WO2011086750A1 - 再生水素化処理用触媒 - Google Patents

再生水素化処理用触媒 Download PDF

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Publication number
WO2011086750A1
WO2011086750A1 PCT/JP2010/069840 JP2010069840W WO2011086750A1 WO 2011086750 A1 WO2011086750 A1 WO 2011086750A1 JP 2010069840 W JP2010069840 W JP 2010069840W WO 2011086750 A1 WO2011086750 A1 WO 2011086750A1
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Prior art keywords
catalyst
analysis
regenerated
regenerated catalyst
hydrotreating
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English (en)
French (fr)
Japanese (ja)
Inventor
信治 木村
睦修 岩波
渉 佐原
聡一郎 今野
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Japan Petroleum Energy Center JPEC
Eneos Corp
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Japan Petroleum Energy Center JPEC
JX Nippon Oil and Energy Corp
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Application filed by Japan Petroleum Energy Center JPEC, JX Nippon Oil and Energy Corp filed Critical Japan Petroleum Energy Center JPEC
Priority to US13/521,801 priority Critical patent/US8795514B2/en
Priority to CN201080061802.3A priority patent/CN102740967B/zh
Priority to SG2012047155A priority patent/SG181933A1/en
Priority to EP10843105.7A priority patent/EP2527034A4/en
Priority to RU2012135471/04A priority patent/RU2532444C2/ru
Publication of WO2011086750A1 publication Critical patent/WO2011086750A1/ja
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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV

Definitions

  • the present invention relates to a regenerated hydrotreating catalyst having excellent catalytic performance for treating petroleum fractions.
  • Crude oil contains sulfur-containing compounds, nitrogen-containing compounds, oxygen-containing compounds, etc. as impurities, and with regard to petroleum fractions obtained from crude oil through distillation and the like, each fraction has hydrogenation activity in the presence of hydrogen.
  • the content of these impurities is reduced by a process called a hydrotreating process which is brought into contact with a catalyst.
  • desulfurization for reducing the content of sulfur-containing compounds is well known.
  • regulations on the content of impurities, including sulfur-containing compounds in petroleum products, and the demand for reduction have become more stringent. Many so-called “sulfur-free” petroleum products are produced. Has been.
  • the hydrotreating catalyst used for hydrotreating the petroleum fraction is exchanged because its activity decreases due to the deposition of coke and sulfur when used for a certain period of time.
  • sulfur-free is required, and in the hydrotreating equipment for petroleum fractions such as kerosene, light oil and vacuum gas oil, high hydrotreating capacity is required, resulting in an increase in the frequency of catalyst replacement. This has led to increased catalyst costs and increased catalyst waste.
  • JP 52-68890 A JP-A-5-123586
  • the regenerated hydrotreating catalyst In using the regenerated catalyst, if the activity of the hydrotreating catalyst can be maintained even if the hydrotreating process and the regenerating process are repeated several times, the regenerated hydrotreating catalyst (hereinafter referred to as “regenerated hydrotreating process”).
  • the advantage of the use of “catalyst” or simply “regenerated catalyst”) is even greater.
  • used hydroprocessing catalyst hereinafter referred to as “used hydroprocessing catalyst” or simply “used catalyst”
  • used hydroprocessing catalyst it is one of the causes of the decrease in the activity of the hydroprocessing catalyst. Even if the activity can be recovered from the viewpoint of coke deposition, etc., the regeneration process itself may decrease the activity of the catalyst.
  • the regeneration catalyst since the catalyst activity after regeneration differs depending on the use history before regeneration of the catalyst, the regeneration treatment method, etc., the regeneration catalyst, particularly the regeneration catalyst after regeneration a plurality of times, does not always have a stable and sufficient activity. In some cases, it is necessary to select the conditions for the regeneration process depending on the history of the used catalyst. Then, when the regenerated catalyst is filled in the hydrotreating facility and the hydrotreating operation is started and it is found that its activity is low, it is necessary to reduce the processing speed of the raw oil, which is a big problem. Become.
  • the present invention has been made to solve the above-described problems, and an object thereof is to provide a regenerated catalyst that exhibits excellent desulfurization activity, and a method for producing petroleum products using the regenerated catalyst.
  • the present invention provides a petroleum fraction obtained by supporting molybdenum and at least one selected from Group 8 to 10 metals of an periodic table on an inorganic carrier containing aluminum oxide.
  • molybdenum composite metal In an X-ray diffraction spectrum, molybdenum composite metal The peak intensity of the oxide is 0.60 or more and 1.10 or less with respect to the reference peak, and a wide-area X-ray absorption fine structure (EXAFS, Extended) of X-ray absorption fine structure analysis (XAFS, X-ray Absorption Fine Structure) In the X-ray Absorption Fine Structure) spectrum, M derived from the residual sulfur peak.
  • the regenerated hydrotreating catalyst characterized in that the peak intensity of the o-S bond is 0.10 or more and 0.60 or less with respect to the reference peak, and an inorganic carrier containing aluminum oxide, molybdenum and a periodic table
  • a regenerated hydrotreating catalyst obtained by supporting at least one selected from Group 8-10 metals and regenerating a hydrotreating catalyst for treating petroleum fractions, having a carbon content 0.15 mass% or more and 3.0 mass% or less, and in the X-ray diffraction spectrum, the peak intensity of
  • the present invention also provides a method for producing a petroleum product, characterized in that hydrotreating of a petroleum fraction is performed using the regenerated hydrotreating catalyst of the present invention.
  • the hydrotreating conditions of the petroleum fraction are as follows: hydrogen partial pressure 3 to 13 MPa, LHSV 0.05 to 5 h ⁇ 1 , reaction temperature 200 ° C. to 410 ° C., hydrogen / oil ratio 100 to 8000 SCF / BBL
  • the boiling point of the petroleum fraction used as the feed oil is preferably in the range of 130 ° C. or higher and 700 ° C. or lower.
  • the present invention has an effect that a highly practical production process using an inexpensive regenerated catalyst having sufficient activity in the production of petroleum products can be realized, and cost reduction, waste emission reduction, This is very useful in terms of improving the efficiency of hydrotreating petroleum fractions.
  • MoO 3 is a diagram for explaining a method of determining proportions.
  • the unused hydrotreating catalyst (hereinafter referred to as “unused catalyst”) corresponding to the regenerated hydrotreating catalyst of the present invention is at least one selected from Group 8-10 metals of the periodic table and molybdenum. (Hereinafter, these are also collectively referred to as “active metals”). As the Group 8-10 metal of the periodic table, iron, cobalt, and nickel are preferable, cobalt and nickel are more preferable, and cobalt is particularly preferable. Periodic table Group 8-10 metals and molybdenum may be used alone or in admixture of two or more.
  • molybdenum-cobalt, molybdenum-nickel, molybdenum-cobalt-nickel or the like is preferably used as a combination of these metals.
  • the periodic table is a long-period type periodic table defined by the International Pure and Applied Chemical Association (IUPAC).
  • the unused catalyst is a catalyst in which the active metal is supported on an inorganic carrier containing aluminum oxide.
  • the inorganic carrier containing aluminum oxide include alumina, alumina-silica, alumina-boria, alumina-titania, alumina-zirconia, alumina-magnesia, alumina-silica-zirconia, alumina-silica-titania, and various zeolites.
  • a carrier obtained by adding a porous inorganic compound such as various clay minerals such as ceviolite and montmorillonite to alumina, among which alumina is particularly preferable.
  • the unused catalyst is an inorganic carrier containing aluminum oxide, at least one selected from 10 to 30% by mass of molybdenum as an oxide, based on the total mass of the catalyst, and Group 8 to 10 metal of the periodic table.
  • a catalyst obtained by supporting 1 to 7% by mass (for example, cobalt and / or nickel) as an oxide is preferable.
  • the precursor of the active metal species used when the active metal is supported on the inorganic carrier is not limited, but inorganic salts, organometallic compounds, etc. of the metal are used, and water-soluble inorganic salts are preferably used.
  • the supporting step it is preferable to support using a solution of these active metal precursors, preferably an aqueous solution.
  • a known method such as an immersion method, an impregnation method, a coprecipitation method, or the like is preferably employed.
  • the support on which the active metal precursor is supported is preferably dried and then calcined in the presence of oxygen, and the active metal species is once converted to an oxide. Further, before the hydrotreating of the petroleum fraction, the active metal is preferably converted into a sulfide by a sulfiding treatment called presulfiding.
  • the active metal species may be converted to a metal sulfide by treating the catalyst charged in the equipment with a catalyst using a sulfur compound called presulfidation. preferable.
  • the conditions for the preliminary sulfidation are not particularly limited, but a sulfur compound is added to the raw oil used for the hydrotreating of the petroleum fraction, the temperature is 200 to 380 ° C., the LHSV is 1 to 2 h ⁇ 1 , and the pressure is the hydrotreating It is preferable that the regenerated catalyst is continuously contacted under the same conditions as in operation and a processing time of 48 hours or longer.
  • a sulfur compound added to the said raw material oil Dimethyl disulfide (DMDS), hydrogen sulfide, etc. are preferable, and it is preferable to add these about 1 mass% with respect to the mass of a raw material oil with respect to raw material oil.
  • the operating conditions in the hydrotreating process of petroleum fractions are not particularly limited, and a small amount of a sulfur compound such as DMDS may be added to the feedstock for the purpose of maintaining a state where the active metal species of the catalyst is sulfide.
  • a sulfur compound such as DMDS
  • the hydrogen partial pressure at the reactor inlet in the hydrotreating step is preferably 3 to 13 MPa, more preferably 3.5 to 12 MPa, and particularly preferably 4 to 11 MPa.
  • the hydrogen partial pressure is less than 3 MPa, coke formation on the catalyst becomes intense and the catalyst life tends to be shortened.
  • the hydrogen partial pressure exceeds 13 MPa, there is a concern that the construction cost of the reactor, peripheral equipment, and the like will increase and the economy will be lost.
  • LHSV in the hydrogenation process is preferably 0.05 ⁇ 5h -1, more preferably 0.1 ⁇ 4.5 h -1, particularly preferably be in the range of 0.2 ⁇ 4h -1.
  • LHSV is less than 0.05 h ⁇ 1 , there is a concern that the construction cost of the reactor becomes excessive and the economic efficiency is lost.
  • LHSV exceeds 5 h ⁇ 1 there is a concern that the feedstock hydrotreatment may not be sufficiently achieved.
  • the hydrogenation reaction temperature in the hydrotreating step is preferably 200 ° C. to 410 ° C., more preferably 220 ° C. to 400 ° C., and particularly preferably 250 ° C. to 395 ° C.
  • the reaction temperature is lower than 200 ° C., the hydrogenation treatment of the raw material oil tends not to be sufficiently achieved.
  • the reaction temperature exceeds 410 ° C., the generation of a gas component as a by-product increases, which is not desirable because the yield of the target refined oil decreases.
  • the hydrogen / oil ratio in the hydrotreating step is preferably 100 to 8000 SCF / BBL, more preferably 120 to 7000 SCF / BBL, and particularly preferably 150 to 6000 SCF / BBL.
  • the hydrogen / oil ratio is less than 100 SCF / BBL, coke formation on the catalyst proceeds at the reactor outlet, and the catalyst life tends to be shortened.
  • the hydrogen / oil ratio exceeds 8000 SCF / BBL, there is a concern that the construction cost of the recycle compressor becomes excessive and the economic efficiency is lost.
  • the reaction type in the hydrotreating step is not particularly limited, but usually, it can be selected from various processes such as a fixed bed and a moving bed, but a fixed bed is preferable.
  • the reactor is preferably tower-shaped.
  • the distillation temperature (boiling point) by distillation test is preferably in the range of 130 to 700 ° C, more preferably in the range of 140 to 680 ° C, particularly preferably 150 to The thing of the range of 660 degreeC is used.
  • the hydrotreating reaction becomes a reaction in the gas phase, and the above-mentioned catalyst tends not to exhibit its performance sufficiently.
  • the content of poisonous substances with respect to the catalyst such as heavy metals contained in the feedstock is increased, and the life of the catalyst is greatly reduced.
  • Other properties of the petroleum fraction used as the feedstock are not particularly limited, but typical properties include a density of 0.8200 to 0.9700 g / cm 3 at 15 ° C. and a sulfur content of 1.0 to 4. 0% by mass.
  • the sulfur content means a sulfur content measured in accordance with “6. Radiation excitation method” of “Crude oil and petroleum products—Sulfur content test method” defined in JIS K 2541-1992.
  • the distillation test means a test conducted in accordance with “6. Decomposition method distillation test method” of “Petroleum product-distillation test method” defined in JIS K 2254.
  • the density at 15 ° C. means a density determined in accordance with “5.
  • the facility for performing the regeneration treatment is not particularly limited, but it is preferably performed in a facility different from the hydrotreating facility for the petroleum fraction. That is, instead of performing the regeneration process while the catalyst is still filled in the reactor of the hydrotreating equipment for petroleum fractions, the catalyst is extracted from the reactor and the extracted catalyst is used as equipment for the regeneration process. It is preferable to move and perform the regeneration process with the equipment.
  • the form for regenerating the used catalyst is not limited, but the process of removing the finely divided catalyst from the used catalyst, and in some cases, the filler other than the catalyst by sieving, removing the oil adhering to the used catalyst It is preferable that the step is constituted in this order from the step of performing (deoiling step), the step of removing coke deposited on the used catalyst, the sulfur content, etc. (regeneration step).
  • a method of volatilizing the oil by heating the used catalyst to a temperature of about 200 to 400 ° C. in an atmosphere substantially free of oxygen, for example, a nitrogen atmosphere is preferably employed.
  • the deoiling step may be performed by a method of washing oil with light hydrocarbons or a method of removing oil by steaming.
  • the spent catalyst is 250 to 700 ° C., preferably 320 to 550 ° C., more preferably 330 to 450 ° C. in an atmosphere where molecular oxygen is present, for example, in the air, particularly in the air stream.
  • a method of oxidizing and removing the deposited coke, sulfur and the like by heating to a temperature of 340 to 400 ° C. is preferably employed.
  • the heating temperature is lower than the lower limit temperature, the removal of the substance having reduced catalytic activity such as coke and sulfur content does not proceed efficiently, the decrease in Mo—S bond strength of molybdenum sulfide is small, molybdenum oxidation There is a tendency that the ratio of goods is small.
  • the heating temperature exceeds the upper limit temperature, the active metal in the catalyst tends to decrease the activity of the resulting regenerated catalyst by forming a composite metal oxide or causing aggregation.
  • the temperature in the regeneration step is preferably within a predetermined temperature range obtained as follows in addition to the above temperature range. That is, a differential thermal analysis of a spent hydrotreating catalyst, and the minimum extreme value when the value obtained by converting the differential calorific value in the measurement temperature region of 100 ° C. or more and 600 ° C. or less to the difference in electromotive force is differentiated twice by temperature. And, of the second smallest extreme value, T1 is the temperature corresponding to the extreme value on the low temperature side, and T2 is the temperature corresponding to the extreme value on the high temperature side, and the temperature range is T1-30 ° C or more and T2 + 30 ° C or less. Preferably there is.
  • the temperature of the regeneration treatment By setting the temperature of the regeneration treatment within the predetermined temperature range, it becomes easy to return the active metal in the sulfide state to the oxide state with the spent catalyst, and the coke deposited on the catalyst is completely burned. Thus, the reduction in the activity of the regenerated catalyst due to being removed can be prevented to a higher degree.
  • the lower limit of the temperature range is preferably T1-20 ° C. or more, particularly preferably T1-10 ° C. or more, and the upper limit of the temperature range is preferably T2 + 20 ° C. or less, particularly preferably T2 + 10 ° C. or less. is there.
  • the time for the regeneration treatment is preferably 0.5 hours or more, more preferably 2 hours or more, further preferably 2.5 hours or more, and particularly preferably 3 hours or more.
  • the treatment time is less than 0.5 hours, the removal of substances having reduced catalytic activity such as coke and sulfur content tends not to proceed efficiently.
  • the amount of residual carbon contained in the regenerated catalyst is based on the mass of the regenerated catalyst, and the lower limit is preferably 0.15% by mass or more, more preferably 0.4% by mass or more, particularly
  • the upper limit is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, and particularly preferably 2.0% by mass or less. If the amount is less than 0.15% by mass, the active metal aggregates due to the thermal history in the regeneration step, and the activity of the regenerated catalyst tends to decrease. On the other hand, when it exceeds 3.0% by mass, the activity of the regenerated catalyst tends to be lowered due to carbon blocking the active sites of the catalyst.
  • residual carbon refers to carbon (coke) remaining in the regenerated catalyst after regenerating the spent hydrotreating catalyst, and remaining in the regenerated hydrotreating catalyst.
  • the amount of carbon is measured in accordance with “Coal and cokes—elemental analysis method using an instrument analyzer” defined in JIS M 8819.
  • the peak intensity derived from the molybdenum composite metal oxide containing molybdenum and at least one selected from Group 8 to 10 metals of the periodic table is the standard.
  • the lower limit with respect to the peak is 0.60 or more, more preferably 0.70 or more, particularly preferably 0.75 or more, and the upper limit is preferably 1.10 or less, more preferably 0.90 or less, particularly preferably 0.8. 85 or less. If it is less than 0.60, the regenerated catalyst is insufficiently oxidized and the activity of the regenerated catalyst is reduced. On the other hand, if it exceeds 1.10, the molybdenum composite oxide aggregates and the activity of the regenerated catalyst is reduced. It is not preferable.
  • the Mo—S bond strength derived from the residual sulfur is compared with the reference peak.
  • the lower limit is 0.10 or more, preferably 0.12 or more, more preferably 0.15 or more
  • the upper limit is 0.60 or less, preferably 0.50 or less. If it is less than 0.10, the molybdenum oxide undergoes a structural change and the activity of the regenerated catalyst is lowered, and if it exceeds 0.60, the sulfur compound of molybdenum is agglomerated and the activity of the regenerated catalyst is lowered. Therefore, it is not preferable.
  • the ratio of MoO 3 obtained by conducting X-ray absorption fine structure analysis on the regenerated catalyst and analyzing the spectrum obtained from the X-ray absorption edge structure region is 77% or more, preferably 80% or more, more preferably Is 85% or more, and the upper limit is 99% or less, preferably 95% or less. If it is less than 77%, agglomeration of molybdenum sulfur compounds will occur and the activity of the regenerated catalyst will decrease, and if it exceeds 99%, the structure of the molybdenum oxide will change and the activity of the regenerated catalyst will decrease, which is not preferable. .
  • FIG. 1 shows the result of X-ray diffraction (XRD) analysis of a sample.
  • XRD X-ray diffraction
  • an X-ray diffraction (XRD) peak of 2 ⁇ 26.5 ⁇ 2 ° attributed to a molybdenum composite metal oxide assumed from the active metal species contained in the catalyst obtained in the regeneration step.
  • the determination of the presence or absence of the peak is preferably performed according to the following criteria.
  • the value of Hm / Ha is the peak intensity with respect to the reference peak of the molybdenum composite metal oxide.
  • Typical conditions for XRD analysis are as follows.
  • X-ray source CuK ⁇ Divergence slit: 1/2 ° light receiving slit: 0.15 mm Scattering slit: 1/2 ° 2 ⁇ : 10-90 ° Step width: 0.02 °
  • FIG. 2 shows the result of X-ray absorption fine structure analysis (XAFS, X-ray Absorption Fine Structure) for a certain sample.
  • XAFS X-ray absorption fine structure analysis
  • XAFS analysis involves irradiating X-rays contained in synchrotron radiation generated by an electron accelerator, or X-rays corresponding to the X-rays, with the energy changed, and the X-ray absorption rate of the substance as X-ray energy.
  • the structure of the substance is analyzed based on the absorption spectrum plotted against it.
  • XAFS measurement is performed by paying attention to molybdenum (Mo K absorption edge) among the active metals contained in the regenerated catalyst.
  • molybdenum Mo K absorption edge
  • the radial distribution curve obtained by performing Fourier transform on the EXAFS region of the acquired spectrum the peak intensity (Mo of the atomic distance of 0.20 nm ⁇ 0.01 attributed to the molybdenum atom-sulfur atom bond derived from residual sulfur (Mo Focusing on ( ⁇ S bond strength), the Mo—S bond strength is determined from the ratio of the peak intensity to the reference peak interatomic distance of 0.13 nm ⁇ 0.01. The determination of the peak is preferably performed according to the following criteria.
  • the EXAFS radial distribution curve is obtained by extracting the EXAFS region from the spectrum of the regenerated hydrotreating catalyst obtained from the XAFS measurement using the XAFS analysis software REX2000 (manufactured by Rigaku Corporation) and Fourier transforming it.
  • the peak derived from the Mo—S bond due to the residual sulfur content is the maximum intensity point Hs with an interatomic distance of 0.20 nm ⁇ 0.01
  • the reference peak is derived from the Mo—O bond.
  • the maximum intensity point Ho with an interatomic distance of 0.13 nm ⁇ 0.01 is set, the value of Hs / Ho is the peak intensity with respect to the reference peak of Mo—S bond.
  • the intensity of the peak in the radial distribution curve obtained from the wide-area X-ray absorption fine structure region of the spectrum obtained by performing the XAFS analysis is defined as the peak height.
  • the analysis was performed using the XAFS analysis integrated software REX2000 (Rigaku) according to the method described in the above.
  • XAFS analysis in the regenerated catalyst of the present invention is carried out by the following method.
  • X-ray source Continuous X-ray spectroscopic crystal: Si (311) Beam size: 1mm x 2mm Detector: Ionization chamber Measurement atmosphere: Air Dwell time: 1 sec Measurement range: Mo K absorption edge (19974.0 to 2008.0 eV)
  • Data analysis (Fourier transform) program REX2000 (manufactured by Rigaku)
  • the X-ray absorption edge structure (XANES, X-ray Absorption Near-Edge Structure) region of the regenerated catalyst obtained in the regeneration step, the X-ray absorption rate is abrupt with respect to the irradiation X-ray energy.
  • a changing region (absorption edge) is referred to, and the XANES spectrum shown in FIG. 4 is obtained by analyzing the spectrum obtained in this region. From this XANES spectrum, information on the chemical state of the atom to be measured can be obtained.
  • the ratio of MoO 3 is determined by pattern fitting using the reference samples MoO 3 and MoS 2 measured under the same conditions.
  • the spectrum is preferably determined according to the following criteria. That is, the spectrum of the regenerated hydrotreating catalyst obtained from the XAFS measurement is extracted with the XAFS analysis software REX2000 (manufactured by Rigaku Corporation), and the above analysis software is used using MoO 3 and MoS 2 measured under the same conditions as the regenerated catalyst.
  • the pattern fitting range when the 20050eV from 19990EV, the ratio of MoO 3 to the sum of MoO 3 and MoS 2 are percentage of MoO 3.
  • the analysis of the spectrum obtained by carrying out the XAFS analysis uses XAFS analysis integrated software REX2000 (Rigaku), and details of data analysis such as taking a baseline when calculating the ratio of molybdenum oxide, "X-ray absorption spectroscopy-XAFS and its application-Ota Toshiaki, edited by IPC (2002), pages 78-79" and XAFS analysis integrated software REX2000 (Rigaku) manual 51-59
  • the analysis was performed using XAFS analysis integrated software REX2000 (Rigaku).
  • the XAFS analysis in the regenerated catalyst of the present invention is omitted here because it is the same as the above analysis conditions.
  • the activity of the unused catalyst (new catalyst) varies depending on the manufacturer, production unit, etc.
  • the regenerated catalyst of the present invention may be used alone as a catalyst for the above-described hydrotreating process of petroleum fractions, or may be used by laminating with an unused catalyst.
  • the ratio of the regenerated catalyst is not particularly limited, but the unused catalyst 100 is used in view of reducing the amount of catalyst waste and ease of separation of the catalyst when replacing the catalyst.
  • 80 or more (mass ratio) is preferable, and 120 or more (mass ratio) is more preferable.
  • Example 1 (Regenerated catalyst) A catalyst in which molybdenum and cobalt are supported on an alumina carrier as active metals and used in a kerosene hydrotreating facility for two years was prepared as shown in Table 1. This spent hydrotreating catalyst is weighed in a 5 mg platinum pan, set in a differential thermal analyzer (manufactured by Rigaku Corporation, Thermo Plus2 series / TG8110), and a sample is taken from room temperature to 700 at an air flow rate of 100 ml / min. Differential thermal analysis was performed by raising the temperature to 10 ° C. at 10 ° C./min.
  • the spent hydrotreating catalyst was regenerated at 350 ° C. (T1 + 100 ° C., T2-50 ° C.) for 4 hours to obtain regenerated catalyst 1.
  • the activity of the regenerated catalyst of the present invention is such that the residual carbon amount, XRD analysis and XAFS analysis are within the applicable range, so that the activity relative to the unused catalyst is about 93% or more. It can be seen that they are expressed (Examples 1 to 4). On the other hand, in Comparative Examples 5 to 8, when any item in the above analysis is out of the applicable range, the activity is about 90% or less relative to the unused catalyst in any case, and the decrease in activity is large.

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CN201080061802.3A CN102740967B (zh) 2010-01-18 2010-11-08 再生氢化处理用催化剂
SG2012047155A SG181933A1 (en) 2010-01-18 2010-11-08 Regenerated hydrotreatment catalyst
EP10843105.7A EP2527034A4 (en) 2010-01-18 2010-11-08 REGENERATED HYDROGENATION CATALYST
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JP5695548B2 (ja) * 2011-12-09 2015-04-08 Ｊｘ日鉱日石エネルギー株式会社 予備硫化済み再生水素化処理用触媒の製造方法、再生水素化処理用触媒の製造方法、水素化処理用触媒の再生処理条件の選別方法、及び石油製品の製造方法
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