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
  • 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
  • C10G45/60—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 characterised by the catalyst used
  • C10G45/64—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 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • 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
  • C10G2300/70—Catalyst aspects
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

• the present invention relates to a process for treating diesel fuel charges in order to be able to extract more recoverable products therefrom than by the usual treatments.
• the present invention relates to a particular combination of two treatments of diesel fuel charges in order to promote the production of diesel and petrol.
• Heavy gas oils (vacuum distillation, VGO, or 370 to 540 ° C cut gas) were generally sent directly to the catalytic cracking unit in order to convert them into lighter, highly recoverable hydrocarbons; however, it is desirable to try to make the best possible use of all the constituents of gas oils, whether they come from atmospheric distillation or from vacuum distillation. We have also realized in recent years, that it was possible to treat gas oils before sending them to catalytic cracking so as to recover many more recoverable products than by catalytic cracking alone.
• Gas oils can also be subjected to a process to remove waxy paraffinic hydrocarbons. This leads to lowering the cloud point of gas oils.
• the present invention relates to a process for the treatment of boiling hydrocarbons in the range of heavy gas oils so as to increase the recovery of light hydrocarbons.
• the present invention also relates to a process for the treatment of heavy gas oils in two stages making it possible to increase the production of diesel oil and of petrol relative to the quantity generally recoverable by catalytic cracking of the same charge.
• the present invention also relates to a process which makes it possible to treat hydrocarbons having a boiling point of between approximately 370 ° C. and 540 ° C. so as to obtain a significant quantity of variable light hydrocarbons.
• the Applicant has unexpectedly found that by first subjecting the charge of boiling hydrocarbons in the range of heavy gas oils to a treatment to remove waxy paraffinic hydrocarbons, by passing over a polymorphic crystalline silica of the silicalite type in appropriate conditions, and subjecting the resulting charge to a light hydrocracking a production of light hydrocarbons was obtained, in particular diesels and gasolines, in quantities clearly improved compared to what could reasonably be expected.
• the fillers used for the process of the invention are heavy gas oils, or vacuum distillation gas oils (VGO), comprising the fraction of hydrocarbons having a boiling point of 370 to 540 ° C. approximately. These feedstocks can contain at most 25% of hydrocarbons having a boiling point below 370 ° C.
• VGO vacuum distillation gas oils
• the process of the invention is particularly suitable for heavy diesel fillers containing significant sulfur contents as high as 4% (by weight).
• a preferred application of the invention lies in the treatment of fillers containing more than about 1% of sulfur.
• a silicalite is used, that is to say a polymorphous crystalline silica which has no exchange capacity compared to zeolites.
• Aluminum can be present in these catalysts, but only in the form of impurities originating from the starting materials and in particular from the source of silica used. The methods for obtaining these materials are given in US Patent 4,061,724 to Grose and Flanigen.
• Silicalites are microporous materials prepared hydrothermally using a reaction mixture comprising tetrapropylammonium cations, alkali metal cations, water and a source of reactive silica.
• a silicalite having pores of about 0.55 nm, and being in the form of crystallites of size less than 8 microns.
• the step of removing waxy paraffinic hydrocarbons can be carried out in any device comprising a reaction zone containing the catalyst of the silicalite type.
• the Applicant has surprisingly found that by subjecting the charge resulting from the first step directly to a light hydrocracking, a final charge containing light hydrocarbons was obtained in significantly greater quantities than that which could be obtained. hope.
• the light hydrocracking reaction is carried out on a conventional light hydrocracking catalyst.
• a conventional light hydrocracking catalyst By way of example, there may be mentioned a Ni-Mo catalyst deposited on alumina and silica, prepared by incorporation of Ni and Mo in the form of oxide followed by drying and then by treatment with sweeping of a mixture of hydrogen and H2S (1-2% vol.) first at 200-250 ° C then up to 320-350 ° C.
• This catalyst can also be partially replaced by a Co-Mo catalyst deposited on alumina, prepared in a similar manner.
• these catalysts In their form oxide, these catalysts generally contain from 3 to 6% by weight of NiO or CoO, and from 10 to 20% by weight of MoO3; they have a specific surface generally between 150 and 300 m2 / g and the pore volume is generally between 0.3 and 0.6 ml / g. These catalysts are commercially available in oxide form.
• the reactions can be carried out in two reactors arranged in cascade and under temperature and pressure conditions which need not necessarily be identical, the Applicant has found that the two reactions could be carried out in the same reactor. proportion different catalysts plays a certain role in obtaining interesting results. Thus, the Applicant has found that 15 to 25% by volume of silicalite should be used, relative to the total catalyst and 85 to 75% by volume of light hydrocracking catalyst.
• the catalysts can be arranged in one or more layers which can be surrounded by layers of inert materials.
• the two stages of the process are carried out in the same reactor, and the various catalysts are thus arranged in several beds, the first bed encountered being constituted by a polymorphic crystalline silica of the type silicalite.
• the charge is passed through the reaction zone containing the catalysts at a temperature between 350 and 450 ° C, and preferably between 380 and 420 ° C, under a pressure between atmospheric pressure and 80 bars, and preferably between 35 and 65 bars, and at an hourly liquid space velocity (LHSV) of between 0.1 and 20 l / l (calculated with respect to all the catalysts), preferably between 0.5 and 5 l / l.
• LHSV hourly liquid space velocity
• hydrogen is introduced into the reaction zone, in an amount such that the hydrogen / hydrocarbon volume ratio is between 50 and 5000 and preferably between 250 and 1000 (the volume of the hydrogen being measured in gaseous state and under standard conditions).
• the hydrogen / hydrocarbon volume ratio is between 50 and 5000 and preferably between 250 and 1000 (the volume of the hydrogen being measured in gaseous state and under standard conditions).
• the gas recovered at the outlet of the reactor is generally recycled.
• part of the recycled gas is permanently drawn off and replaced by hydrogen.
• the Applicant has also observed a synergistic effect by achieving another embodiment of the process of the invention, in which the load is subjected to a light hydrocracking before the removal of the waxy paraffinic hydrocarbons.
• this effect is notably weaker than when light hydrocracking constitutes the second stage of the process, but the quality of the cut 250-370 ° C is better.
• the catalyst for removing the waxy paraffinic hydrocarbons and the light hydrocracking catalyst are mixed. Intermediate values of the conversion rates and of the properties of the cut 250-370 ° C. are obtained.
• Silicalite (Union Carbide; pore size of approximately 0.55 nm, and crystallites of less than 8 ⁇ m) were used as catalysts, and a Ni-Mo catalyst on Al2O3 / SiO2 having the following properties: - specific surface: 153 m2 / g - pore volume: 0.53 ml / g - NiO: 3.6% by weight - MoO3: 19.6% by weight.
• the latter catalyst was pretreated by subjecting it to drying at 130 ° C.
• the sulfurized Ni-Mo catalyst contained about 10% by weight of sulfur.
• a 2.5 cm inside diameter reactor was filled with 20% by volume (i.e. 7 cm in height) of silicalite and 80% by volume (i.e. 28 cm in height) of Ni-Mo catalyst, all between two layers inert material (each 40 cm high).
• a charge of hydrocarbons was passed into the reactor in normal mode, the charge successively passing through the silicalite, then the Ni-Mo.
• the feed is a vacuum distillation gas oil having the following properties: - fraction ⁇ 180 ° C 0.10% by weight - fraction 180-250 ° C 2.55% by weight - fraction 250-370 ° C 18.39% by weight - fraction 370-500 ° C 64.55% by weight - fraction 500 + ° C 14.41% by weight - density d 15/4 : 0.91 - sulfur content: 1.42% by weight - total nitrogen 1010 ppmp - basic nitrogen 267 ppmp
• the refinery hydrogen (called “pure” but containing about 85% hydrogen) was passed at a partial hydrogen pressure of at least 40 bars.
• Example 1 The procedure described in Example 1 was repeated, replacing the Ni-Mo catalyst for half with a Co-Mo catalyst on alumina (commercially available under the name Ketjen 742) and for the other half with a Ni-Mo catalyst on Al2O3 / SiO2. The charge passed successively through the silicalite, the Co-Mo and then the Ni-Mo.
• Example 2 The procedure described in Example 1 was repeated, reversing the catalysts, the charge successively passing through Ni-Mo and then silicalite. The results are shown in Table 2.
• composition of some effluents and some properties of certain cuts are listed in Table 4, compared with the values of Example 1A.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Crystallography & Structural Chemistry (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)

Applications Claiming Priority (2)

Publications (4)

Family

ID=19730635

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (9)

Citations (5)

Family Cites Families (20)

• 1986
  • 1986-02-03 LU LU86288A patent/LU86288A1/fr unknown
• 1987
  • 1987-02-02 JP JP62020601A patent/JP2879793B2/ja not_active Expired - Lifetime
  • 1987-02-03 US US07/010,223 patent/US4810356A/en not_active Expired - Lifetime
  • 1987-02-03 DE DE8787870016T patent/DE3775426D1/de not_active Expired - Lifetime
  • 1987-02-03 EP EP87870016A patent/EP0233169B2/de not_active Expired - Lifetime

Patent Citations (5)

Also Published As

Similar Documents

Legal Events