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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
  • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
  • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
• • 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • 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
  • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
  • C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
• • 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
• • 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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
  • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
• • 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
  • C10G2300/1088—Olefins
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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
  • C10G2300/4006—Temperature
• • 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
  • C10G2400/04—Diesel oil
• • 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
  • C10G2400/08—Jet fuel

Definitions

• the present invention is in the field of refining processes for converting an olefinic fraction having predominantly 4 to 6 carbon atoms in a so-called middle distillate cut having predominantly 10 to 20 carbon atoms.
• This middle distillate cut may be a kerosene cut or a diesel cut.
• the present invention uses a purification step for removing nitrogen compounds contained in the feed followed by an oligomerization step to produce the desired kerosene or diesel fuel cut.
• hydrocarbon cut (02) comprising at least partly hydrocarbons having a number of carbon atoms of between 6 and 10, of which at least 2% by weight of olefins, in the presence of at least one catalyst promoting the dimerization and alkylation reactions of the species present in the mixture resulting from said contacting,
• step b) a separation of the effluents from step b) into at least two slices of which:
• This patent does not describe any pretreatment step, in particular purification of the feedstock (01).
• Patent FR 2 887 555 describes a process for preparing a diesel cut from a C 2 -C 12 olefinic cut comprising the following steps:
• step 1) oligomerization of a C2-C12, preferably C3-C7 and even more preferably C3-C5 olefinic hydrocarbon fraction, 2) a separation of the product mixture obtained in step 1), in three sections, including an intermediate section with a final boiling point of between 200 and 220 ° C.
• This process therefore uses a very broad olefinic fraction as filler and uses two distinct oligomerizations. It does not mention the possibility of a pretreatment of said charge, including purification against any nitrogen compounds contained in said charge.
• the patents FR 2 871 167 and FR 2 871 168 describe processes for producing diesel fuel cut from gasoline cuts comprising a first step of separation of the normal and isoolefins, the oligomerization step relating only to the normal olefins.
• the process according to the present invention does not require any prior separation of the normal and iso olefins.
• the process according to the present invention does not use any alkylation step and therefore does not require any BTX-type cutting.
• FIG. 1 represents a diagram of the process according to the invention using a single oligomerization unit preceded by a step of purification of the charge on resins.
• the process according to the present invention uses a single oligomerization unit.
• the process can be defined as a process for producing an average distillate cut having predominantly from 10 to 22 carbon atoms from an olefinic feed having predominantly between 3 and 8 carbon atoms, and preferably between 4 and 6 carbon atoms. carbon, comprising the following sequence of steps:
• the feed consists of a section of olefinic hydrocarbons containing from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms. It contains from 20% to 100%) of olefins, preferably from 20% to 80% of olefins, and more preferably from 40% to 60% of olefins.
• It can come from a fluidised bed catalytic cracking unit or from a naphtha steam cracking unit, or from an alcohol dehydration unit or from a Fischer-Tropsch synthesis unit or from other available sources. from refining or petrochemical units.
• the filler (1) is introduced into a purification unit (PUR) which contains an acidic resin for example of polystyrene-divinylbenzene functionalized with sulphonic groups, as described in the international patent application filed under the number WO 2011/135206. .
• PUR purification unit
• the density of the acidic sites is greater than 0.5 meq / gram, preferably greater than 1 meq / gram and more preferably between 1 and 5 meq / gram (meq is the abbreviation of milliequivalent).
• the Amberlyst products sold by Rohm and Haas are representatives of this family of compounds and may by way of non-limiting example, be used in the context of the present invention.
• the operating conditions of the purification unit are as follows:
• the VVH or space velocity is defined as the ratio of the volume flow rate of charge to be treated on the volume of resin contained in the purification unit.
• This purification unit is mainly intended to eliminate the nitrogenous compounds contained in the feed and which constitute poisons with respect to the catalysts used in the downstream oligomerization unit.
• the effluent (2) leaving the purifying unit (PUR) is optionally sent to a separation unit (DIST1) for extracting a gasoline cut (3 ') with a good octane number and which can thus join the gasoline pool (POOL).
• DIST1 separation unit
• Part of this species (3 ') can also be directed to the oligomerization unit (OLG).
• the effluent (2) from the purification unit (PUR), or the effluent (3) from the separation unit (DIST1) when it exists, is sent to the oligomerization unit (OLG ) which operates under the following operating conditions:
• the catalyst used is a silica-alumina type catalyst, or
• the effluent (4) of the oligomerization unit (OLG) is separated in a distillation column (DIST2) in at least 4 sections:
• raffinate a head section (6) called raffinate, corresponding to an LPG type cut
• HT total hydrogenation unit
• the oligomerization catalyst when it is of amorphous silico aluminate type, may be chosen from silica-aluminas or siliceous aluminas, and preferably sliculated aluminas.
• the weight ratio SiO 2 / Al 2 O 3 is between 0.1 and 10, and preferably between 0.2 and 1.
• a preferred catalyst is that marketed by AXENS under the name IP 811 TM.
• the oligomerization catalyst when based on zeolite, preferably comprises at least one zeolite selected from the group consisting of aluminosilicate zeolites having an overall Si / Al atomic ratio greater than 10, and a pore structure 8, 10 or 12MR.
• zeolite selected from the group consisting of aluminosilicate zeolites having an overall Si / Al atomic ratio greater than 10 and a pore structure of 8, 10 or 12MR.
• Said zeolite is more preferably selected from the group consisting of zeolites: ferrierite, chabazite, zeolites Y and US-Y, ZSM-5, ZSM-12, NU-86, mordenite, ZSM-22, NU-10, ZBM -30, ZSM-11, ZSM-57, ZSM-35, IZM-2, ITQ-6 and IM-5, SAPO, taken alone or in admixture.
• said zeolite is selected from the group consisting of ferrierite zeolites, ZSM-5, Mordenite and ZSM-22, taken alone or as a mixture. Even more preferably, the zeolite used is ZSM-5.
• the filler is a light gasoline that comes from an FCC unit, under the name LCN (Light Cut Naphta).
• the charge has a density of 0.6548.
• It also contains organic nitrogen compounds totaling a content of 11.6 ppm by weight expressed as elemental nitrogen and 15 ppm by weight of elemental sulfur.
• the raw feed is injected into the reactor, from bottom to top, at a rate of 36 g / h corresponding to a VVH (hourly space velocity) of 1 hr -1 .
• the remaining portion of the total effluent of purification step a) is collected and fed to the oligomerization reactor containing 60 grams of the IP 811 TM oligomerization catalyst manufactured by AXENS.
• the charge of the oligomerization reactor is composed of the hydrocarbon effluent obtained after conversion of the charge C5-C6 on Amberlyst TM 36WET resin during the purification step a).
• the oligoménsation step is operated in the presence of cata IP 811 at a pressure of 5 MPa and a VVH of 0.5 h-1 between 160 ° C and 200 ° C. An average increase of ° C per 100 h is necessary to keep the conversion of n-pentenes constant around 70%.
• the olefin content observed after hydrogenation is very low (bromine number ⁇ 0.8 g / 100 g). ) to provide a kerosene cut, the characteristics of which are as follows:
• the operating conditions of purification step a) are carried out with the same filler and the same resin as in Example 1: 60 ° C., at 30 bars, kept unchanged for 500 hours.
• the initial conversion of the iso-olefins is 80%), progressively decreasing, and that of the normal olefins is less than 5%.
• the analysis of the total nitrogen on the total effluent shows a value of less than 1 ppm by weight.
• the conditions of the oligomerization step b) are as follows:
• the charge is composed of an LCN cut mixture described in Example 1 and a C4 cut from an FCC unit.
• It also contains organic nitrogen compounds totaling a content of 7.6 ppm by weight expressed as elemental nitrogen and 14 ppm by weight of elemental sulfur.
• the feedstock is injected into the reactor from bottom to top at a rate of 32 g / h (corresponding to a. WH lh "1).
• the pressure is maintained at 30 bars effective and the temperature is gradually increased between 80 ° C and 140 ° C, in order to maintain constant conversion of the iso-olefins C5 between 85% and 90%.
• the conversion of isobutene is greater than 95%.
• n-olefins An average increase of 10 ° C every 200 hours is necessary to achieve this goal. Under these conditions, the conversion of n-olefins is between 20% and 30% for n-C4 and between 10% and 20% for n-C5.
• a 150+ cup (33% by weight) which is then hydrogenated to provide a kerosene cut.
• the hydrogenation is carried out with a nickel catalyst at 180 ° C. under 50 bar of hydrogen with a WH of 0.5 and a hydrogen flow rate of 50 NL / h and a feed rate of 48 g / h.
• the olefin content observed after hydrogenation is very low (bromine number ⁇ 0.8 g / 100 g).
• the characteristics of the kerosene cut obtained are as follows:
• the charge of the oligomerization reactor is composed of the hydrocarbon effluent obtained after transformation of a C4-C5-C6 load on Amberlyst TM 36WET resin during the previous step. It contains 14% butanes, 12% butenes; 3% isopentenes, 13% n-pentenes, 17% pentanes, 4% hexenes; 5% hexanes and 32% C7 + olefins
• the oligomerization step operates in the presence of the catalyst IP 811 and at a temperature of 170 ° C., under a pressure of 5 MPa, and at a weight hourly weight of 0.5 h -1, so as to obtain an average conversion of C4-C5-C6 olefins around 80%. After distillation, the following cuts are obtained:
• the total effluent is collected to be used in the oligomerization step b)
• Zeolite ZSM-5 is a commercial zeolite of Si / Al ratio equal to 40 in its NH4 + form.
• the catalyst is prepared by mixing the ZSM-5 zeolite with a SB3-type alumina supplied by CONDEA.
• the kneaded paste is then extruded through a die of diameter 1.4 mm.
• the extrudates thus obtained are dried at 120 ° C. for 5 hours and then calcined in dry air at 550 ° C. for 2 hours in air.
• the weight content of zeolite is 60% by weight.
• the charge of the oligomerization reactor is composed of the hydrocarbon effluent from step a.
• the oligomerization step b) operates in the presence of the zeolite catalyst C2 described above at a temperature of 235 ° C., at a pressure of 5 MPa and at an hourly weight speed. from 1h-1.
• cetane number 50; Flash point: 57 ° C; Crystallization point: ⁇ -65 ° C; density: 0.785

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

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• 2011
  • 2011-05-12 FR FR1101444A patent/FR2975103B1/fr active Active
  • 2011-09-19 FR FR1102873A patent/FR2975104B1/fr active Active
• 2012
  • 2012-03-13 EP EP12713203.3A patent/EP2707462B1/de active Active
  • 2012-03-13 WO PCT/FR2012/000088 patent/WO2012153011A2/fr not_active Ceased
  • 2012-03-13 WO PCT/FR2012/000087 patent/WO2012153010A2/fr not_active Ceased
  • 2012-03-13 EP EP12713204.1A patent/EP2707461A2/de not_active Ceased
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