EP0474545B1 - Verfahren zum Süssen in einem festen Bett von sauren Petroleumdestillaten mit einem Siedebereich zwischen 125 und 350 Grad - Google Patents

Verfahren zum Süssen in einem festen Bett von sauren Petroleumdestillaten mit einem Siedebereich zwischen 125 und 350 Grad Download PDF

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Publication number
EP0474545B1
EP0474545B1 EP91402340A EP91402340A EP0474545B1 EP 0474545 B1 EP0474545 B1 EP 0474545B1 EP 91402340 A EP91402340 A EP 91402340A EP 91402340 A EP91402340 A EP 91402340A EP 0474545 B1 EP0474545 B1 EP 0474545B1
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EP
European Patent Office
Prior art keywords
distillate
water
distillates
process according
catalyst
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Expired - Lifetime
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EP91402340A
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English (en)
French (fr)
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EP0474545A1 (de
Inventor
Patrick Ansquer
Jean-Michel Orgebin
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TotalEnergies Marketing Services SA
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Total Raffinage Distribution SA
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    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen

Definitions

  • the present invention relates to a fixed-bed softening process for acid petroleum distillates with cutting temperatures of between approximately 125 and approximately 350 ° C.
  • This process is particularly intended to soften distillates and, more specifically, kerosenes, with an acid number higher than 0.03 mg of KOH per gram, for which it is difficult, with conventional processes, to obtain distillates.
  • conform to the specifications required for their use namely, mainly their acid number, their mercaptan content and their color.
  • the acidity of the distillates is measured by an acid number, which is determined by standard ASTM D 3242 and which effectively corresponds to the additional acidity of the naphthenic and carboxylic acids and of the phenol compounds present in these distillates.
  • the first step consists in reducing, at least partially, the acidity of the distillates before the oxidation reaction of the mercaptans, either by prewashing them with basic solutions, in order to dissolve in acids the phenolic acids and compounds, generators of poisons of the catalyst, either by filtering them in order to trap these acids or these phenol compounds on the filter and thus to purify the distillates.
  • This step is well described in American patents no. 3,398,086, 4,033,860 and 4,121,999 and in French patent no. 2,392,103.
  • the second step consists in oxidizing the mercaptans still present in these distillates, by putting them in the presence of a metallic phthalocyanine deposited on a support, an oxidizing agent and a basic solution, often alkaline, with a pH generally between 9 and 14.
  • the third stage corresponds to a finishing treatment of the softened distillates, comprising washing with water, to extract the residual alkaline compounds and possibly certain soluble salts of oxidation products of the residual phenol compounds, then drying, by passage over a salt filter, and a discoloration, by passing over a clay filter, which fixes the oxidation products still present, color generators.
  • EP-A-0 376 774 describes a process for softening an petroleum cut, in which the catalytic oxidation reaction of the mercaptans is carried out in the absence of an aqueous phase and in the presence of an oxidizing agent and in which the water molecules formed during this reaction are removed from the catalytic support by periodic washing of the latter using a water-miscible solvent.
  • the problems posed by high acidity petroleum cuts are however not mentioned in this document.
  • the aim of the present invention is therefore a softening process which makes it easier to treat, industrially, distillates and, in particular, kerosene with a high acid number, in the absence of basic solutions such as soda in any of the processing steps, with a view to simultaneously obtaining the acidity, mercaptan content and color characteristics targeted for the sweetened distillates.
  • the present invention also aims to reduce the number of treatment steps and, therefore, the number of reactors, while limiting the number of stops of the unit for washing deposits on the supported catalyst.
  • the object of the present invention is therefore a process for softening acid petroleum distillates, with cutting temperatures of between approximately 125 and approximately 350 ° C., the acid number of which is greater than or equal to 0.03 mg of KOH per gram, characterized in that the reduction of the acidity and the oxidation of the mercaptans necessary for the softening of these distillates are carried out jointly in a single step, by passing these distillates, in the presence of an oxidizing agent, but in the absence of a basic solution, in particular of alkali hydroxide, on an oxidation catalyst with a specific surface of between 1 and 10 m2 / g and, preferably, between 2 and 6 m2 / g, and of which the microporous volume is between 0.01 and 0.10 cm3 / g and, preferably, between 0.02 and 0.05 cm3 / g, at a temperature between 30 and 80 ° C and, preferably between 35 and 45 ° C, in the presence of an oxidizing agent corresponding to an oxygen supply,
  • an excess of oxygen, relative to the stoichiometry, is particularly necessary for the distillates with high acid number, but this action will preferably be combined with the temperature and the spatial reaction speed, in order to avoid a deterioration in the color of the distillates softened by the process according to the invention.
  • the surface properties of the support of the oxidation catalyst make it possible for these compounds to pass through the support, hitherto considered to be poisons of the catalyst.
  • Another unexpected advantage of the invention is therefore to reduce the frequency of the periodic catalyst washing operations in order to restore its activity, the active sites no longer being covered with deposits.
  • not only does such a method limit the number of reactors, but it allows the operator to reduce the capacity of the softening reactor, by operating at an hourly space velocity at least twice as fast as that used in the conventional processes.
  • a preferred oxidation catalyst is that consisting of a solid absorbent support impregnated with a metal chelate, which comprises, in% by weight, between 0.05 and 5% of metal chelate, between 5 and 35% of pyrolyzed carbon and between 60 and 90% of a mineral matrix whose hydration rate is between 1 and 20% and preferably between 2 and 10%.
  • the metal chelate is a cobalt phthalocyanine.
  • the distillates treated by this process usually have a drying effect on the supported catalyst, which, at over time, deactivates the supported catalyst.
  • This is, in particular, the case for the catalyst described in European patent No. 252,853.
  • the Applicant has chosen to add water, continuously or batchwise, to the catalyst, preferably by injecting water into the distillate to be treated before entering the reactor, in order to maintain its hydration rate between 1 and 20%.
  • water continuously or batchwise, to the catalyst, preferably by injecting water into the distillate to be treated before entering the reactor, in order to maintain its hydration rate between 1 and 20%.
  • the quantity of water injected will be 0.05 to 0.20 times the volume of catalyst loaded in the reactor and this for a short period of time, between 10 and 30 minutes, without stop the softening reaction, unlike conventional methods.
  • the method according to the invention makes it possible to reduce the acid number from 50 to 100%, for distillates whose initial acid number is greater than 0.03 mg of KOH / g.
  • This will be particularly the case for kerosene from the distillation of crude oils, such as "Zuluf” and "Heavy Iran", for which the steps of prewash with soda and washing with water, according to the processes known, have hitherto been essential for obtaining sweetened distillates conforming to the specifications required for marketing.
  • the method according to the invention can be implemented in an industrial unit such as that shown schematically in the attached single figure.
  • This unit includes a reactor 1, in which the fixed bed of the oxidation catalyst is installed, a salt filter 2, for drying the softened distillate, and a clay 3 to discolor it.
  • the reactor 1 is supplied at its upper part by a pipe 4 for supplying the distillate, a water inlet pipe 5, on which will advantageously be placed a pump 6 for regulating the quantity of water to be injected continuously or discontinuously, and a pipe 7 for injecting air or an oxidizing agent.
  • An outlet pipe for the softened distillate 8 is placed at the bottom of the reactor 1; it leads to a decanter 9 intended for the elimination of water by a line 14.
  • a pipe 10 evacuates the softened distillate towards the top of the salt filter 2 and the pipe 11 from the bottom of the salt filter 2 routes it to the top of the clay filter 3.
  • the latter has at its base a line 12 for evacuating the softened distillate in accordance with the specifications required for its marketing.
  • process A The purpose of the present example is to study the respective performances of the process of the invention, called process A, and of a conventional process in three stages using sodium hydroxide, called process T (control process).
  • catalyst A The catalysts used in processes A and T will be called catalyst A and catalyst T respectively. Their characteristics are given in Table 1 below:
  • the oxidizing agent is oxygen in the air.
  • process A leads to a reduction in acidity, a reduction in the mercaptan content and a color of the sweetened distillate as good as with the process T, but with twice the hourly space velocity and a lower number of treatment steps (no more prewash with soda, nor washing with water of the softened product), without the use of soda, which avoids recycling problems of the latter.
  • Operating at an hourly space velocity twice as high in process A as in process T will allow the manufacturer to limit the capacity of the softening reactor.

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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)
  • Seasonings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paper (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)
  • Lubricants (AREA)

Claims (7)

  1. Verfahren zur Aufbereitung von sauren Eröldestillaten mit einem Siedebereich zwischen etwa 125°C und etwa 350°C und mit einer Säurezahl größer als oder gleich 0,03 mg KOH/g im Festbett, dadurch gekennzeichnet, daß die zur Aufbereitung der Destillate erforderliche Aciditätsverringerung und nötige Mercaptanoxydation gemeinsam in einem einzigen Schritt durchgeführt werden, wobei das Destillat in Gegenwart eines Oxydationsmittels, aber in Abwesenheit einer basischen Lösung, insbesondere einer Alkalihydroxyd - Lösung, über einen Oxydationskatalysator mit einer spezifischen Oberfläche zwischen 1 und 10 m²/Gramm, vorzugsweise zwischen 2 und 6 m² /Gramm, und mit einem Mikroporenvolumen zwischen 0,01 und 0,10 cm³/Gramm, vorzugsweise zwischen 0,02 und 0,05 cm³/Gramm, bei einer Temperatur zwischen 30 und 80°C, vorzugsweise zwischen 35 und 45°C, mit einer Luftmenge im Reaktor, welche einer Sauerstoffzugabe zwischen dem 0,9- und 2fachen, vorzugsweise zwischen dem 1- und 1,4fachen der für die Reaktion erforderlichen stöchiometrischen Menge entspricht, unter einem Druck zwischen 1 und 30 Bar, vorzugsweise zwischen 2 und 15 Bar, und mit einer stündlichen Raumgeschwindigkeit des zu behandelnden Destillats zwischen 0,5 und 6 v.v.h., vorzugsweise zwischen 1 und 4 v.v.h., geleitet wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Oxydationskatalysator aus einem absorbierenden festen Support besteht, welcher mit einem Metallchelat imprägniert ist, und folgende Zusammensetzung aufweist:
       zwischen 0,05 und 10 Gew.-% Metallchelat
       zwischen 5 und 35 Gew.-% pyrolisierter Kohlenstoff
       zwischen 60 und 90 Gew.-% mineralische Matrix mit einem Hydratationsgrad zwischen 1 und 20 %.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es sich beim Metallchelat um ein Kobaltphthalocyanin handelt.
  4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß zum Rehydratisieren des Katalysators dem Reaktor kontinuierlich oder diskontinuierlich Wasser zugeführt wird, vorzugsweise durch Auflösung des Wassers in dem zu behandelnden Destillat.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß zwischen 100 und 500 ppm Wasser kontinuierlich in das Destillat eingespritzt werden.
  6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß ein Wasservolumen, welches 5 bis 20 % des Katalysatorvolumens darstellt, in weniger als 30 Minuten diskontinuierlich eingespritzt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das aufbereitete Destillat anschließend einer Endbehandlung unterworfen wird, welche darin besteht, daß es ein Salfilter und dann ein Tonfilter ohne Phase des Waschens mit Wasser durchströmt.
EP91402340A 1990-09-03 1991-09-02 Verfahren zum Süssen in einem festen Bett von sauren Petroleumdestillaten mit einem Siedebereich zwischen 125 und 350 Grad Expired - Lifetime EP0474545B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9010942A FR2666344B1 (fr) 1990-09-03 1990-09-03 Procede d'adoucissement en lit fixe de distillats petroliers acides de temperatures de coupe comprises entre environ 125 et environ 350 degre c.
FR9010942 1990-09-03

Publications (2)

Publication Number Publication Date
EP0474545A1 EP0474545A1 (de) 1992-03-11
EP0474545B1 true EP0474545B1 (de) 1994-05-04

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EP91402340A Expired - Lifetime EP0474545B1 (de) 1990-09-03 1991-09-02 Verfahren zum Süssen in einem festen Bett von sauren Petroleumdestillaten mit einem Siedebereich zwischen 125 und 350 Grad

Country Status (9)

Country Link
US (1) US5382354A (de)
EP (1) EP0474545B1 (de)
KR (1) KR920006485A (de)
CN (1) CN1028765C (de)
AT (1) ATE105325T1 (de)
DE (1) DE69101893T2 (de)
DK (1) DK0474545T3 (de)
ES (1) ES2053297T3 (de)
FR (1) FR2666344B1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2947185B1 (fr) 2009-06-26 2011-07-01 Total Sa Procede de traitement de gaz acides
CA2781361A1 (en) * 2009-12-04 2011-06-09 Exxonmobil Research And Engineering Company Method for increasing color quality and stability of fuel field of the invention

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013257B1 (de) * 1978-12-22 1983-06-22 Ciba-Geigy Ag Verfahren zur Erhöhung der Lichtechtheit, Fluoreszenzpolarisation und Fluoreszenzquantenausbeute von Cyaninfarbstoffen, stabilisierte Cyaninfarbstoffzubereitung, Verfahren zu ihrer Herstellung und ihre Verwendung
IS1740B (is) * 1982-02-05 1999-12-31 Albright & Wilson Uk Limited Samsetning á hreinsivökva
MX167884B (es) * 1983-12-22 1993-04-20 Albright & Wilson Composicion detergente liquida
FR2601263B1 (fr) * 1986-07-11 1988-11-25 Total France Nouveau produit composite catalytique pour l'oxydation des mercaptans et son utilisation pour l'adoucissement des coupes petrolieres.
GB8724254D0 (en) * 1987-10-15 1987-11-18 Unilever Plc Hair treatment product
FR2640636B1 (fr) * 1988-12-21 1991-04-05 Total France Procede d'adoucissement en lit fixe de coupes petrolieres
FR2651791B1 (fr) * 1989-09-08 1994-05-20 Total France Cie Raffinage Distr Procede d'adoucissement en lit fixe de coupes petrolieres.

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Publication number Publication date
ATE105325T1 (de) 1994-05-15
DK0474545T3 (da) 1994-06-13
DE69101893T2 (de) 1994-11-10
CN1060105A (zh) 1992-04-08
DE69101893D1 (de) 1994-06-09
FR2666344A1 (fr) 1992-03-06
KR920006485A (ko) 1992-04-27
US5382354A (en) 1995-01-17
FR2666344B1 (fr) 1992-12-18
EP0474545A1 (de) 1992-03-11
CN1028765C (zh) 1995-06-07
ES2053297T3 (es) 1994-07-16

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