EP0011906B1 - Process for selective hydrogenation of dienes in pyrolysis gasoline - Google Patents

Process for selective hydrogenation of dienes in pyrolysis gasoline Download PDF

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Publication number
EP0011906B1
EP0011906B1 EP79200716A EP79200716A EP0011906B1 EP 0011906 B1 EP0011906 B1 EP 0011906B1 EP 79200716 A EP79200716 A EP 79200716A EP 79200716 A EP79200716 A EP 79200716A EP 0011906 B1 EP0011906 B1 EP 0011906B1
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EP
European Patent Office
Prior art keywords
reactor
hydrocarbon mixture
via line
dienes
reactors
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79200716A
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German (de)
English (en)
French (fr)
Other versions
EP0011906A1 (en
Inventor
John Graham Christy
Joannes Baptista Wijffels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP0011906A1 publication Critical patent/EP0011906A1/en
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Publication of EP0011906B1 publication Critical patent/EP0011906B1/en
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • This invention relates to a process for the selective hydrogenation of dienes in pyrolysis gasoline.
  • pyrolysis gasoline is obtained as a by-product in the preparation of ethylene and/or propene by means of high- temperature pyrolysis (e.g. cracking in the presence of steam) of gaseous or liquid hydrocarbons, such as naphtha or gas oil.
  • Pyrolysis gasolines on the one hand are extremely unstable owing to the presence of a relatively high proportion of highly olefinically unsaturated hydrocarbons, and on the other hand contain aromatic compounds and alkenes having a high octane number which are particularly valuable and are in themselves useful as stable motor gasoline components.
  • the highly olefinically unsaturated compounds which mainly consist of dienes, for example those of the cyclopentadiene type, have to be removed therefrom. This removal may be achieved by partial hydrogenation of the dienes to mono-olefins. Because the hydrogenation of mono-olefins in general leads to a reduction in octane number, such a hydrogenation is to be avoided as much as possible. Moreover, in doing so the hydrogen consumption is kept to a desired low level.
  • the invention provides a solution for this problem by using at least three consecutive reactors and a specific recirculation pattern.
  • the invention provides a process for the selective hydrogenation of dienes in pyrolysis gasoline which comprises catalytic hydrogenation of the pyrolysis gasoline in at least three consecutive reactors, in at least two of the said consecutive reactors recirculating part of the hydrocarbon mixture emerging from a reactor over that reactor, no recirculation of the hydrocarbon mixture emerging from the last of the consecutive reactors being carried out over that reactor.
  • the number of consecutive reactors is three. More reactors may be used, and the recirculation as described may be carried out over more than two reactors, but in general the advantage to be achieved (less hydrogenation of mono-olefins at a preset amount of dienes in the ultimate product) does not compensate for the drawbacks which consist of building and handling of an extra reactor.
  • the catalyst with hydrogenating activity to be used in the reactors very suitably consists of a support comprising one or more metals of Group VIB and/or Group VIII of the Periodic System of Elements and/or compounds of these metals.
  • the support very suitably consists of alumina, silica or silica alumina. Catalysts comprising platinum or palladium are very suitable.
  • the most preferred catalyst comprises partially sulphided nickel on alumina as a support.
  • the catalyst very suitably is in the form of one or more fixed beds in the reactors, and the catalytic hydrogenations are preferably carried out by passing a mixture of liquid and hydrogen-containing gas in downflow over the catalyst according to the trickle flow technique.
  • the starting hydrocarbon oil which is present partly in the liquid phase and partly in the vapour phase is allowed to flow downward in the presence of hydrogen or of a hydrogen-containing gas over a catalyst in the form of a fixed bed, the unvaporized part of the starting material flowing over the catalyst particles in the form of a thin liquid layer.
  • the recirculation ratios over the respective reactors are to be chosen such that in each of these reactors the ratio of the dienes hydrogenated to mono-olefins on the one hand and the mono-olefins hydrogenated to paraffins on the other hand, is high because in this way the overall hydrogen consumption is kept low.
  • the weight ratio of the hydrocarbon mixture recirculated to the first reactor and the pyrolysis gasoline fed thereto very suitably is from 5 to 15, in particular from 9 to 11.
  • the preferred weight ratio of the hydrocarbon mixture recirculated to the second reactor and the hydrocarbon mixture emerging from the first reactor which is fed to the second reactor has been found to be from 2 to 4.
  • the hydrogen to be employed in the catalytic hydrogenation may be pure or in the form of a hydrogen-containing gas.
  • the gases employed should preferably contain more than 50% by volume of hydrogen.
  • Very suitable are, for example, the hydrogen-containing gases obtained in the catalytic reforming or steam- reforming of gasoline fractions, and mixtures of hydrogen and light hydrocarbons. Any excess of hydrogen-containing gas is advantageously recycled, possibly after the previous removal of undesired components therefrom.
  • the catalytic hydrogenations are very suitably carried out at the following conditions in the reactors: a temperature in the range from 50-250°C, preferably 50-150°C, a total pressure in the range from 10-80 bar a and a hydrogen partial pressure in the range from 5-60 bar a.
  • the liquid hourly space velocity of the hydrocarbon mixture which is fed to a reactor for the first time may vary for any reactor.
  • the space velocity of the last-mentioned hydrocarbon mixture is to be multiplied by the recirculation ratio used for that reactor.
  • the liquid hourly space velocities of the mixtures obtained after combination of the recycle liquid and the hydrocarbon mixture which is fed to a particular reactor for the first time are between 5 and 50 and preferably between 10 and 20 kg mixture per litre catalyst per hour. At lower space velocities the extent of heat release of the hydrogenation reaction may be such that temperature control becomes difficult if not impossible.
  • the space velocities of the hydrocarbon mixtures fed for the first time to a particular reactor to which recycling is taking place will in general be less than 5 kg per litre catalyst per hour.
  • the space velocity very suitably ranges from 2-20 and preferably from 5-10 kg feed per litre catalyst per hour.
  • the ratio of fresh gas to fresh feed very suitably is from 50-500 NI gas per kg feed, and the ratio of recycle gas to fresh feed from 200-500 NI gas per kg feed.
  • FIG. 1 represents a simplified flow diagram of a suitable embodiment of the process according to the invention.
  • various auxiliary devices such as pumps, cocks, valves, control valves, etc. have been omitted.
  • a pyrolysis gasoline is fed in via line 1, and after mixing with a hydrogen-containing gas supplied via line 2, introduced into reactor R1 via line 3.
  • Reactor R1 contains one or more fixed beds of catalyst.
  • the effluent of R1 is led via line 4 to separation vessel V1 in which gas and liquid (the latter consisting substantially of hydrocarbons) are separated. Part of the liquid is transported via line 5, mixed with pyrolysis gasoline from line 1 and recirculated to R1 via line 3.
  • the remainder of the liquid in V1 and the gas are forwarded via line 6, mixed with a liquid stream emerging from separating vessel V2 via line 7, and fed to reactor R2 via line 8.
  • Reactor R2 contains one or more fixed beds of catalyst.
  • the effluent from reactor R2 is forwarded via line 9 to separation vessel V2, in which vessel liquid and gas are separated. Part of the liquid is recycled via line 7 as described, and the remainder of the liquid and the gas from V2 are fed to reactor R3 via line 10.
  • the effluent from reactor R3, which reactor contains one or more fixed beds of catalyst, is led to separation vessel V3 via line 11. In V3 gas and liquid are separated.
  • the liquid is removed via line 12 as the final product of the process, the gas from V3 is (if desired after purification) forwarded via line 13 to line 2, in which line fresh hydrogen-containing gas is fed via line 14.
  • Fresh feed in line 1 consisted of a pyrolysis gasoline which contained 60.2%w dienes and 20.0%w mono-olefins. This feed was added at a space velocity of 1.48 kg/I catalyst in Rl/hour.
  • the catalyst in all reactors consisted of partially sulphided nickel on alumina, the amount of nickel being 10.7%w on carrier.
  • the inlet temperature of R1 was 63°C, the temperature at the outlet of this reactor was 90°C, the average pressure in R1 was 62.5 bar a (H Z partial pressure 45.4 bar a).
  • the effluent of R1 was separated in V1 at 90°C, and 10 times the amount of liquid fed via line 1 was recycled from V1 via line 5 (recycle ratio 10). This recycle liquid contained 18.4%w dienes.
  • the remainder of the liquid and the gas in V1 were led via line 6 at a space velocity of 4.13 kg/I catalyst in R2/hour to reactor R2.
  • the inlet temperature of R2 was 83°C, the outlet temperature 104°C and the average pressure 61.5 bar a (H Z partial pressure 40.6 bar a).
  • the effluent from R2 was separated at 104°C in separator V2 in liquid and gas, and 3.2 times the amount of liquid fed via line 6 was recycled from V2 via line 7 to R2 (recycle ratio 3.2).
  • the recycle liquid contained 5.8%w dienes.
  • the remainder of the liquid and gas in V2 were forwarded via line 10 to reactor R3 at a space velocity of 6.89 kg/I catalyst in R3/hour.
  • the inlet temperature of R3 was 90°C, the outlet temperature 123°C and the average total pressure 59.5 bar a (H 2 partial pressure 34.4 bar a).
  • the efflient of R3 was separated in V3, and the liquid removed as final product of the process via line 12. This product contained 0.5%w diolefins and 72.7%w mono-olefins.
  • the gas from V3 was recycled via line 13 and mixed with fresh hydrogen-containing gas, the latter containing 94.1 mol.% hydrogen, 4.6 mol.% methane, 1.0 mol.% nitrogen and 0.3 mol.% water.
  • Fresh gas was supplied via line 14 in an amount of 233 NI H 2/ kg fresh feed.
  • Recycle gas via line 13 a mounted to 300 NI/kg fresh feed and contained 75.0 mol.% hydrogen, 11.8 mol.% methane, 6.2 mol.% nitrogen, 2.0 mol.% water, the remainder consisting of hydrocarbons with at most 6 carbon atoms.
  • the amount of hydrogen consumed per kg feed for undesired mono-olefin saturation was 0.002 kg.
  • Fresh feed in line 1 consisted of a pyrolysis gasoline which contained 60.2%w dienes and 20.0%w mono-olefins. This feed was added at a space velocity of 0.42 kg/I catalyst in R1/hour.
  • the catalyst in both reactors consisted of partially sulphided nickel on alumina, the amount of nickel being 10.7%w on carrier.
  • the inlet temperature of R1 was 63°C
  • the temperature at the outlet of this reactor was 90°C
  • the average pressure in R1 was 62.5 bar a (H 2 partial pressure of 40 bar a at reactor outlet.
  • the effluent of R1 was separated in V1 at 90°C, and 13 times the amount of liquid fed via line 1 was recycled from V1 via line 5 (recycle ratio 13).
  • This recycle liquid contained 5.8%w dienes.
  • the remainder of the liquid and the gas in V1 were forwarded via line 6 to reactor R2 at a space velocity of 6.89 kg/I catalyst in R2/hour.
  • the inlet temperature of R2 was 90°C, the outlet temperature 123°C and the average total pressure 59.5 bar a (H 2 partial pressure 32 bar a at reactor outlet).
  • the effluent of R2 was separated in V2 and the liquid removed as final product of the process via line 8. This product contained 0.5%w diolefins and 69.9%w mono-olefins.
  • the gas from V2 was recycled via line 9 and mixed with fresh hydrogen-containing gas, containing 94.1 mol.% hydrogen, 4.6 mol.% methane, 1.0 mol.% nitrogen and 0.3 mol.% water.
  • Fresh gas was supplied via line 10 in an amount of 244 Ni/kg fresh feed.
  • Recycle gas via line 9 amounted to 300 NI/kg fresh feed and contained 73.8 mol.% hydrogen, 12.8 mol.% methane, 6.7 mol.% nitrogen, 2.3 mol.% water, the remainder consisting of hydrocarbons with at most 6 carbon atoms.
  • the amount of hydrogen consumed per kg of feed for undesired mono-olefin saturation was 0.003 kg, which is 50% higher than in the Example according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP79200716A 1978-12-04 1979-12-03 Process for selective hydrogenation of dienes in pyrolysis gasoline Expired EP0011906B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7847093 1978-12-04
GB4709378 1978-12-04

Publications (2)

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EP0011906A1 EP0011906A1 (en) 1980-06-11
EP0011906B1 true EP0011906B1 (en) 1983-02-23

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EP79200716A Expired EP0011906B1 (en) 1978-12-04 1979-12-03 Process for selective hydrogenation of dienes in pyrolysis gasoline

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EP (1) EP0011906B1 (enrdf_load_stackoverflow)
JP (1) JPS5575487A (enrdf_load_stackoverflow)
AU (1) AU529535B2 (enrdf_load_stackoverflow)
CA (1) CA1140065A (enrdf_load_stackoverflow)
DE (1) DE2964927D1 (enrdf_load_stackoverflow)
ZA (1) ZA796520B (enrdf_load_stackoverflow)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19524969A1 (de) * 1995-07-08 1997-01-09 Huels Chemische Werke Ag Verfahren zur Herstellung von 3.3.5-Trimethylcyclohexanon
DE19524971A1 (de) * 1995-07-08 1997-01-09 Huels Chemische Werke Ag Verfahren zur katalytischen Selektivhydrierung von mehrfach ungesättigten organischen Substanzen
DE19524970A1 (de) * 1995-07-08 1997-01-09 Huels Chemische Werke Ag Verfahren zur Herstellung von 2-Ethylhexanal
MX2007005181A (es) 2004-10-28 2007-06-20 Scient Games Royalty Corp Juego de loteria jugando en una figura geometrica utilizando indicios con valores de punto variable.
WO2006074423A2 (en) 2005-01-07 2006-07-13 Scientific Games International, Inc. Lottery game utilizing nostalgic game themes
EP1897613A1 (en) 2005-05-23 2008-03-12 Repsol Ypf Nickel catalyst, method of obtaining same and use thereof
JP2007326955A (ja) * 2006-06-07 2007-12-20 Mitsui Chemicals Inc オレフィン類の製造方法
WO2015140590A1 (en) * 2014-03-21 2015-09-24 Haldor Topsøe A/S Reactor system and method for the treatment of a gas stream
CN107646028B (zh) 2015-01-29 2021-07-16 鲁姆斯科技公司 由蒸汽裂化器c5进料制备c5烯烃
EP4549617A1 (en) 2023-10-31 2025-05-07 Basf Se Preparation of saturated or ethylenically unsaturated (cyclo)aliphatic compounds by hydrogenation of ethylenically or acetylenically unsaturated (cyclo)aliphatic compounds using hydrogen with low deuterium content

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1289849A (fr) * 1960-05-17 1962-04-06 Shell Int Research Procédé de raffinage par hydrogénation catalytique d'essences obtenues par craquage thermique d'huiles d'hydrocarbures en présence de vapeur d'eau
US3492220A (en) * 1962-06-27 1970-01-27 Pullman Inc Hydrotreating pyrolysis gasoline
US3470085A (en) * 1967-11-20 1969-09-30 Universal Oil Prod Co Method for stabilizing pyrolysis gasoline
GB1210128A (en) * 1968-03-04 1970-10-28 Air Prod & Chem Catalytic hydrogenation of unsaturated hydrocarbons
JPS4925402A (enrdf_load_stackoverflow) * 1972-06-30 1974-03-06

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JPS5575487A (en) 1980-06-06
JPS6338394B2 (enrdf_load_stackoverflow) 1988-07-29
DE2964927D1 (en) 1983-03-31
AU529535B2 (en) 1983-06-09
CA1140065A (en) 1983-01-25
ZA796520B (en) 1980-11-26
AU5336479A (en) 1980-06-12
EP0011906A1 (en) 1980-06-11

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