 (en) | Gas conversion using hydrogen from syngas to desulfurize liquid hydrocarbons for a gas well | |
KR20030041105A (en) | Highly active fischer-tropsch synthesis using doped, thermally stable catalyst support | |
US4778826A (en) | Conversion of a lower alkane | |
WO2002094746A1 (en) | Process for the preparation of linear olefins and use thereof to prepare linear alcohols | |
EP0199475B2 (en) | Fischer-Tropsch conversion of synthesis gas to hydrocarbons | |
CA1171432A (en) | Process for the preparation of hydrocarbons | |
US6740683B2 (en) | Chemicals from synthesis gas | |
US5776988A (en) | Process for converting synthesis gas into hydrocarbons | |
US5786393A (en) | Liquid phase process for converting synthesis gas | |
US4654458A (en) | Conversion of a lower alkane | |
CN109701596A (en) | Catalyst system | |
US2470216A (en) | Process for synthesizing motor fuels of high antiknock value | |
WO2017085603A2 (en) | Methods for the conversion of co2 into syngas for use in the production of olefins | |
Davis | Technology development for iron Fischer-Tropsch catalysts | |
JPH03181435A (en) | Production of dimethyl ether | |
NO314506B1 (en) | Apparatus and method for the synthesis of substantially linear saturated C5 </N> + hydrocarbons | |
CA1234396A (en) | Process for the preparation of hydrocarbons | |
CN109701601A (en) | Combination catalyst system and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
NUG | Patent has lapsed |
Ref document number: 8103437-3 Effective date: 19910131 Format of ref document f/p: F |