EP1062302B1 - Procede de reduction de l'indice d'acidite total du petrole brut - Google Patents

Procede de reduction de l'indice d'acidite total du petrole brut Download PDF

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Publication number
EP1062302B1
EP1062302B1 EP98942321A EP98942321A EP1062302B1 EP 1062302 B1 EP1062302 B1 EP 1062302B1 EP 98942321 A EP98942321 A EP 98942321A EP 98942321 A EP98942321 A EP 98942321A EP 1062302 B1 EP1062302 B1 EP 1062302B1
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Prior art keywords
oil
petroleum feed
kpa
water
metal
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EP98942321A
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German (de)
English (en)
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EP1062302A1 (fr
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Roby Bearden, Jr.
Saul Charles Blum
William Neergaard Olmstead
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries

Definitions

  • the present invention is directed to a method for reducing the Total Acid Number (TAN) of crude oils, a number that is based on the amount of carboxylic acids, especially naphthenic acids, that are present in the oil.
  • TAN Total Acid Number
  • naphthenic acid removal by conversion or absorption.
  • many aqueous materials can be added to crudes or crude fractions to convert the naphthenic acids to some other material, e.g., salts, that can either be removed or are less corrosive.
  • Other methods for naphthenic acid removal are also well known including absorption, on zeolites, for example.
  • one common practice for overcoming naphthenic acid problems is the use of expensive corrosion resistant alloys in refinery or producer equipment that will encounter relatively high naphthenic acid concentrations.
  • Another common practice involves blending of crudes with high TAN with crudes of lower TAN, the latter, however being significantly more costly than the former.
  • Lazar, et al. (US 1,953,353) teaches naphthenic acid decomposition of topped crudes or distillates, effected at atmospheric pressure between 600 and 750°F (315.6 to 398.9°C). However, it only recognizes CO 2 as the sole gaseous non-hydrocarbon, naphthenic acid decomposition product and makes no provision for avoiding buildup of reaction inhibitors.
  • U.S. Patent No. 2,921,023 describes removal of naphthenic acids from heavy petroleum fractions by hydrogenation with a molybdenum oxide-on-silica/alumina catalyst. More specifically, the process preferentially hydrogenates oxo-compounds and/or olefinic compounds, for example, naphthenic acids, in the presence of sulfur compounds contained in organic mixtures without affecting the sulfur compounds. This is accomplished by subjecting the organic mixture to the action of hydrogen at temperatures between 450 and 600°F (232.2 to 315.6°C), in the presence of a molybdenum oxide containing catalyst having a reversible water content of less than about 1.0 wt%. Catalyst life is prolonged by regeneration.
  • WO 96/06899 describes a process for removing essentially naphthenic acids from a hydrocarbon oil.
  • the process includes hydrogenation at 1 to 50 bar (100 to 5000 kPa) and at 100 to 300°C (212 to 572°F) of a crude that has not been previously distilled or from which a naphtha fraction has been distilled using a catalyst consisting of Ni-Mo or Co-Mo on an alumina carrier.
  • the specification describes the pumping of hydrogen into the reaction zone. No mention is made of controlling water and carbon dioxide partial pressure.
  • U.S. Patent No. 3,617,501 describes an integrated process for refining whole crude but does not discuss TAN reduction.
  • the first step of the process includes hydrotreating a feed, which can be a whole crude oil fraction, using a catalyst comprising one or more metals supported on a carrier material.
  • the metals are metal oxides or sulfides, such as molybdenum, tungsten, cobalt, nickel and iron supported on a suitable carrier material such as alumina or alumina that contains a small amount of silica.
  • the catalyst can be employed in the form of fixed bed, a slurry or fluidized bed reactor. With regard to slurry operation, no mention is made of catalyst particle size, catalyst concentration in feed or the use of unsupported catalysts (i.e., no carrier).
  • British Patent 1,236,230 describes a process for the removal of naphthenic acids from petroleum distillate fractions by processing over supported hydrotreating catalysts without the addition of gaseous hydrogen. No mention is made of controlling water and carbon dioxide partial pressure.
  • Another method for removal of such acids as described in WO96/25471 includes treatment at temperatures of at least about 400°F (204.44°C), preferably at least about 600°F (315.56°C) while sweeping the reaction zone with an inert gas to remove inhibitors indigenous to or formed during the treatment.
  • this approach is debited by the volatilization of some of the naphthenic acids, which are found in distillate and light oil fractions that flash during the thermal treatment.
  • treatment temperatures may be too high for this method to be used in downstream applications where it is desirable to destroy the acids prior to pipestill furnaces, i.e., at temperatures of about 550°F (287.78°C) or below.
  • the instant invention is directed to a method for destroying carboxylic acids in whole crudes and crude fractions.
  • the invention comprises a method for reducing the amount of carboxylic acids in petroleum feeds comprising the steps of (a) adding to said petroleum feed a catalytic agent comprising an oil soluble or oil dispersible compound of a metal selected from the group consisting of Group VB, VIB, VIIB and VIII metals, wherein the amount of metal in said petroleum feed is at least about 5 wppm, (b) heating said petroleum feed with said catalytic agent in a reactor at a temperature of 400 to 800°F (204.44 to 426.67°C), under a hydrogen pressure of 15 psig to 1000 psig (204.75 to 6996.33 kPa) and (c) sweeping the reactor containing said petroleum feed and said catalytic agent with hydrogen-containing gas at a rate sufficient to maintain the combined water and carbon dioxide partial pressure below about 50 psia (about 344.75 kPa).
  • TAN is defined as the weight in milligrams of potassium hydroxide required to neutralize all acidic constituents in one gram of oil. (See ASTM method D-664.)
  • Vacuum bottoms conversion is defined as the conversion of material boiling above 1025°F (551.67°C) to material boiling below 1025°F (551.67°C).
  • Figure 1 is the calculated partial pressure for water as a function of reactor pressure and rate of hydrogen-containing gas sweep for the process of the instant invention.
  • the instant invention removes or destroys carboxylic acids (e.g., naphthenic acids) contained in petroleum feeds such as whole crude oils (including heavy crudes) and fractions thereof such as vacuum gas oil fractions, topped crudes, vacuum resids, atmospheric resids, topped crudes and vacuum gas oil.
  • carboxylic acids e.g., naphthenic acids
  • the instant method reduces TAN by at least about 40% in the petroleum feed.
  • the process is run at temperatures from 400 to 800°F (204.44 to 426.67°C), more preferably 450 to 750°F (232.22 to 398.89°C), and most preferably 500 to 650°F (260.00 to 343.33°C).
  • Hydrogen pressures range from atmospheric to 2000 psig (atmospheric to 13891.33 kPa), preferably 15 psig to 1000 psig (204.75 to 6996.33 kPa), and most preferably 50 psig to 500 psig (446.08 to 3548.83 kPa).
  • the amount of catalyst, calculated as catalyst metal or metals, used in the process ranges from at least about 5, preferably 10 to 1000 parts per million weight (wppm) and most preferably 20 to 500 wppm of the petroleum feed being treated.
  • less than about 40% of the vacuum bottoms component of the feed i.e., the fraction boiling above about 1025°F (551.67°C) is converted to material boiling below about 1025°F (551.67°C) and, more preferably, less than about 30% vacuum bottoms conversion occurs.
  • Catalyst particle size ranges from 0.5 to 10 microns, preferably 0.5 to 5 microns, and most preferably about 0.5 to 2.0 microns.
  • Catalysts are prepared from precursors, also referred to herein as catalytic agents, such as oil soluble or oil dispersible compounds of Group VB, VIB, VIIB, or VIII metals and mixtures thereof. Suitable catalyst metals and metal compounds are disclosed in U.S. Patent No. 4,134,825.
  • An example of an oil soluble compound is the metal salt of a naphthenic acid such as molybdenum naphthenate.
  • oil dispersible compounds are phosphomolybdic acid and ammonium heptamolybdate, materials that are first dissolved in water and then dispersed in the oil as a water-in-oil mixture, wherein droplet size of the water phase is below about 10 microns.
  • a catalyst precursor concentrate is first prepared wherein the oil-soluble or oil- dispersible metal compound(s) is blended with a portion of the process feed to form a concentrate that contains at least about 0.2 wt% of catalyst metal, preferably about 0.2 to 2.0 wt% catalyst metal. See for example U.S. Patent No. 5,039,392 or 4,740,295.
  • the resultant precursor concentrate can be used directly in the process or first converted to a metal sulfide concentrate or an activated catalyst concentrate prior to use.
  • Catalyst precursor concentrate can be converted to a metal sulfide concentrate by treating with elemental sulfur (added to the portion of feed used to prepare the concentrate) or with hydrogen sulfide at 300 to 400°F (148.89 to 204.44°C) for 10-15 minutes (e.g., see U.S. Patent Nos. 5,039,392; 4,479,295; and 5,620,591.
  • the metal sulfide concentrate can be converted into catalyst concentrate by heating at 600 to 750°F (315.56 to 398.89°C for a time sufficient to form the catalyst. (e.g., see U.S. Patent Nos. 5,039,392; 4,740,295; and 5,620,591).
  • the catalyst of the concentrate consists of nano-scale metal sulfide sites distributed on a hydrocarbonaceous matrix that is derived from the oil component of the concentrate. Overall particle size can be varied, but falls within the range of 0.5 to 10 microns, preferably in the range of 0.5 to 5.0 microns and, more preferably, 0.5 to 2.0 microns.
  • the precursor concentrate the metal sulfide concentrate, or the catalyst concentrate.
  • the petroleum feed is mixed with the concentrate to obtain the desired concentration of metal in the feed i.e., at least about 5 wppm, preferably 10 to 1000 wppm.
  • catalyst having a particle size of 0.5 to 10 microns, preferably 0.5 to 5 microns and most preferably 0.5 to 2.0 microns are formed in the heating step of the process in the TAN conversion reactor.
  • Preferred metals include molybdenum, tungsten, vanadium, iron, nickel, cobalt, and chromium.
  • heteropolyacids of the metals can be used.
  • Molybdenum is particularly well suited to the process of the instant invention.
  • Preferred molybdenum compounds are molybdenum naphthenates, dithiocarbamate complexes of molybdenum (e.g., see U.S. Patent No. 4,561,964 ), phosphomolybdic acid and phosphorodithioate complexes of molybdenum (e.g. MOLYVAN® -L, molybdenum di(2-ethylhexyl) phosphorodithioate, supplied by R.T. Vanderbilt Company.
  • MOLYVAN® -L molybdenum di(2-ethylhexyl) phosphorodithioate
  • small particle catalysts that are useful for the practice of the instant process include metals-rich ash from the controlled combustion of petroleum coke (e.g., see U.S. Patent Nos. 4,169,038; 4,178,227; and 4,204,943 ). Finely divided iron based materials, satisfying the particle size constraints noted herein, such as red mud from the processing of alumina can also be used.
  • Water vapor and carbon dioxide resulting from the decomposition of carboxylic acids act as inhibitors for the decomposition of remaining carboxylic acids.
  • Water is a particularly strong inhibitor.
  • a preflash step may be used to remove substantially all of the water.
  • water can have a strong inhibiting effect on the rate of carboxylic acid destruction.
  • Carbon dioxide is also an inhibitor but to a much lower degree.
  • the catalyst can be left in the treated crude (depending on the metal type and concentration) or removed by conventional means such as filtration.
  • Conradson Carbon content of the product i.e., the components of the product that yield coke under pyrolysis conditions.
  • Conradson Carbon in the product is increased relative to that contained in the feed. This effect is illustrated in comparative Examples 5 of Table 2.
  • the growth or increase of Conradson Carbon can be totally inhibited and Conradson Carbon components can be converted to non-Conradson Carbon components.
  • Conradson Carbon conversion will range from 0 to 5%, more preferably, from about from 5 to 20% and, most preferably, from 10 to 40%.
  • This example was carried out in a 300 cc stirred autoclave reactor.
  • the reactor was operated in a batch mode with respect to the crude that was charged. Hydrogen was flowed through the autoclave to maintain constant hydrogen partial pressure and to control the pressure of water and carbon dioxide in the reaction zone.
  • the reactor was charged with 100 g of the Kome/Bolobo blend and 0.61 g. of MOLYVAN®-L * (8.1 wt% Mo), flushed with hydrogen and then pressured to 350 psig (2514.58 kPa) with hydrogen at room temperature. Hydrogen flow was then started through the autoclave at a rate of 0.1 liter/min while maintaining a pressure of 350 psig (2514.58 kPa) by use of a backpressure regulator at the reactor outlet. The reactor was then heated to 625°F (329.44°C) with stirring and was held at 625°F (329.44°C) for 60 minutes at 350 psig (2514.58 kPa).
  • the calculated partial pressures of hydrogen and water** were, respectively, 329 psia (2268.46 kPa) and 13 psia (89.64 kPa).
  • the reactor Upon cooling to 250°F (121.11°C), the reactor was vented and flushed with hydrogen to recover light hydrocarbon products including hydrocarbons that are normally gaseous at room temperature.
  • Example #1 illustrates the degree of TAN conversion obtained when Kome/Bolobo crude blend was heated at 625°F (329.44°C) for one hour in the absence of catalyst and hydrogen.
  • the procedure of Example #1 was repeated except that MOLYVAN®-L was omitted and that the run was carried out with an inert gas sweep at a reactor pressure of 30 psig (308.18 kPa).
  • TAN for the reactor product was 3.40.
  • Example #1 illustrates destruction of TAN in Kome/Bolobo crude (Table 2) using a small amount of a highly dispersed catalyst at relatively mild conditions and with a water partial pressure in the reactor below 20 psia (137.9 kPa). Such treatment provides substantially greater TAN reduction than can be attained by thermal treatment alone at comparable time and temperature (Example #2).
  • the feedstock used in this example was dry Campo-1-Bare crude.
  • Mo was supplied as a catalyst precursor concentrate which was prepared in the following way. A solution of 8 g. of Fisher reagent grade phosphomolybdic acid was dissolved in 92 g. of deionized water. Next, 10 g. of solution was injected into 90 g. of Campo-1-Bare crude while stirring at 176°F (80°C) in a 300 cc Autoclave Engineer's Magnedrive Autoclave. After stirring for 10 minutes at 176°F (80°C), the autoclave was swept with nitrogen and the temperature increased to 300°F (148.89°C) to remove water. The resultant precursor concentrate contained 0.45 wt% Mo.
  • the autoclave was charged with 99.43 g. of dry Campo-1-Bare crude and 0.57 g of precursor concentrate to provide a reactor charge that contained 25 wppm Mo.
  • the reactor was flushed with hydrogen and then pressured to 50 psig (446.08 kPa) with hydrogen sulfide.
  • the reactor pressure was increased to 300 psig (2169.83 kPa) with hydrogen and a flow of hydrogen of 0.12 liters/min. (380 SCF/B) was started through the autoclave. Pressure was maintained by use of a backpressure regulator at the reactor gas-outlet line.
  • Example #3 The procedures of Example #3 were repeated except that the run was carried out at a pressure of 400 psig (2859.33 kPa) and that water was fed to the reactor at the rate of 0.033 g/min. The partial pressure of water in the reactor during the run was about 92 psia (634.34 kPa). There were recovered 0.05 g. of catalyst containing residue, and 96.4 g. of product liquid blend that had a TAN of 0.43 and contained 15.4 wt% Conradson Carbon.
  • Example #4 The procedures of Example #4 were repeated except that catalyst was not added and that the experiment was carried out at 300 psig (2169.83 kPa) with argon as the sweep gas. There was recovered 97.4 g. of product liquid blend that had a TAN of 0.63 and contained 17.9 wt.% Conradson Carbon. Water partial pressure in the reactor was about 92 psia (634.34 kPa).
  • Example #3 The procedures of Example #3 were repeated with the following changes.
  • the reactor was charged with 98.86 g. of crude and 1.14 g. of precursor concentrate which provided a reactor charge that contained 50 wppm Mo.
  • the run was carried out at 750°F (398.89°C) for 62 minutes at 300 psig (2169.83 kPa) with a hydrogen sweep of 0.12 liters/min. (380 SCF/B). Water was fed to the reactor at the rate of 0.017 g./min. to provide a water partial pressure in the reactor of 55 psia (379.22 kPa).
  • Example #6 The procedures of Example #6 were repeated except that the sweep rate of hydrogen was 0.24 liters/min (780 SCF/B), which resulted in a water partial pressure in the reactor of 26 psia (179.27 kPa). There were recovered 0.04 g. of catalyst residue and 96.8 g. of product liquid blend which had a TAN of 0.12, contained 15.4 wt% Conradson Carbon and a kinematic viscosity of 918 centistokes at 104°F (40°C).
  • Example #3 with Example #4 illustrates the inhibiting effect of water on TAN conversion as does the comparison of Example #6 with Example #7, where a decrease in water partial pressure from 55 to 26 psia (379.22 to 179.27 kPa) reduced TAN from 0.31 to 0.12.
  • Comparison of Example #4 with Example #5 illustrates that use of catalyst plus hydrogen, in accordance with the process of this invention, gives higher TAN conversion at a given water partial pressure than can be obtained by thermal treatment in the absence of hydrogen and catalyst TABLE 3 Example No.

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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)

Claims (10)

  1. Procédé de réduction de la quantité d'acides carboxyliques dans une charge pétrolière, comprenant les étapes consistant :
    (a) à ajouter à ladite charge pétrolière un agent catalytique comprenant un composé soluble ou dispersable dans les huiles d'un métal choisi dans les métaux des groupes VB, VIB, VIIB et VIII, la quantité dudit métal ajoutée à ladite charge pétrolière étant d'au moins 5 ppm en poids;
    (b) à chauffer ladite charge pétrolière avec ledit agent catalytique dans un réacteur à une température dans la plage de 204,44 à 426,67°C (400 à 800°F) sous une pression manométrique d'hydrogène de 204,75 à 6996,33 kPa (15 à 1000 psig); et
    (c) à balayer le réacteur contenant ladite charge pétrolière et ledit agent catalytique par un gaz qui contient de l'hydrogène pour maintenir la pression partielle combinée d'eau et de dioxyde de carbone en dessous de 344,75 kPa (50 psia).
  2. Procédé selon la revendication 1, dans lequel ledit agent catalytique comprend un concentré de précurseur de catalyseur d'un composé métallique soluble ou dispersable dans les huiles préparé dans une charge pétrolière choisie parmi les bruts entiers, les bruts étêtés, les résidus atmosphériques, les résidus sous vide, le gasoil obtenu sous vide et leurs mélanges.
  3. Procédé selon la revendication 1, dans lequel ledit agent catalytique comprend un concentré de sulfure métallique d'un composé métallique soluble ou dispersable dans les huiles préparé dans une charge pétrolière choisi parmi les bruts entiers, les bruts étêtés, les résidus atmosphériques, les résidus sous vide, le gasoil obtenu sous vide et leurs mélanges.
  4. Procédé selon la revendication 3, dans lequel le concentré de sulfure métallique est chauffé à une température et pendant une période suffisantes pour former une dispersion de particules de catalyseur de 0,5 à 10 micromètres qui comprennent un composant de sulfure métallique en association avec un solide carboné dérivé de ladite charge pétrolière dans laquelle ledit sulfure métallique est dispersé.
  5. Procédé selon la revendication 1, dans lequel ledit agent catalytique est une dispersion de particules de catalyseur de 0,5 à 10 micromètres qui comprennent un composant de sulfure métallique en association avec un solide carboné dérivé de ladite charge pétrolière.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit métal est choisi parmi le molybdène, le tungstène, le vanadium, le fer, le nickel, le cobalt, le chrome et leurs mélanges.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit composé métallique soluble ou dispersable dans les huiles est un tungstène ou un molybdène hétéropolyacide.
  8. Procédé selon la revendication 7, dans lequel ledit composé métallique soluble ou dispersable dans les huiles est choisi parmi l'acide phosphomolybdique, le naphténate de molybdène et le dialkyl phosphorodithioate de molybdène.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel la pression partielle combinée de l'eau et des oxydes de carbone est maintenue inférieure à 206,85 kPa (30 psia).
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'eau est sensiblement éliminée de la charge pétrolière avant ladite étape de chauffage.
EP98942321A 1997-08-29 1998-08-28 Procede de reduction de l'indice d'acidite total du petrole brut Expired - Lifetime EP1062302B1 (fr)

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US92044797A 1997-08-29 1997-08-29
US920447 1997-08-29
US72764 1998-05-05
US09/072,764 US5914030A (en) 1997-08-29 1998-05-05 Process for reducing total acid number of crude oil
PCT/US1998/018041 WO1999010453A1 (fr) 1997-08-29 1998-08-28 Procede de reduction de l'indice d'acidite total du petrole brut

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CN1894377A (zh) * 2003-12-19 2007-01-10 国际壳牌研究有限公司 生产原油产品的系统,方法和催化剂
BRPI0405572A (pt) * 2003-12-19 2005-08-30 Shell Int Research Métodos de produzir um produto de petróleo bruto e combustìvel de transporte, combustìvel de aquecimento, lubrificantes ou substâncias quìmicas, e, produtos de petróleo bruto
KR101898289B1 (ko) * 2011-01-10 2018-09-13 에스케이이노베이션 주식회사 탄화수소류 유분 내의 유기산을 저감하는 방법
US10195588B1 (en) * 2017-11-28 2019-02-05 Uop Llc Process for making and using iron and molybdenum catalyst for slurry hydrocracking

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US2921023A (en) * 1957-05-14 1960-01-12 Pure Oil Co Removal of naphthenic acids by hydrogenation with a molybdenum oxidesilica alumina catalyst
NO303837B1 (no) * 1994-08-29 1998-09-07 Norske Stats Oljeselskap FremgangsmÕte for Õ fjerne hovedsakelig naftensyrer fra en hydrokarbonolje
CA2212775C (fr) * 1995-02-17 2007-04-17 Exxon Research And Engineering Company Decomposition thermique des acides naphteniques

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DK1062302T3 (da) 2002-04-02
CN1268968A (zh) 2000-10-04
NO20000948D0 (no) 2000-02-25
CA2295917C (fr) 2005-06-07
AU9040498A (en) 1999-03-16
ID24702A (id) 2000-08-03
DE69804026T2 (de) 2002-10-31
DE69804026D1 (de) 2002-04-04
BR9811387A (pt) 2000-08-29
CN1105769C (zh) 2003-04-16
AU733884B2 (en) 2001-05-31
WO1999010453A1 (fr) 1999-03-04
JP2001514300A (ja) 2001-09-11
JP4283988B2 (ja) 2009-06-24
CA2295917A1 (fr) 1999-03-04
RU2184762C2 (ru) 2002-07-10
EP1062302A1 (fr) 2000-12-27
NO20000948L (no) 2000-02-25

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