WO2006088314A1 - Procede permettant de produire un combustible diesel faiblement aromatique et a tres faible teneur en soufre - Google Patents

Procede permettant de produire un combustible diesel faiblement aromatique et a tres faible teneur en soufre Download PDF

Info

Publication number
WO2006088314A1
WO2006088314A1 PCT/KR2006/000528 KR2006000528W WO2006088314A1 WO 2006088314 A1 WO2006088314 A1 WO 2006088314A1 KR 2006000528 W KR2006000528 W KR 2006000528W WO 2006088314 A1 WO2006088314 A1 WO 2006088314A1
Authority
WO
WIPO (PCT)
Prior art keywords
gasoil
distillate
hydrodesulfurization
straight
less
Prior art date
Application number
PCT/KR2006/000528
Other languages
English (en)
Inventor
Ik Sang Yoo
Myung Jun Kim
In Ho Cho
Cheol Woo Park
Gyoo Tae Kim
Jae Wook Ryu
Jee Sun Shin
Sung Bum Park
Original Assignee
Sk Energy Co., Ltd.
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 Sk Energy Co., Ltd. filed Critical Sk Energy Co., Ltd.
Priority to JP2007556068A priority Critical patent/JP2008530336A/ja
Priority to CN2006800047726A priority patent/CN101120075B/zh
Publication of WO2006088314A1 publication Critical patent/WO2006088314A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0269—Cleaning
    • B21B45/0275—Cleaning devices
    • B21B45/0278—Cleaning devices removing liquids
    • B21B45/0284—Cleaning devices removing liquids removing lubricants
    • 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
    • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B15/0085—Joining ends of material to continuous strip, bar or sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B21B45/06—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing of strip material
    • 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
    • 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
    • C10G45/12—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 containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B15/0007—Cutting or shearing the product
    • B21B2015/0014—Cutting or shearing the product transversely to the rolling direction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B2015/0057—Coiling the rolled product
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/06—Gasoil

Definitions

  • the present invention relates to a process for producing ultra low sulfur diesel fuel through a hydrogen addition catalytic reaction. More particularly, the present invention relates to a process for producing ultra low sulfur and low aromatic diesel fuel, in which the straight-run gasoil effluent from a crude distillation unit is separated to afford a feedstock having properties good enough for it to be treated in a post- hydrodesulfurization process, thereby not only utilizing pre-existing hydrodesulfurizaion units to the maximum, but also significantly reducing aromatic levels.
  • Examples of representative process techniques include a SynSat process developed in the early 1900 to reduce sulfur and aromatic levels, and an HDS-HAD process, developed around 2000 on the basis of HAD (hydro-dearomatization) catalysts.
  • HAD hydro-dearomatization
  • 98-64338 discloses that the sulfur content of straight run gasoil can be lowered to 100 ppm or less by hydro- desulfurization in the presence of a catalyst comprising a mineral support, a Group VIB metal, a Group VIII metal, and phosphorus (step 1), and that if at least part of the steam stripping stream from the effluent of step 1 is allowed to pass, along with hydrogen, through a catalyst bed in which VIII metal and halogen are impregnated into a mineral support, an aromatic content less than 5 vol% and a sulfur content less than 50 ppm (preferably, 10 ppm) can be achieved.
  • a catalyst comprising a mineral support, a Group VIB metal, a Group VIII metal, and phosphorus
  • U. S. Pat. No. 6,824,673 discloses a process for producing diesel having a sulfur content of 10 wppm or less and a total aromatic amount of 15 wt% or less.
  • This process aiming to overcoming the problem of conventional hydrodesulfurization/aromatic saturation processes that require high pressures for operation, comprises the treatment of a distillate feedstock in a first hydrodesulfurization stage in the presence of a hydrogen-containing treatment gas and a hydrodesulfurization catalyst to partially desulfurize the feedstock.
  • the stripped liquid phase stream is then treated in a second hydrodesulfurization stage, also in the presence of a hydrogen-containing treatment gas and a hydrodesulfurization catalyst.
  • the stripped liquid phase stream After being transferred to an aromatic hydrogenation stage, the stripped liquid phase stream is reacted with a hydrogen-containing treatment gas in the presence of an aromatic hydrogenation catalyst to hydrogenate the aromatics thereof.
  • This process requires the addition of many process stages and considerably alters pre-existing processes, thus not overcoming the problem of conventional processes in terms of process convenience and economic benefit.
  • straight run gasoil which is used as hydrodesulfurization process feedstock
  • straight run gasoil which is used as hydrodesulfurization process feedstock
  • the present inventors developed an effective design in which distillates having a certain boiling point or lower are separated from the straight run gasoil and used as hydrodesulfurization process feedstock while the residual heavy distillates of high boiling points are produced into half-finished diesel products.
  • the present invention provides a process for producing low aromatic and ultra low sulfur diesel fuel, comprising: a) separating the straight-run gasoil effluent from a crude distillation unit into distillates on the basis of a cut point set in a range from 320 to 36O 0 C; b) subjecting the distillates with the cut point or less to hydrodesulfurization in the presence of a hydrodesulfurization catalyst under a condition including a pressure of 30-80 kg/cm 2 , a temperature of 320-38O 0 C, a liquid hourly space velocity of 0.1-2.0 hr "1 , and an H 2 /oil ratio of 150-1000 Nm 3 /kl; and c) recovering a gas oil distillate that has undergone the hydrodesulfurization of step b).
  • the process further comprisesireforming at least a part of the gasoil distillate having a boiling point exceeding the cut point by means of selective hydrocracking; nitrogen adsorption/dewaxing/hydrodesulfurization; or hydro-desulfurization/dewaxing processes; and separating a light gasoil distillate from a stream obtained after the reforming step and pooling the diesel distillate with the light gasoil distillate obtained in step b).
  • the distillate remainder after the separation of diesel distillate from the stream effluent from the post-treatment process can be used as feedstock for other processes.
  • the process in accordance with the present invention brings about a significant reduction in aromatic levels as well as achieving the ultra low sulfur level meeting the standard imposed by advanced nations.
  • the process of the present invention enjoys the advantage of maximally utilizing pre-existing deep sulfurization process facilities and requiring minimal investment therein, requiring neither major modification of preexisting process facilities nor the addition of new process facilities.
  • the present invention can decrease the reaction temperature required for the achievement of a predetermined sulfur level, thereby extending the life span of the catalyst used and reducing the hydrogen amount consumed. Further, a distillate with boiling points exceeding the cut point can be converted into clean half-finished diesel products through suitable reforming processes, as well.
  • FIG. 1 is a conceptual view showing a process for treating straight-run gasoil in a separate process so as to maximize the efficiency of a post-process in accordance with the present invention
  • FIG. 2 is a graph in which the distribution of nitrogen compounds in straight run gasoil is plotted against boiling points
  • FIG. 3 is a schematic process view showing a strategy for reforming a gasoil distillate separated from the straight-run gas oil at a boiling point exceeding the cut point through a selective hydrocracking process in accordance with an embodiment of the present invention
  • FIG. 4 is a schematic process view showing a strategy for reforming a gasoil distillate separated from the straight-run gas oil at a boiling point exceeding the cut point through nitrogen adsorption/dewaxing/hydro-desulfurization processes in accordance with another embodiment of the present invention
  • FIG. 5 is a schematic process view showing a strategy for reforming a gasoil distillate separated from the straight-run gas oil at a boiling point exceeding the cut point through hydro-desulfurization/dewaxing processes in accordance with a further embodiment of the present invention
  • FIG. 6 is a graph in which saturation rates of mono-aromatic compounds in a base distillate and a 340°C-distillate are plotted against reaction temperatures, obtained in Example 3;
  • FIG. 7 is a graph showing saturation rates of mono-aromatic compounds in a base distillate, a 340°C-distillate and a 360°C-distillate, obtained in Example 3; and FIG. 8 is a graph in which saturation rates of mono-aromatic compounds are plotted against reaction temperatures according to the CoMo catalyst and the CoMo- NiMo [90- 10] catalyst, obtained in Example 4.
  • HDC selective hydrocracking
  • the present invention is, as described above, developed on the basis of the unexpected finding that the properties of feedstock, especially the heavy components of straight run gasoil, greatly influence the saturation or hydrogenation of aromatics as well as the reduction of sulfur levels under deep desulfurization conditions. Accordingly, the distillation properties of feedstock are optimized so as to overcome the problems of conventional processes, that is, the huge investment requirement and increased operation costs, and to maximally utilize preexisting deep desulfurization units, and the inevitable loss of diesel fuel is effectively compensated for by introducing a new process to produce clean diesel (half-finished) products having sulfur and aromatic levels meeting the standard of WWFC Category 4, thereby compensating for the inevitable loss of diesel.
  • FIG. 1 shows distribution properties of nitrogen (N) compounds in straight run gasoil plotted against boiling points.
  • straight run gasoil of the distillates obtained from CDU upon fractional distillation usually has a boiling point from about 200 to 460°C, and typically from about 200 to 390°C, according to the ASTM D 86 standard.
  • straight run gasoil preferably contains sulfur in an amount of about 2.0 wt% and has a nitrogen content of about 400 ppm or less.
  • hydrodesulfurization reaction or process means a reaction or process which is effected with hydrogen-containing treatment gas in the presence of a catalyst able to remove hetero-atoms, particularly sulfur and nitrogen atoms, from feedstock, and to hydrogenate aromatics.
  • RS compound serving as classification standards for refractory sulfur (RS) compounds based on the dibenzothiophene (DBT) structure
  • DBT dibenzothiophene
  • distribution properties over a TBP(true boiling point) cut range of each group of methyl substitutes are important factors to determine temperature criteria for separating straight-run gasoil.
  • RS compound are dibenzothiophene derivatives such as A- methyl dibenzothiophene, 4,6-dimethyl dibenzothiophene, etc.
  • DBTs having one or no methyl substitutes (IC- DBTs) are very easy to desulfurize and are distributed at 32O 0 C or less on the basis of fractional distillation.
  • DBTs are distributed predominantly within a temperature range from about 320 to 34O 0 C when two methyl substitutes (2C-DBTs) are present, within a temperature range from about 340 to 36O 0 C when three methyl substitutes (3C-DBTs) are present, and within a temperature range higher than 36O 0 C if four or more methyl substitutes are present.
  • straight-run gasoil is divided into straight-run light gasoil and straight-run heavy gasoil typically on the basis of a boiling point of 38O 0 C.
  • straight-run light gasoil may be divided into distillates having boiling points not less than and not more than the chosen boiling point (that is, cut point).
  • the distillate exceeding the chosen boiling point is a mixture of a heavy distillate of the straight-run light gasoil and the straight-run heavy gasoil, and is subjected to a separate post-reformation process.
  • straight-run light gasoil is divided into distillates having boiling points not less than and not more than the chosen boiling point.
  • the distillate exceeding the chosen boiling point is subjected to a separate post-reformation process.
  • the distillates below the chosen boiling point can be hydrodesulfurized in a deep desulfurization condition using pre-existing process units. Meanwhile, at least part of the distillates exceeding the chosen boiling point are treated in a separate post-reformation unit.
  • this strategy according to the present invention can greatly reduce the required facility investment compared to conventional process techniques, thereby solving the economic problem of total additional investment.
  • the cut point which is the criteria for dividing straight-run gasoil, is set at a maximum of about 36O 0 C, in consideration of the distillation properties of straight-run gasoil. If necessary, the cut point may be decreased down to about 32O 0 C. Therefore, the cut point is preferably set in the range from about 320 to 360 0 C. When account is taken of the distribution properties of RS compounds, the cut point is more preferably set at about 340 0 C.
  • Such deep desulfurization conditions may include a reaction pressure of 30-80 kg/cm 2 , a reaction temperature of about 320-38O 0 C, a liquid hourly space velocity (LHSV) of about 0.1-2.0 hr "1 , and an H 2 /oil ratio of about 150-1000 Nm 3 /kl.
  • LHSV liquid hourly space velocity
  • the deep desulfurization of the distillate below the cut point is performed at a reaction pressure of about 50-70 kg/cm 3 , a reaction temperature of about 350 ⁇ 370°C, an LHSV of about 0.5-1.0 hr '1 , and an H 2 /0U ratio of 300-500 Nm 3 /kl.
  • the hydrodesulfurization is conducted to reduce sulfur levels below 10 ppm and preferably below 5 ppm.
  • the distillate obtained below the boiling point can be reduced in sulfur level to 5 ppm or less, and to as low as 1-2 ppm in some case.
  • the reaction temperature necessary for the reduction of sulfur levels to meet the criterion can be decreased by 18 0 C or more.
  • a typical catalyst for use in hydrodesulfurization comprises a porous refractory support (e.g., ⁇ -alumina, silica, zeolite, or combinations thereof) on which a first metal component, identified as Mo and a second metal component, selected from a group consisting of Co, Ni, W, and combinations thereof, are deposited.
  • the first metal component is used in an amount of about 10-30 wt% based on the total weight of the catalyst and preferably in an amount of about 12-20 wt%, while the second metal component amounts to about 2-10 wt%, and more preferably to about 3 ⁇ 7 wt% of the catalyst weight.
  • the second metal component of the catalyst preferably comprises a combination of two or more metal ingredients, for example, CoMo-NiMo or CoMo- NiW, rather than a single ingredient.
  • the second metal component is composed of a single ingredient (for example, CoMo)
  • the distillates separated below a certain cut point have multi-ring aromatics, such as di- or more ring aromatics, decreased to 2 wt% or less, which is expected to be the standard for multi-ring aromatic levels in the future.
  • the distillates obtained at the chosen boiling point or less can be allowed to contain sulfur in an amount of 5 ppm or less and aromatics in an amount of 15 wt% or less when they are subjected to hydrodesulfurization under a deep desulfurization conditions.
  • the distillates obtained at boiling points exceeding the chosen cut point are transferred into post-reformation processes where ultra low sulfur and low aromatic diesel fuels can be produced. These reforming processes can be effected through the three embodiments illustrated below. In this regard, FIGS.
  • 3 to 5 suggest a selective hydrocracking process, a nitrogen adsorption/dewaxing/hydrodesulfurization process, and a hydrodesulfurization/dewaxing process, respectively, through which the gasoil distillates that obtained straight-run gasoil at boiling points higher than a predetermined cut point can be reformed.
  • Crude oil 1, 11, 21 is split into the components thereof in a crude distillation unit 100, 110, 120 according to boiling point by fractional distillation. While distillates 2, 12, 22 lighter than straight-run gasoil and distillates 5, 15, 25 heavier than straight-run gasoil are additionally separated, the distillate 3, 13, 23 obtained at or below a cut point from the straight-run gasoil is transferred to a hydrodesulfurization unit 101, 111, 121 operating under deep desulfurization conditions. The distillate 6, 16, 26 effluent from the hydrodesulfurization unit is recovered and carried into a diesel storage unit 103, 113, 123.
  • distillate 4, 14, 24 having a boiling point higher than the cut point is converted into higher valued fractions through a post-reformation process.
  • as much distillate as possible is reformed into diesel fuel which meets the required low aromatic and ultra low sulfur standards and is then pooled, along with the distillate 6, 16, 26, in the diesel storage unit.
  • a (hydro)dewaxing process may be conducted as shown in FIGS. 4 and 5. Representative reaction conditions in the selective hydrocracking unit 102, the nitrogen adsorption/dewaxing/hydrodesulfurization unit 112, and the hydrodesulfurization/dewaxing unit 122 are summarized in Table 2, below.
  • a conventional silica-alumina or zeolite based catalyst may be used.
  • a conventional silica gel, silica-alumina, or zeolite based adsorbent may be used.
  • a conventional zeolite-based catalyst may be used.
  • the above-mentioned hydrodesulfurization catalyst may be used.
  • a hydrotreating or hydrofinishing process may be further performed before or after the post-reformation process, so as to improve the color or stability of the product.
  • FIG. 7 shows saturation rates of mono-aromatic compounds in each of the base distillate, the 340°C-distillate, and the 360°C-distillate.
  • the hydrogenation conversion rate of aromatic compounds increases as the distillation temperature of the straight-run gasoil decreases.
  • the increase of the hydrogenation conversion rate somewhat slowed in the range from 36O 0 C to 34O 0 C. It is believed that the slow increase rate is attributed to the hydrogen reactivity limit of the CoMo catalyst.
  • the temperature at each step is determined by the inlet temperature and H 2 quench rates in consideration of the caloric value in each reactor, because the reaction in each reactor is exothermic.
  • the reaction temperature is the weight average bed temperature (WABT) of each reactor.
  • Hydrotreating or hydrof ⁇ nishing step This may be performed at low temperatures using a conventional heat exchange net in order to improve the coloration and stability of the product.
  • Example 1 In order to examine whether nitrogen ingredients could be effectively removed from the distillate obtained from the straight-run gasoil at higher than the cut point or more by adsorption as shown in FIG. 4, the 340°C+(l)distillate prepared in Example 1 was treated with modified silica adsorbent under the conditions of temperature of 70°C, LHSV of 1.5 hr "1 , and pressure of 7 kg/cm 2 . The rate of removal of nitrogen from the distillate was measured to be 78% (total nitrogen level reduced from 526 ppm to 116 ppm).
  • Example 5 the same condition as in Example 5, except for hydrogen partial pressure.

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)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Le procédé décrit en repose sur la constatation que la réactivité de l'hydrogénation avec les composants aromatiques, ainsi que la réactivité de la désulfuration, sont étroitement corrélées avec les caractéristiques de distillation d'une charge d'alimentation de francs de distillation. Ce procédé permet de séparer l'effluent de gazole d'une unité de distillation de brut de manière à permettre l'obtention d'une charge d'alimentation présentant des propriétés suffisamment bonnes pour permettre son traitement par un processus de post-hydrodésulfuration, ce qui non seulement permet une exploitation maximale des unités d'hydrodésulfuration préexistantes, mais permet également de réduire de manière notable les taux d'aromatiques. Ce procédé permet de produire un combustible diesel respectant la norme WWFC catégorie 4, tout en requérant le minimum possible d'investissements dans de nouvelles installations.
PCT/KR2006/000528 2005-02-17 2006-02-15 Procede permettant de produire un combustible diesel faiblement aromatique et a tres faible teneur en soufre WO2006088314A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2007556068A JP2008530336A (ja) 2005-02-17 2006-02-15 低芳香族且つ超低硫黄軽油の製造方法
CN2006800047726A CN101120075B (zh) 2005-02-17 2006-02-15 生产超低硫和低芳族柴油燃料的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2005-0013261 2005-02-17
KR1020050013261A KR101156370B1 (ko) 2005-02-17 2005-02-17 저방향족 및 초저유황 경유를 제조하는 방법

Publications (1)

Publication Number Publication Date
WO2006088314A1 true WO2006088314A1 (fr) 2006-08-24

Family

ID=36916686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2006/000528 WO2006088314A1 (fr) 2005-02-17 2006-02-15 Procede permettant de produire un combustible diesel faiblement aromatique et a tres faible teneur en soufre

Country Status (4)

Country Link
JP (1) JP2008530336A (fr)
KR (1) KR101156370B1 (fr)
CN (1) CN101120075B (fr)
WO (1) WO2006088314A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008083094A1 (fr) * 2006-12-29 2008-07-10 Uop Llc Procédé de conversion d'hydrocarbures
EP2447340A1 (fr) * 2010-10-28 2012-05-02 IFP Energies Nouvelles Procédé de reformage de coupes hydrocarbonées
WO2013070566A1 (fr) * 2011-11-09 2013-05-16 Exxonmobil Research And Engineering Company Production de distillats de faible point de trouble
WO2013019586A3 (fr) * 2011-07-29 2013-07-11 Saudi Arabian Oil Company Hydrotraitement de courants d'hydrocarbures avec extraction des aromatiques
WO2013019585A3 (fr) * 2011-07-29 2013-07-11 Saudi Arabian Oil Company Procédé intégré d'isomérisation et d'hydrotraitement
US20150182952A1 (en) * 2013-12-18 2015-07-02 Lorena ALVAREZ CONTRERAS OBTENTION OF LOW LOADING CATALYSTS FOR DEEP HYDROCARBONS HYDRODESULFURIZATION BASED OF CoMoS, WITH NiMoS HYDRODENITROGENANT ADDITIVE, SUPPORTED ON THREE-DIMENSIONAL NANOSTRUCTURED MESOPOROUS MATERIALS
US10047305B2 (en) 2012-12-10 2018-08-14 Total Marketing Services Method for obtaining hydrocarbon solvents with boiling point above 300°C. and pour point lower than or equal to −25°C

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101133369B1 (ko) * 2007-08-24 2012-04-06 에스케이이노베이션 주식회사 유동층 접촉 분해 유분으로부터 청정 석유제품 및 방향족제품을 제조하는 방법
CN102041089A (zh) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 一种生产低硫和超低硫柴油的加氢处理方法
WO2013019587A2 (fr) * 2011-07-29 2013-02-07 Saudi Arabian Oil Company Procédé intégré d'hydrotraitement et d'isomérisation à séparation des aromatiques
KR102398989B1 (ko) 2020-04-01 2022-05-18 한국기초과학지원연구원 탄화수소 유분으로부터 황화합물을 제거하는 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042716A (en) * 1996-12-20 2000-03-28 Institut Francais Du Petrole Process for transforming a gas oil cut to produce a dearomatised and desulphurised fuel with a high cetane number
US20040045870A1 (en) * 2000-11-11 2004-03-11 Johannes Wrisberg Hydroprocessing process and method of retrofitting existing hydroprocessing reactors
US6736963B2 (en) * 2001-07-31 2004-05-18 Bp Corporation North America Inc. Multiple stage process for removal of sulfur from components for blending of transportation fuels
US6824673B1 (en) * 1998-12-08 2004-11-30 Exxonmobil Research And Engineering Company Production of low sulfur/low aromatics distillates
US20050029161A1 (en) * 1998-04-09 2005-02-10 Marcel Aussillous Process for improving the cetane number of a gas oil cut

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0649873B2 (ja) * 1990-06-15 1994-06-29 日揮株式会社 軽油の脱硫方法
WO2002040617A1 (fr) * 2000-11-17 2002-05-23 Jgc Corporaton Procédé de désulfuration de fraction gazole, gazole désulfuré, et désulfurant pour fraction gazole

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042716A (en) * 1996-12-20 2000-03-28 Institut Francais Du Petrole Process for transforming a gas oil cut to produce a dearomatised and desulphurised fuel with a high cetane number
US20050029161A1 (en) * 1998-04-09 2005-02-10 Marcel Aussillous Process for improving the cetane number of a gas oil cut
US6824673B1 (en) * 1998-12-08 2004-11-30 Exxonmobil Research And Engineering Company Production of low sulfur/low aromatics distillates
US20040045870A1 (en) * 2000-11-11 2004-03-11 Johannes Wrisberg Hydroprocessing process and method of retrofitting existing hydroprocessing reactors
US6736963B2 (en) * 2001-07-31 2004-05-18 Bp Corporation North America Inc. Multiple stage process for removal of sulfur from components for blending of transportation fuels

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008083094A1 (fr) * 2006-12-29 2008-07-10 Uop Llc Procédé de conversion d'hydrocarbures
EP2447340A1 (fr) * 2010-10-28 2012-05-02 IFP Energies Nouvelles Procédé de reformage de coupes hydrocarbonées
FR2966836A1 (fr) * 2010-10-28 2012-05-04 IFP Energies Nouvelles Procede de reformage de coupes hydrocarbonees.
US9023194B2 (en) 2010-10-28 2015-05-05 IFP Energies Nouvelles Process for reforming hydrocarbon cuts
CN103827265B (zh) * 2011-07-29 2016-08-17 沙特阿拉伯石油公司 芳族抽提烃流的加氢处理
WO2013019586A3 (fr) * 2011-07-29 2013-07-11 Saudi Arabian Oil Company Hydrotraitement de courants d'hydrocarbures avec extraction des aromatiques
WO2013019585A3 (fr) * 2011-07-29 2013-07-11 Saudi Arabian Oil Company Procédé intégré d'isomérisation et d'hydrotraitement
CN103827265A (zh) * 2011-07-29 2014-05-28 沙特阿拉伯石油公司 芳族抽提烃流的加氢处理
US10351785B2 (en) 2011-07-29 2019-07-16 Saudi Arabian Oil Company Integrated isomerization and hydrotreating apparatus
US10100261B2 (en) 2011-07-29 2018-10-16 Saudi Arabian Oil Company Integrated isomerization and hydrotreating process
WO2013070566A1 (fr) * 2011-11-09 2013-05-16 Exxonmobil Research And Engineering Company Production de distillats de faible point de trouble
US9028673B2 (en) 2011-11-09 2015-05-12 Exxonmobil Research And Engineering Company Production of low cloud point distillates
US10047305B2 (en) 2012-12-10 2018-08-14 Total Marketing Services Method for obtaining hydrocarbon solvents with boiling point above 300°C. and pour point lower than or equal to −25°C
US10836968B2 (en) 2012-12-10 2020-11-17 Total Marketing Services Method for obtaining hydrocarbon solvents with boiling point above 300° C. and pour point lower than or equal to −25° C
US20150182952A1 (en) * 2013-12-18 2015-07-02 Lorena ALVAREZ CONTRERAS OBTENTION OF LOW LOADING CATALYSTS FOR DEEP HYDROCARBONS HYDRODESULFURIZATION BASED OF CoMoS, WITH NiMoS HYDRODENITROGENANT ADDITIVE, SUPPORTED ON THREE-DIMENSIONAL NANOSTRUCTURED MESOPOROUS MATERIALS

Also Published As

Publication number Publication date
CN101120075B (zh) 2011-11-16
KR20060091990A (ko) 2006-08-22
CN101120075A (zh) 2008-02-06
KR101156370B1 (ko) 2012-06-13
JP2008530336A (ja) 2008-08-07

Similar Documents

Publication Publication Date Title
WO2006088314A1 (fr) Procede permettant de produire un combustible diesel faiblement aromatique et a tres faible teneur en soufre
Song An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel
US6972086B2 (en) Process comprising two gasoline hydrodesulfurization stages and intermediate elimination of H2S formed during the first stage
US8632675B2 (en) Co-processing of diesel biofeed and heavy oil
CA2880515C (fr) Hydrocraquage de residus
CA2931187C (fr) Hydrocraquage des gas-oils a un rendement de produits distilles accru
WO2005118749A1 (fr) Procede de desulfuration et de deparaffinage d'une charge d'hydrocarbures presentant une temperature d'ebullition situee dans la plage d'ebullition du gazole
KR20080058417A (ko) 수소처리 및 수소화 분해 방법 및 장치
KR20020068369A (ko) 탄화수소 원료로부터 황을 제거하는 방법
WO2012003272A1 (fr) Procédé pour la préparation d'huiles de base de lubrifiant de groupe ii et de groupe iii
EP2751227A2 (fr) Raffinage intégré de brut avec formation réduite de coke
CN106147839B (zh) 一种降低汽油硫含量的方法
CN114929842A (zh) 用于改进馏出物的冷流性质的经改性的超稳定y(usy)沸石催化剂
CN112601802B (zh) 0℃下无浑浊重质基础油和用于生产的方法
CA2292314C (fr) Un procede de production de carburants diesels de qualite superieure et de point de solidification bas a partir d'huiles de fractionnement
US6447673B1 (en) Hydrofining process
CA2853924A1 (fr) Pretraitement de naphtas de craquage catalytique fluide (fcc) et hydrotraitement selectif
CA2402126C (fr) Production de distillats a faible teneur en soufre et en composes aromatiques
Boumendjel et al. Hazy-free at 0 C heavy base oil and a process for producing
JP2000313891A (ja) 燃料油の脱硫方法および燃料油の脱硫システム
JP2002146365A (ja) 脱硫軽油の製造方法および脱硫軽油
CN118146834A (zh) 一种清洁柴油的生产方法
CA2960404A1 (fr) Configuration de catalyseur visant a ameliorer l'activite d'hydrocraquage

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2007556068

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 200680004772.6

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 3599/CHENP/2007

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06715979

Country of ref document: EP

Kind code of ref document: A1