EP1142979A2 - Procédé de desacidification de destillats de pétrole acides - Google Patents

Procédé de desacidification de destillats de pétrole acides Download PDF

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Publication number
EP1142979A2
EP1142979A2 EP01106644A EP01106644A EP1142979A2 EP 1142979 A2 EP1142979 A2 EP 1142979A2 EP 01106644 A EP01106644 A EP 01106644A EP 01106644 A EP01106644 A EP 01106644A EP 1142979 A2 EP1142979 A2 EP 1142979A2
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EP
European Patent Office
Prior art keywords
adsorbent
process according
adsorbents
petroleum
distillates
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.)
Withdrawn
Application number
EP01106644A
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German (de)
English (en)
Other versions
EP1142979A3 (fr
Inventor
Bernhard Rosengarten
Ulrich Dr. Balfanz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ruhr Oel GmbH
Original Assignee
Ruhr Oel GmbH
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 Ruhr Oel GmbH filed Critical Ruhr Oel GmbH
Publication of EP1142979A2 publication Critical patent/EP1142979A2/fr
Publication of EP1142979A3 publication Critical patent/EP1142979A3/fr
Withdrawn legal-status Critical Current

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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents

Definitions

  • the invention relates to a process for deacidifying acidic petroleum distillates with a boiling range of 140 to 350 ° C and an acid number between 0.05 and> 0.015 mg KOH / g.
  • the process particularly concerns the deacidification of kerosene, from which Aircraft fuels such as Jet A 1 are produced.
  • Aircraft fuels such as Jet A 1 are produced.
  • These aviation fuels are subject to certain specifications according to different standards such as DERD 2494 or ASTM D 1655, in which the Limit values for certain components of the fuel are set.
  • the critical parameters of these fuels are acidity and sulfur content and the content of mercaptans. These parameters are therefore in the specifications limited to certain limit values.
  • the acidity of the distillates is mainly caused by carboxylic acids and phenolic compounds. These connections can, especially when using basic materials such as sodium hydroxide or similar substances meet, form salts or soaps that cause harmful effects in the fuel. So can salt crystals that are do not dissolve in the fuel, lead to clogging of the fuel filter.
  • the soaps can bind small amounts of water, such as at low temperatures they can prevail at great heights, freeze out.
  • Sulfur contaminants in aircraft fuel can cause cadmium corrosion lead and especially organic sulfur compounds cause corrosion on the turbines.
  • the acidic petroleum distillate is produced in three different ways Steps.
  • the mercaptan compounds are then removed in a second step. This are oxidized using metal phthalocyanine compounds on supports, Oxidizing agents and aqueous alkaline solutions implemented.
  • a third step the final treatment of the distillate takes place. There this is washed with water to remove the remaining alkaline compounds and to remove salts that have formed. This is followed by drying by passing through the distillate through a salt filter and decolorize the distillate by passing through a sound filter.
  • Newer methods of the prior art therefore essentially aim at this to avoid treatment with alkalis.
  • alkalis for example, as a replacement used for the alkalis, aqueous ammonia solutions.
  • EP 0 474 545 B1 describes a process for sweetening petroleum distillates, in a single step in the absence of basic solutions the acidity levels aimed at for the sweetened distillates, mercaptan levels and color characteristics can be achieved. This will reduce the acidity and the mercaptan oxidation together in a single step carried out.
  • the distillates are in the presence of an oxidizing agent, preferably a metal chelate passed over an oxidation catalyst.
  • This Oxidation catalyst also contains pyrolyzed carbon and large ones Portions of mineral matrix with a degree of hydration of 1 - 20% by weight. In this process, the distillate is transferred only by transfer the oxidation catalyst neutralizes the acids and the phenolic compounds and oxidizes the mercaptans.
  • oxidation catalysts consisting of an absorbent solid impregnated with metal chelates Carriers are relatively expensive to manufacture and therefore such cleaning Manufacturing costs for aircraft fuels should increase significantly.
  • Hydrotreating processes as an alternative to sweetening processes for lowering the acid number have the disadvantage that this process is more expensive since, among other things, additional H 2 is consumed.
  • the technical object of the invention is a method for deacidifying to provide acidic petroleum distillates that are used more cost-effectively is carried out and also without the use of aqueous alkaline solutions can be.
  • Preferred inorganic adsorbents are those selected from the Group predominantly silicon dioxide-containing adsorbents, predominantly aluminum oxide-containing Adsorbents and zeolitic molecular sieves or mixtures thereof used.
  • the use of activated aluminum oxide is particularly preferred or silica gel.
  • adsorbents preferably have a specific surface area of 100-1800 m 2 / g, preferably 100-850 m 2 / g and a micropore volume of 0.2-0.4 cm 3 / g.
  • the method is used in particular for deacidifying kerosene, which are used for the production of aircraft fuels.
  • the process is preferably at temperatures of 30-150 ° C, preferably 45 - 120 ° C, a pressure of 1 - 20 bar, preferably 2 - 10 bar and a specific load on the column containing the adsorbent of 0.5-10 kg of petroleum distillate / kg adsorbent / h carried out.
  • the adsorbent is regenerated by thermal treatment with hot Gases at temperatures of 250 - 350 ° C or by washing with a polar organic solvents in any case where higher molecular weight Phenols are present as impurities in the petroleum distillate.
  • the process according to the invention is preferably carried out in two columns, that can be operated in parallel or in series.
  • a pillar can be used in the meantime be taken out of operation for regeneration without the entire process must be interrupted.
  • Low-sulfur petroleum distillates are preferably used for the process because here the mercaptan concentrations are already close to the required specifications lie. Such low-sulfur petroleum distillates can be made using appropriate Crude oils or by mixing low-sulfur distillates with sulfur-rich distillates can be produced with little effort.
  • Figure 1 shows experimental results of deacidification of straight run kerosene with an adsorbent based on Al 2 O 3, for example Alcoa CDX.
  • the acid numbers of the kerosene used were between 0.02 and 0.04 mg KOH / g. After deacidification, acid numbers were achieved which are in the range 0.002-0.015 mg KOH / g.
  • Fig. 2 shows the possible different operating modes for the adsorption and Desorption processes in the columns.
  • the number 1 denotes the feed of the distillates from the top column, number 2 the flow of the distillates after deacidification.
  • the number 3 denotes the inlet of the regeneration gas and the number 4 the flow of the regeneration gas.
  • With the number 5 is the inlet of a polar Desorbent denotes and with the number 6 the process of desorbent.
  • Number 7 denotes the columns, number 8 the top column and number 9 the pool.
  • the columns 7 can be operated in different operating modes. So can both columns 7 are operated in a parallel operating mode. Then it will be the adsorption was carried out simultaneously on both reactors. The distillates are then led from the top column via the feed 1 into the reactors 7, where the adsorption is carried out. The products are over the drain 2 in the pool 9 collected. Alternatively, the columns can also be connected in series.
  • a second alternative operating mode provides that one of the reactors regenerates is, while the adsorption takes place in the other reactor.
  • the polar liquid desorbent preferably via the inlet 5 of led through the column above. Desorption of that in the column takes place Adsorbent, after which the desorbent is removed via the outlet 6.
  • An organic solvent can be used as polar desorbent.
  • the column is then flushed dry with hot gas from below.
  • the other continues to operate in the adsorption mode.
  • the regeneration process instead of using a polar liquid desorbent as thermal regeneration of the adsorbent can be carried out at temperatures of 250 - 350 ° C. Hot nitrogen or hot methane is fed in from below via feed 3 passed through the reactor.
  • Fig. 3 shows the reduction of the acid number in medium oil with fresh adsorbent and Adsorbent after desorption with methanol.

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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)
EP01106644A 2000-04-06 2001-03-16 Procédé de desacidification de destillats de pétrole acides Withdrawn EP1142979A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2000117260 DE10017260A1 (de) 2000-04-06 2000-04-06 Kontinuierlicher Prozeß zur Jet-Erzeugung mittels Adsorbentien
DE10017260 2000-04-06

Publications (2)

Publication Number Publication Date
EP1142979A2 true EP1142979A2 (fr) 2001-10-10
EP1142979A3 EP1142979A3 (fr) 2002-03-06

Family

ID=7637876

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01106644A Withdrawn EP1142979A3 (fr) 2000-04-06 2001-03-16 Procédé de desacidification de destillats de pétrole acides

Country Status (2)

Country Link
EP (1) EP1142979A3 (fr)
DE (1) DE10017260A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2327526A (en) * 1940-06-22 1943-08-24 Standard Oil Dev Co Recovery of phenols from mineral oils
US3457165A (en) * 1967-07-17 1969-07-22 Universal Oil Prod Co Treatment of hydrocarbon distillates to remove acidic organic material employing a fixed bed containing a solid alkali metal hydroxide
JPS55161886A (en) * 1979-06-04 1980-12-16 Matsushita Electric Ind Co Ltd Purification of kerosene
US5389240A (en) * 1993-08-02 1995-02-14 Uop Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2327526A (en) * 1940-06-22 1943-08-24 Standard Oil Dev Co Recovery of phenols from mineral oils
US3457165A (en) * 1967-07-17 1969-07-22 Universal Oil Prod Co Treatment of hydrocarbon distillates to remove acidic organic material employing a fixed bed containing a solid alkali metal hydroxide
JPS55161886A (en) * 1979-06-04 1980-12-16 Matsushita Electric Ind Co Ltd Purification of kerosene
US5389240A (en) * 1993-08-02 1995-02-14 Uop Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 199404 Derwent Publications Ltd., London, GB; Class H02, AN 1994-033140 XP002186419 & SU 1 786 060 A (HYDRO-CARBON RAW MAT RES INST), 7. Januar 1993 (1993-01-07) *
PATENT ABSTRACTS OF JAPAN vol. 005, no. 035 (C-046), 5. März 1981 (1981-03-05) & JP 55 161886 A (MATSUSHITA ELECTRIC IND CO LTD), 16. Dezember 1980 (1980-12-16) *

Also Published As

Publication number Publication date
DE10017260A1 (de) 2001-10-25
EP1142979A3 (fr) 2002-03-06

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