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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• • 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
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4081—Recycling aspects
• • 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

• the present invention relates to a process for hydrotreating a mixture of hydrocarbon compounds comprising from four to eight carbon atoms, rich in olefins and monoaromatic compounds. It concerns more particularly the hydrotreatment of the sections resulting from the distillation of crude oils, steam cracking, catalytic reforming, cracking catalytic, coking or any process producing such cuts and cuts from the processing of coal such as coal essences.
• the present application therefore relates to a process which neither requires nor pretreatment of the catalyst, or introduction of nitrogenous gaseous compounds into hydrogenation gas. It aims at a simple process which can be easily implemented whatever the hydrotreatment unit, with a little catalyst expensive compared to catalysts containing noble metals such as platinum and palladium, which can adapt to fillers whose composition can vary in concentration of olefins and monoaromatic compounds and which allows good desulfurization of the feed.
• olefins is meant here the monoolefinic and diolefinic compounds generally present in the charges sent for hydrotreatment.
• the present invention therefore relates to a hydrotreatment process a mixture of hydrocarbon compounds from C4 to C8, rich in olefins and monoaromatic compounds, by hydrogenation in the presence of a catalyst solid, characterized in that an ammonia precursor is introduced into the charge of hydrocarbon compounds and that the catalyst comprises at least a transition metal supported on at least one refractory oxide.
• Transition metal means any transition metal except so-called noble metals, in particular platinum and palladium.
• One of the advantages of the process is linked to the introduction of a precursor of ammonia in the charge which makes it possible to release, during the reaction, from gaseous ammonia which is present during the selective hydrogenation reaction olefins and which can be recovered and recycled with unused hydrogen.
• this method makes it possible to control precisely the amount of ammonia released during the reaction hydrotreating. In addition, it helps to limit unwanted reactions oligomerization while maintaining excellent catalyst activity for the desired reactions for selective hydrogenation of olefins and charge desulfurization.
• the Applicant has found that from a on the other hand, the oligomerization of aromatic compounds results from the presence of acid sites on the catalyst, these sites being of variable acid forces.
• the efficiency of the hydrotreatment reaction depends on the electrodeficiency of the catalytic support which itself is correlated with its acidity.
• injected not more than 1000 ppm by weight of molar equivalent nitrogen of precursor of ammonia in the feed is injected not more than 1000 ppm by weight of molar equivalent nitrogen of precursor of ammonia in the feed.
• 5 to 1000 ppm by weight of nitrogen molar equivalent will be injected nitrogen precursor, and preferably from 10 to 200 ppm.
• the ammonia precursors are chosen from nitrogen compounds capable of releasing ammonia gas under hydrotreatment conditions.
• the ammonia precursor is chosen from linear and branched amines, polyamines, imines, and urea and its derivatives.
• the amines and polyamines are chosen from the group consisting of mono, di and trialkylamines comprising from 1 to 10 carbon atoms by alkyl group, the alkyl groups being linear or cyclic, and polyalkylamines comprising from 1 to 5 atoms nitrogen, each alkyl group comprising from 1 to 6 carbon atoms in linear or branched form.
• Preferred amines and polyamines are selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, cyclohexylamine, cycloheptylamine, dimethylamine, diethylamine dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, dimethylenetriamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine and tetrapropylenepentamine, cyclohexylamine, triethylamine and ethylenediamine being preferred.
• the catalyst necessary for the process according to the invention consists of at least minus one metal chosen from the group consisting of nickel, cobalt, molybdenum, vanadium and tungsten; nickel alone and combinations nickel / molybdenum, cobalt / molybdenum and nickel / tungsten are preferred.
• This or these metals are supported on at least one refractory oxide chosen from alumina, silica, silicoalumines, aluminophosphates, zirconia, magnesia and the oxides of titanium, rutile and anatase, these oxides occurring in amorphous or crystalline form.
• the operation is carried out at a temperature between 50 and 400 ° C., under a pressure between 10 6 Pa and 10 7 Pa, preferably between 3 ⁇ 10 6 Pa and 6 ⁇ 10 6 Pa, and a hvv varying from 0.5 to 10h -1 .
• ammonia gaseous excess formed can be recycled into the recycle gas rich in hydrogen. This has the advantage of limiting the amount of precursor of ammonia injected into the load.
• This example describes the conditions under which the invention is achieved by presenting the gain brought by the introduction of precursor of ammonia in an industrial load to be hydrotreated and this for different ammonia precursors and for different concentrations thereof.
• the benzene content was measured using the UOP 744-86 method referenced in the "Laboratory test methods for petroleum and its products", published by UOP Process Division, (UOP Inc. 20 UOP Plaza-Algonquin Mt Prospect Roads-Des Plains-Illinois 60016).
• the olefin content is determined by measuring the number of bromine in application of standard ASTM D1159, and the sulfur content by method ASTM D2622.
• Three ammonia precursors were used on a hydrotreatment pilot unit for 100 ml of catalyst, at a temperature of 200 ° C., a pressure of 26.5 ⁇ 10 5 Pa, operating with an H2 / hydrocarbon ratio of 230NI / l, wh of the charge being 1.6h -1 .
• These precursors are triethyleneamine or TEA, cyclohexylamine or CHA and ethylenediamine or EDA.
• the present example aims to emphasize the effectiveness of the process whatever either the relative concentrations of the load in olefins and in compounds monoaromatic.
• cyclohexylamine or CHA is used as ammonia precursor.

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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)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2000
  • 2000-11-07 EP EP00203887A patent/EP1205531A1/de not_active Withdrawn
• 2001
  • 2001-11-06 AU AU2002219087A patent/AU2002219087A1/en not_active Abandoned
  • 2001-11-06 JP JP2002542022A patent/JP4900885B2/ja not_active Expired - Fee Related
  • 2001-11-06 WO PCT/EP2001/012989 patent/WO2002038701A1/fr active IP Right Grant
  • 2001-11-06 ES ES01993659T patent/ES2363494T3/es not_active Expired - Lifetime
  • 2001-11-06 AT AT01993659T patent/ATE509997T1/de not_active IP Right Cessation
  • 2001-11-06 EP EP01993659A patent/EP1334167B1/de not_active Expired - Lifetime
  • 2001-11-06 US US10/416,058 patent/US7399402B2/en not_active Expired - Fee Related
  • 2001-11-06 KR KR1020037006246A patent/KR100591577B1/ko not_active IP Right Cessation

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