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WO2003018717A1 - Ameliorations dans le traitement de reduction de soufre dans des essences catalytiques et dans des distillats intermediaires de petrole brut au moyen de gel de silice - Google Patents

Ameliorations dans le traitement de reduction de soufre dans des essences catalytiques et dans des distillats intermediaires de petrole brut au moyen de gel de silice Download PDF

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Publication number
WO2003018717A1
WO2003018717A1 PCT/MX2002/000084 MX0200084W WO03018717A1 WO 2003018717 A1 WO2003018717 A1 WO 2003018717A1 MX 0200084 W MX0200084 W MX 0200084W WO 03018717 A1 WO03018717 A1 WO 03018717A1
Authority
WO
WIPO (PCT)
Prior art keywords
silica gel
filter
water
sulfur
regeneration
Prior art date
Application number
PCT/MX2002/000084
Other languages
English (en)
Spanish (es)
Inventor
Israel Quiroz Franco
Mariano FERNÁNDEZ GARCIA
Original Assignee
Fians Capital S.A. De C.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fians Capital S.A. De C.V. filed Critical Fians Capital S.A. De C.V.
Publication of WO2003018717A1 publication Critical patent/WO2003018717A1/fr

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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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention is related to production processes of catalytic gasoline and intermediate distillates of crude oil. More particularly, the invention relates to processes for reducing the sulfur content in catalytic gasoline and in petroleum intermediate distillates; and specifically, with the purification of the silica gel filter used in said processes.
  • Said regeneration is necessary since the silica gel is saturated with sulfur and, correspondingly, decreases its effectiveness.
  • the regeneration is carried out by washing with hot air to ensure that the sulfur is oxidized to SO2 and thus removed from the silica gel; for which the filter is isolated, temporarily removing it from the production line, and heated air is injected through it at a temperature of around 450 ° C, until the regeneration of the silica gel is completed, as specified clearly in said patent application.
  • the filter is subsequently cooled and when it reaches the temperature of the refinery's service air, the gel-packed filter is in a position to be reconnected to the production line to be used again in the filtration.
  • the regeneration step which in the Mexican application 99/2593 is carried out with heated air at an elevated temperature, can also be carried out, in an easier, faster and less complicated manner, using a procedure called closed cycle, and that involves the steps of: washing the filter with water at a temperature at least equivalent to the boiling point, until the water comes out clear and without traces of sulfates; dry the filter at 115 ° C; and purify the wash water, to remove traces of sulfur derivatives thereof.
  • the wet water vapor, produced can be reused by drying it previously. This way of regenerating the filter forms the basis for the improvement patent referred to in this description.
  • Figure 1 is a conventional flow chart of the process, in which the situation of two filters packed with silica gel is shown; filters to be regenerated in accordance with the present invention.
  • Figure 2 is a conventional diagram of the assembly for the regeneration of the silica gel contained in the filters of the present invention; Y
  • FIG. 3 is a conventional diagram of the sulfur absorption process in the filter loaded with silica gel, and the subsequent regeneration process thereof.
  • the crude oils are subjected to a series of operations in combined plants, which essentially comprise atmospheric towers, in which products such as primary gasoline, turbosine or naphtha and diesel are obtained; and vacuum distillation towers, in which high vacuum diesel oils are obtained, which are recovered as charges for catalytic plants.
  • catalytic gasoline is obtained as the main product, by means of a catalytic thermal cracking operation of high-vacuum diesel fuels from, among other sources, the vacuum distillation towers referred to in the preceding paragraph. It is in this environment that the invention of the Mexican patent application is used cited above, and where the improvement referred to in this application will apply.
  • the hydrocarbon stream does not substantially lose its sulfur content, so it is normally sent to a desbutanizing tower (not shown), in which, in addition to eliminating light hydrocarbons, such as butane, propane, etc., it is about removing as much sulfur as possible, subjecting the current to a treatment known as "Merox", which is indicated in 3.
  • a treatment known as "Merox" which is indicated in 3.
  • the reduction of sulfur in treatment 3 is limited.
  • the aforementioned Mexican application taught the installation of two filters 4 and 5, loaded with silica gel, at the exit of catalytic gasoline from the chemical treatment Merox 3.
  • the purpose of these filters is to absorb the non-eliminated sulfur in treatment 3, by passing the gasoline through silica gel.
  • the pair of filters 4 and 5 works alternately; that is, one of them (4) is put into operation until the silica gel is close to the saturation point with sulfur, at which point the other filter 5 is connected, while the filter 4 is regenerated by hot air. It is necessary to note that, although only two filters 4 and 5 have been illustrated, each of them can be replaced by a train of filters, so their number could be greater.
  • the number 7 represents the line through which the regeneration means of the filters 4 and 5 are passed countercurrently, when that operation should be performed; while the number 9 identifies the upper filter regeneration valve that, through line 8, connects with a sulfur plant (not shown).
  • FIG. 3 is a flow chart, much more detailed, illustrating the regeneration system referred to in the present improvement.
  • the dry hot steam inlet (without moisture) has been identified with “A”; with “B”, the sulfur-containing water outlet to the bitter water recovery plant; and with “C” the entrance of virgin demineralized water.
  • filters 4 and 5 are arranged in the same relation with respect to the towers 1 , 2 and 3 also defined in said previous application.
  • the improvement of the invention lies is in the way of regenerating filters 4 and 5.
  • one of the filters 4, 5 (which can be representative of a train of filters) is put into operation.
  • the silica gel contained in the filter retains the sulfur contained in the stream of filtration, is saturated with the result that the sulfur content in the product is increasing.
  • the filter is removed from the line, replacing it with the other (5, 4) (which can also be representative of a filter train). While this other filter is in operation, the filter removed from the line is subjected to the regeneration steps.
  • the filter to be regenerated is first subjected to a washing step, as shown with the dotted lines, until the moment the outlet water is clean and clear, without yellow color. At that time it will be free of sulfur. The absence of sulfates is checked visually or (preferred) by a test commonly used with cadmium acetate. If it is verified that the water is clear and clear, the water will be used again for regeneration, in a closed cycle.
  • the water used will be at an elevated temperature, preferably equivalent to at least the boiling point. This will produce, as usual, wet steam, which can be used repeatedly, drying it. Preferably, the steam is reheated. Once the silica gel has been washed with the water at a temperature at least equivalent to the boiling point, as stated above, it is dried, preferably at a temperature of about
  • the filter is able to be used again in the filtration of gasoline or other sulfur-containing product.
  • the regeneration step allows the silica silica to be reused practically without limits; as long as the practice of regenerating it is observed every time it is saturated.
  • the results will invariably remain within the scale of indicated reductions, always below 0.1%.

Landscapes

  • 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)

Abstract

L'invention concerne une amélioration dans le traitement chimique de réduction du contenu de soufre d'une essence catalytique et des distillats intermédiaires du pétrole brut, au moyen d'au moins un filtre rempli de gel de silice. L'amélioration consiste à régénérer le gel de silice par son lavage à l'eau à une température au moins équivalente à la température d'ébullition.
PCT/MX2002/000084 2001-08-24 2002-08-23 Ameliorations dans le traitement de reduction de soufre dans des essences catalytiques et dans des distillats intermediaires de petrole brut au moyen de gel de silice WO2003018717A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MXPA/A/2001/008582 2001-08-24
MXPA01008582 MXPA01008582A (es) 2001-08-24 2001-08-24 Mejoras en tratamiento para reduccion de azufre en gasolinas cataliticas y en destilados intermedios de crudo, con silica gel.

Publications (1)

Publication Number Publication Date
WO2003018717A1 true WO2003018717A1 (fr) 2003-03-06

Family

ID=33129115

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/MX2002/000084 WO2003018717A1 (fr) 2001-08-24 2002-08-23 Ameliorations dans le traitement de reduction de soufre dans des essences catalytiques et dans des distillats intermediaires de petrole brut au moyen de gel de silice

Country Status (2)

Country Link
MX (1) MXPA01008582A (fr)
WO (1) WO2003018717A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4405276A1 (de) * 1994-02-19 1995-08-24 Otto Luft Klimatech Gmbh Verfahren zur Abscheidung von Ethylenoxid aus Abluft- oder Abgasströmen
US6111162A (en) * 1996-04-22 2000-08-29 Snamprogetti S.P.A. Process for removing oxygenated contaminants from hydrocarbon streams

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4405276A1 (de) * 1994-02-19 1995-08-24 Otto Luft Klimatech Gmbh Verfahren zur Abscheidung von Ethylenoxid aus Abluft- oder Abgasströmen
US6111162A (en) * 1996-04-22 2000-08-29 Snamprogetti S.P.A. Process for removing oxygenated contaminants from hydrocarbon streams

Also Published As

Publication number Publication date
MXPA01008582A (es) 2003-02-27

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