Non-destructive process for removing metals, metal ions and metal oxides from alumina-based materials

Patent metadata

Field	Value
Publication number	US-2020207635-A1
Application number	US-201816640454-A
Country	US
Kind code	A1
Filing date	Jul 27, 2018
Priority date	Aug 23, 2017
Publication date	Jul 2, 2020
Grant date	—

Abstract

The present disclosure describes a non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials without destroying alumina, allowing the regeneration of alumina-based catalysts. Known conventional procedures and/or methods for removing metals, metal ions and metal oxides present in alumina-based materials use some inorganic acid or its mixtures to carry out digestion, which modifies the properties of alumina and those of any other element contained in the material, destroying alumina and preventing its reuse. The present disclosure is characterized by using an extracting agent that sequesters metals, metal ions and/or metal oxides present in alumina-based materials without modifying their properties. The employed extracting agent is an alcohol. The non-destructive process introduced in the present invention reaches metal (M) removal rates of at least 42% when using a continuous flow reactor and of at least 27% when a batch reactor is employed.

First claim

1 . A non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials, comprising the following stages:
a) mixing of starting materials, the starting materials comprising one of a solid material or a mixture of solid materials that contains at least one of metals, metal ions or metal oxides, with an extracting agent, resulting in an obtained mixture; b) reaction of the obtained mixture at a temperature in a range of about 10° C. to about 350° C. for a time in a range of about 10 minutes to about 500 hours, resulting in a reacted mixture; c) separation by one of centrifugation, decantation or filtration of the reacted mixture to obtain a solid; d) washing of the solid with one of water, an alcohol, an ammonium hydroxide solution, or with a hydrocarbon or hydrocarbon mixture; and e) drying of the solid, said solid containing a low content of metals, metal ions and/or metal oxides.

2 . The non-destructive process, according to claim 1 , wherein the starting materials comprise alumina-based materials that contain at least one of the following chemical elements or a mixture thereof: Si, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt or Au.

3 . The non-destructive process, according to claim 2 , wherein the metals, metal ions or metal oxides present in the alumina-based materials are found in organic form as at least one of powders, ground or original-form materials, the original-form materials comprising extrudates or spheres.

4 . The non-destructive process, according to claim 1 , wherein the extracting agent is a polyol.

5 .The non-destructive process, according to claim 1 , wherein the temperature is in a range of about 10° C. to about 300° C. and the time is in a range of about 1 h to about 96 h.

6 . The non-destructive process, according to claim 1 , wherein the washing of the solid is carried out with at least one of distilled water, methanol, ethanol, or propanol, with an ammonium hydroxide solution from 1 to 35 wt. %, or with one of hydrodesulfurized naphtha, reforming product or a hexane/heptane mixture.

7 . The non-destructive process, according to claim 1 , wherein the process is carried out in a batch reactor or in a continuous flow reactor.

8 . The non-destructive process, according to claim 1 , further comprising pressurization and cooling operations carried out with nitrogen, and wherein the pressure ranges from about 0.5 kg/cm 2 to about 75 kg/cm 2 .

9 . The non-destructive process, according to claim 7 , wherein, when the continuous flow reactor is employed, metal removal percentages of at least about 42% of the metals initially contained in the starting materials are achieved.

10 . The non-destructive process, according to claim 7 , wherein, when the batch reactor is employed, metal removal percentages of at least about 27% of the metals initially contained in the starting materials are accomplished.

11 . The non-destructive process, according to claim 1 , wherein the process results in a regeneration of alumina-based catalysts, in a recovery or recycling of metals and in a reuse of alumina from catalysts used mainly in oil industry processes as hydrotreating, isomerization and naphtha catalytic reforming.

12 . A non-destructive process for removing metals, metal ions and metal oxides present in alumina-based materials without destroying alumina, comprising:
a) compaction of starting materials, the starting materials comprising one of solid material or a mixture of solid materials that contain at least one of metals, metal ions or metal oxides with a temperature increase from about 50° C. to about 300° C., and feeding of an extracting agent, said extracting agent comprising an alcohol, at a flow rate from about 1 mL/h to about 500 mL/h per solid gram, while maintaining a consistent pressure and temperature for a time period of about 1 h to about 150 h; b) interruption of the feeding of the extracting agent, and decreasing the temperature about 150° C. to about 50° C. to cool down the reaction system, resulting in a solid material; c) washing of the solid material with one of an alcohol, or a hydrocarbon or hydrocarbon mixture, at a flow rate from about 1 mL/H to about 500 mL/h per solid gram for a time in a range of about 30 minutes to about 85 hours, and subsequently stopping the flow rate, increasing the system temperature about 10° C. to about 25° C., and increasing the pressure conditions about 1 Kg/cm 2 , resulting in recovered solid material with a low content of metals, metal ions, or metal oxides; and d) drying of the recovered solid material;
wherein the process is carried out in a continuous flow reactor.

13 . The non-destructive process, according to claim 12 , wherein the starting materials comprise alumina-based materials that contain at least one of the following chemical elements or a mixture thereof: Si, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt or Au.

14 . The non-destructive process, according to claim 13 , wherein the metals, metal ions or metal oxides present in the alumina-based material are in inorganic form as at least one of a powder, a ground material or an original form material, the organic form material comprising an extrudate or sphere.

15 . The non-destructive process, according to claim 12 , wherein the alcohol is a polyol.

16 . The non-destructive process, according to claim 12 , wherein the washing of the solid material is done with one of a methanol, ethanol, propanol or with hydrodesulfurized naphtha, reforming product or a hexane/heptane mixture, and is carried out at a flow rate from about 1 mL/h to about 300 mL/h per solid gram, for a time period of about 24 h to about 80 h.

17 . The non-destructive process, according to claim 12 , wherein the pressure in the continuous flow reactor ranges from about 0.5 kg/cm 2 to about 75 kg/cm 2 .

18 . The non-destructive process, according to claim 17 , wherein the pressurization and cooling are done with nitrogen.

19 . The non-destructive process, according to claim 12 , wherein the process results in at least about 42% of each of the metals initially contained in the starting materials being removed.

20 . The non-destructive process, according to claim 12 , wherein the process results in a regeneration of alumina-based catalysts, in a recovery or recycling of metals and in a reuse of alumina from catalysts used mainly in oil industry processes as hydrotreating, isomerization and naphtha catalytic reforming catalysts.

Assignees

• Mexicano Inst Petrol

Inventors

• Perez Romo Patricia
• Aguilar Barrera Candido
• Navarrete Bolanos Juan
• Reyes Robles Santos Glorindo

Classifications

• C10G2300/706

  Catalytic metal recovery · CPC title

• C10G45/58

  to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins (C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00) · CPC title

• C10G45/02

  to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing · CPC title

• C10G35/04

  Catalytic reforming · CPC title

• B01J38/02

  Heat treatment · CPC title