EP0599702B1 - Procédé d'elimination de mercure et eventuellement d'arsenic dans des hydrocarbures - Google Patents
Procédé d'elimination de mercure et eventuellement d'arsenic dans des hydrocarbures Download PDFInfo
- Publication number
- EP0599702B1 EP0599702B1 EP93402804A EP93402804A EP0599702B1 EP 0599702 B1 EP0599702 B1 EP 0599702B1 EP 93402804 A EP93402804 A EP 93402804A EP 93402804 A EP93402804 A EP 93402804A EP 0599702 B1 EP0599702 B1 EP 0599702B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mercury
- process according
- charge
- catalyst
- per
- 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.)
- Expired - Lifetime
Links
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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
Definitions
- the present invention relates to the removal of mercury and possibly arsenic in hydrocarbons. More specifically the invention relates to a process for which compounds containing mercury in the charge to be treated are converted to elemental mercury, the charge is split into enriched and depleted mercury cuts, then sections containing mercury are cleaned by contact with a mass of mercury capture.
- liquid condensates by-products of the gas production
- some crude oils may contain many trace metal compounds and often in the form of organometallic complexes. These metal compounds are very often poisonous catalysts used during transformations of these cuts into commercial products.
- Mercury is particularly toxic for the activity of precious metals and moreover is a powerful corrosive to aluminum parts, seals and welds.
- Applicant's processes present good performances for the demercurization and the de-arsenification of liquid hydrocarbons serving as feedstocks for various processes treatment.
- Applicant's US Patent 4,911,825 clearly shows the advantage of capturing mercury and possibly arsenic in a two-step process.
- the first step is to contacting the charge in the presence of hydrogen with a catalyst containing at least one metal from the group consisting of nickel, cobalt, iron and palladium.
- Mercury is not (or very little) captured by the catalyst but it is activated on this catalyst so as to be captured, in the second stage, by a mass containing sulfur or compounds sulfur.
- the applicant's patent application WO-90/10684 describes a process for removing mercury and possibly arsenic present in liquid hydrocarbons.
- This invention relates to catalysts having the property of resisting poisoning by sulfur (thioresistance). These new catalysts allow the capture of mercury and arsenic under conditions too severe for the catalysts described in the prior art. They not only contain at least one metal from the group consisting of Ni, Co, Fe, Pd but also at least one metal chosen from the group formed by chromium, molybdenum, tungsten and uranium.
- the object of the present invention relates more precisely to a process for removing mercury and possibly arsenic, in which the mercury of the compounds present in the hydrocarbon charge to purifying is transformed into elemental mercury in a first step.
- the effluent from this stage is divided into at least two defined sections by their initial and final boiling temperatures.
- the enriched cuts in mercury i.e. having a residual content higher than that acceptable for subsequent use, the acceptable content being hereinafter called "maximum admissible content"
- Mercury-depleted cuts, (having a content of mercury less than or equal to the content acceptable for use can be used directly.
- the transformation of compounds containing mercury to elemental mercury is carried out by a catalytic process in the presence of hydrogen.
- Patent application J03026790-A describes a process in which the liquid charge undergoes a heat treatment at least 200 ° C to converting mercury-containing compounds to elemental mercury, then the elemental mercury is captured by a mass of capture of mercury based on metal sulfide (Mo, Co ).
- the method according to the present invention comprises a step to transform mercury compounds into elemental mercury.
- This step is carried out in a temperature range of up to 120 at 400 ° C, more preferably from 130 to 250 ° C and preferably 140-220 ° C.
- the operating pressures will preferably be chosen from 1 to 60 bars and more advantageously from 5 to 40 bars and again more preferred from 15 to 35 bars.
- the flow of hydrogen, when the hydrogen is used, related to the catalyst is for example between 1 and 500 volumes (gas at normal conditions) per volume of catalyst per hour.
- a preferred catalyst is that composed of at least one element M chosen from the group formed by iron, nickel, cobalt, molybdenum, tungsten and palladium.
- Metal M must be in at least reduced form for 20% of its totality, i.e. in the sulphide form at least for 5% of whole.
- nickel, cobalt, tungsten and / or molybdenum Preferably nickel, cobalt, tungsten and / or molybdenum.
- the solid mineral dispersant can be chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays and aluminous cements. It will preferably have a large surface, a sufficient pore volume and an adequate average pore diameter.
- the BET surface should be greater than 50 m 2 / g and preferably between about 100 and 350 m 2 / g.
- the support must have a pore volume, measured by nitrogen desorption, of at least 0.5 cm 3 / g and preferably between 0.6 and 1.2 cm 3 / g and an average pore diameter at least equal. at 70 x 10 -10 m and preferably greater than 80 x 10 -10 m.
- the effluent leaving this stage of transformation of the compounds of mercury to elemental mercury is then split in half or several cuts.
- the light cup (s) is (are) brought into contact at least one mass for capturing mercury in the gas phase or in liquid phase assuming the elemental mercury content is higher than the maximum admissible content.
- cups with an initial boiling temperature above 40 ° C are treated in liquid phase.
- the heaviest fractions (having a boiling temperature higher than 180 ° C for example) are directly valued when their elemental mercury content is lower than the content maximum allowable.
- the maximum allowable elemental mercury content is predetermined value which could have been set by the operator himself, for take into account the effects of corrosion, product quality ... or else may be that set by national regulations, as part of the environmental protection for example.
- elementary mercury is found mainly in the fraction (s) with an initial boiling point lower than 180 ° C and most often less than 160 ° C.
- Splitting is done according to the rules of the skilled person and the operator will choose, according to the production criteria, the number of cuts and cutting points.
- the mercury capture masses in the process of the invention can be all those known to those skilled in the art for the capture of elementary mercury in the hydrocarbon liquid phase. In what concerns the capture of mercury in the gas phase, all the masses of capture of elementary mercury known to the skilled person acceptable. One or more identical collecting masses or different can be used for the same cut or cuts different.
- the volume ratio of the catalyst the capture mass may vary between 1:10 and 5: 1.
- the temperature at which the capture takes place is below 220 ° C, more preferably below 180 ° C and more preferably below 120 ° C.
- the invention applies particularly well to charges containing from 10 -3 to 5 milligrams of mercury per kilogram of charge (mg / kg or ppm) and from 0 to 5 milligrams of arsenic per kilogram of charge and from 0 to 4% total sulfur weight.
- An important advantage of the invention is to allow the use of the calorific energy of the effluent from the stage of transformation of mercury compounds.
- the effluent leaves the transformation stage at a temperature from 120-400 ° C, and more generally from 140-220 ° C.
- this effluent must be cooled before reaching the mercury capture mass, the capture reaction being carried out below 220 ° C and more generally below 120 ° C (a preferred value being of the order of 70 ° C.).
- the outgoing effluent is fractionated. Energy much of the heat required for this operation is provided by the effluent itself.
- the outgoing light fraction (s) that will pass over the mass of capture have temperatures below 220 ° C, more general below 180 ° C and even better below 160 ° C.
- the method according to the invention makes it possible to better integrate the balance sheet thermal.
- Another advantage of the present invention is to reduce the volume of the charge to be treated on the mercury capture mass. So lighter equipment can be provided, resulting in substantial gains investment costs.
- Catalyst Fifteen kilograms of a macroporous alumina support in the form of beads of 1.5-3 mm in diameter and having a specific surface of 160 m 2 / g, a total pore volume of 1.05 cm 3 / g and a macroporous volume (diameter> 0.1 ⁇ m) of 0.4 cm 3 / g is impregnated with 20% by weight of nickel in the form of an aqueous nitrate solution. After drying at 120 ° C for 5 h and thermal activation at 450 ° C for 2 h under air sweep, beads containing 25.4% by weight of nickel oxide are obtained.
- Capture mass Fifteen kilograms of the support used for the preparation of catalyst A are impregnated with 10% by weight of copper in the form of an aqueous solution of copper nitrate trihydrate. After drying at 120 ° C for 5 h and thermal activation at 450 ° C for 2 h under air sweep, beads containing 12.5% by weight are obtained copper oxide. These beads are then impregnated with a solution of 10% by weight of ammonium sulfide. The product is activated at 120 ° C for 2 h under nitrogen flow. This mass was used in the reactor There for all the examples below.
- a reactor was charged with 50 cm 3 of the mass of mercury capture.
- a heavy condensate of liquefied gas with nitrogen is then passed over the collection mass, in ascending flow.
- the charge flow rate is 400 cm 3 / h and that of nitrogen 3.5 l / h.
- the test was carried out at 20 ° C under a pressure of 35 bars.
- the test was conducted for a period of 5 days resulting in very low mercury capture efficiencies, from 27 to 5%. Content arsenic in the effluent was 60 to 75 ⁇ g / kg. So a mass of capture of elemental mercury is not very effective for direct purification gross charges.
- the tests were carried out with two reactors in series: a reactor I in which the catalyst is placed (50 cm 3 ) and a reactor II, after reactor I, in which the capture mass (50 cm 3 ) is placed.
- the catalyst works at 180 ° C and the mass of mercury capture at 20 ° C.
- the flow is ascending in the two reactors.
- the catalyst was reduced to 300 ° C. under a flow rate of 20 l / h of hydrogen at 2 bar of pressure for 6 h.
- the reactor was cooled to the reaction temperature 180 ° C.
- a heavy condensate of liquefied gas with hydrogen is then passed over the catalyst and the effluent obtained is brought into contact with the capture mass.
- the charge flow rate is 400 cm 3 / h and that of hydrogen 3.5 l / h.
- the test was carried out under 35 bars of pressure. The condensate used during this test is identical to that of the previous test.
- the catalyst was loaded into the reactor 1, reduced as indicated above, then cooled to 180 ° C. We do then pass over the catalyst, under conditions identical to those of Example 2, heavy condensate with hydrogen.
- Example 3 shows that, contrary to the simple hypothesis taking into account the boiling point of elementary mercury, integration a step of converting the mercury-containing compounds into elementary mercury (and possibly the arsenic capture), of a fractionation and capture of mercury in light cuts allow to purify all the load by treating only the fractions the lighter from the effluent from the first stage (66.9% of the total charge).
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)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
- un traitement thermique non catalytique (par exemple en chauffant la charge à traiter à une température supérieure à 180 °C) ou catalytique (sans hydrogène) permettant la rupture des liaisons entre le mercure et, par exemple, des radicaux hydrocarbonés et l'obtention de mercure élémentaire et les sous-produits de ces radicaux, ou
- la conversion catalytique en présence d'hydrogène (ou des composés contenant de l'hydrogène naissant), préalablement ajouté dans la charge, permettant l'hydrogénolyse, par exemple, des complexes organomercuriques en mercure élémentaire et des hydrocarbures.
- <60 °C représentant 12,7 % poids de la charge (densité égale à 632 kg/m3), teneur en mercure de 233 µg/kg, arsenic non détecté (< 5 µg/kg)
- de 60 à 160 °C représentant 54,1 % poids de la charge (densité égale à 768 kg/m3), teneur en mercure de 3829 µg/kg, arsenic non détecté, et
- >160 °C représentant 33.1 % poids de la charge (densité égale à 836 kg/m3), mercure et arsenic (< 5 µg/kg) non détecté. (A cause du facteur de dilution nécessaire pour rendre cette coupe acceptable pour la minéralisation, la limite de détection de mercure (< 10 µg/kg) est plus élevée que dans les autres cas.)
- à 20 °C et avec un débit de charge de 100 cm3/h pour la coupe légère (<60 °C) et
- à 70 °C et avec un débit de 400 cm3/h pour la coupe intermédiaire (60 - 160 °C).
Claims (13)
- Procédé d'élimination du mercure dans une charge hydrocarbonée caractérisé en ce qu'il comporte une étape de transformation du mercure contenu dans les composés de la charge en mercure élémentaire, en ce que l'effluent issu de cette transformation est fractionné en au moins deux coupes présentant des teneurs en mercure différentes, en ce que la ou les coupe(s) à point d'ébullition initial inférieur à 180 °C et présentant une teneur en mercure supérieure à la teneur maximale admissible est (sont) mise(s) au contact d'au moins une masse de captation du mercure, la ou les autre(s) coupe(s) n'étant pas nécessairement traitées sur une masse de captation du mercure.
- Procédé selon la revendication 1, caractérisé en ce que l'étape de transformation a lieu entre 120 et 400 °C et sous une pression de 1 à 60 bars.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que l'étape de transformation consiste en un traitement thermique non catalytique.
- Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'étape de transformation consiste en un traitement thermique en présence d'un catalyseur et en l'absence d'hydrogène.
- Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'étape de transformation consiste en une conversion catalytique en présence d'hydrogène, à raison de 1 à 500 volumes de gaz dans les conditions normales par volume de catalyseur par heure.
- Procédé selon l'une des revendications 4 ou 5, caractérisé en ce que le catalyseur comprend au moins un élément M choisi dans le groupe formé par le fer, le nickel, le cobalt, le molybdène, le tungstène et le palladium, et au moins 20 % (en poids) M se trouvant sous forme réduite, le catalyseur comprenant également un support solide choisi dans le groupe formé par l'alumine, les silice-alumines, la silice, les zéolithes, le charbon actif, les argiles et les ciments alumineux.
- Procédé selon l'une des revendications 4 ou 5, caractérisé en ce que le catalyseur comprend au moins un élément M choisi dans le groupe formé par le fer, le nickel, le cobalt, le molybdène, le tungstène et le palladium et au moins 5 % (en poids) de M se trouvant sous forme de sulfure, le catalyseur comprenant également un support solide choisi dans le groupe formé par l'alumine, les silice-alumines, la silice, les zéolithes, le charbon actif, les argiles et les ciments alumineux.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la (ou les) coupe(s) à point d'ébullition initial inférieur à 160 °C est (sont) mise(s) au contact d'au moins une masse de captation du mercure.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la mise au contact avec la (les) masse(s) de captation a lieu à une température inférieure à 220 °C, avec une VVH de 1 à 50 h-1.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le rapport volumique du catalyseur utilisé dans l'étape de transformation à (aux) masse(s) de captation varie entre 1:10 et 5:1.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la charge à traiter renferme de 10-3 à 5 mg de mercure par kg de charge.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la charge à traiter renferme de 0 à 5 mg d'arsenic par kg de charge.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la charge à traiter renferme de 0 à 4 % poids de soufre par kg de charge.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9214224 | 1992-11-24 | ||
FR9214224A FR2698372B1 (fr) | 1992-11-24 | 1992-11-24 | Procédé d'élimination de mercure et éventuellement d'arsenic dans des hydrocarbures. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0599702A1 EP0599702A1 (fr) | 1994-06-01 |
EP0599702B1 true EP0599702B1 (fr) | 1998-04-22 |
Family
ID=9435929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93402804A Expired - Lifetime EP0599702B1 (fr) | 1992-11-24 | 1993-11-18 | Procédé d'elimination de mercure et eventuellement d'arsenic dans des hydrocarbures |
Country Status (7)
Country | Link |
---|---|
US (1) | US5384040A (fr) |
EP (1) | EP0599702B1 (fr) |
JP (1) | JP2630732B2 (fr) |
KR (1) | KR100283602B1 (fr) |
DE (1) | DE69318111T2 (fr) |
FR (1) | FR2698372B1 (fr) |
MY (1) | MY110789A (fr) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6117333A (en) * | 1997-04-22 | 2000-09-12 | Union Oil Company Of California | Removal of hydrocarbons, mercury and arsenic from oil-field produced water |
FR2803597B1 (fr) * | 2000-01-07 | 2003-09-05 | Inst Francais Du Petrole | Procede de captation du mercure et d'arsenic d'une coupe d'hydrocarbures distillee |
US6793805B2 (en) * | 2000-05-05 | 2004-09-21 | Institut Francais du Pétrole | Process for capturing mercury and arsenic comprising evaporation then condensation of a hydrocarbon-containing cut |
RU2389752C2 (ru) * | 2005-02-24 | 2010-05-20 | Джей Джи Си КОРПОРЕЙШН | Установка для удаления ртути из жидкого углеводорода |
US7968063B2 (en) * | 2005-02-24 | 2011-06-28 | Jgc Corporation | Mercury removal apparatus for liquid hydrocarbon |
JP5192653B2 (ja) * | 2006-03-31 | 2013-05-08 | 日本インスツルメンツ株式会社 | 水銀還元用触媒、水銀変換ユニットおよびこれを用いた排気ガス中の全水銀測定装置 |
US7476365B2 (en) * | 2006-04-21 | 2009-01-13 | Saudi Arabian Oil Company | Apparatus for removing mercury from natural gas |
FR2987368B1 (fr) | 2012-02-27 | 2015-01-16 | Axens | Procede d'elimination de mercure contenu dans une charge hydrocarbure avec recycle d'hydrogene |
CA2883357C (fr) | 2012-08-30 | 2021-04-20 | Chevron U.S.A. Inc. | Traitement, procede et systeme d'elimination de metaux lourds presents dans des fluides |
SG11201501705PA (en) | 2012-09-07 | 2015-04-29 | Chevron Usa Inc | Process, method, and system for removing heavy metals from fluids |
US9574140B2 (en) | 2013-03-14 | 2017-02-21 | Conocophillips Company | Removing mercury from crude oil |
AU2014228640B2 (en) | 2013-03-14 | 2017-06-22 | Conocophillips Company | Removing mercury from crude oil |
US9447336B2 (en) | 2013-10-17 | 2016-09-20 | Conocophillips Company | Removing mercury from crude oil using a stabilizer column |
US10179880B2 (en) * | 2014-10-31 | 2019-01-15 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
FR3039164B1 (fr) | 2015-07-24 | 2019-01-25 | IFP Energies Nouvelles | Procede d'elimination de mercure d'une charge hydrocarbonee lourde en amont d'une unite de fractionnement |
FR3039163B1 (fr) | 2015-07-24 | 2019-01-25 | IFP Energies Nouvelles | Procede d'eliminiation du mercure d'une charge en aval d'une unite de fractionnement |
FR3039161B1 (fr) | 2015-07-24 | 2019-01-25 | IFP Energies Nouvelles | Procede de traitement de coupes hydrocarbures comprenant du mercure |
EP3668634B1 (fr) | 2017-08-15 | 2022-11-30 | ConocoPhillips Company | Procédé d'élimination du mercure présent dans du pétrole brut |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2628338B1 (fr) * | 1988-03-10 | 1991-01-04 | Inst Francais Du Petrole | Procede pour l'elimination du mercure dans les hydrocarbures |
JPH0819421B2 (ja) * | 1988-05-16 | 1996-02-28 | 三井石油化学工業株式会社 | 炭化水素系油中の微量水銀類の除去方法 |
US4986898A (en) * | 1988-05-16 | 1991-01-22 | Mitsui Petrochemical Industries, Ltd. | Method of removing mercury from hydrocarbon oils |
JPH0819422B2 (ja) * | 1988-06-14 | 1996-02-28 | 三井石油化学工業株式会社 | 炭化水素系油中の微量水銀類の除去方法 |
JP2578514B2 (ja) * | 1989-03-03 | 1997-02-05 | 三井石油化学工業株式会社 | 液体炭化水素化合物中の水銀の除去方法 |
FR2644472B1 (fr) * | 1989-03-16 | 1991-06-21 | Inst Francais Du Petrole | Procede pour l'elimination du mercure et eventuellement d'arsenic dans les hydrocarbures |
JPH07103377B2 (ja) * | 1989-06-23 | 1995-11-08 | 日揮株式会社 | 液状炭化水素中の水銀除去法 |
JPH0411690A (ja) * | 1990-04-16 | 1992-01-16 | Jgc Corp | 液状炭化水素中の水銀の除去方法 |
JP2887694B2 (ja) * | 1990-04-16 | 1999-04-26 | 日揮株式会社 | 液状炭化水素中の水銀の除去方法 |
JPH0747750B2 (ja) * | 1990-04-27 | 1995-05-24 | 日揮株式会社 | 液状炭化水素中の水銀除去法 |
-
1992
- 1992-11-24 FR FR9214224A patent/FR2698372B1/fr not_active Expired - Lifetime
-
1993
- 1993-01-22 US US08/007,682 patent/US5384040A/en not_active Expired - Lifetime
- 1993-11-18 DE DE69318111T patent/DE69318111T2/de not_active Expired - Lifetime
- 1993-11-18 EP EP93402804A patent/EP0599702B1/fr not_active Expired - Lifetime
- 1993-11-23 KR KR1019930024958A patent/KR100283602B1/ko not_active IP Right Cessation
- 1993-11-24 JP JP5292915A patent/JP2630732B2/ja not_active Expired - Lifetime
- 1993-11-24 MY MYPI93002454A patent/MY110789A/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP0599702A1 (fr) | 1994-06-01 |
MY110789A (en) | 1999-04-30 |
DE69318111T2 (de) | 1998-08-20 |
DE69318111D1 (de) | 1998-05-28 |
US5384040A (en) | 1995-01-24 |
FR2698372A1 (fr) | 1994-05-27 |
JP2630732B2 (ja) | 1997-07-16 |
FR2698372B1 (fr) | 1995-03-10 |
KR100283602B1 (ko) | 2001-05-02 |
JPH06207183A (ja) | 1994-07-26 |
KR940011609A (ko) | 1994-06-21 |
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