Process for obtaining metal-organic materials with structure type MIL-101 (Cr) and MIL-101-Cr-MX+

Patent metadata

Field	Value
Publication number	US-9777029-B2
Application number	US-201514964478-A
Country	US
Kind code	B2
Filing date	Dec 9, 2015
Priority date	Dec 17, 2014
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

The present invention relates to a process for obtaining materials with Metal Organic atomic structure and called MOF (MOF: Metal Organic Framework) type MIL-101 (Cr) and MIL-101-Cr-M X+ (MIL: Material from Institute Lavoisier), where M X+ can be any metal cation, such as Mg 2+ , Al 3+ or Ti 4+ , using for its synthesis metal epoxides and alkoxides, avoiding the use of hydrofluoric acid (HF) or bases as synthesis controlling agents.
The process of the present invention for the preparation of materials MOF MIL-101 (Cr) and MOF MIL-101-Cr-M X+ where M X+ can be any metal cation, such as Mg 2+ , Al 3+ or Ti 4+ , consisting of:
a) Synthesizing MOF MIL-101 (Cr) with epoxides, or
Synthesizing MOF MIL-101-Cr-M X+ with metal alkoxides; and
b) Purifying the synthesized MOF. in order to obtain 100% pure materials, with a controlled mesoporosity associated with a hysteresis P/P 0 from 0.7 to 0.99, BET surface area from 2,500 to 3,500 m 2 /g, pore volume from 1.1 to 2.2 cm 3 /g, and pore diameter from 15 to 55 nm.

First claim

The invention claimed is:

1. A process for obtaining a metal-organic framework of chromium(III) terephthalate (MIL-101-Cr) or a metal-organic framework of chromium(III) terephthalate with an additional metal ion M X+ (MIL-101-Cr-M X+ ), consisting of:
a) Synthesizing the MIL-101-Cr with epoxides, or
Synthesizing the MIL-101-Cr M X+ with metal alkoxides, where M X+ is any metal cation; and
b) Purifying the synthesized MIL-101-Cr or MIL-101-Cr-M X+ ;
in order to obtain 100% pure materials with controlled mesoporosity associated with a hysteresis P/P 0 from 0.7 to 0.99, BET surface area from 2,500 to 3,500 m 2 /g, pore volume from 1.1 to 2.2 cm 3 /g, and pore diameter from 15 to 55 nm.

2. The process of claim 1 , wherein step a) for synthesizing MIL-101-Cr comprises:
adding water to a mixing tank, and starting constant stirring at room temperature;
adding terephthalic acid, and stirring 5-15 minutes;
adding a chromium salt, maintaining stirring for 10 to 30 minutes, and applying pulses with an ultrasound probe with 75 to 85% amplitude for a time of 4 to 8 minutes, to form a solution;
adding an epoxide, to the solution and stirring for 5 to 15 minutes to form a final solution;
pouring the final solution in to a reactor and closing the reactor to start hydrothermal treatment for 20 to 28 hours, at 170-190° C., 150 to 250 rpm and at autogenous pressure of 160 to 200 psi; and
allowing the reactor to cool to room temperature and recovering a final reaction mixture.

3. The process of claim 1 , wherein step a) for synthesizing MIL-101-Cr-M X+ consists of:
adding water to a mixing tank and initiating constant stirring at room temperature;
adding a chromium salt and terephthalic acid, and stirring for 5 to 15 minutes and applying pulses with an ultrasound probe with 75 to 85% amplitude for a time of 4 to 8 minutes;
adding a metal alkoxide and dissolving while maintaining stirring for 5 to 15 minutes, applying pulses with an ultrasound probe with 75 to 85% amplitude for a time of 4 to 8 minutes to form a final solution;
pouring the final solution in a reactor and closing the reactor to start hydrothermal treatment for 20 to 28 hours, at 170-190° C. with no stirring and at autogenous pressure; and
allowing the reactor to cool and recovering a sample.

4. The process of claim 1 , wherein step a) provides a yield of 95 to 98% weight.

5. The process of claim 1 , wherein step b) comprises:
performing a first washing by adding 25 to 250 ml of acetone to the synthesized MIL-101-Cr or MIL-101-Cr-M X+ to provide a mixture comprising liquid and MIL-101-Cr or MIL-101-Cr-M X+ as suspension; stirring the mixture for 30 to 90 minutes, then filtering the mixture to recover a solid;
subjecting the recovered solid to a second washing with the same characteristics as the first wash, and filtering again to recover a powder; and
drying the recovered powder at 100-140° C. for 10 to 14 hours.

6. The process of claim 1 , wherein M X+ is selected from Mg 2+ , Al 3+ and Ti 4+ .

7. The process of claim 2 , wherein the stirring step further comprises applying pulses with an ultrasound probe with 75 to 85% amplitude for a time of 4 to 8 minutes.

8. The process of claim 2 , wherein the chromium salt is Cr(NO 3 ) 3 .9H 2 O.

9. The process of claim 2 , wherein the epoxide is propylene oxide.

10. The process of claim 2 , wherein the hydrothermal treatment in the reactor is conducted for 22 to 26 hours at 175-185° C., 175-225 rpm and autogenous pressure of 170-190 psi.

11. The process of claim 3 , wherein the chromium salt is Cr(NO 3 ) 3 .9H 2 O.

12. The process of claim 3 , wherein the metal alkoxide is Mg(OCH 2 CH 3 ) 2 .

13. The process of claim 3 , wherein the hydrothermal treatment in the reactor is conducted for 22 to 26 hours at 175-185° C. without stirring and at autogenous pressure.

14. The process of claim 2 , wherein step b) comprises:
performing a first washing by adding 175 to 225 ml of acetone to the synthesized MIL-101-Cr + to provide a mixture comprising liquid and MIL-101-Cr as suspension; stirring the mixture for 30 to 90 minutes, then filtering the mixture to recover a solid;
subjecting the recovered solid to a second washing with the same characteristics as the first wash, and filtering again to recover a powder; and
drying the recovered powder at 100-140° C. for 10 to 14 hours.

15. The process of claim 3 , wherein step b) comprises:
performing a first washing by adding 35 to 65 ml of acetone to the synthesized MIL-101-Cr-M X+ to provide a mixture comprising liquid and MIL-101-Cr-M X+ as suspension; stirring the mixture for 30 to 90 minutes, then filtering the mixture to recover a solid;
subjecting the recovered solid to a second washing with the same characteristics as the first wash, and filtering again to recover a powder; and
drying the recovered powder at 100-140° C. for 10 to 14 hours.

Assignees

• Inst Mexicano Del Petróleo
• Mexicano Inst Petrol

Inventors

• Mora Vallejo Rodolfo Juventino
• Montoya De La Fuente J Ascención
• Laredo Sánchez Georgina Cecilia
• Meneses Ruíz Edith
• Castillo Munguía J Jesús
• Zapata Rendón Beatriz

Classifications

• C07F11/005 Primary

  compounds without a metal-carbon linkage · CPC title