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WO2024166132A1 - Catalyseur d'hydrogénation à base de nickel monométallique et son procédé de préparation - Google Patents

Catalyseur d'hydrogénation à base de nickel monométallique et son procédé de préparation Download PDF

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Publication number
WO2024166132A1
WO2024166132A1 PCT/IN2024/050120 IN2024050120W WO2024166132A1 WO 2024166132 A1 WO2024166132 A1 WO 2024166132A1 IN 2024050120 W IN2024050120 W IN 2024050120W WO 2024166132 A1 WO2024166132 A1 WO 2024166132A1
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Prior art keywords
nickel
ppm
alumina
range
ranging
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Sudarshanreddy RAGIREDDY
Pradyut Kumar DHAR
Gnanasekaran VALAVARASU
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Hindustan Petroleum Corp Ltd
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Hindustan Petroleum Corp Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • 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
    • C10G65/02—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

Definitions

  • the present invention relates to a process for preparation of a mono-metallic hydrogenating catalyst. More specifically, the present invention relates to a process for preparation of a monometallic nickel-based hydrogenating catalyst, a mono-metallic nickel-based hydrogenating catalyst, and uses thereof in the preparation of de-aromatized hydrocarbon solvents having aromatic content less than 100 ppm through selective hydrogenation of distillates having boiling point in range of 150° C to 350° C.
  • Dearomatized hydrocarbon solvents commonly known as D-solvents or D-series, are considered an ideal replacement for traditional hydrocarbon solvents such as mineral or white spirits, kerosene etc. With its low to extremely low aromatic content (less than 0.1%), dearomatized fluids still provide optimal solvency in many applications such as printing inks, paint, coatings, metal working fluids, industrial and institutional cleaning, adhesives, sealants, drilling fluids etc., and maintain good safety, health, and environmental standards.
  • the processes for obtaining de-aromatized hydrocarbon solvents involve conversion of the aromatic compounds present in hydrocarbon feed to the corresponding saturated hydrocarbons by reacting the aromatic compounds with hydrogen in the presence of a suitable catalyst under appropriate process conditions. Further, the hydrogenated petroleum distillates obtained from the hydrogenation reaction are usually stabilized by the removal of the light, volatile hydrocarbon components.
  • de-aromatized solvents are prepared from expensive hydrocarbon feedstock and the processes used for this purpose require harsh hydrogenation reaction conditions.
  • the art continues to develop processes for reaction of niche hydrocarbon feedstock with hydrogen to produce de-aromatized hydrocarbon solvents in an efficient and cost-effective manner.
  • a hydrogenating catalyst which has high selectivity, high active metal reducibility, and having less severe process condition requirements along with efficient de-aromatization capabilities is highly desirable.
  • IN202047044783 provides a method for preparing a nickel and copper based bimetallic catalyst for hydrogenating aromatic compounds.
  • the method involves step a) contacting the nickel precursor with support and step b) contacting the copper precursor with the support.
  • the applicant has discovered that the pre-impregnation (with respect to the impregnation of the nickel precursor) of a copper precursor on the support makes it possible to obtain better results in terms of reducibility of the nickel compared to a post-impregnation of the copper precursor (with respect to the impregnation of the nickel precursor), this being for identical catalyst reduction operating conditions (temperature, time, reducing gas).
  • IN202147031138 provides a process for preparing a selective hydrogenation catalyst, comprising a step of forming a Ni-Cu alloy in pre-impregnation. It has been observed by the applicant that, during the preparation of the catalyst, carrying out a step of bringing the support into contact with a solution simultaneously containing a copper-based metal precursor and a nickel-based metal precursor, followed by a step of drying and reducing in the presence of a reducing gas at low temperature (between 150° C.
  • the other objective of the present invention is to provide a mono-metallic hydrogenating catalyst comprising nickel metal dispersed on a refractory metal oxide support.
  • the other objective of the present invention is to provide a process for preparing de-aromatized hydrocarbon solvents by subjecting distillates having boiling point in range of 150° C to 350° C in presence of a mono-metallic hydrogenating catalyst comprising nickel metal dispersed on a refractory metal oxide support.
  • It is another objective of the present invention is to provide a process for preparing dearomatized hydrocarbon solvents having aromatic content less than 100 ppm by subjecting distillates having boiling point in range of 150° C to 350° C in presence of a mono-metallic hydrogenating catalyst comprising nickel metal dispersed on a refractory metal oxide support.
  • the present invention discloses a process for preparation of a mono-metallic hydrogenating catalyst comprising nickel metal dispersed on an alumina support.
  • the process involves preparation of an alumina support, loading of nickel on the said alumina support using a multistage spray impregnation process, drying the said nickel sprayed alumina support and calcining the dried nickel loaded alumina support to obtain the mono-metallic nickel-based hydrogenating catalyst.
  • the alumina support is obtained by extruding alumina dough prepared by mixing alumina powder with an acid using a trilobite dye and drying the wet alumina extrudes for a duration of 5 to 15 hours at a temperature range of 60 to 120 °C followed by calcining at a temperature range of 450 to 550 °C for a duration of 2 to 10 hours.
  • the wet alumina extrudes is preferably dried for 10 to 12 hours at a temperature range of 80 to 100 °C and calcined at a temperature range of 450 to 550 °C for a duration of 2 to 10 hours.
  • the acid mixed in the alumina powder to prepare alumina dough is selected from phosphoric acid, nitric acid, and acetic acid. Further, the acid is nitric acid.
  • the alumina powder is one or more selected from boehmite, pseudo boehmite, gibbsite, direct alumina, aluminum hydroxide, aluminum chlorides, aluminum sulfates, dawsonites and the alumina powder has surface area in range of 200 to 400 m2/gr. Further, the alumina powder is pseudo-boehmite, phosphorous modified alumina, and a combination thereof and has surface area in range of 250 to 330 m2/gr.
  • the alumina support thus obtained is then loaded with nickel using a multi-stage spray impregnation process wherein precursor solutions of nickel with varying concentration is sprayed on the alumina support with intermittent drying steps.
  • the precursor solutions of varying concentration are prepared by dissolving 0.2 mol % to 1.5 mol % of one or more nickel salt selected from nickel (II) nitrate hexahydrate and nickel (II) acetate tetrahydrate in water. Further, the precursor solutions are prepared by dissolving 0.4 mol % to 0.6 mol % of nickel (II) nitrate hexahydrate in water.
  • the intermittent drying step involves initial drying under vacuum at a temperature range of 50 to 100 °C, followed by drying in an oven at a temperature range of 60 to 120 °C, and then air drying at a temperature range of 450 to 550 °C for a duration of 4 to 12 hours. Further, the intermittent drying involves initial drying under vacuum at a temperature range of 60 to 80 °C, followed by drying in an oven at a temperature range of 80 to 100 °C, and then air drying at a temperature range of 450 to 520 °C for a duration of 8 to 12 hours.
  • the nickel loaded alumina support obtained at the end of multi-stage spray impregnation process is subjected to calcination at a temperature range of 450 to 550 °C for a duration of 2 to 10 hours to obtain the mono-metallic hydrogenating catalyst. Further, the calcination is carried out at a temperature range of 480 to 520 °C for a duration of 4 to 8 hours to obtain mono-metallic hydrogenating catalyst.
  • the present invention further provides a mono-metallic hydrogenating catalyst comprising 10 to 60 weight % of nickel metal dispersed on a refractory metal oxide support for producing dearomatized hydrocarbon solvents through selective hydrogenation of heavy and middle hydrocarbon distillate having aromatic content in range of 5000 ppm to 40000 ppm, and sulfur content ranging from 0 ppm to 1 ppm.
  • the mono-metallic catalyst has reducibility of nickel metal in the range of 80 % to 90 % at a reduction temperature in the range of 440 to 480 °C.
  • the refractory metal oxide is one or more selected from the group consisting of alumina, silica, titania, and zirconia.
  • the alumina support in the mono-metallic hydrogenating catalyst is alumina or modified alumina.
  • the modified alumina is a phosphorous modified alumina.
  • the present invention further provides a process for preparing de-aromatized hydrocarbon solvents having aromatic content less than 100 ppm from a heavy hydrocarbon feedstream by subjecting the said feedstream to distillation followed by catalytic hydrotreatment of distillate having boiling point in the range of 180° C to 550° C in presence of a hydrotreatment catalyst, isodewaxing, fractionation, and subjecting the fraction having boiling point in range of 150° C to 350° C and aromatic content in range of 5000 ppm to 40000 ppm to selective hydrogenation in presence of a mono-metallic hydrogenating catalyst comprising nickel metal dispersed on a refractory metal oxide support.
  • the fractionated hydrocarbon feedstream utilized in the process for preparation of dearomatized solvents is a low-cost hydrocarbon feedstream having high aromatic content ranging from 5000 ppm to 20,000 ppm, and sulfur content ranging from 0 ppm to 1 ppm. Further, the aromatic content of the hydrocarbon feedstream is in range of 5000 ppm to 40000 ppm and sulfur content is in range of 0.5 ppm to 1 ppm.
  • the feedstream comprises one or more selected from crude oil, heavy vacuum gas oil, and lube base oil.
  • the de-aromatized solvent preparation process starts with the distillation of heavy hydrocarbon feedstream to obtain a first distillate having boiling point in range of 180° C to 550° C.
  • the first distillate is then subjected to hydrotreatment in presence of a hydrotreatment catalyst to obtain a hydrotreated hydrocarbon stream having sulfur content of less than 100 ppm,
  • the hydrotreatment of the first distillate is carried out at a reactor temperature ranging from 300° C to 450 °C, reactor pressure ranging from 60 bar to 180 bar, weight hourly space velocity (WHSV) ranging from 0.5 h -1 to 3.0 h -1 , and volume ratio of hydrogen to heavy hydrocarbon stream ranging from 100 Nm 3 /m 3 to 1500 Nm 3 /m 3 .
  • WHSV weight hourly space velocity
  • the hydrotreatment of the first distillate is carried out at a reactor temperature ranging from 350° C to 400 °C, reactor pressure ranging from 100 bar to 150 bar, weight hourly space velocity (WHSV) ranging from 0.75 h -1 to 1.25 h and volume ratio of hydrogen to heavy hydrocarbon stream ranging from 400 Nm 3 /m 3 to 1000 Nm 3 /m 3
  • WHSV weight hourly space velocity
  • the hydrotreated hydrocarbon stream having sulfur content less than 100 ppm is further subjected to isodewaxing which is mainly done to isomerize hydrocarbons and fractionation to obtain a second distillate having boiling point in the range of 150° C to 350° C.
  • the second distillate is further subjected to selective hydrogenation in presence of nickel-based mono-metallic catalyst to obtain de-aromatized solvents having aromatic content of dearomatized solvent obtained is in a range of 5 ppm to 100 ppm and sulfur content in range of 0.5 to 1 ppm.
  • the aromatic content of de-aromatized solvents obtained is in a range of 20 ppm to 50 ppm.
  • the selective hydrogenation of the second distillate is carried out at a reactor temperature ranging from 80 °C to 200 °C, reactor pressure ranging from 25 bar to 35 bar, liquid hourly space velocity (LHSV) ranging from 0.25 h-1 to 2.0 h-1, and volume ratio of hydrogen to second distillate ranging from 40 Nm3/m3 to 100 Nm3/m3. Further, the selective hydrogenation of the second distillate is carried out at a reactor temperature ranging from 140 °C to 180 °C, reactor pressure ranging from 10 bar to 45 bar, liquid hourly space velocity (LHSV) ranging from 0.5 h-1 to 1.0 h-1, and volume ratio of hydrogen to second distillate ranging from 50 Nm3/m3 to 70 Nm 3 /m 3 .
  • LHSV liquid hourly space velocity
  • the reactor pressure and volume ratio of hydrogen to second distillate is advantageously low in comparison to other processes for the preparation of de-aromatized solvents from heavy hydrocarbon feedstream.
  • the process for preparation of a mono-metallic nickel-based hydrogenating catalyst disclosed herein involves preparation of a refractory metal oxide support, loading of nickel on the said refractory metal oxide support using a multi-stage spray impregnation process, drying the said nickel sprayed refractory metal oxide support and calcining the dried nickel loaded refractory metal oxide support to obtain the mono-metallic nickel-based hydrogenating catalyst.
  • the refractory metal oxide support used in the process is selected from alumina, silica, titania, and zirconia.
  • the refractory metal oxide support is selected from alumina support, modified alumina support and combination thereof.
  • the modified alumina support is a phosphorus modified alumina support.
  • the refractory metal oxide support is an alumina support prepared by extruding alumina dough using a dye of 2 mm X 3 mm Trilobite shape, drying the wet alumina extrudes and calcining the dried alumina extrudes to obtain alumina support.
  • the refractory metal oxide support is a phosphorous modified alumina support prepared by extruding alumina dough using a dye of 2 mm X 3 mm Trilobite shape, drying the wet alumina extrudes, calcining the dried alumina extrudes, and spraying solution of phosphoric acid on the dried alumina extrudes to obtain phosphorous modified alumina support.
  • the alumina dough used for preparing the alumina support or modified alumina support is prepared by mixing commercially available alumina powder with an acid selected from nitric acid, acetic acid, and phosphoric acid.
  • acid is nitric acid.
  • the alumina powder is selected from boehmite, pseudo boehmite, gibbsite, direct alumina, aluminum hydroxide, aluminum chlorides, aluminum sulfates, and dawsonites.
  • alumina powder is boehmite or pseudo boehmite.
  • the surface area of alumina powder used for preparing the alumina dough is in the range of 200 to 400 m2/gr. In the most preferred embodiment, the surface area of alumina powder is in the range of 250 to 330 m2/gr.
  • the process disclosed herein involves drying of wet alumina extrudes during the preparation of alumina support to obtain dried alumina extrudes.
  • the wet alumina extrudes is dried for 5 to 15 hours at a temperature range of 60 to 120 °C. In most preferred embodiments, the wet alumina extrudes is dried for 10 to 12 hours at a temperature range of 80 to 100 °C.
  • the dried alumina extrudes is then calcined to obtain the alumina support ready for loading of nickel.
  • the calcination of dried alumina extrudes is carried out at a temperature range of 450 to 550 °C for a duration of 2 to 10 hours to obtain calcined alumina support.
  • the dried alumina extrudes are calcined at a temperature range of 480-520 °C for a duration of 4 to 8 hours.
  • the calcination is preferably performed in an open-air furnace.
  • the alumina support obtained after calcination is ready for loading of nickel metal using a multi-stage spray impregnation process.
  • the spray impregnation step methodology used herein for loading nickel metal on the alumina support is a crucial step in the preparation of the monometallic hydrogenation catalyst disclosed herein.
  • the reducibility of the active phase of nickel on the refractory metal oxide support in the disclosed mono-metallic hydrogenating catalyst is greatly improved even in the absence of promoter when nickel is loaded on the alumina support through spray impregnation in a staged manner using an aqueous solution having specified concentration of nickel salt instead of single-stage spray impregnation.
  • the mono-metallic nickel-based hydrogenating catalyst disclosed herein has reducibility of the active phase of nickel in the range of 80 % to 90 % at a reduction temperature in the range of 440 to 480 °C. It is also devised through experimentation that best catalytic efficiency is obtained when spray impregnation is done in two stages.
  • the multi-stage spray impregnation process used in the process disclosed herein involves spraying of nickel precursor solution on the alumina support in multiple steps with intermittent drying steps.
  • the precursor solutions of nickel salt is prepared by dissolving 0.2 mol % to 1.5 mol % of one or more nickel salt selected from nickel (II) nitrate hexahydrate and nickel (II) acetate tetrahydrate in water.
  • the aqueous solution of nickel salt is prepared by dissolving 0.4 mol % to 0.6 mol % of nickel (II) nitrate hexahydrate in water.
  • the multi-stage spray impregnation used in the process disclosed herein involves intermittent drying of alumina support sprayed with precursor solution.
  • the wet nickel sprayed alumina support is dried initially under vacuum at a temperature range of 50 to 100 °C, followed by drying in an oven at a temperature range of 60 to 120 °C, and then air drying at a temperature range of 450 to 550 °C for a duration of 4 to 12 hours.
  • the wet nickel sprayed alumina support is dried initially under vacuum at a temperature range of 60 to 80 °C, followed by drying in an oven at a temperature range of 80 to 100 °C, and then air drying at a temperature range of 450 to 520 °C for a duration of 8 to 12 hours.
  • the alumina support loaded with nickel obtained after the multi-stage spray impregnation process is calcined to obtain the mono-metallic nickel-based hydrogenation catalyst.
  • the calcination is carried out at a temperature range of 450 to 550 °C for a duration of 2 to 10 hours in muffle air-furnace. In the most preferred embodiments, the calcination is carried out at a temperature range of 480 to 520 °C for a duration of 4 to 8 hours to obtain mono-metallic nickel-based hydrogenating catalyst.
  • the mono-metallic hydrogenating catalyst provided by the present invention comprises nickel loaded on refractory metal oxide.
  • the mono-metallic catalyst comprises 10 to 60 weight percent of nickel metal. In the most preferred embodiments, the weight percent of nickel metal in the mono-metallic catalyst is 30 to 50 percent by weight.
  • the mono-metallic hydrogenating catalyst has reducibility of nickel metal in the range of 80 % to 90 % at a reduction temperature in the range of 440 to 480 °C.
  • the refractory metal oxide support on which nickel is loaded is selected from alumina, silica, titania, and zirconia.
  • the refractory metal oxide support is an alumina support or modified alumina support.
  • the modified alumina support is phosphorus modified alumina support.
  • the mono-metallic hydrogenating catalyst disclosed herein can be advantageously used to produce de-aromatized solvents with aromatic content in a range of 5 ppm to 100 ppm and sulfur content in a range of 0.5 ppm to 1 ppm from middle and heavy distillates having aromatic content in range of 5000 ppm to 40000 ppm, and sulfur content ranging from 0 ppm to 1 ppm.
  • the middle and heavy distillates have aromatic content in range of 5000 to 20000 ppm.
  • the aromatic content in the de-aromatized solvents is in range of 20 ppm to 50 ppm.
  • the process for preparation of de-aromatized solvents disclosed herein can be used advantageously to produce de-aromatized solvents with aromatic content in a range of 5 ppm to 100 ppm and sulfur content in a range of 0.5 ppm to 1 ppm from a distillate having boiling point in the range of 150° C to 350° C, aromatic content in range of 5000 ppm to 40000 ppm, and sulfur content in range of 0 ppm to 1 ppm.
  • the distillate has aromatic content in range of 5000 to 20000 ppm.
  • the aromatic content in the de-aromatized solvents is in range of 20 ppm to 50 ppm.
  • the process for preparing de-aromatized hydrocarbon solvents from the selective hydrogenation of a hydrocarbon feedstream disclosed herein involves distillation of a heavy hydrocarbon feedstream, followed by catalytic hydrotreatment, fractionation and catalytic selective hydrogenation.
  • the hydrocarbon feedstream utilized for the production of de-aromatized solvents is one or more selected from crude oil, heavy vacuum gas oil, and lube base oil.
  • the hydrocarbon feedstream is distilled to obtain a first distillate having boiling point in the range of 180° C to 550° C.
  • the first distillate is then subjected to hydrotreatment in presence of hydrotreating catalyst to obtain a hydrocarbon stream having sulfur content of less than 100 ppm
  • the hydrotreating catalyst used in the process comprises one or more active metals selected from cobalt, nickel, and molybdenum-phosphorus impregnated on one or more support selected from alumina, silica, titania, and zirconia.
  • the hydrotreatment of the first distillate in the process is carried out at a reactor temperature ranging from 300° C to 450 °C, reactor pressure ranging from 60 bar to 180 bar, weight hourly space velocity (WHSV) ranging from 0.5 h -1 to 3.0 h -1 , and volume ratio of hydrogen to heavy hydrocarbon stream ranging from 100 Nm 3 /m 3 to 1500 Nm 3 /m 3 .
  • reactor temperature ranging from 300° C to 450 °C
  • reactor pressure ranging from 60 bar to 180 bar
  • WHSV weight hourly space velocity
  • volume ratio of hydrogen to heavy hydrocarbon stream ranging from 100 Nm 3 /m 3 to 1500 Nm 3 /m 3 .
  • the hydrotreatment of the first distillate is carried out at a reactor temperature ranging from 350° C to 400 °C, reactor pressure ranging from 100 bar to 150 bar, weight hourly space velocity (WHSV) ranging from 0.75 h -1 to 1.25 h -1 , and volume ratio of hydrogen to heavy hydrocarbon stream ranging from 400 Nm 3 /m 3 to 1000 Nm 3 /m 3
  • WHSV weight hourly space velocity
  • the hydrocarbon stream having sulfur content of less than 100 ppm is then isodewaxed and fractionated to obtain a second distillate having boiling point in the range of 150° C to 350° C.
  • the second distillate is then subjected to selective hydrogenation in the presence of a monometallic nickel-based hydrogenating catalyst to obtain the de-aromatized hydrocarbon solvents aromatic content in a range of 5 ppm to 100 ppm and sulfur content in a range of 0.5 ppm to 1 ppm.
  • the aromatic content of de-aromatized solvent obtained is in a range of 20 ppm to 50 ppm.
  • the selective hydrogenation of the second distillate in the process is carried out at a reactor temperature ranging from 80 °C to 200 °C, reactor pressure ranging from 25 bar to 35 bar, liquid hourly space velocity (LHSV) ranging from 0.25 h' 1 to 2.0 h’ 1 , and volume ratio of hydrogen to second distillate ranging from 40 Nm 3 /m 3 to 100 Nm 3 /m 3 .
  • reactor temperature ranging from 80 °C to 200 °C
  • reactor pressure ranging from 25 bar to 35 bar
  • LHSV liquid hourly space velocity
  • volume ratio of hydrogen to second distillate ranging from 40 Nm 3 /m 3 to 100 Nm 3 /m 3 .
  • the selective hydrogenation of the second distillate in the process is carried out at a reactor temperature ranging from 140 °C to 180 °C, reactor pressure ranging from 10 bar to 45 bar, liquid hourly space velocity (LHSV) ranging from 0.5 h' 1 to 1.0 h’ 1 , and volume ratio of hydrogen to second distillate ranging from 50 Nm 3 /m 3 to 70 Nm 3 /m 3 .
  • reactor temperature ranging from 140 °C to 180 °C
  • reactor pressure ranging from 10 bar to 45 bar
  • LHSV liquid hourly space velocity
  • volume ratio of hydrogen to second distillate ranging from 50 Nm 3 /m 3 to 70 Nm 3 /m 3 .
  • the reactor pressure and volume ratio of hydrogen to second distillate is advantageously low in comparison to other processes for the preparation of de-aromatized solvents from hydrocarbons.
  • Example 1.2 Preparation of Ni dispersed on alumina support 37.5 grams of alumina extrudes prepared as per the process disclosed in Example- 1 above is then dispersed with nickel metal through spray impregnation wherein a solution containing 182 grams of Ni(NO3)2.6H2O in 70 ml of distilled water is sprayed on the extrudes and wet extrudes is dried under vacuum at 70 °C followed by e drying in an oven at 100 °C and further drying at 120 °C for 12 hours.
  • the dried extrudes is then subjected to calcination at 450 °C at a heating rate 5 °C/min for a duration of 5 hours in an open-air muffle furnace to obtain a catalyst comprising nickel metal dispersed on an alumina support.
  • Example 1.3 Preparation of Ni dispersed on alumina support though two-stage spray impregnation
  • alumina extrudes prepared as per the process disclosed in Example- 1 above is then dispersed with nickel metal through spray impregnation wherein a solution containing 96 grams of Ni(NO3)2.6H2O in 40 ml of distilled water is sprayed on the extrudes and wet extrudes is dried under vacuum at 70 °C followed by drying in an oven at 100 °C and further drying at 120 °C for 12 hours.
  • the dried extrudes is then sprayed with a solution containing 86 grams of Ni(NO3)2.6H2O in 40 ml of distilled water and the wet extrudes is then dried under vacuum at 70 °C followed by drying at 120 °C for 12 hours.
  • the dried extrudes is then subjected to calcination at 450 °C at a heating rate 5 °C/min for a duration of 5 hours in an open -air muffle furnace to obtain a catalytic system comprising nickel metal dispersed on alumina support.
  • Example 1.4 Preparation of Ni dispersed on phosphorous modified alumina support
  • alumina extrudes prepared as per the process disclosed in example 1.1 is sprayed with a phosphoric acid solution (H3PO4) containing 3 wt. % of phosphoric acid in 20 ml of water to obtain phosphorous modified alumina extrudes.
  • H3PO4 phosphoric acid solution
  • 37.5 grams of this phosphorous modified alumina extrudes is dispersed with nickel metal through spray impregnation wherein a solution containing 182 grams of Ni(NO3)2.6H2O in 150 ml of distilled water is sprayed on the extrudes and wet extrudes is dried under vacuum at 70 °C followed by e drying in an oven at 100 °C and further drying at 120 °C for 12 hours.
  • Example 1.5 Preparation of Ni dispersed on alumina support through 4 -stage spray impregnation
  • alumina extrudes prepared as per the process disclosed in Example- 1 above is then dispersed with nickel metal through spray impregnation wherein a solution containing 36.4 grams of Ni(NO3)2.6H2O in 20 ml of distilled water is sprayed on the extrudes and wet extrudes is dried under vacuum at 70 °C followed by drying in an oven at 100 °C and further drying at 120 °C for 12 hours. Similarly, 10% of metal loading is done in subsequent 4 steps and the final wet extrudes is dried under vacuum at 70 °C followed by drying at 120 °C for 12 hours.
  • the dried extrudes is then subjected to calcination at 450 °C at a heating rate 5 °C/min for a duration of 5 hours in an open-air muffle furnace to obtain a catalytic system comprising nickel metal dispersed on alumina support.
  • a hydrocarbon feedstream comprising 8500 ppm of monoaromatics, 115 ppm of di-aromatics, and 52 ppm of poly-aromatics is subjected to a hydrogenation reaction in presence of monometallic catalyst prepared in Example- 1.2, 1.3, 1.4, and 1.5 at a temperature of 160 °C, pressure of 30 bar, H2/HC ratio of 100 Nm3/m3 and LHSV of 0.71 s' 1 at 24 hours TOS and the amount of monoaromatics, diaromatics and polyaromatics in the output stream is ascertained to determine de-aromatization efficiency of the catalysts.
  • Table-2 Content of monoaromatics, diaromatics, and polyaromatics in the output stream
  • Example 4 Obtaining low sulfur 2 nd distillate from 1 st distillate for production of dearomatized hydrocarbon solvents
  • First distillate having IBP of 341 Deg C and FBP of 507 Deg C with sulfur of 1.2 wt% was hydrotreated at 348 Deg C, hydrogen to feed ratio of 664 Nm 3 /m 3, WHSV 0.92 Hr 1 , pressure 145 barg, using hydrotreating catalyst of Nickel-Cobalt on alumina. Then the hydrotreated stream was isodewaxed and fractionated to obtain second distillate having IBP of 160 Deg C and FBP of 336 Deg C having sulfur less than 1 ppm and aromatics 6800 ppm.
  • Example 5 Time on stream study of mono-metallic hydrogenation catalyst prepared using Example 1.3 for production of de-aromatized hydrocarbon solvents

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un catalyseur d'hydrogénation monométallique à base de nickel, un procédé de préparation dudit catalyseur. Ledit catalyseur est utilisé dans la préparation de solvants désaromatisés présentant une très faible teneur en composés aromatiques et une très faible teneur en soufre. L'invention concerne également un catalyseur monométallique comprenant 10 à 60 pour cent en poids de nickel métallique chargé sur un oxyde métallique réfractaire et présentant une réductibilité du nickel métallique dans la plage de 80 % à 90 % à une température de réduction dans la plage de 440 à 480°C. L'invention concerne en outre un procédé d'hydrogénation sélective d'un flux d'alimentation en hydrocarbures présentant une teneur en aromatiques élevée dans la plage de 5 000 ppm à 40 000 ppm en présence du catalyseur d'hydrogénation monométallique afin d'obtenir des solvants désaromatisés présentant une teneur en composés aromatiques inférieure à 100 ppm.
PCT/IN2024/050120 2023-02-09 2024-02-07 Catalyseur d'hydrogénation à base de nickel monométallique et son procédé de préparation Ceased WO2024166132A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011080515A2 (fr) * 2010-01-04 2011-07-07 Johnson Matthey Plc Catalyseur et procédé de fabrication de catalyseur
EP3388499A1 (fr) * 2017-04-11 2018-10-17 Hindustan Petroleum Corporation Ltd. Procédé de préparation de solvants d'hydrocarbures désaromatisés

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011080515A2 (fr) * 2010-01-04 2011-07-07 Johnson Matthey Plc Catalyseur et procédé de fabrication de catalyseur
EP3388499A1 (fr) * 2017-04-11 2018-10-17 Hindustan Petroleum Corporation Ltd. Procédé de préparation de solvants d'hydrocarbures désaromatisés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JERRY F. KRIZ: "Nickel-containing catalysts for hydroprocessing of aromatic oils", FUEL, vol. 74, no. 12, 1 December 1995 (1995-12-01), GB, pages 1852 - 1857, XP093155132, ISSN: 0016-2361, DOI: 10.1016/0016-2361(95)80018-D *

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