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WO2006037368A1 - Procede destine a diminuer la teneur en acide organique dans des charges d'hydrocarbures - Google Patents

Procede destine a diminuer la teneur en acide organique dans des charges d'hydrocarbures Download PDF

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Publication number
WO2006037368A1
WO2006037368A1 PCT/EP2004/011361 EP2004011361W WO2006037368A1 WO 2006037368 A1 WO2006037368 A1 WO 2006037368A1 EP 2004011361 W EP2004011361 W EP 2004011361W WO 2006037368 A1 WO2006037368 A1 WO 2006037368A1
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
process according
oil feed
crude oil
acids
Prior art date
Application number
PCT/EP2004/011361
Other languages
English (en)
Inventor
Elizabeth Marques Moreira
Claudia Maria De Lacerda Alvarenga Baptista
Paul O'connor
Henrique Soares Cerqueira
Original Assignee
Petroleo Brasileiro S.A.-Petrobras
Albemarle Netherlands B.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 Petroleo Brasileiro S.A.-Petrobras, Albemarle Netherlands B.V. filed Critical Petroleo Brasileiro S.A.-Petrobras
Priority to PCT/EP2004/011361 priority Critical patent/WO2006037368A1/fr
Publication of WO2006037368A1 publication Critical patent/WO2006037368A1/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

Definitions

  • the present invention relates to a process for reducing the organic acid content of crude oil feeds.
  • Naphthenic acids are predominantly monocarboxylic acids having one or more cycloaliphatic groups alkylated in various positions with short chain aliphatic groups and containing a polyalkylate chain terminating in the carboxylic acid function. They are represented by a general formula C n FWzOa, where n indicates the carbon number and z specifies a homologous series. The z is equal to 0 for saturated acyclic acids and increases to 2 in monocyclic naphthenic acids, to 4 in bicyclic naphthenic acids, to 6 in tricyclic acids, and to 8 in tetracyclic acids.
  • Naphthenic acids in the range of C 7 to C12 consist mainly of monocyclic acids. The more complex acids contain larger proportions of multicyclic condensed compounds.
  • the molecular weight of the naphthenic acids present in crude oils generally varies between 200 and 700.
  • US 6,086,751 discloses reduction of the acidity by means of a moderate thermal treatment, at temperatures in the range of 320 to 42O 0 C and reaction times of
  • Another possibility is pre-treatment of the crude oil under fixed bed hydrotreating conditions - temperature: 200-370 0 C, H 2 partial pressure: 50-500psi - for selectively converting low-molecular weight acids, which are thought to be the main cause of corrosion (US 5,871 ,636 and US 5,910,242).
  • a Group Vl metal or a Group VIlI noble metal may be used as catalyst.
  • the drawback to such a process is the investment (and catalyst) cost and the hydrogen consumption.
  • a slurry reactor may also be used for the hydrogenation of naphthenic acids, achieving complete elimination of the acids using a similar catalyst and pressure, but at higher (380-450 0 C) temperatures.
  • adsorbents to adsorb the acids.
  • WO 04/005434 discloses a reduction of the naphthenic acidity of desalted and dewatered petroleum oils by using an adsorbent.
  • Disclosed adsorbents include carbon black and spent or coked FCC catalysts.
  • US 5,389,240 discloses a fixed bed process for sweetening liquid hydrocarbon feedstocks.
  • the first step in this process involves the removal of naphthenic acids; the second step is the removal of mercaptans from an alkaline environment.
  • Petroleum fractions having an end boiling point up to about 600 0 C and TAN values of 0.003 to 4 mg KOH/g can be treated by this process.
  • Disclosed petroleum feedstocks are kerosine, middle distillates, light gas oil, heavy gas oil, jet fuel, diesel fuel, heavy naphtha, lube oil, stove oil, and heating oil; with kerosine with a TAN of 0.01-0.06 mg KOH/g being preferred.
  • the sulfur levels of these petroleum fractions is about 0.05-0.8 wt% (as S).
  • the first step involves flowing the feedstock in the presence of oxygen or air and at a preferred temperature of 30-80 0 C through a fixed bed of an adsorbent containing a metal oxide solid solution.
  • the metal oxide solid solution contains a divalent and a trivalent metal oxide and is prepared by calcining a hydrotalcite-like material at a temperature between 400-750 0 C.
  • reaction temperature during naphthenic acid removal may be as high as 400°C
  • the use of such a high temperature in said process will never be considered by those skilled in the art.
  • First of all, such temperatures would result in thermal cracking of the petroleum fractions, which is in general undesired.
  • Second, the use of such high temperatures in this oxygen- requiring process will result in the formation of (a) explosive mixtures of light cracking products and oxygen and (b) undesired O-containing compounds like phenols.
  • Crude oils contain far more heavy metal and hetero atom (S, N) contaminants than the petroleum fractions of US 5,389,240 do. Crude oil feeds usually have a sulfur content of at least 1.5 wt% (as S), typically 2-3 wt%, although sulfur levels above 5 wt% are possible.
  • anionic clays and their heat-treated forms can be successfully used for the removal of organic acids from crude and heavy oils.
  • the present invention therefore relates to a process for reducing the organic acid content of crude oil feeds by contacting a crude oil feed with an adsorbent comprising an anionic clay or a heat-treated form thereof in a reactor vessel under agitation and under a flow of inert gas at a temperature in the range 200 to 500 0 C.
  • crude oils with a TAN up to 10 can be treated. Further, this process at the same time reduces the viscosity of the crude oil. Crude oil feed
  • Crude oil feeds that may be used in the process of the invention include any organic acid-containing crude oil that is liquid or liquefiable at the temperature applied during the process. Both whole crudes, i.e. unrefined, undistilled crudes, and topped crudes may be used.
  • the crude oil feed preferably has a Conradson Carbon content of at least 3, more preferably of at least 5.
  • Their sulfur content preferably is at least 1.5 wt% (as S), more preferably 2-3 wt%.
  • the Total Acid Number (TAN) of the crude oil feed preferably is up to 10, more preferably 2 to 5. This Total Acid Number refers to the amount of milligrams of KOH required for neutralizing one gram of oil and is determined using ASTM D- 664-04.
  • the adsorbent to be used in the process of the present invention comprises an anionic clay or a heat-treated form thereof.
  • the adsorbent may contain a matrix material, such as alumina, silica, silica-alumina and/or magnesia.
  • a matrix material such as alumina, silica, silica-alumina and/or magnesia.
  • Other materials that may be present in the adsorbent include compounds containing metals selected from the group consisting of Ca, Ba, K, and Na.
  • the adsorbent preferably contains 50-100 wt%, more preferably 80 to 100 wt% of (heat-treated) anionic clay.
  • the adsorbent is preferably used in the form of shaped particles, such as microspheres, extrudates, beads, or pellets. These particles have a diameter of preferably 0.1-100 mm, more preferably 0.1-10 mm, and most preferably 0.1-3 mm.
  • the BET surface area of the (heat-treated) anionic clay preferably ranges from 60 to 300 m 2 /g, more preferably from 150 to 250 m 2 /g.
  • Anionic clays are layered structures corresponding to the general formula
  • M 2+ is a divalent metal
  • M 3+ is a trivalent metal
  • X is an anion with valance z, such as CO 3 2" , OH " , or any other anion normally present in the interlayers of anionic clays. It is more preferred that m/n should have a value of 2 to 4, more particularly a value close to 3.
  • anionic clays are also referred to as layered double hydroxides and hydrotalcite-like materials.
  • Anionic clays have a crystal structure consisting of positively charged layers built up of specific combinations of metal hydroxides between which there are anions and water molecules.
  • Hydrotalcite is an example of a naturally occurring anionic clay in which Al is the trivalent metal, Mg is the divalent metal, and carbonate is the predominant anion present.
  • Meixnerite is an anionic clay in which Al is the trivalent metal, Mg is the divalent metal, and hydroxyl is the predominant anion present.
  • the brucite-like main layers are built up of octahedra alternating with interlayers in which water molecules and anions, more particularly carbonate ions, are distributed.
  • the interlayers may contain anions such as NO 3 " , OH, Cl “ , Br “ , r, SO 4 2” , SiO 3 2” , CrO 4 2” , BO 3 2” , MnO 4 ' , HGaO 3 2' , HVO 4 2" ,
  • anionic clays Upon thermal treatment at a temperature above about 20O 0 C, anionic clays are transformed into so-called solid solutions, i.e. mixed oxides that are re-hydratable to anionic clays. At higher temperatures, above about 800 0 C, spinel-type structures are formed. These are not re-hyd ratable to anionic clays.
  • thermally treated anionic clays that can be used in the process of the present invention include solid solutions and spinel-type materials, with solid solutions being preferred.
  • Suitable trivalent metals (M 3+ ) present in the (thermally treated) anionic clay include Al 3+ , Ga 3+ , In 3+ , Bi 3+ , Fe 3+ , Cr 3+ , Co 3+ , Sc 3+ , La 3+ , Ce 3+ , and combinations thereof.
  • Suitable divalent metals (M 2+ ) include Mg 2+ , Ca 2+ , Ba 2+ , Zn 2+ , Mn 2+ , Co 2+ , Mo 2+ , Ni 2+ , Fe 2+ , Sr 2+ , Cu 2+ , and combinations thereof.
  • anionic clays are Mg-Al and Ca-Al anionic clays.
  • Anionic clays with any type of stacking can be used, e.g. conventional 3Ri stacking or the 3R 2 stacking described in WO 01/012550.
  • Suitable anionic clays can be prepared by any known process. Examples are co- precipitation of soluble divalent and trivalent metal salts and slurry reactions between water-insoluble divalent and trivalent metal compounds, e.g. oxides, hydroxides, carbonates, and hydroxycarbonates. The latter method provides an inexpensive route to anionic clays.
  • the process according to the present invention is conducted in a slurry phase reactor, by mixing the adsorbent with the crude oil feed.
  • the adsorbent/oil weight ratio in the slurry preferably is in the range of 0.01 to 1 , more preferably 0.02 to 0.08.
  • the process is conducted under an inert gas flow.
  • Suitable inert gases include nitrogen and argon.
  • light gases may be produced, such as butanes and lighter, H 2 O, CO, and CO 2 . This gas formation may be due to decomposition of the organic acids and/or some cracking of the crude oil feed.
  • the temperature in the reactor ranges from 200 0 C to 500 0 C, preferably from 250 to 400°C, and more preferably from 300 to 350 0 C.
  • the latter range is preferred, because it results in minimized thermal cracking of the crude oil feed. Above this temperature, gas production and coke deposition will increase. On the other hand, some thermal cracking of the crude oil may be desired and higher temperatures are then preferred.
  • the pressure in the reactor is preferably atmospheric, more preferably in the range of 0.1 to 1.0 MPa.
  • the crude oil feed is preferably contacted with the adsorbent for a period of 15 minutes to 5 hours, more preferably 30 to 120 minutes.
  • the adsorbent may be removed from the oil feed using a conventional solid/liquid separation technique, such as decantation or centrifugation.
  • the oil fraction can then be further refined, whereas the adsorbent may be regenerated by calcination, i.e. controlled burning in the presence of air, at a temperature of 200-40Q°C.
  • the adsorbent and oil feed are not separated, and the slurry obtained from the process of the invention can be submitted to further refining during which the adsorbent may be present as a useful additive.
  • Figure 1 illustrates a laboratory scale installation suitable for performing the process of the invention.
  • the adsorbent was loaded in the reactor (2), which was then closed and purged with a stream of nitrogen at a flow rate of 100 mL/min for nearly 30 minutes. Cooling water was turned on and the adsorbent was heated up to 80 0 C.
  • the flow rate of nitrogen was then reduced to 5 mL/min and reactor (2) was heated to the contacting temperature, under constant agitation with an impeller (3) at about 300 rpm.
  • the condenser (5) and the cold finger (6) were used to condense the light gases formed.
  • the process was conducted for 60 minutes, after which the TAN of the treated oil was measured. To this end, a sample of the treated oil feed was centrifuged at ambient temperature for 5 minutes at 2,000 rpm and the TAN of the liquid phase was determined using a MetrohmTM titration processor employing ASTM Method D- 664.
  • the adsorbent used was a powder containing 100 wt% of either Mg/AI anionic clay or a solid solution prepared by calcining this anionic clay at 350 0 C (Example 4) or 400 0 C (Example 5).
  • the anionic clay had a specific surface area of about 200 m 2 /g.
  • the Table further shows that a contacting temperature of 350 0 C is preferred above one of 250°C.
  • Example T ( 0 C) Adsorbent Adsorbent/oil TAN (wt/wt) (mg KOH/g oil)

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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)

Abstract

L'invention concerne un procédé destiné à réduire la teneur en acide organique d'une charge de pétrole brut par mise en contact de cette charge d'huile avec un adsorbant contenant de l'argile anionique ou une forme traitée à chaud de celle-ci dans une cuve de réacteur sous agitation et sous un flux de gaz inerte à une température comprise entre 200 et 500 °C.
PCT/EP2004/011361 2004-10-04 2004-10-04 Procede destine a diminuer la teneur en acide organique dans des charges d'hydrocarbures WO2006037368A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1700634A1 (fr) 2005-03-09 2006-09-13 Albemarle Netherlands B.V. Procédé pour la revalorisation d'un catalyseur usé de craquage catalytique fluide
EP2105486A1 (fr) 2008-03-25 2009-09-30 KiOR Inc. Faible nombre d'acide bio brut total
US8377152B2 (en) 2010-10-29 2013-02-19 Kior, Inc. Production of renewable bio-distillate
US8628589B2 (en) 2011-02-11 2014-01-14 Kior, Inc. Renewable heating oil
CN103540339A (zh) * 2013-10-21 2014-01-29 中国石油化工股份有限公司 一种可有效降低基础油酸值的润滑油料精制方法
US8669405B2 (en) 2011-02-11 2014-03-11 Kior, Inc. Stable bio-oil
US9062264B2 (en) 2010-10-29 2015-06-23 Kior, Inc. Production of renewable bio-gasoline
US9295957B2 (en) 2007-11-28 2016-03-29 Saudi Arabian Oil Company Process to reduce acidity of crude oil
US9315739B2 (en) 2011-08-18 2016-04-19 Kior, Llc Process for upgrading biomass derived products
US9382489B2 (en) 2010-10-29 2016-07-05 Inaeris Technologies, Llc Renewable heating fuel oil
US9447350B2 (en) 2010-10-29 2016-09-20 Inaeris Technologies, Llc Production of renewable bio-distillate
US9617489B2 (en) 2011-02-11 2017-04-11 Inaeris Technologies, Llc Liquid bio-fuels
WO2017063004A3 (fr) * 2015-10-05 2017-06-22 University Of Pretoria Catalyseur et procédé de réduction de composés oxygénés
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0278535A1 (fr) * 1987-01-13 1988-08-17 Akzo N.V. Composition catalytique et absorbant contenant une argile anionique
US5389240A (en) * 1993-08-02 1995-02-14 Uop Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening
US20020092812A1 (en) * 1998-10-08 2002-07-18 Dennis Stamires Situ formed anionic clay-containing bodies
WO2004005434A1 (fr) * 2002-07-05 2004-01-15 Petroleo Brasileiro S.A.- Petrobras Procede pour reduire l'acidite naphtenique d'huiles minerales

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0278535A1 (fr) * 1987-01-13 1988-08-17 Akzo N.V. Composition catalytique et absorbant contenant une argile anionique
US5389240A (en) * 1993-08-02 1995-02-14 Uop Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening
US20020092812A1 (en) * 1998-10-08 2002-07-18 Dennis Stamires Situ formed anionic clay-containing bodies
WO2004005434A1 (fr) * 2002-07-05 2004-01-15 Petroleo Brasileiro S.A.- Petrobras Procede pour reduire l'acidite naphtenique d'huiles minerales

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1700634A1 (fr) 2005-03-09 2006-09-13 Albemarle Netherlands B.V. Procédé pour la revalorisation d'un catalyseur usé de craquage catalytique fluide
US9656230B2 (en) 2007-11-28 2017-05-23 Saudi Arabian Oil Company Process for upgrading heavy and highly waxy crude oil without supply of hydrogen
US10010839B2 (en) 2007-11-28 2018-07-03 Saudi Arabian Oil Company Process to upgrade highly waxy crude oil by hot pressurized water
US9295957B2 (en) 2007-11-28 2016-03-29 Saudi Arabian Oil Company Process to reduce acidity of crude oil
EP2105486A1 (fr) 2008-03-25 2009-09-30 KiOR Inc. Faible nombre d'acide bio brut total
US9382489B2 (en) 2010-10-29 2016-07-05 Inaeris Technologies, Llc Renewable heating fuel oil
US8454712B2 (en) 2010-10-29 2013-06-04 Kior, Inc. Production of renewable bio-distillate
US8506658B2 (en) 2010-10-29 2013-08-13 Kior, Inc. Production of renewable bio-distillate
US9850440B2 (en) 2010-10-29 2017-12-26 Inaeris Technologies, Llc Production of renewable bio-gasoline
US9062264B2 (en) 2010-10-29 2015-06-23 Kior, Inc. Production of renewable bio-gasoline
US8377152B2 (en) 2010-10-29 2013-02-19 Kior, Inc. Production of renewable bio-distillate
US9447350B2 (en) 2010-10-29 2016-09-20 Inaeris Technologies, Llc Production of renewable bio-distillate
US9617489B2 (en) 2011-02-11 2017-04-11 Inaeris Technologies, Llc Liquid bio-fuels
US8669405B2 (en) 2011-02-11 2014-03-11 Kior, Inc. Stable bio-oil
US8628589B2 (en) 2011-02-11 2014-01-14 Kior, Inc. Renewable heating oil
US9315739B2 (en) 2011-08-18 2016-04-19 Kior, Llc Process for upgrading biomass derived products
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
CN103540339B (zh) * 2013-10-21 2015-10-28 中国石油化工股份有限公司 一种可有效降低基础油酸值的润滑油料精制方法
CN103540339A (zh) * 2013-10-21 2014-01-29 中国石油化工股份有限公司 一种可有效降低基础油酸值的润滑油料精制方法
WO2017063004A3 (fr) * 2015-10-05 2017-06-22 University Of Pretoria Catalyseur et procédé de réduction de composés oxygénés
US10786806B2 (en) 2015-10-05 2020-09-29 University Of Pretoria Oxygenate reduction catalyst and process

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