Patent Application
20200207635
The present disclosure deals with a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials whose main application is in the regeneration of alumina-based catalysts, the recovery and/or recycling of metals and the reuse of alumina catalysts employed mainly in oil industry processes as hydrotreating, isomerization and naphtha catalytic reforming catalysts.
In this sense, it is important to point out that such catalysts are used mainly to eliminate sulfur, nitrogen and silicon compounds as well as to increase the octane number and isomerize compounds present in the feedstock currents of hydrotreating, isomerization and naphtha catalytic reforming processes used in the oil industry.
There are different procedures and/or methods for removing metal oxides present in alumina-based materials such as those reported in:
In this sense, it is important to note that the procedures and/or known methods for removing metals, metal ions and metal oxides from alumina-based materials, such as those mentioned above, use some kind of inorganic acid or inorganic base, or a mixture thereof, to carry out a digestion process, which modifies the alumina properties and those of any other element present in the material, destroying alumina and preventing its reuse.
The above technologies, known by the applicant, were surpassed by the non-destructive process of the present disclosure due to the removal of metals, metal ions and metal oxides present in alumina-based materials without destroying alumina; for this reason, one embodiment of the present disclosure is focused on the regeneration of alumina-based catalysts, the recovery and/or recycling of metals and the reuse of alumina from catalysts employed mainly in the oil industry as hydrotreating, isomerization and naphtha catalytic reforming catalysts.
Then, an objective of the present disclosure is to provide a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials that allows the reuse of alumina.
Another objective of the present disclosure is to introduce a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials that is mainly used in the regeneration and recovery and/or recycling of metals from catalysts that are mainly used to eliminate sulfur, nitrogen and silicon compounds and also to increase the octane number and isomerize compounds in feedstocks of hydrotreating, isomerization and naphtha catalytic reformation processes in the oil industry.
An additional objective of the present disclosure is to present a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials that forms alkoxides, coordination compounds and/or chelates with oxidized metals without modifying the properties of the alumina-based material.
Another objective of the present disclosure is to provide a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials that uses a sequestering or complexing agent of metals, metal ions and/or metal oxides present in alumina-based materials without modifying substantially the content of other materials present in the alumina-based material.
The previous and other objectives concerning the present disclosure will be described with more clarity and in detail in the following chapters.
The present disclosure deals with a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials without destroying alumina; then, one object of the present disclosure is regeneration of alumina-based catalysts, recovery and/or recycling of metals and reusing alumina from catalysts employed mainly in oil industry processes as hydrotreating, isomerization and naphtha catalytic reforming catalysts.
In this sense, it is important to mention that such catalysts are used mainly to eliminate sulfur, nitrogen and silicon compounds and to increase the octane number and isomerize compounds present in feedstocks of hydrotreating, isomerization and naphtha catalytic reforming processes in the oil industry.
The non-destructive process of the present disclosure includes the following stages:
The non-destructive process of the present disclosure is applied in alumina-based materials that contain, among others, the following chemical elements and/or their mixtures: Si, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt and Au.
The metals, metal ions and/or metal oxides present in the alumina-based material to which the non-destructive process of the present disclosure is applied, may be found in inorganic form.
The alcohol employed at stage a) as extracting agent to mix the solid material that contains the metals, metal ions and/or metal oxides may be a polyol, and in some embodiments may be glycerin, ethylene glycol and/or 1,5-pentanodiol, which present excellent properties to extract selectively the metals, metal ions and/or metal oxides without modifying the properties of the alumina-based material. The aforementioned is achieved because glycerin, ethylene glycol and/or 1,5-pentanediol act as complexing or sequestering agents of the metals, metal ions and/or metal oxides deposited in the alumina-based material, producing a gel that contains the metals, metal ions and/or metal oxides that are removed from the solid.
The washing from stage d) may be performed with distilled water, methanol, ethanol, propanol, with an ammonium hydroxide solution from 1 to 35 wt. % or with hydrodesulfurized naphtha, reforming compound or a hexane/heptane mixture.
The non-destructive process of the present disclosure takes place in a batch reactor (batch), with or without stirring, or in a continuous flow reactor, with or without pressure from 0.5 to 75 kg/cm2.
In a continuous flow reactor, the non-destructive process of the present disclosure may include the following stages:
In the non-destructive process featured in the present disclosure, pressurization and cooling of the system in a continuous flow reactor may be carried out with nitrogen.
What follows is the description of some practical examples aimed at offering a better understanding of the present disclosure without limiting its scope.
An exhausted catalyst obtained from a naphtha hydrotreating industrial plant was oxidized by using an O2/N2 mixture, being submitted afterwards to an elemental composition analysis of molybdenum and nickel. The corresponding results are shown in Table No. 1.
10 g of an exhausted and oxidized catalyst (Table No. 1) were ground to pass through a 100 mesh sieve and mixed with 600 mL of glycerin in a batch reactor. The mixture was heated from 20 to 250° C. and stirred at 100 rpm for 10 h; afterwards, the mixture was allowed to cool down to 100° C. The solid was separated from glycerin by centrifugation and washed with 500 mL of an isopropanol aqueous solution. Finally, the solid was dried in an oven at 60° C. for 8 h. This very solid was analyzed by atomic absorption, finding that 48 and 55% of molybdenum and nickel, respectively, had been removed from the initial catalyst content.
10 g of an exhausted and oxidized catalyst (Table No. 1), which was featured in Example No. 1, were ground to pass through a 200 mesh sieve and mixed with 1200 mL of glycerin in a batch reactor. The mixture was heated from 20 to 250° C. and stirred at 100 rpm for 10 h; afterwards, the mixture was allowed to cool down to 110° C. The solid was separated from glycerin by centrifugation and washed with 500 mL of reforming product. Finally, the solid was dried in an oven at 60° C. for 8 h. The obtained solid was analyzed by atomic absorption, finding that 52 and 63% of molybdenum and nickel, respectively, had been removed from the initial catalyst content.
10 g of an exhausted and oxidized catalyst (Table No. 1), which was used in Example No. 1, were ground to pass through a 200 mesh sieve and mixed with 600 mL of ethylene glycol in a batch reactor. The mixture was heated from 20 to 180° C. and stirred at 100 rpm for 10 h. After, the mixture was allowed to cool down to 110° C., separating the solid from ethylene glycol by centrifugation and washing it with 500 mL of ethanol. Finally, the solid was dried in an oven at 60° C. for 8 h. The as-obtained solid was analyzed by atomic absorption, finding that 31 and 39% of molybdenum and nickel, respectively, had been removed from the starting catalyst content.
An exhausted catalyst obtained from a naphtha hydrotreating industrial plant was oxidized using an O2/N2 mixture and afterwards submitted to an elemental composition analysis of molybdenum and cobalt, obtaining the results featured in Table No. 2.
10 g of an exhausted and oxidized catalyst (Table No. 2) were ground to pass through a 100 mesh sieve and mixed with 600 mL of glycerin in a batch reactor. The mixture was heated from 20 to 240° C. and stirred at 100 rpm for 12 h. After, the mixture was cooled down to 100° C. and the solid was separated from glycerin by centrifugation and washed with 500 mL of hydrodesulfurized naphtha. Finally, the solid was dried in an oven at 60° C. for 8 h and analyzed by atomic absorption, finding that 46 and 42% of molybdenum and cobalt, respectively, had been removed from the initial catalyst content.
10 g of an exhausted and oxidized catalyst (Table No. 2), which was used in Example No. 4, were ground to pass through a 100 mesh sieve and mixed with 600 mL of ethylene glycol in a batch reactor. The mixture was heated from 20 to 170° C. and stirred at 100 rpm for 15 h. Afterwards, the mixture was cooled down to110° C. and the solid was separated from ethylene glycol by centrifugation and washed with 500 mL of an ammonium hydroxide solution at 35 wt. %. Finally, the solid was dried in an oven at 60° C. for 8 h. The solid was analyzed by atomic absorption, finding that 32 and 33% of molybdenum and cobalt, respectively, had been removed from the starting catalyst content.
A fresh catalyst, in its oxidized form, for naphtha hydrotreating, was submitted to elemental composition analysis of molybdenum and nickel. The results are shown in Table No. 3.
10 g of a fresh catalyst (Table No. 3) were ground to pass through a 100 mesh sieve and mixed with 1200 mL of glycerin in a batch reactor. The mixture was heated from 20 to 265° C. and stirred at 100 rpm for 18 h. Afterwards, the mixture was cooled down to 100° C. and the solid was separated from glycerin by centrifugation and washed with 500 mL of a hexane/heptane mixture. Finally, the solid was dried in an oven at 60° C. for 8 h and analyzed by atomic absorption, finding that 55 and 68% of molybdenum and nickel, respectively, had been removed from the initial catalyst content.
A fresh catalyst, in its oxidized form, for naphtha catalytic reforming, was submitted to an elemental composition analysis of platinum and rhenium. The obtained results are shown in Table No. 4.
10 g of a fresh catalyst (Table No. 4) were ground to pass through a 200 mesh sieve and mixed with 1500 mL of glycerin in a batch reactor. The mixture was heated from 20 to 275° C. and stirred at 100 rpm for 15 h. Afterwards, the mixture was cooled down to 100° C. and the solid was separated from glycerin by centrifugation and washed with 500 mL of reforming product. Finally, the solid was dried in an oven at 60° C. for 8 h and analyzed by atomic absorption, finding that 36 and 39% of platinum and rhenium, respectively, had been removed from the initial catalyst content.
10 g of a fresh catalyst (Table No. 4), which was used in Example No. 7, were ground to pass through a 100 mesh sieve and mixed with 1000 mL of ethylene glycol in a batch reactor. The mixture was heated from 20 to 160° C. and stirred at 100 rpm for 20 h. Afterwards, the mixture was cooled down to110° C. and the solid was separated from ethylene glycol by centrifugation and washed with 500 mL of methanol. Finally, the solid was dried in an oven at 60° C. for 8 h. The solid was analyzed by atomic absorption, finding that 28 and 27% of platinum and rhenium, respectively, had been removed from the starting catalyst content.
14 g of exhausted catalyst (Table No. 1), which was used in Examples No. 1 to 3, were ground to pass through a 40 mesh sieve and compacted in a continuous flow tubular reactor, pressurizing at 5.0 kg/cm2 using nitrogen; afterwards, the temperature was increased from 25 to 180° C. at 60° C./min, starting the glycerin feeding at 350 mL/h and increasing the temperature up to 260° C. at 60° C./h, keeping the same pressure (5.0 kg/cm2) and temperature at 260° C. for 24 h. After 24 h, the temperature was decreased from 260 to 120° C. at 60° C./h; then, the glycerin feeding was stopped and nitrogen was fed, decreasing the temperature from 120 to 60° C. at 180° C./h and adjusting the system pressure to 2 kg/cm2. The solid was washed by feeding methanol at 280 mL/h for 2 h, stopping the methanol flow to set the system at 20° C. and 0.8 kg/cm2. The recovered solid was dried in an oven at 100° C. for 5 h and analyzed by atomic absorption, finding that 56 and 64% of molybdenum and nickel, respectively, had been removed from the initial catalyst content.
14 g of exhausted catalyst (Table No. 1), which was used in Examples No. 1 to 3 and 9, were ground to pass through a 60 mesh sieve and compacted in a continuous flow tubular reactor, pressurizing at 10.0 kg/cm2 using nitrogen; afterwards, the temperature was increased from 25 to 180° C. at 60° C./min, starting the ethylene glycol feeding at 350 mL/h and increasing the temperature up to 270° C. at 60° C./h, keeping the same pressure (10.0 kg/cm2) and temperature at 270° C. for 24 h. After 24 h, the temperature was decreased from 270 to 120° C. at 60° C./h; then, the ethylene glycol feeding was stopped and nitrogen was fed, decreasing the temperature from 120 to 60° C. at 180° C./h and adjusting the system pressure to 2 kg/cm2. The solid was washed by feeding ethanol at 280 mL/h for 2 h, stopping the ethanol flow to set the system at 20° C. and 0.8 kg/cm2. The recovered solid was dried in an oven at 100° C. for 5 h and analyzed by atomic absorption, finding that 59 and 65% of molybdenum and nickel, respectively, had been removed from the initial catalyst content.
14 g of exhausted catalyst (Table No. 1), which was used in Examples No. 1 to 3, 9 and 10, were ground to pass through a 60 mesh sieve and compacted in a continuous flow tubular reactor, pressurizing at 25.0 kg/cm2 using nitrogen; afterwards, the temperature was increased from 25 to 180° C. at 60° C./min, starting the 1,5-pentanediol feeding at 350 mL/h and increasing the temperature up to 250° C. at 60° C./h, keeping the same pressure (25.0 kg/cm2) and temperature at 250° C. for 30 h. After 30 h, the temperature was decreased from 250 to 120° C. at 60° C./h; then, the 1,5-pentanediol feeding was stopped and nitrogen was fed, decreasing the temperature from 120 to 60° C. at 180° C./h and adjusting the system pressure to 2 kg/cm2. The solid was washed by feeding reforming product at 280 mL/h for 2 h, stopping the reforming product flow to set the system at 20° C. and 0.8 kg/cm2. The recovered solid was dried in an oven at 100° C. for 5 h and analyzed by atomic absorption, finding that 53 and 60% of molybdenum and nickel, respectively, had been removed from the starting catalyst content.
14 g of exhausted catalyst (Table No. 2), which was used in Examples No. 4 and 5, were ground to pass through a 20 mesh sieve and compacted in a continuous flow tubular reactor, pressurizing at 15.0 kg/cm2 using nitrogen; afterwards, the temperature was increased from 25 to 180° C. at 60° C./min, starting the glycerin feeding at 350 mL/h and increasing the temperature up to 250° C. at 60° C./h, keeping the same pressure (15.0 kg/cm2) and temperature at 250° C. for 30 h. After 30 h, the temperature was decreased from 250 to 120° C. at 60° C./h; then, the glycerin feeding was stopped and nitrogen was fed, decreasing the temperature from 120 to 60° C. at 180° C./h and adjusting the system pressure to 2 kg/cm2. The solid was washed by feeding propanol at 280 mL/h for 2 h, stopping the propanol flow to set the system at 20° C. and 0.8 kg/cm2. The recovered solid was dried in an oven at 100° C. for 5 h and analyzed by atomic absorption, finding that 52 and 53% of molybdenum and cobalt, respectively, had been removed from the starting catalyst content.
14 g of exhausted catalyst (Table No. 4), which was used in Examples No. 7 and 8, were ground to pass through a 60 mesh sieve and compacted in a continuous flow tubular reactor, pressurizing at 30.0 kg/cm2 using nitrogen; afterwards, the temperature was increased from 25 to 180° C. at 60° C./min, starting the glycerin feeding at 350 mL/h and increasing the temperature up to 260° C. at 60° C./h, keeping the same pressure (30.0 kg/cm2) and temperature at 260° C. for 24 h. After 24 h, the temperature was decreased from 260 to 120° C. at 60° C./h; then, the glycerin feeding was stopped and nitrogen was fed, decreasing the temperature from 120 to 60° C. at 180° C./h and adjusting the system pressure to 2 kg/cm2. The solid was washed by feeding heptane at 280 mL/h for 2 h, stopping the heptane flow to set the system at 20° C. and 0.8 kg/cm2. The recovered solid was dried in an oven at 100° C. for 5 h and analyzed by atomic absorption, finding that 42 and 42% of platinum and rhenium, respectively, had been removed from the initial catalyst content.
750 g of fresh catalyst (Table No. 3), which was used in Example No. 6, in its commercial size ( 1/20″) and shape (tetralobular), were compacted in a continuous flow tubular reactor, pressurizing at 20.0 kg/cm2 using nitrogen; afterwards, the temperature was increased from 25 to 280° C. at 60° C./min, starting the ethylene glycol feeding at 3325 mL/h, keeping the same pressure (20.0 kg/cm2) and temperature at 280° C. for 80 h. After 80 h, the temperature was decreased from 280 to 120° C. at 60° C./h; then, the ethylene glycol feeding was stopped and nitrogen was fed, decreasing the temperature from 120 to 60° C. at 180° C./h and adjusting the system pressure to 8 kg/cm2. The solid was washed by feeding hydrodesulfurized naphtha at 1800 mL/h for 6 h, stopping the hydrodesulfurized naphtha flow to set the system at 20° C. and 0.8 kg/cm2. The recovered solid was dried in an oven at 100° C. for 5 h and analyzed by atomic absorption, finding that 70 and 78% of molybdenum and nickel, respectively, had been removed from the starting catalyst content.
To better visualize the advantages of the non-destructive process featured in the present disclosure, a summary of the main data from Examples No. 1 to 12, which were shown with illustrative purposes and without limited scope, is shown in Table No. 5.
The results in Table No. 5 show that the non-destructive process of the present disclosure displayed a higher removal percentage of metals (M) when a continuous flow tubular reactor was used (metal removal of at least 42%) than when employing a batch reactor (metal removal of at least 27%).
To emphasize the benefits provided by the non-destructive process featured in the present disclosure, the following example is given:
1.0 g of fresh catalyst (Table No. 3), which was used in Examples No. 6 and 14, was ground to pass through a 200 mesh sieve and mixed with 50 mL of butanol and refluxed for 6 h at 80° C.; after 6 h, the temperature was decreased to 20° C. and the solid was filtered, dried at 60° C. and analyzed by atomic absorption, finding that 7.5 and 9.1% of molybdenum and nickel, respectively, had been removed from the initial catalyst content.
The results obtained in this example, in comparison with those from Examples No. 1 to 3, 6, 9 to 11 and 14, show the following main features of the non-destructive process introduced in the present disclosure:
| Number | Date | Country | Kind |
|---|---|---|---|
| MX/A/2017/010801 | Aug 2017 | MX | national |
The present application is a national stage entry under 35 U.S.C. 371 of PCT Patent Application No. PCT/MX2018/050017, filed Jul. 27, 2018, which claims priority to Mexican Patent Application MX/a/2017/010801, filed Aug. 23, 2017, the entire contents of each of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/MX2018/050017 | 7/27/2018 | WO | 00 |
