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WO2020117119A1 - Procédé de conversion de glycérol en propane - Google Patents

Procédé de conversion de glycérol en propane Download PDF

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Publication number
WO2020117119A1
WO2020117119A1 PCT/SE2019/051231 SE2019051231W WO2020117119A1 WO 2020117119 A1 WO2020117119 A1 WO 2020117119A1 SE 2019051231 W SE2019051231 W SE 2019051231W WO 2020117119 A1 WO2020117119 A1 WO 2020117119A1
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WIPO (PCT)
Prior art keywords
glycerol
catalyst
nickel
petroleum refinery
alumina
Prior art date
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Ceased
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PCT/SE2019/051231
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English (en)
Inventor
Christian Hulteberg
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Biofuel Solution I Malmo AB
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Biofuel Solution I Malmo AB
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Application filed by Biofuel Solution I Malmo AB filed Critical Biofuel Solution I Malmo AB
Publication of WO2020117119A1 publication Critical patent/WO2020117119A1/fr
Anticipated expiration legal-status Critical
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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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/635—0.5-1.0 ml/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0201—Impregnation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
    • C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals 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
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/882—Molybdenum and cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/28—Propane and butane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the invention relates to process for converting glycerol to propane. Further, the invention relates to a process for improving the yield of liquefied petroleum gas, and in particular propane, in a petroleum refinery.
  • Propane normally traded as liquefied petroleum gas or LPG, is a good energy carrier, especially in rural areas.
  • the propane used today is typically a derivative of crude oil. Similar to natural gas, LPG thus contributes to a net emission of greenhouse gases when used. Biogas has emerged as a green alternative to natural gas.
  • liquid hydrocarbon fuels e.g. gasoline and diesel
  • biodiesel e.g. methyl esters of fatty acids derived from tri-glycerides
  • conversion of e.g. tall oil to hydrocarbons to be used on their own, or to be blended with diesel derived from crude oil has emerged as way of reducing the carbon footprint.
  • a process for production of normal alkanes by hydrotreating mixtures of triglycerides and vacuum gasoil over a catalyst is disclosed.
  • renewable resources there is a similar desire to move towards using renewable resources also for the production of LPG or propane.
  • Examples in the art addressing this need include processes for converting glycerol, obtained as side product in biodiesel production, to ethane, ethane, or propane (cf. WO 2010/052208 and US 2009/0054701).
  • renewable resources There is, however, much capital and infrastructure needed for setting up dedicated plants for producing propane from sources not contributing to net emissions of greenhouse gases when used, hereon forth called renewable resources.
  • An object of the invention is to alleviate, at least one of the above stated problem.
  • a process for converting glycerol to propane in a petroleum refinery is provided.
  • crude oil is fractioned and refined to eventually provide various hydrocarbon fractions, e.g. LPG, gasoline, kerosene, diesel etc.
  • various hydrocarbon fractions e.g. LPG, gasoline, kerosene, diesel etc.
  • petroleum refinery intermediate streams e.g. naphtha, kerosene (middle distillate), light gas oil, heavy gas oil, or vacuum gas oil
  • petroleum refinery typically includes other unit operations, e.g. hydrotreatment and cracking (cf. Fig. 1 showing an exemplary flow scheme for petroleum refining).
  • hydrotreatment is a process to reduce sulfur, aromatics, nitrogen, and oxygen in petroleum refinery intermediate streams.
  • hydrotreatment is used to enhance the combustion quality, density and smoke point of distillates, as it serves to reduce sulfur, aromatics, nitrogen, and oxygen.
  • Compounds comprising sulfur, nitrogen, and oxygen and/or being aromatic are by hydrotreatment converted into more volatile compounds, e.g. hydrogen sulfide, ammonia, and water, which may be removed from the petroleum refinery intermediate stream.
  • a petroleum refinery intermediate stream e.g. gas oil (sometimes denoted atmospheric gas oil), or vacuum oil
  • Cracking is a process in which complex organic, often aromatic, molecules, such as kerogens, or long-chain hydrocarbons are broken down into smaller and simpler molecules, such as lighter hydrocarbons. Cracking typically lowers the amount of aromatics. Further, the boiling point of long-chain hydrocarbons, by cracking them into hydrocarbons with shorter carbon chains, is lowered. In short, cracking is the breaking of carbon-carbon bonds in the starting material.
  • glycerol may be hydrotreated as a mixture with a petroleum refinery intermediate stream, though some adjustments to the standard process may be required to provide an effective process.
  • Treating, glycerol as a mixture with a petroleum refinery intermediate stream may further be advantageous, as dilution of the glycerol will attenuate the oligomerization and/or polymerization of glycerol monomers upon heating the glycerol stream, thus improving the yield of propane and lowering de-activation of the hydrotreatment catalyst
  • the process for converting glycerol to propane in a petroleum refinery comprises the steps of:
  • glycerol a petroleum refinery intermediate stream, such as vacuum gas oil and/or gas oil (atmospheric gas oil), to provide a mixed stream comprising glycerol;
  • a petroleum refinery intermediate stream such as vacuum gas oil and/or gas oil (atmospheric gas oil)
  • the glycerol is mixed with the petroleum refinery intermediate stream before being introduced into the reactor.
  • the glycerol and the petroleum refinery intermediate stream, respectively are fed separately to the reactor and mixed therein.
  • the amount of the petroleum refinery intermediate exceeds the amount of glycerol.
  • the glycerol may be mixed with the petroleum refinery intermediate stream in a ratio of less than 50:50 on a weight basis.
  • the glycerol may be mixed with the petroleum refinery intermediate stream in a ratio of from 10:90 to 40:60 on a weight basis.
  • the catalyst may be a supported, porous heterogeneous catalyst comprising nickel, or cobalt, and molybdenum.
  • the support may be alumina, such as delta-(6)- alumina.
  • the catalyst may comprise 1 to 6 wt.% nickel or cobalt. Further, the catalyst may comprise 5 to 15 wt.% molybdenum. According to an embodiment, the catalyst comprises nickel and molybdenum. According to such an embodiment, the catalyst may comprise 2 to 5 wt.% nickel, and 5 to 10 wt.% molybdenum.
  • the support may, according to such an embodiment be delta(6)-alumina.
  • the catalyst is typically used in its sulfide form.
  • the support of the supported, heterogeneous catalyst is aluminum oxide, AI2O3 (alumina).
  • the crystal structure of the alumina is preferably delta phase. Further, preferably the alumina comprises;
  • the alumina support may be in the form of an extrudate having a diameter of
  • the catalyst is a heterogeneous catalyst obtainable by a two-step procedure, starting from a pre-shaped, e.g. extrudated, support of porous delta-alumina.
  • the first step is an incipient wetness impregnation, where the desired amount of ammonium molybdate is deposited on the catalyst using a water solution that is allowed to fill the catalyst pore system entirely.
  • the second step is an incipient wetness impregnation with a water solution containing the nitrate or acetate salt of nickel or cobalt, with citric acid added up to a stoichiometric amount to the nickel or cobalt.
  • the catalyst may then be transferred to its sulfide state by reaction with a sulfur-containing hydrocarbon or hydrogen sulfide before use.
  • the catalyst is a heterogeneous catalyst obtainable by procedure outlined below.
  • porous delta-alumina acting as support, is impregnated with aqueous solution of ammonium molybdate to fill the catalyst pore system.
  • the catalyst is dried and calcined.
  • the alumina support with molybdate is impregnated with an aqueous solution comprising a nitrate or acetate salt of cobalt or nickel and citric acid (added in ratio of 0.5 to 1 mol citric acid per mol cobalt or nickel) to fill the catalyst pore system.
  • the catalyst is once more dried and calcined.
  • the provided catalyst is used in its sulfide form.
  • the catalyst may be transferred to its sulfide state by reaction with a sulfur-containing hydrocarbon or hydrogen sulfide before use.
  • citric acid By adding citric acid, the pH is lowered, whereby changing the adsorption properties of cobalt and nickel to enhance the activity of the final catalyst.
  • the support is typically porous to increase the ratio of active surface area per weight unit.
  • the alumina support defining the structure of the catalyst, is thus porous. Further, smaller pore size does typically provide higher efficiency. However, for the present process, a catalyst with somewhat larger pores is preferred. It was found (cf. examples 4 and 5) that a conventional hydrotreatment catalysts with smaller pores (diameter of about 60
  • Angstrom is by far less efficient compared to a catalyst with larger pores (e.g. diameter of about 120 Angstrom). Seemingly, the catalyst with smaller pores is more prone to deactivation resulting from carbonization, which, without being bound to any theory, may explain its lower activity. Accordingly, the average pore diameter of the catalyst thus exceeds 60 Angstrom. Preferably, the average pore diameter of the catalyst is at least 80 Angstrom, or even at least 100 Angstrom, such as about 120 Angstrom. Thus, the average pore diameter of the catalyst may be 80 to 200 Angstrom such as 100 to 140 Angstrom. The average pore diameter of the catalyst may be determined using nitrogen physisorption at liquid nitrogen temperatures and calculated using e.g.
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901- 2:2006.
  • a representative sample is extracted using the procedure of ISO 8213 : 1986. The sample is first degassed under vaccuum and at temperatures above
  • the analysis is then performed using one of four methods: static volumetric method, flow volumetric method, carrier gas method or gravimetric method. According to an embodiment, the analysis is performed using the static volumetric method.
  • the adsorbed gas typically nitrogen
  • the adsorption/desorption isotherm the adsorption/desorption isotherm
  • liquid nitrogen temperature 77 Kelvin
  • the t-plot method is used for determining if the sample contain mesopores. Thereafter one of two methods can be employed, algebraic methods, such as the Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (1):373- 380. doi: 10.1021/jaOl 145al26], or non-localised denisity function theory, as described in ISO 15901-3:2007.
  • the non-localised density function theory as described in ISO 15901-3:2007 is used.
  • the algebraic method of Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (l):373-380; doi: 10.1021/jaOl 145al26] is used.
  • the calculated values for incremental pore volume are then expressed as a function of pore diameter.
  • the average poor diameter is calculated from the thus obtained pore size distribution. As recognized by the skilled person, the average poor diameter is the pore diameter with 50% of the total pore volume above as well as below the pore diameter value.
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-2:2006 using the static volumetric method and the algebraic method of Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (l):373-380;
  • the alumina support thus has average pore diameter exceeding 60 Angstrom.
  • the average pore diameter of the alumina support is at least 80 Angstrom, or even at least 100 Angstrom, such as about 120 Angstrom.
  • the average pore diameter of the alumina support may be 80 to 200 Angstrom such as 100 to 140 Angstrom.
  • the average pore diameter of the alumina support may be determined using nitrogen physisorption at liquid nitrogen temperatures and calculated using e.g. the BJH (Barret, Joyner, and Halenda) method assuming cylindrical pores (cf. Barrett EP, Joyner LG, Halenda PP (1951) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms. J Am Chem Soc 73 (l):373-380. doi: 10.1021/ja01145al26).
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901- 2:2006.
  • a representative sample is extracted using the procedure of ISO 8213 : 1986. The sample is first degassed under vaccuum and at temperatures above
  • the analysis is then performed using one of four methods: static volumetric method, flow volumetric method, carrier gas method or gravimetric method. According to an embodiment, the analysis is performed using the static volumetric method.
  • the adsorbed gas typically nitrogen
  • the adsorption/desorption isotherm the adsorption/desorption isotherm
  • liquid nitrogen temperature 77 Kelvin
  • the t-plot method is used for determining if the sample contain mesopores. Thereafter one of two methods can be employed, algebraic methods, such as the Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (1):373- 380. doi: 10.1021/jaOl 145al26], or non-localised denisity function theory, as described in ISO 15901-3:2007.
  • the non-localised density function theory as described in ISO 15901-3:2007 is used.
  • the algebraic method of Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (l):373-380; doi: 10.1021/jaOl 145al26] is used.
  • the calculated values for incremental pore volume are then expressed as a function of pore diameter.
  • the average poor diameter is calculated from the thus obtained pore size distribution. As recognized by the skilled person, the average poor diameter is the pore diameter with 50% of the total pore volume above as well as below the pore diameter value.
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-2:2006 using the static volumetric method and the algebraic method of Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (l):373-380;
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901- 2:2006 using the static volumetric method and the non-localised density function theory described in ISO 15901-3:2007.
  • the average pore diameter is determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-2:2006 using the static volumetric method and the algebraic method of Barrettt, Joyner and Halenda method [J Am Chem Soc 73 (l):373-380;
  • the pore volume of the support may be at least 0.75 ml/g.
  • the pore volume of the alumina support may be determined using nitrogen physisorption at liquid nitrogen temperatures and calculated using the method suggested by Barret et al (cf. above).
  • the alumina support has a surface area of 120 ⁇ 10 m 2 /g.
  • the density of the alumina support may be 0.42 to 0.56 g/ml.
  • the hydrotreatment takes place in a rector to which glycerol, a petroleum refinery intermediate stream, and hydrogen is fed.
  • the glycerol and the petroleum refinery intermediate stream may be fed as a mixture (preferred) or separately to the reactor.
  • the catalyst is present.
  • the reactor may be operated as a fixed bed reactor. Typically, the reactor is operated at a total pressure of 60 to 120 bar and at a temperature of 330 to 420 °C.
  • the partial pressure of hydrogen may be 20 to 70 bar.
  • the petroleum refinery intermediate stream is a petroleum refinery intermediate stream as defined in Table 1, such as heavy naphtha, kerosene (middle distillate), light gas oil (atmospheric light gas oil), heavy gas oil (atmospheric heavy gas oil), or vacuum gas oil.
  • the petroleum refinery intermediate stream is preferably a stream already being subject to hydrotreatment step in the petroleum refinery.
  • the petroleum refinery intermediate stream is light gas oil (atmospheric light gas oil), heavy gas oil
  • the petroleum refinery intermediate stream may be light gas oil (atmospheric light gas oil) or vacuum gas oil, as defined in Table 1.
  • glycerol may be added to any hydrotreatment step in a petroleum refinery. Further, glycerol may also be added to other unit operation(s) in a petroleum refinery able to convert glycerol to propane, such as to a hydro cracker and/or to a catalytic cracker.
  • the mixed stream of glycerol and the petroleum refinery intermediate stream may still be a liquid stream if being high boiling.
  • the mixed stream may thus be hydrotreated in liquid state.
  • the mixed stream may be hydrotreated in gaseous state.
  • the process may comprise the step of pre-heating the glycerol before being mixed with the petroleum refinery intermediate stream.
  • the petroleum refinery intermediate-stream may be fed from the initial distillation of crude oil, this stream may already be heated.
  • the petroleum refinery intermediate-stream is very lipohilic, whereas glycerol is highly hydrophilic. In liquid state, they are thus not miscible, whereas the gaseous forms are.
  • the mixed stream may be hydrotreated as a two-phase system, it is preferred to affect the solubility of glycerol in the petroleum refinery intermediate stream.
  • a surfactant is thus present in the step of mixing the glycerol with the petroleum refinery intermediate stream.
  • the surfactant is mixed with the glycerol before mixing the glycerol with the petroleum refinery intermediate stream.
  • the surfactant may be added in a weight ratio, with respect to glycerol, of 1 : 10 or less. However, preferably the ratio is lower than 1 :10.
  • the surfactant may thus be added in a weight ratio, with respect to glycerol, of 1 :25 or less such as of 1 : 100 or less.
  • the surfactant may thus be added in a weight ratio, with respect to glycerol of 1 :25 to 1 :500, such as 1 :50 to 1 :250, or 1 :75 to 1 :150.
  • the he surfactant As the he surfactant is to be present in the hydrotreatment, it should be essentially free from metal. There is a low tolerance to metals entering the hydrotreatment
  • the surfactant is a polymeric surfactant.
  • Polymeric surfactants are macromolecules, which contain both hydrophilic and hydrophobic parts in their structure.
  • One type of polymeric surfactants is derived by the polymerization of a surface-active monomer. Such polymeric surfactants also known as polysoaps.
  • Another type of polymeric surfactants is derived by copolymerization of a hydrophobic and a hydrophilic monomer. This kind of copolymers can thus have a random, a gradient, or a block structure.
  • Amphiphilic diblock copolymers are basically the macromolecular transposition of low-molecular weight surfactants and,
  • polymeric surfactants comprises of EO/PO block copolymers, acrylic/styrene copolymers, methacrylic copolymers, poly hydroxystearate derivatives and alkyd PEG resin derivatives.
  • a preferred polymeric surfactant is Hypermer B246-SO sold by Croda.
  • the source of the glycerol is not essential in terms of successfully converting the glycerol. However, in terms of providing a process for producing propane from a renewable resource, at low cost, the source of the glycerol is of importance. According to an embodiment, the glycerol thus stems from glycerol obtained as side product in biodiesel production.
  • the glycerol to be mixed with the petroleum refinery intermediate stream may be provided from a methyl transesterification process, wherein a triglyceride and methanol are the starting materials.
  • the glycerol to be mixed with the petroleum refinery intermediate stream may be aqueous glycerol comprising at least 75 wt.% glycerol and up to 25 wt.% water.
  • the aqueous glycerol may comprise at least 80 wt.% glycerol and up to 20 wt.% water, at least 85 wt.% glycerol and up to 15 wt.% water, or at least 90 wt.% glycerol and up to 10 wt.% water.
  • salts e.g. inorganic salts
  • they may be removed by use of a combination of anion and cation exchange resins.
  • Anion and cation exchange resins are preferred over, e.g. traditional distillation process as they require much lower energy input for the purification.
  • the aqueous glycerol comprises less than 100 ppm inorganic salts, such as less than 50 ppm inorganic salts, less than 25 ppm inorganic salts, or less 15 ppm inorganic salts.
  • a fraction comprising propane is separated.
  • a fraction comprising propane is typically easily separated from other hydrocarbons originating from the petroleum refinery intermediate stream, having significantly higher boiling point, e.g. by distillation.
  • the separated fraction comprising propane is a liquid petroleum gas fraction.
  • typical unit operations apart from fractional distillation and hydrotreatment, typically include cracking.
  • Cracking serves to crack higher hydrocarbons to lower hydrocarbons. Further, cracking may serve to crack aromatics to hydrocarbons. Examples of cracking include catalytic cracking and/or hydro cracking.
  • the refined, mixed stream is subject to cracking before separating a fraction comprising propane from the refined, mixed stream.
  • the cracking may be catalytic cracking and/or hydro cracking. Such cracking may further increase the content of propane.
  • a catalyst with somewhat larger pores it was found to be advantageous to use a catalyst with somewhat larger pores.
  • an alumina supported, heterogeneous and porous catalyst comprising nickel, or cobalt, and molybdenum, and having an average pore diameter exceeding 60 Angstrom, to convert glycerol to propane in a petroleum refinery by hydrotreatment of a mixture of glycerol and a petroleum refinery intermediate stream with hydrogen over the catalyst.
  • the mixture of glycerol and the petroleum refinery intermediate stream may further comprise a surfactant to provide one-phase system.
  • the average pore diameter of the catalyst may be at least 80 Angstrom, such as at least 100 Angstrom. Further, the average pore diameter of the catalyst may be 80 to 200 Angstrom, such as 100 to 140 Angstrom.
  • the average pore diameter of the catalyst may be determined as has been describe herein above. Accordingly, the average pore diameter is, according to an embodiment, determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-2:2006.
  • the alumina support may have average pore diameter exceeding 60 Angstrom.
  • the average pore diameter of the alumina support is at least 80 Angstrom, or even at least 100 Angstrom, such as about 120 Angstrom.
  • the average pore diameter of the alumina support may be 80 to 200 Angstrom, such as 100 to 140 Angstrom.
  • the average pore diameter of the alumina support may be determined as has been describe herein above. Accordingly, the average pore diameter is, according to an embodiment, determined from the pore size distribution determined by gas adsorption in accordance with ISO 15901-2:2006.
  • the pore volume of the support may be at least 0.75 ml/g.
  • the pore volume of the alumina support may be determined using nitrogen physisorption at liquid nitrogen temperatures and calculated using the method suggested by Barret et al. (cf. above).
  • the alumina support has a surface area of 120 ⁇ 10 m 2 /g.
  • the density of the alumina support may be 0.42 to 0.56 g/ml.
  • the catalyst is a supported, heterogeneous and porous catalyst comprising nickel, or cobalt, and molybdenum.
  • the support may be alumina, such as delta-(6)- alumina.
  • the catalyst may comprise 1 to 6 wt.% nickel or cobalt. Further, the catalyst may comprise 5 to 15 wt.% molybdenum. According to an embodiment, the catalyst comprises nickel and molybdenum. According to such an embodiment, the catalyst may comprise 2 to 5 wt.% nickel, and 5 to 10 wt.% molybdenum.
  • the support may, according to such an embodiment be delta(6)-alumina.
  • the catalyst is typically used in its sulfide form.
  • the catalyst may be a porous and heterogeneous catalyst obtainable by:
  • the mixture of glycerol and the petroleum refinery intermediate stream may comprise a surfactant.
  • Fig. 1 depicts an exemplary flow scheme for petroleum refining. Examples
  • Example 1 mixed stream comprising glycerol and light gas oil
  • a 10% by weight glycerol solution in a light gas oil was prepared by mixing 1 g of surfactant (Hypermer B246-SO sold by Croda) with 100 g of aqueous glycerol of 95% purity and mixing it slowly with 900 g of light gas oil (boiling point 260 to 315°C). The mixing was performed using moderate stirring at 25°C and by slowly adding the glycerol and surfactant to the mixture.
  • surfactant Hydrophilic acid
  • Example 2 - mixed stream comprising slvcerol and vacuum gas oil
  • a 10% by weight glycerol solution in a vacuum gas oil was prepared by mixing 1 g of surfactant (Hypermer B246-SO sold by Croda) with 100 g of aqueous glycerol of 95% purity and mixing it slowly with 900 g of vacuum gas oil (boiling point 425 to 600°C). The mixing was performed using moderate stirring at 50°C and by slowly adding the glycerol and surfactant to the mixture.
  • the catalyst was prepared in two steps, starting from a pre-shaped support of porous delta-alumina provided by Sasol GmbH.
  • the alumina support had an average pore diameter of 120 Angstrom, a pore volume of 0.77 ml/g and a specific surface area of 118 m 2 /g.
  • the support was in a granular form sieved to between 10 and 20 mesh, resulting in 0.5 to 1 mm particles of irregular shape.
  • the first step was an incipient wetness impregnation where the desired amount of ammonium molybdate was deposited on the catalyst using a water solution that was allowed to entirely fill the catalyst pore system, followed by drying and calcination.
  • concentration of the ammonium molybdate tetra hydrate as purchased from Sigma Aldrich (99% purity) was 190 g/liter.
  • the catalyst was dried at ambient temperature for 4 h and then at 120°C for 12 h. The temperature was thereafter increased by 4°C/min from 120°C to 500°C.
  • the second step was an incipient wetness impregnation with a water solution containing the nitrate salt of nickel, with citric acid added up to a stoichiometric amount to the nickel, followed by drying and calcination
  • the purpose of the citric acid is to lower the pH to change the adsorption properties of the nickel or cobalt to enhance the activity of the final catalyst.
  • the second step of catalyst preparation was performed starting from the catalyst intermediate from step one after it has been allowed to cool to ambient temperature.
  • the second incipient wetness impregnation was performed using a mixture of deionized water, nickel nitrate hexahydrate (Sigma Aldrich, 99% purity) and citric acid mono hydrate (Sigma Aldrich, 99% purity).
  • the concentrations of nickel nitrate hexahydrate was 209 g/liter, and citric acid monohydrate was 106 g/liter respectively.
  • the catalyst was dried at ambient temperature for 4 h and then at 120°C for 12 h. The temperature was thereafter increased by 4°C/min from 120°C to 500°C.
  • the catalyst is then transferred to its sulfide state by reaction with sulfur-containing hydrocarbons or hydrogen sulfide before use.
  • hydrogen sulphide at 1,000 ppm concentration in hydrogen was used at a gas hourly space velocity of 500 starting at ambient temperature and increasing the temperature with 2°C/min to 400°C and holding at this temperature for 4 h.
  • the resulting catalyst had an average pore diameter of 117 Angstrom, a pore volume of 0.75 ml/g, a surface area of 113 m 2 /g, a Ni concentration of 3.1 wt% and a Mo concentration of 8.9 wt%.
  • two catalyst consisting of 3 wt% Ni and 8 wt% Mo supported on alumina, one commercial (with 60 Angstrom in average pore diameter) and the another one with 117 Angstrom in average pore diameter (cf. example 3), were used.
  • the two catalysts were loaded in one reactor each with a 15 mm inner diameter and operated as a fixed bed with a liquid hourly space velocity of 1.5 h 1 using a simulated vacuum gas oil feedstock mixed with 10% by weight glycerol as prepared in example 1.
  • the reactor was operated for 200 h using each catalysts at 100 bar and 360°C.
  • the operation of the reactor with the small-pore catalyst showed an increase in propane production and the yield was calculated to 76%.
  • the propane production corresponded to a yield of 91%.
  • Post mortem analysis of the catalysts showed that the small pore catalyst was containing 10.8% by weight heavy carbon residue, while the corresponding number for the open-pore catalyst was 1.7% by weight. As can be seen, difference between the two catalysts was even more pronounced for hydrocarbon feedstock with higher boiling point (light gas oil vs vacuum gas oil).
  • another catalyst was prepared following the same method as in example 3, but omitting the citric acid from the second impregnation solution. This resulted in a much lower dispersion of the active Ni and Mo phase.
  • the catalysts were analyzed using hydrogen chemisorption. Firstly, the catalysts were reduced at 400°C using a gas stream consisting of 4% hydrogen in He. Thereafter, an isotherm adsorption at 40°C was measured twice on the same sample. The difference between the two were calculated and represent the chemisorbed hydrogen.
  • the volume adsorbed by the catalyst prepared without citric acid was 0.109 ml of hydrogen adsorbed per gram of catalyst, while the catalyst prepared with citric acid was 0.189 ml of hydrogen adsorbed per gram of catalyst. There is thus a significant effect on the dispersion by adding the citric acid.

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Abstract

L'invention concerne un procédé de conversion de glycérol en propane dans une raffinerie de pétrole. Dans le procédé, du glycérol est mélangé avec un courant intermédiaire de raffinerie de pétrole, tel que du gazole sous vide et/ou du gazole léger, pour fournir un courant mixte comprenant du glycérol. Le courant mixte comprenant du glycérol est raffiné par hydrotraitement dans un réacteur dans la raffinerie de pétrole avec de l'hydrogène sur un catalyseur poreux, l'hydrotraitement réduisant le glycérol en propane, pour fournir un courant mixte raffiné ayant une teneur relative accrue en propane. Ensuite, une fraction comprenant du propane est séparée du courant mixte raffiné.
PCT/SE2019/051231 2018-12-05 2019-12-05 Procédé de conversion de glycérol en propane Ceased WO2020117119A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990243A (en) * 1989-05-10 1991-02-05 Chevron Research And Technology Company Process for hydrodenitrogenating hydrocarbon oils
US20090054701A1 (en) 2007-08-24 2009-02-26 Ramin Abhari Flexible glycerol conversion process
WO2010052208A2 (fr) 2008-11-05 2010-05-14 Biofuel-Solution Ab Procédé pour la préparation d'hydrocarbures inférieurs à partir de glycérol
US20100228068A1 (en) 2006-08-16 2010-09-09 Bioecon International Holding N.V. Production of linear alkanes by hydrotreating mixtures of triglycerides with vacuum gasoil
US20110046423A1 (en) * 2009-08-24 2011-02-24 Conocophillips Company Hydrotreating carbohydrates
US20140163272A1 (en) * 2012-12-11 2014-06-12 Ujjal K. Mukherjee Conversion of triacylglycerides-containing oils to hydrocarbons

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990243A (en) * 1989-05-10 1991-02-05 Chevron Research And Technology Company Process for hydrodenitrogenating hydrocarbon oils
US20100228068A1 (en) 2006-08-16 2010-09-09 Bioecon International Holding N.V. Production of linear alkanes by hydrotreating mixtures of triglycerides with vacuum gasoil
US20090054701A1 (en) 2007-08-24 2009-02-26 Ramin Abhari Flexible glycerol conversion process
WO2010052208A2 (fr) 2008-11-05 2010-05-14 Biofuel-Solution Ab Procédé pour la préparation d'hydrocarbures inférieurs à partir de glycérol
US20110046423A1 (en) * 2009-08-24 2011-02-24 Conocophillips Company Hydrotreating carbohydrates
US20140163272A1 (en) * 2012-12-11 2014-06-12 Ujjal K. Mukherjee Conversion of triacylglycerides-containing oils to hydrocarbons

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BARRETT EPJOYNER LGHALENDA PP: "The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms", J AM CHEM SOC, vol. 73, no. 1, 1951, pages 373 - 380, XP001145601, DOI: 10.1021/ja01145a126
BARRETTTJOYNERHALENDA, J AM CHEM SOC, vol. 73, no. 1, pages 373 - 380

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