US20170240820A1 - Production of high quality diesel fuel and lubricant from high boiling aromatic carbonaceous material - Google Patents

Production of high quality diesel fuel and lubricant from high boiling aromatic carbonaceous material Download PDF

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US20170240820A1
US20170240820A1 US15/504,365 US201515504365A US2017240820A1 US 20170240820 A1 US20170240820 A1 US 20170240820A1 US 201515504365 A US201515504365 A US 201515504365A US 2017240820 A1 US2017240820 A1 US 2017240820A1
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product
hydrotreated
providing
aromatics
process according
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US15/504,365
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Angelica Hidalgo Vivas
Gert Bue Larsen
Rasmus Gottschalk Egeverg
Søren Selde Enevoldsen
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Topsoe AS
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Haldor Topsoe AS
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Assigned to HALDOR TOPSOE A/S reassignment HALDOR TOPSOE A/S ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LARSEN, Gert Bue, EGEBERG, Rasmus Gottschalk, ENEVOLDSEN, SOREN SELDE, VIVAS, ANGELICA HIDALGO
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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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G2300/20—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
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • 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
    • C10G2400/10—Lubricating oil

Definitions

  • the present invention relates to a process for the production of a high quality hydrocarbon fraction boiling above 190° C., which may be used to provide high quality diesel fuel and lubricant base stocks from high boiling aromatic carbonaceous feedstock such as tar, typically originating from the processing of coal, but also from other heavy hydrocarbon sources.
  • the invention relates to a process for the production of quality diesel and lubricant base stocks from a carbonaceous material in which high levels of nitrogen, oxygen and aromatics are present.
  • the carbonaceous material is subjected to hydrogenation and catalytic conversion typically by a highly active process involving active catalysts and process conditions in a hydrotreating process in optional combination with a hydrocracking process.
  • the output of this process is multiple product streams, one of which is a lubricant base stock which falls within high quality industry standards such API Group II or API Group III base oil stock classification.
  • Tar is often considered an undesirable by-product from coal processing, and there is cost and effort associated with the disposal of surplus tar. This has sparked interest for an efficient conversion of the tar into products with an actual market demand.
  • One such market demand is lubricant base stocks which are required for the blending of a wide range of finished lubricants for automotive, marine, industrial, and other applications. Most lubricant base stocks are traditionally manufactured from mineral crude oils. However, the present invention generates a high quality lubricant base stock by processing and upgrading an otherwise not very desirable industrial by-product.
  • GB 761,755 and GB 935,712 describe processes in which purified coal tar fractions are hydrogenated.
  • GB 935,712 describes hydrogenation of a coal tar with the objective of forming cycloalkanes, which are not suited for use as diesel fuel or lubricant base stock.
  • GB 761,755 describes a process for conversion of acid and base free coal tar fractions into decahydronaphthalene and other cycloalkanes. Both processes describe a procedure with an initial removal of heteroatoms by hydrogenation or other means, followed by a separate hydrogenation of aromatics. Such operation would in an industrial setting correspond to a two stage operation.
  • CN1243814C describes a two stage process for production of gasoline, diesel and lubricants, in which the H 2 :oil ratio is between 1100:1 and 1300:1 Nm 3 /m 3 .
  • the feed to the process contained 1606 ppm sulfur and 8636 ppm nitrogen, and the hydrotreated product mixture contained 100 ppm nitrogen, and an undisclosed amount of sulfur.
  • the hydrotreated product mixture is subsequently hydrocracked and fractionated into gasoline, diesel and lubricant base oil. The yield of the different fractions is not disclosed.
  • the lubricant base oil fraction comprises 11.4% aromatics, which does not meet the requirements for API Group II or API Group III base oils.
  • the diesel fraction comprises 53.2% aromatics and has a cetane number of 37, which indicate a diesel which was not fully hydrotreated.
  • CN103146424 relates to a two stage process for production of fuel and lubricants, in which light products from hydrotreatment in the first stage are separated from heavy products prior to dewaxing of heavy products in a second stage.
  • the patent claims cover a wide range of process conditions, but only a single set of process conditions have been evaluated experimentally.
  • the catalyst employed for hydrotreatment is only moderately active, and hydrotreatment is only conducted to a sulfur level around 300 wt ppm, which also indicates only moderate hydrodenitrogenation.
  • the lubricant product has a moderate viscosity index (VI) of 102, which only is sufficient for API Group II base stock classification.
  • the gasoline fraction comprises 2% oxygen and 0.03 wt % sulfur, which is indicative of a gasoline product which has only been moderately hydrotreated.
  • Group VIII shall be construed as elements from the periodic table according to the CAS definition, i.e. as the elements of the combined 1990 IUPAC Groups 8, 9 and 10.
  • Group VIB shall be construed as the elements of the combined 1990 IUPAC Group 6.
  • a cold flow parameter or a cold flow property shall be understood as a temperature reflecting the viscosity of a hydrocarbon mixture at low temperatures, including the parameters cloud point, pour point, freezing point and cold filter plugging point (CFPP). Common for these parameters are that they define the requirement to low viscosity of diesel under cold conditions as it is also specified in the standard EN 590 specifying requirements to diesel, and the improvement of cold flow properties or of any one of these parameters shall unless stated otherwise be understood as equivalent.
  • boiling in a given range shall be understood as a hydrocarbon mixture of which at least 80 wt % boils in the stated range.
  • naphtha shall be understood as a hydrocarbon product boiling in the range 20-150° C.
  • diesel shall be understood as a hydrocarbon product boiling in the range 150-390° C., even though it may not fulfill all formal requirements for commercial diesel.
  • lubricants shall be understood as a hydrocarbon product boiling above 350° C. and having attractive viscosity properties.
  • deep hydrotreatment shall be understood as the hydrotreatment to a very low level of sulfur and nitrogen, typically below 30 wt ppm, below 20 wt ppm or even below 10 wt ppm.
  • base oil shall be understood as a raw material for production of lubricants, which may not fulfill all requirements to lubricant products, such as cold flow properties.
  • a fraction shall be understood as a part of a stream.
  • the part of the stream in a fraction may be defined simply by splitting the stream or by the boiling point of the fraction, either as the boiling range from a fractionator or as a vapour or liquid stream from a separator operating at a given pressure and temperature.
  • excess hydrogen shall be understood as the provision of hydrogen beyond what is stoichiometrically required for all hydrotreatment reactions to occur.
  • Viscosity Index shall be understood as a measure of the temperature influence of lubricant oil viscosity, in accordance with ASTM standard D2270. Increasing VI indicates decreasing temperature influence on viscosity, which is preferred.
  • single stage shall be understood as a section of the process in which no stream is withdrawn. Typically a single stage does not include equipment such as compressors, by which the pressure is increased.
  • API base oil classifications is a series of quality definitions for base oils, and are a.o. used for trading the oil.
  • API base oil Group III requirements include less than 300 wt ppm sulfur, at least 90% saturates and a VI above 120.
  • API base oil Group II requirements include less than 300 wt ppm sulfur, at least 90% saturates and a VI between 80 and 120.
  • standards by other organisations such as SAE exist, and base oils may also be traded based on individual product specifications, often with a minimum VI of 110.
  • coal gasification shall be understood as a process comprising coking processes, which destructively distill the coal feedstock, to produce coke with a high carbon content, a gas phase and a liquid phase, coal tar.
  • the coal tar produced is differentiated by its mode of production—either a high temperature or low temperature process.
  • High temperature coal tars are the condensation products obtained by the cooling of the gas evolved at processing temperatures of greater than about 700° C. and up to about 1350° C. Typically, temperatures for the low temperature process ranged from about 200° C. to about 700° C.
  • Tar is a heavy hydrocarbonaceous liquid. Terms such as coal tar and coke oven tar may be used to indicate the source of the tar.
  • tar is typically a product of coal gasification. Such coal tar is characterized by a high presence of heteroatoms (especially nitrogen, sulfur and oxygen) as well as a high content of aromatics.
  • aromatics shall be defined by well-established chemical definitions. However, when quantified, aromatics amounts are determined and defined according to the established ASTM D-6591 method.
  • a broad embodiment of the present disclosure relates to a process for removal of at least 20%, 40% or 80% of the aromatics content of the fraction boiling above 190° C. from a heavy hydrocarbonaceous feedstock comprising at least 30 wt % aromatics, at least 3000 wt ppm nitrogen and at least 0.5 wt % oxygen said method being carried out in a single stage in which no intermediate stream is withdrawn and comprising the steps of
  • the material catalytically active in hydrotreatment comprises a group VIII metal compound, a group VIB metal compound and an oxidic support, taken from the group consisting of alumina, silica, titania and combinations thereof with the associated benefit of such a catalyst being highly active in hydrodenitrogenation, while being substantially inactive in hydrocracking, such that the yield loss is minimized.
  • the hydro-treatment conditions involve a hydrogen pressure from 120, 140 or 160 to 200 bar with the associated benefit of such a high hydrogen pressure supporting deep hydrotreatment, and thus providing the low amount of nitrogen required for high saturation of aromatics.
  • the hydro-treatment conditions involve a temperature from 340° C. or 360° C. to 400 or 420° C. with the associated benefit of ensuring a high activity, but still avoiding thermal cracking.
  • the hydro-treatment conditions involve a liquid hourly space velocity of 0.1 hr ⁇ 1 or 0.2 hr ⁇ 1 to 0.5 hr ⁇ 1 , 0.6 hr ⁇ 1 or 1.0 hr ⁇ 1 with the associated benefit of such conditions providing a very high conversion with respect to hydrodenitrogenation and dearomatization, while avoiding a very large reactor size.
  • the material catalytically active in hydroprocessing is a material catalytically active in hydrocracking such as a material comprising a metal component selected from Group VIII and/or VIB of the Periodic System and being supported on a carrier containing one or more oxides taken from the group consisting of alumina, silica, titania, silica-alumina, molecular sieves, zeolites, ZSM-11, ZSM-22, ZSM-23, ZSM-48, SAPO-5, SAPO-11, SAPO-31, SAPO-34, SAPO-41, MCM-41, zeolite Y, ZSM-5 and zeolite beta with the associated benefit of such a hydrocracking processs of converting high boiling products to lower boiling products, e.g. for providing increased diesel yield of the hydroprocessed product over the hydrotreated product.
  • a material catalytically active in hydrocracking such as a material comprising a metal component selected from Group VIII and/or VIB of the Periodic System and being supported on
  • reaction step in the presence of a material catalytically active in hydrocracking is carried out a temperature between 200° C. and 400° C.
  • At least 80 wt % of either said hydrotreated product or said hydroprocessed product is a fraction boiling above 360° C. with the associated benefit that such a high boiling product having a low aromatic content will be a valuable lubricant base oil.
  • the hydroprocessed product fraction boiling above 360° C. is a lubricant or a lubricant base stock having a viscosity index of at least 110 or 120 with the associated benefit that such a lubricant has a high value.
  • the final boiling point of this fraction will be below 600° C.
  • At least 80 wt % of either said hydrotreated product or said hydroprocessed product is a fraction boiling between 150 and 350° C., with the associated benefit that such a product having a low aromatic content will be a valuable diesel product or diesel blend component.
  • said fraction boiling between 150 and 350° C. is a diesel or a diesel blend stock having a cetane index of at least 35, 38 or 40, with the associated benefit that such a product will be of immediate use as a valuable diesel product.
  • cetane index will be below 70, 90 or 100.
  • a feedstock according to the present disclosure comprises high amounts of aromatics (>30 wt %) as well as high amounts of heteroatoms, especially oxygen (>0.5 wt %) and nitrogen (>3000 wt ppm).
  • Such feedstocks may originate as side streams from production of coke, or from gasification or so-called destructive distillation of coal, as well as from pyrolysis processes.
  • According to the prior art such feedstocks have been hydrotreated with the objective of providing naphtha for gasoline production and middle distillate for diesel production.
  • the naphtha and diesel have however not been of high quality, and a yield of low quality heavy hydrocarbons has also reduced the economics of the process.
  • the high amount of oxygen in the hydrocarbon structures may contribute to the formation of high boiling hydrocarbons with a high viscosity index by rupturing the molecular structure during hydrodeoxygenation, and providing a product with a high amount of paraffins.
  • the typical design will be driven by cost optimization, such that the process engineer will select a process with sufficient hydrotreatment for meeting official sulfur standards, in order to reduce reactor size, catalyst cost, hydrogen consumption and to yield losses.
  • a hydrocracking process step as in CN1243814C may be added, as this would provide the highest possible diesel yield by conversion of high boiling hydrocarbons to lower boiling hydrocarbons.
  • some hydrodenitrogenation takes place during hydrocracking.
  • the extra cost is rewarded by a yield of high quality lubricant and diesel, which surprisingly outweighed the extra cost of deep hydrotreatment.
  • a requirement to the hydrogenation process used according to the present disclosure therefore is a combination of high hydrodenitrogenation activity with a high dearomatization activity.
  • This combined high activity may be obtained by employing a high H 2 partial pressure, which shifts the hydrotreatment equilibria towards hydrogenated products.
  • the feedstock includes high amounts of heteroatoms, the requirement for high H 2 excess in combination with low space velocity becomes especially important.
  • the conditions required for sufficient hydrodenitrogenation depend on the specific feedstock and the specific catalyst used, but in general a high pressure, a high hydrogen purity and a catalyst highly active in hydrodenitrogenation and dearomatization, a.o. due to a high surface area and a high dispersion of active metals are beneficial for the process according to the present disclosure.
  • a process for dearomatization would be favored by the same conditions as those favoring hydrodenitrogenation.
  • organic nitrogen is known to inhibit the dearomatization by adsorption to the active sites, and therefore it is important that organic nitrogen is removed extensively if a high dearomatization is to be observed. If the process activity is moderate, hydro-denitrogenation of organic nitrogen molecules may not be completed until a position proximate to the exit of the reactor, and in this case, the initial part of the reactor will contain catalyst which is highly inhibited with respect to hydro-dearomatization by the presence of organic nitrogen on the active sites of the catalyst surface. In such a case the product mixture from hydrogenation will have a low nitrogen level, but an intermediate or even high aromatics level.
  • the dearomatization will only be active in the section of the reactor which contains catalytically active material not inhibited by the nitrogen. Dearomatization will proceed as a saturation reaction providing saturated hydrocarbon rings or as a ring opening reaction, providing normal or branched paraffins.
  • a catalyst active in hydro-denitrogenation and hydro-dearomatization is the Haldor Tops ⁇ e A/S TK-609T HyBRIMTM catalyst.
  • This catalyst is based on HyBRIM technology, according to which the active metals (Ni and Mo) are highly dispersed, to provide a high amount of active sites at the edge of the dispersed metal particles.
  • This objective of deep hydrotreatment can be achieved by a conventional but severe hydrotreating step that normally involves operation at temperatures between 340° C. and 420° C., hydrogen pressures from 120 bars up to 200 bars, while the space velocity (LHSV) is quite low at 0.1 hr ⁇ 1 to 0.6 hr ⁇ 1 or 1.0 hr ⁇ 1 .
  • the inlet temperature may often be lower by 20° C. or more, as significant hydrodeoxygenation occurs, which is highly exothermic. If the temperature is increased further there is risk that thermal cracking occurs, which gives a yield loss.
  • the high hydrogen pressure is required to shift the thermodynamical equilibrium to promote the saturation of aromatics, and may require a purity of hydrogen above 90% or even 95%.
  • the H 2 /oil ratio is preferably in the range 2000-3000 Nm 3 /m 3 , as the high amount of heteroatoms in the process consumes a high amount of hydrogen, and the catalyst is preferably highly active.
  • the hydrotreating catalyst comprises a sulfided metal component selected from the non-noble metals of Group VIII and VIB of the Periodic System and being supported on a carrier containing alumina, silica, titania or combinations thereof, and optionally in combination with further promoting constituents.
  • These catalysts are preferably those employed conventionally, such as mixed cobalt and/or nickel and molybdenum sulfides (Co—Mo, Ni—Mo, Ni—W) supported on alumina, silica, silica-alumina or combinations of these.
  • the hydrotreating catalyst is Ni—Mo/alumina, Co—Mo/alumina or Ni—W/alumina.
  • a hydroisomerization catalyst or a hydrocracking catalysts may be included to improve the cold flow properties of the liquid product.
  • a hydroisomerization catalyst or a hydrocracking catalysts may be included to improve the cold flow properties of the liquid product.
  • both diesel and lubricant fractions may require dewaxing by hydroisomerisation, it is possible that the hydroisomerisation is carried out on the full product mixture, but separate treatment of the diesel and the lubricant fraction may also be preferred in order to reduce the yield loss.
  • the hydroisomerization catalyst comprises a metal component selected from Group VIII and/or VIB of the Periodic System and being supported on a carrier containing alumina, silica, titania, silica-alumina, molecular sieves, zeolites, ZSM-11, ZSM-22, ZSM-23, ZSM-48, SAPO-5, SAPO-11, SAPO-31, SAPO-34, SAPO-41, MCM-41, zeolite Y, ZSM-5, and zeolite beta.
  • the hydroisomerization catalyst is Ni—W supported on a carrier containing alumina, zeolite beta and silica-alumina.
  • the hydroisomerisation step may be carried out in the same reactor and/or same catalyst bed as the previous step(s) or it may be carried out in a separate reactor.
  • the catalyst bed may therefore be a combination of catalysts active in hydrodeoxygenation (HDO), hydrotreatment (HDS, HDN, HDA), hydroisomerisation (HI) and hydrocracking (HC).
  • the hydroisomerization step involves operation between 200 and 500° C., at pressures up to 200 bars.
  • the hydrotreating step and hydroisomerization step are carried out at a hydrogen pressure of 1-200 bar and at a temperature of 250-450° C., preferably at a pressure of 10-150 bar and a temperature of 250-410° C. and at a liquid hourly space velocity of 0.1-10 h ⁇ 1 .
  • the H 2 /oil ratio is preferably in the range 100-3000 Nm 3 /m 3 .
  • the hydroisomerization catalyst converts the normal paraffins into iso-paraffins with better cold-flow properties.
  • the bifunctional hydroisomerization catalyst contains both acidic sites typically associated with the oxide carrier and hydrogenation sites typically associated with the metal component. If the active metal component is one or more Group VIII noble metals, the hydroisomerization should preferably be carried out in a separate process stage after separation of hydrogen sulfide, ammonia and water, or at least in a separate reactor or catalyst bed and the feed to the hydroisomerization catalyst should be virtually free of nitrogen and sulfur species, i.e. contain less than 100 wtppm sulfur and less than 100 wtppm nitrogen, preferably less than 10 wtppm sulfur and less than 10 wtppm nitrogen.
  • the step may be carried out in a sour environment and the costly installment of equipment to remove H 2 S and NH 3 formed in the previous step(s) is thus not necessary.
  • a metal sulfide e.g. Ni—Mo—S, Co—Mo—S, Ni—W—S
  • FIG. 1 illustrates the present disclosure
  • FIG. 2 illustrates a process employing an embodiment of the present disclosure.
  • FIG. 1 an embodiment of the present disclosure is illustrated.
  • a heavy hydrocarbonaceous feedstock 32 having a high content of nitrogen, oxygen and aromatics, such as pretreated coal tar, is directed to a single hydrotreatment reactor 34 having one or more reactor beds, with optional addition of hydrogen 26 from a hydrogen rich gas 14 which mainly for temperature control may be done between reactor beds.
  • a deep hydrotreated product may be withdrawn, which has a low nitrogen content, and thus high dearomatization has been possible in the zones furthest downstream in the reactor. Therefore the hydrotreated hydrocarbon product 48 has a low content of aromatics.
  • FIG. 2 a process, employing an embodiment of the present disclosure is illustrated, including a number of optional elements, included to illustrate one way of pretreating a raw coal tar prior to deep hydrotreatment.
  • a raw coal tar 2 is directed as feed to an optional feed fractionation column 4 , in which a heavy asphalt fraction 6 may be withdrawn, before the coal tar 8 is directed to a pump 10 , after which the pressurized coal tar 12 is combined with a hydrogen rich recycle stream 14 , providing a hydrotreatment feedstock 16 .
  • the hydrotreatment feedstock 16 is heated in heat exchanger 18 and fired heater 20 , before being directed to a hydrodemetallization (HDM) reactor 22 , comprising a metal guard material 24 , having a high metal absorption capacity and a hydrotreatment activity.
  • HDM hydrodemetallization
  • demetallized feedstock effluent 28 may be appropriately adjusted in heat exchanger 30 and directed as a heavy hydrocarbonaceous feedstock 32 to three hydrotreatment reactors in series 34 , 40 , 46 , with optional intermediate cooling, 38 , 44 and 50 of the partially hydrotreated hydrocarbon products 36 , 42 and 48 .
  • 3 reactors are shown in series, each with 3 reactor beds, but in practice it may be fewer reactors or more reactors, and fewer or more reactor beds.
  • the catalyst in the three reactors comprises in general a material catalytically active in hydrotreatment, but the specific composition in each reactor or each reactor bed may be tailored to the specific heavy hydrocarbonaceous feedstock, e.g. based on the amount of oxygen in the feedstock, which would be hydrogenated in exothermal hydrodeoxygenation reactions.
  • a hydrotreated hydrocarbon product 48 is provided at the outlet of the third hydrotreatment reactor.
  • the third reactor 46 may however also be fully or partially bypassed by line 52 if so required, e.g. until the conditions require that the third reactor is put in use, e.g. due to deactivation of the first and second reactors.
  • the hydrotreated hydrocarbon product is directed as a hydrotreated product 54 to a further hydroprocessing reactor 56 , or alternatively the further hydroprocessing reactor is by-passed by line 62 .
  • the further hydroprocessing reactor 56 may be either operating as a hydroisomerisation reactor, or as a hydrocracking reactor. If the further hydroprocessing reactor 56 is operating as a hydrocracking reactor, the product 58 will have reduced boiling point and a reduced yield of high boiling products, as these will be hydrocracked to form especially middle distillate products for e.g. diesel. Typically a hydrocracking reactor will involve a certain amount of yield loss, by conversion into light hydrocarbons.
  • the product 58 will have only moderate change in boiling point, but instead a conversion of linear paraffins to branched paraffins will occur, which is beneficial as the cold flow properties of the isomerized product will be improved; i.e. the pour point will be lower.
  • a reduction of viscosity index may also be observed as a result of paraffin isomerization.
  • the yield loss will be moderate, but very often hydroisomerisation will be carried out only on a specific fraction after fractionation not shown in the figures, in a separate reactor to reduce yield loss even further.
  • the hydroisomerisation catalyst is similar to a hydrocracking catalyst, but selectivity is increased by operating at less severe conditions.
  • the hydroprocessed hydrocarbon 58 may be cooled in cooler 60 and separated in a high pressure separator 66 , to a vapor stream 72 and a product stream 68 .
  • the vapor stream 72 is pressurized in compressor 74 and combined with make-up hydrogen 76 .
  • the product stream is depressurized in a low pressure separator (or optionally more), and an amount 78 may be directed for liquid recycle.
  • Another amount of a hydroprocessed product 80 is directed to a fractionator 82 .
  • the fractionator is fractionating the product based on boiling point into a fuel gas stream 84 , a naphtha stream 86 , a middle distillate (or diesel) stream 88 and an unconverted oil (or lubricant base stock) stream 90 .
  • the stream 48 may be separated into a heavy and a lighter stream.
  • the lighter stream may be directly available as a diesel product or possibly require isomerization to improve the cold flow properties, whereas the heavy stream may require hydrocracking to yield a product in a desirable boiling range.
  • the hydrotreated product By separating the hydrotreated product into a light fraction and a heavy fraction, it becomes possible to treat each fraction of the hydrotreated product optimally—which may or may not involve hydroprocessing of that fraction. This can reduce one or more of the total reactor size, the yield loss and the consumption of hydrogen, and it may even lead to a more attractive product mix.
  • By providing a fractionator prior to the further hydroprocessing it may also be possible to avoid the fractionator 82 downstream further hydroprocessing.
  • one or both of the optional separations may be carried out in simple gas liquid separators, operating at suitable pressure and temperature, or in a more complex distillation based fractionator operating at low pressure, providing a better separation. It may be beneficial to maintain an elevated pressure during separation as this will be more energy efficient, since the pressure in downstream reactors may not have to be re-established.
  • a hydrotreatment catalyst was made as follows. Alumina powder, alumina gel and diluted nitric acid are mixed for 12 minutes and extruded, in 1/20′′ trilobe shape. The extrudates are dried for 2 hours at 200° C. and then calcined at 550° C. The extrudates are then impregnated with an acidic NiMo solution prepared with phosphoric acid, molybdenum trioxide and nickel carbonate, adjusting the amounts to produce a catalyst with 16 wt % Ni, 3 wt % Mo and 3 wt % P. The catalyst is calcined at 370° C. for 2 hours.
  • the experiments were carried out in a unit with two isothermal reactors in series.
  • the first reactor was loaded with 63 ml of commercial demetallization catalyst TK-743, followed by commercial dearsenation catalyst TK-47, whilst the second reactor was loaded with commercial hydrotreatment catalyst TK-609T HyBRIMTM from Haldor Tops ⁇ e A/S.
  • the catalyst beds in both reactors were diluted by 40 vol % inert carborundum (SiC) prior to loading in order to improve the liquid distribution of the reactors. Pure hydrogen was used in once-through mode.
  • the feed for the experiments was a tar from gasification of coal, having the properties of Table 1.
  • the determination of aromatic content was carried out according to method ASTM D6591.
  • the product according to Experiment 1 is having a 5 wt % yield of a fraction with excellent lubricant base stock properties, as well as about 70 wt % diesel of good quality.
  • the product of experiments 2 and 3 were deeply hydrotreated, and included middle distillate and lube base oil of good quality, but the lower severity of hydrotreatment was reflected in a higher aromatic content. This was reflected in a lower product quality; for the middle distillate a lower cetane index and for the lube base oil a lower VI.
  • the lubricant products according to the prior art were documented to have inferior VI of only 105. This is assumed to be due to insufficient dearomatization, which again is believed to be related to insufficient hydrodenitrogenation.
  • examples 1 and 2 show a high extent of saturation of all aromatics
  • example 3 shows a high extent of saturation of di-aromatics and tri-aromatics.
  • the high viscosity index lubricant fraction of the present disclosure indicates that this fraction has a high content of paraffins.
  • the middle distillate of experiment 1 has a higher cetane index that the middle distillates of experiments 2 and 3, which is also believed to indicate a high paraffin content.

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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)
US15/504,365 2014-09-16 2015-09-14 Production of high quality diesel fuel and lubricant from high boiling aromatic carbonaceous material Abandoned US20170240820A1 (en)

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EP14184953 2014-09-16
EP14184953.9 2014-09-16
PCT/EP2015/070952 WO2016041901A1 (fr) 2014-09-16 2015-09-14 Production de lubrifiant et de carburant diesel de haute qualité à partir de matière carbonée aromatique à point d'ébullition élevé

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GB761755A (en) * 1952-10-08 1956-11-21 Coal Tar Res Ass Improvements in the production of fully hydrogenated polynuclear aromatic hydrocarbons
NL262303A (fr) * 1960-03-30
GB1593403A (en) * 1977-07-26 1981-07-15 Mobil Oil Corp Effect of catalyst and src concentration on hydroprocessing of recycle solvent/solvent refined coal (src) blends
US5462651A (en) * 1994-08-09 1995-10-31 Texaco Inc. Hydrodearomatization of hydrocarbon oils using novel "phosphorus treated carbon" supported metal sulfide catalysts
CN100348702C (zh) * 2005-10-28 2007-11-14 中国石油化工集团公司 一种燃料油的生产方法
US8394255B2 (en) * 2008-12-31 2013-03-12 Exxonmobil Research And Engineering Company Integrated hydrocracking and dewaxing of hydrocarbons
CN102836727A (zh) * 2011-06-23 2012-12-26 中国石油天然气集团公司 一种具有高脱氮和脱芳烃活性加氢催化剂的制备方法
US9029301B2 (en) * 2011-12-15 2015-05-12 Exxonmobil Research And Engineering Company Saturation process for making lubricant base oils
CN103805245B (zh) * 2012-11-07 2016-04-27 中国石油化工股份有限公司 一种加氢裂化和加氢脱芳组合的加氢方法

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CN106687565A (zh) 2017-05-17
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