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US 2015/0306579 A1Published application
A hydrotreating catalyst, production and use thereof
AssigneesChina Petroleum & Chemical Corporation, Fushun Research Institute of Petroleum and Petrochemicals, Sinopec
InventorsZhanlin Yang, Hong Jiang, Zhaoji Tang, Jifeng Wang, Derong Wen, Dengling Wei
Life of this patent
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Abstract
This invention relates to a hydrotreating catalyst suitable for heavy distillate oil hydrodesulfurization, production and use thereof. The present hydrotreating catalyst exhibits significantly improved heavy distillate oil (deep) hydrodesulfurization activity.
Claims13
A hydrotreating catalyst, which is in a particulate form, and comprises a porous refractory carrier (preferably one or more selected from the group consisting of porous refractory oxides, more preferably one or more selected from the group consisting of porous inorganic refractory oxides, more preferably one or more selected from the group consisting of oxides of a Group II, Group III or Group IV element in the element periodic table, more preferably one or more selected from the group consisting of silica, alumina, magnesia, silica-alumina, silica-magnesia and alumina-magnesia, further preferably alumina) and an active metal component A, an active metal component B, an active metal component C and optionally an auxiliary component supported on the porous refractory carrier, the active metal component A is Ni, the active metal component B is one or more selected from the group consisting of Group VIII metals other than Ni in the element periodic table, preferably one or more selected from the group consisting of Group VIII non-noble metals other than Ni in the element periodic table, more preferably Co, the active metal component C is one or more selected from the group consisting of Group VIB metals in the element periodic table, preferably one or more selected from the group consisting of Mo and W, more preferably Mo, the auxiliary component is one or more selected from the group consisting of fluorine, silicon, phosphorus, titanium, zirconium and boron, preferably one or more selected from the group consisting of fluorine and phosphorus, more preferably phosphorus,
- wherein,
- the concentration distribution of the active metal component A meets the following condition (I) or (II),
- Condition (I):
- throughout the cross-section of each individual catalyst particle, the concentration thereof substantially uniformly distributes,
- Condition (II):
- throughout the cross-section of each individual catalyst particle, the concentration thereof meets the following formulas (1) and (2) at the same time:
- CAout>CA1/2>1, preferably CAout>CA1/2>CA3/4>1, more preferably CA1/4>CAout>CAopt>1, more preferably CAout/CA1/2=1.5-2.6, preferably 1.7-2.5, further preferably CAout/CA1/4=1.2-1.8, preferably 1.3-1.7, further preferably CA1/4/CA1/2=1.1-1.7, preferably 1.2-1.6, Formula (1)
- CAout≧1.5, preferably CAout≧2.0, more preferably CAout≧2.4, but CAout≦5.0, preferably CAout≦4.0, Formula (2)
- wherein the symbol CAout represents the ratio of the concentration of the active metal component A at an arbitrary position point PA on the outmost edge of the cross-section of the catalyst particle to the concentration of the active metal component A at the central point on the cross-section of the catalyst particle, and assuming that the length value of the line segment connecting the central point and the position point PA on the cross-section of the catalyst particle is LA, the symbol CA1/2 represents the ratio of the concentration of the active metal component A at the position point on the line segment (½)LA away from the position point PA to the concentration of the active metal component A at the central point on the cross-section of the catalyst particle, the symbol CA1/4 represents the ratio of the concentration of the active metal component A at the position point on the line segment (¼)LA away from the position point PA to the concentration of the active metal component A at the central point on the cross-section of the catalyst particle, the symbol CA3/4 represents the ratio of the concentration of the active metal component A at the position point on the line segment (¾)LA away from the position point PA to the concentration of the active metal component A at the central point on the cross-section of the catalyst particle, the symbol CAopt represents the ratio of the concentration of the active metal component A at an arbitrary position point on the line segment (not including the central point and the position point PA) to the concentration of the active metal component A at the central point on the cross-section of the catalyst particle,
- and, the concentration distribution of the active metal component B meets the following condition (III) or (IV),
- Condition (III):
- throughout the cross-section of each individual catalyst particle, the concentration thereof substantially uniformly distributes.
- Condition (IV):
- throughout the cross-section of each individual catalyst particle, the concentration thereof meets the following formulas (3) and (4) at the same time:
- CBout<CB1/2<1, preferably CBout<CB1/4<CB1/2<CB3/4<1, more preferably CBout<CBopt<1, more preferably CBout/CB1/2=0.2-0.8, preferably 0.2-0.7, further preferably CBout/CB1/4=0.3-0.9, preferably 0.3-0.85, further preferably CB1/4/CB1/2=0.4-0.9, preferably 0.4-0.87, Formula (3)
- CBout≦0.80, preferably CBout≦0.70, preferably CBout≦0.68, preferably CBout≦0.60, but CBout≧0.10, preferably CBout≧0.20, Formula (4)
- wherein the symbol CBout represents the ratio of the concentration of the active metal component B at an arbitrary position point PB on the outmost edge of the cross-section of the catalyst particle to the concentration of the active metal component B at the central point on the cross-section of the catalyst particle, and assuming that the length value of the line segment connecting the central point and the position point PB on the cross-section of the catalyst particle is LB, the symbol CB1/2 represents the ratio of the concentration of the active metal component B at the position point on the line segment (½)LB away from the position point PB to the concentration of the active metal component B at the central point on the cross-section of the catalyst particle, the symbol CB1/4 represents the ratio of the concentration of the active metal component B at the position point on the line segment (¼)LB away from the position point PB to the concentration of the active metal component B at the central point on the cross-section of the catalyst particle, the symbol CB3/4 represents the ratio of the concentration of the active metal component B at the position point on the line segment (¾)LB away from the position point PB to the concentration of the active metal component B at the central point on the cross-section of the catalyst particle, the symbol CBopt represents the ratio of the concentration of the active metal component B at an arbitrary position point on the line segment (not including the central point and the position point PB) to the concentration of the active metal component B at the central point on the cross-section of the catalyst particle,
- with the proviso that, the concentration distribution of the active metal component A and the concentration distribution of the active metal component B do not meet the conditions (I) and (III) at the same time,
- preferably, the concentration distribution of the active metal component A meets the condition (II), and at the same time, the concentration distribution of the active metal component B meets the condition (IV).
16 more elements
A process for producing a hydrotreating catalyst, comprising at least the following steps:
- (1-1) By unsaturated impregnation, onto a particulate porous refractory carrier (preferably one or more selected from the group consisting of porous refractory oxides, more preferably one or more selected from the group consisting of porous inorganic refractory oxides, more preferably one or more selected from the group consisting of oxides of a Group II, Group III or Group IV element in the element periodic table, more preferably one or more selected from the group consisting of silica, alumina, magnesia, silica-alumina, silica-magnesia and alumina-magnesia, further preferably alumina), an adsorbent I is supported, and optionally an organic alcohol having a carbon atom number of 1-5 (especially a monohydric alcohol or polyol, preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, glycerin, pentaerythritol and xylitol) is simultaneously supported, wherein the adsorbent I is one or more selected from the group consisting of an organic carboxylic acid (especially a monohydric or polyhydric carboxylic acid, preferably a dihydric carboxylic acid) having a carbon atom number of 2-15 and an ammonium salt thereof, preferably one or more selected from the group consisting of acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, monochloroacetic acid, mercaptoacetic acid, mercaptopropionic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, diaminocyclohexane tetraacetic acid and ammonium salts thereof, the adsorbent I is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier, the organic alcohol is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier,
- (1-2) Onto the product obtained from the step (1-1), an active metal component B, optionally an active metal component C and optionally an auxiliary component are supported, wherein the active metal component B is one or more selected from the group consisting of Group VIII metals other than Ni in the element periodic table, preferably Co, the active metal component C is one or more selected from the group consisting of Group VIB metals in the element periodic table, preferably one or more selected from the group consisting of Mo and W, more preferably Mo, the auxiliary component is one or more selected from the group consisting of fluorine, silicon, phosphorus, titanium, zirconium and boron, preferably one or more selected from the group consisting of fluorine and phosphorus, more preferably phosphorus, and
- (1-3) Before the beginning of the step (1-1) and/or after the completion of the step (1-2), onto the porous refractory carrier, an active metal component A, optionally the active metal component C and optionally the auxiliary component are supported, wherein the active metal component A is Ni,
- with the proviso that the active metal component C is supported through at least one out of the step (1-2) and the step (1-3) (preferably through a combination of the step (1-2) and the step (1-3)),
- or,
- comprising at least the following steps:
- (2-1) By saturated impregnation or oversaturated impregnation, onto a particulate porous refractory carrier (preferably one or more selected from the group consisting of porous refractory oxides, more preferably one or more selected from the group consisting of porous inorganic refractory oxides, more preferably one or more selected from the group consisting of oxides of a Group II, Group III or Group IV element in the element periodic table, more preferably one or more selected from the group consisting of silica, alumina, magnesia, silica-alumina, silica-magnesia and alumina-magnesia, further preferably alumina), an adsorbent II is supported, wherein the adsorbent II is a polyol having a number averaged molecular weight Mn (by the GPC method) of 400-10000, preferably a polyol having a number averaged molecular weight Mn (by the GPC method) of 1000-8000, more preferably polyether glycol (especially polyethylene glycol) having a number averaged molecular weight Mn (by the GPC method) of 1000-8000, the adsorbent II is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier;
- (2-2) Onto the product obtained from the step (2-1), an active metal component A, optionally an active metal component C and optionally an auxiliary component are supported, wherein the active metal component A is Ni, the active metal component C is one or more selected from the group consisting of Group VIB metals in the element periodic table, preferably one or more selected from the group consisting of Mo and W, more preferably Mo, the auxiliary component is one or more selected from the group consisting of fluorine, silicon, phosphorus, titanium, zirconium and boron, preferably one or more selected from the group consisting of fluorine and phosphorus, more preferably phosphorus, and
- (2-3) Before the beginning of the step (2-1) and/or after the completion of the step (2-2), onto the porous refractory carrier, an active metal component B, optionally the active metal component C and optionally the auxiliary component are supported, wherein the active metal component B is one or more selected from the group consisting of Group VIII metals other than Ni in the element periodic table, preferably Co,
- with the proviso that the active metal component C is supported through at least one out of the step (2-2) and the step (2-3) (preferably through a combination of the step (2-2) and the step (2-3)),
- or,
- comprising at least the following steps:
- (3-1) By unsaturated impregnation, onto a particulate porous refractory carrier (preferably one or more selected from the group consisting of porous refractory oxides, more preferably one or more selected from the group consisting of porous inorganic refractory oxides, more preferably one or more selected from the group consisting of oxides of a Group II, Group III or Group IV element in the element periodic table, more preferably one or more selected from the group consisting of silica, alumina, magnesia, silica-alumina, silica-magnesia and alumina-magnesia, further preferably alumina), an adsorbent I is supported, and optionally an organic alcohol having a carbon atom number of 1-5 (especially a monohydric alcohol or polyol, preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, glycerin, pentaerythritol and xylitol) is simultaneously supported, wherein the adsorbent I is one or more selected from the group consisting of organic carboxylic acids having a carbon atom number of 2-15 (especially monohydric or polyhydric carboxylic acids, preferably dihydric carboxylic acids) and ammonium salts thereof, preferably one or more selected from the group consisting of acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, monochloroacetic acid, mercaptoacetic acid, mercaptopropionic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, diaminocyclohexane tetraacetic acid and ammonium salts thereof, the adsorbent I is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier, the organic alcohol is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier,
- (3-2) Onto the product obtained from the step (3-1), an active metal component B, optionally an active metal component C and optionally an auxiliary component are supported, wherein the active metal component B is one or more selected from the group consisting of Group VIII metals other than Ni in the element periodic table, preferably Co, the active metal component C is one or more selected from the group consisting of Group VIB metals in the element periodic table, preferably one or more selected from the group consisting of Mo and W, more preferably Mo, the auxiliary component is one or more selected from the group consisting of fluorine, silicon, phosphorus, titanium, zirconium and boron, preferably one or more selected from the group consisting of fluorine and phosphorus, more preferably phosphorus,
- (3-3) By saturated impregnation or oversaturated impregnation, onto the product obtained from the step (3-2), an adsorbent II is supported, wherein the adsorbent II is a polyol having a number averaged molecular weight Mn (by the GPC method) of 400-10000, preferably a polyol having a number averaged molecular weight Mn (by the GPC method) of 1000-8000, more preferably polyether glycol (especially polyethylene glycol) having a number averaged molecular weight Mn (by the GPC method) of 1000-8000, the adsorbent II is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier;
- (3-4) Onto the product obtained from the step (3-3), an active metal component A, optionally the active metal component C and optionally the auxiliary component are supported, wherein the active metal component A is Ni, and
- (3-5) Optionally before the beginning of the step (3-1), after the completion of the step (3-2), while before the beginning of the step (3-3) and/or after the completion of the step (3-4), onto the porous refractory carrier, the active metal component C and optionally the auxiliary component are supported,
- with the proviso that the active metal component C is supported through at least one out of the step (3-2), the step (3-4) and the step (3-5) (preferably through a combination of the step (3-2) and the step (3-4)),
- or,
- comprising at least the following steps:
- (4-1) By saturated impregnation or oversaturated impregnation, onto a particulate porous refractory carrier (preferably one or more selected from the group consisting of porous refractory oxides, more preferably one or more selected from the group consisting of porous inorganic refractory oxides, more preferably one or more selected from the group consisting of oxides of a Group II, Group III or Group IV element in the element periodic table, more preferably one or more selected from the group consisting of silica, alumina, magnesia, silica-alumina, silica-magnesia and alumina-magnesia, further preferably alumina), an adsorbent II is supported, wherein the adsorbent II is a polyol having a number averaged molecular weight Mn (by the GPC method) of 400-10000, preferably a polyol having a number averaged molecular weight Mn (by the GPC method) of 1000-8000, more preferably polyether glycol (especially polyethylene glycol) having a number averaged molecular weight Mn (by the GPC method) of 1000-8000, wherein the adsorbent II is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier;
- (4-2) Onto the product obtained from the step (4-1), an active metal component A, optionally an active metal component C and optionally an auxiliary component are supported, wherein the active metal component A is Ni, the active metal component C is one or more selected from the group consisting of Group VIB metals in the element periodic table, preferably one or more selected from the group consisting of Mo and W, more preferably Mo, the auxiliary component is one or more selected from the group consisting of fluorine, silicon, phosphorus, titanium, zirconium and boron, preferably one or more selected from the group consisting of fluorine and phosphorus, more preferably phosphorus,
- (4-3) By unsaturated impregnation, onto the product obtained from the step (4-2), an adsorbent I is supported, and optionally an organic alcohol having a carbon atom number of 1-5 (especially a monohydric alcohol or polyol, preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, glycerin, pentaerythritol and xylitol) is simultaneously supported, wherein the adsorbent I is one or more selected from the group consisting of organic carboxylic acids (especially monohydric or polyhydric carboxylic acids, preferably dihydric carboxylic acids) having a carbon atom number of 2-15 and ammonium salts thereof, preferably one or more selected from the group consisting of acetic acid, oxalic acid, lactic acid, malonic acid, tartaric acid, malic acid, citric acid, trichloroacetic acid, monochloroacetic acid, mercaptoacetic acid, mercaptopropionic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, diaminocyclohexane tetraacetic acid and ammonium salts thereof, the adsorbent I is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier, the organic alcohol is used with an amount of 0.1-10 wt % relative to the amount of the porous refractory carrier,
- (4-4) Onto the product obtained from the step (4-3), an active metal component B, optionally the active metal component C and optionally the auxiliary component are supported, wherein the active metal component B is one or more selected from the group consisting of Group VIII metals other than Ni in the element periodic table, preferably Co, and
- (4-5) Optionally before the beginning of the step (4-1), after the completion of the step (4-2), while before the beginning of the step (4-3) and/or after the completion of the step (4-4), onto the porous refractory carrier, the active metal component C and optionally the auxiliary component are supported,
- with the proviso that the active metal component C is supported through at least one out of the step (4-2), the step (4-4) and the step (4-5) (preferably through a combination of the step (4-2) and the step (4-4)).
23 more elements
Dependencies are inferred from the claim text.