EP0375547B1 - Procédé de valorisation des gaz issus du craquage catalytique et de diminution de la teneur en benzène des essences - Google Patents

Procédé de valorisation des gaz issus du craquage catalytique et de diminution de la teneur en benzène des essences Download PDF

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Publication number
EP0375547B1
EP0375547B1 EP89403571A EP89403571A EP0375547B1 EP 0375547 B1 EP0375547 B1 EP 0375547B1 EP 89403571 A EP89403571 A EP 89403571A EP 89403571 A EP89403571 A EP 89403571A EP 0375547 B1 EP0375547 B1 EP 0375547B1
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EP
European Patent Office
Prior art keywords
fraction
benzene
mordenite
gases
catalytic cracking
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 - Lifetime
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EP89403571A
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German (de)
English (en)
French (fr)
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EP0375547A1 (fr
Inventor
Bernard Juguin
Francis Raatz
Christine Travers
Germain Martino
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil

Definitions

  • the present invention relates to a process for upgrading gases from catalytic cracking and for producing gasoline with a low benzene content and an improved octane number.
  • the gases from catalytic cracking which can represent up to around 5% of the products from an FCC unit, are currently only little or not valued, apart from their use as fuel inside the refinery who produces them.
  • These gases are generally composed mainly of hydrogen, methane, ethane, ethylene and nitrogen, accompanied by carbon monoxide and dioxide, propane, propene and a little butane, butenes, pentanes and pentenes.
  • the content of mono-olefins in these gases is of the order of 20 to 30% by weight. Given the large capacity of the catalytic cracking units, it is therefore economically very advantageous to transform these olefins into products with higher added value.
  • the method according to the invention makes it possible to jointly solve these two problems; it is therefore suitable for refiners with both a catalytic reforming unit and a catalytic cracking unit.
  • a reformate is fractionated into a light fraction enriched in benzene and a heavy fraction depleted in benzene, the light fraction is reacted with a cracking gas containing at least one monoolefin from C2 to C5, contact with a mordenite catalyst defined below, so as to obtain an alkylated fraction, and said alkylated fraction is mixed with said heavy fraction.
  • This alkylation reaction is carried out in the presence of an acidic zeolitic catalyst arranged in the form of a fixed bed, at a temperature of approximately 50 to 350 ° C (preferably between 150 and 300 ° C), under a pressure of 2 to 10 MPa (preferably between 3 and 7 MPa), with a flow rate of liquid hydrocarbons (space velocity) of approximately 0.5 to 10 volumes per volume of catalyst and per hour, and with a molar ratio of benzene / olefins between 0.2 and 5 (preferably between 0.6 and 1.5).
  • an acidic zeolitic catalyst arranged in the form of a fixed bed, at a temperature of approximately 50 to 350 ° C (preferably between 150 and 300 ° C), under a pressure of 2 to 10 MPa (preferably between 3 and 7 MPa), with a flow rate of liquid hydrocarbons (space velocity) of approximately 0.5 to 10 volumes per volume of catalyst and per hour, and with a molar ratio of benzene / olefins between 0.2 and 5 (preferably
  • the zeolitic catalyst used in the invention namely a dealuminated mordenite with an overall Si / Al atomic ratio of between 30 and 75, makes it possible to treat the gases resulting from catalytic cracking without any prior separation.
  • gases may contain, for example, 0.1 to 2% by weight, of carbon monoxide.
  • EP-0084748, EP-0097552, EP-0196965 (small pore mordenites) and FR-87/12932 were used to convert methanol or isomerize olefins.
  • mordenites are preferably prepared as follows, to obtain the best results.
  • the non-decomposable cations generally Na+, present in the starting mordenite are eliminated.
  • one or more exchanges can be carried out in dilute solutions of acids such as HCl or in NH4 + solutions.
  • the important point is that, at the end of this first step which can be described as decationization, almost all of the alkaline cations are eliminated (% Na between 150 and 1000 ppm, and preferably between 300 and 800 ppm ), and that the solid obtained is a form H or a precursor of form H (example NH4 +) not dealuminated substantially (% dealumination 10% and preferably 5%).
  • the NH4 + form will be chosen as the H form precursor.
  • form H or the precursor of form H, little or no dealuminated is subjected to a treatment under steam at a temperature above 450 ° C, for example at 450-650 ° C, and preferably 550 to 600 ° C.
  • the water content (by volume) of the calcination atmosphere will advantageously be greater than 20% and preferably 40%.
  • a solid is obtained which is characterized by the presence of amorphous zones in small quantities, which are precursors of the secondary porous network, and by a crystalline structure practically free from structural defects.
  • the presence of amorphous zones in zeolites treated at high temperature under water vapor is a known phenomenon.
  • the crystallinity levels measured by X-ray diffraction are generally greater than 80% and, more specifically, 90%.
  • Solids calcined under water vapor are also characterized by the presence, in the structural micropores, of extra lattice aluminum species, a subsequent acid attack is therefore necessary, because these micropores are practically plugged.
  • this acid attack must be optimized.
  • Acid attack is the third step in the preparation of the catalysts. At this point it is important to preserve or liberate the strong acid sites from the solids.
  • the acid attack must therefore be strong enough to, on the one hand, eliminate the cationic aluminum formed during the treatment under water vapor, and which are poisons of strong sites, and, on the other hand, to release the microporosity. structural.
  • the acid sites of the Brönsted type linked to extra-network species being of medium or low strength, it is not essential to proceed to their total elimination.
  • the acid attack should not, however, be too strong, so as to avoid excessive dealumination of the structural aluminum.
  • the force to be retained for the acid attack depends closely on the characteristics attained after calcination under steam and, in particular, on the crystal mesh.
  • concentrations of acid solutions (HCl, H2SO4) HNO3, etc.) will be used between 0.5 and 5 N and preferably between 1 and 3 N.
  • concentrations of solutions acids between 5 and 20 N and preferably between 7 and 12 M (the Si / Al framework ratios are determined by infrared spectroscopy for ratios between 30 and 40, and by 2 duSi NMR for higher ratios).
  • Si / Al ratios that is to say greater than 40 and more specifically greater than 60, it is advantageous to have recourse to several cycles of calcination under water vapor-acid attack.
  • the single figure illustrates a particular embodiment of the invention.
  • a reformate from a catalytic reforming unit, line 1 is sent to the distillation column 2; a fraction of boiling point above 85 ° C. is collected at the bottom of this first column, which is sent, via line 3, to the storage tank 4. At the top of this first column 2, it leaves via the line 5, a fraction of a boiling point below 85 ° C., which is mixed with gases arriving, via line 6, from a catalytic cracking unit. The resulting mixture is then sent, via line 7, to the heat exchanger 8, then, via line 9, to the preheating furnace 10, and finally, via line 11, to the inlet of the reactor. alkylation 12.
  • the effluent is introduced via line 13 into the heat exchanger 8, then at the outlet of the latter it is directed through line 14 in a second stripping column 15.
  • a mixture of hydrogen, carbon monoxide, carbon dioxide, nitrogen, oxygen, methane and ethane is released, which can either be evacuated to the torch via line 16, or be sent, via line 17, to the preheating furnace 10 of the alkylation section, to be used as fuel there.
  • a product is drawn off which is sent, via line 18, to a third stabilization column 19.
  • a mixture composed of propane and butanes is collected which is evacuated, via line 20, to a storage of liquefied petroleum gases (LPG) before being marketed.
  • LPG liquefied petroleum gases
  • a gasoline is drawn off which is sent, via line 21, to the storage tank 4 where it is mixed with the fraction of boiling point above 85 ° C. coming from the line 3 from the bottom of the reformate fractionation column 2.
  • the resulting mixture (line 22) is a gasoline fraction with a low benzene content and a high octane number.
  • Three catalysts B1, B2, B3 are prepared.
  • the raw material used to prepare these various catalysts is a small pore mordenite from the governing Chimique de la Grande Paroisse, referenced Alite 150; its anhydrous chemical formula is Na, Al O2 (SiO2) 5.5 , its benzene adsorption capacity is 1% by weight relative to the weight of dry solid, and its sodium content is 5, 3% by weight.
  • Five hundred grams of this powder are immersed in a 2M solution of ammonium nitrate, and the suspension is brought to 95 ° C for 2 hours.
  • the product is washed with water at 20 ° C. for 20 minutes, with a V / P ratio equal to 4.
  • the sodium content expressed as a percentage by weight relative to the dry zeolite increases from 5, 5 to 0.2%.
  • the product is then filtered, and different batches are subjected to calcination in a confined atmosphere, at a higher or lower temperature depending on the degree of dealumination of the frame that is to be obtained (Table 1).
  • the duration of the calcination is fixed at 2 hours.
  • the partial pressure of water vapor inside the reactor is around 90%.
  • the crystallinity of the various solids, after this calcination step, is greater than or equal to 90%.
  • Each modified solid is then shaped by kneading with an aluminum type binder, at a rate of 20% by weight of binder, then passage through a die.
  • the extrudates obtained, with a diameter of 1.2 mm, are then dried and calcined between 150 and 550 ° C. in stages of approximately one hour.
  • Three catalysts B′1, B′2, B′3 are prepared. These catalysts differ from those described in Example 1A, in that the raw material used to prepare them is no longer Alite 150 mordenite from the cios Chimique de la Grande Paroisse, but a large pore mordenite from TOYO-SODA , referenced TSZ 600 NAA. Its chemical formula, in the anhydrous state, is Na, AlO2 (SiO2) 5.1 , and its sodium content of 5.7%.
  • the three catalysts B1, B2, B3, prepared in Example 1A were tested by alkylation of a top fraction (boiling point below 85 ° C) of a reformate from a catalytic reforming unit , by gases from a catalytic cracking unit.
  • mordenites having a ratio global Si / Al atomic between 30 and 75 are much less selective, and they lead to the formation of paraffins (methane, ethane, propane, butanes and pentanes ); mordenites having an overall Si / Al atomic ratio greater than 75 are a little more selective, but less active since they do not completely transform the olefins (ethylene, propene, butenes, pentenes) contained in the charge.
  • Example 2A The three catalysts B′1, B′2 and B′3, prepared in Example 1B, were also tested under the same operating conditions, and with the same charge as the catalysts B1, B2 and B3; the results obtained, presented in table V, are very close to those obtained with the catalysts B1, B2 and B3.
  • Example 2A it can be seen that it is preferable to work with mordenites whose overall Si / Al atomic ratio is between 30 and 75.

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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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP89403571A 1988-12-22 1989-12-19 Procédé de valorisation des gaz issus du craquage catalytique et de diminution de la teneur en benzène des essences Expired - Lifetime EP0375547B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8817164 1988-12-22
FR8817164A FR2640994B1 (ja) 1988-12-22 1988-12-22

Publications (2)

Publication Number Publication Date
EP0375547A1 EP0375547A1 (fr) 1990-06-27
EP0375547B1 true EP0375547B1 (fr) 1992-06-24

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EP89403571A Expired - Lifetime EP0375547B1 (fr) 1988-12-22 1989-12-19 Procédé de valorisation des gaz issus du craquage catalytique et de diminution de la teneur en benzène des essences

Country Status (10)

Country Link
EP (1) EP0375547B1 (ja)
JP (1) JPH02225593A (ja)
KR (1) KR930006819B1 (ja)
AT (1) ATE77640T1 (ja)
CA (1) CA2006550A1 (ja)
DE (1) DE68901921T2 (ja)
ES (1) ES2034718T3 (ja)
FR (1) FR2640994B1 (ja)
GR (1) GR3005500T3 (ja)
ZA (1) ZA899770B (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2033250C (en) * 1990-01-16 1998-08-18 Lawrence A. Smith, Jr. Octane improvement process
US5252197A (en) * 1992-09-28 1993-10-12 Abb Lummus Crest Inc. Process for upgrading gasolines and other hydrocarbon mixtures
IT1397886B1 (it) 2009-12-23 2013-02-04 Eni Spa Procedimento per la produzione di componenti di carburanti per autotrazione.

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140622A (en) * 1977-11-03 1979-02-20 Uop Inc. Process to reduce the benzene content of gasoline
FR2519335B1 (fr) * 1982-01-04 1986-05-02 Azote & Prod Chim Production d'hydrocarbures a partir de methanol en presence de catalyseurs du type zeolithe

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Publication number Publication date
ZA899770B (en) 1990-09-26
KR930006819B1 (ko) 1993-07-24
KR900009942A (ko) 1990-07-06
DE68901921D1 (de) 1992-07-30
ES2034718T3 (es) 1993-04-01
FR2640994A1 (ja) 1990-06-29
ATE77640T1 (de) 1992-07-15
EP0375547A1 (fr) 1990-06-27
CA2006550A1 (fr) 1990-06-22
DE68901921T2 (de) 1992-12-10
GR3005500T3 (ja) 1993-05-24
JPH02225593A (ja) 1990-09-07
FR2640994B1 (ja) 1993-05-14

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