Process for obtaining adsorbent material based on porous silicates for reduction of sulfur and nitrogen in oil fractions

Patent metadata

Field	Value
Publication number	US-10010864-B2
Application number	US-201314062522-A
Country	US
Kind code	B2
Filing date	Oct 24, 2013
Priority date	Oct 24, 2012
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

The present invention relates to the process of obtaining adsorbent materials based upon supported metal species on porous silicates, and their use for reducing the amount of sulfur and nitrogen contaminants in petroleum fractions and products derived of, i.e., light and heavy gas oils, FCC gasoline and fuels, where FCC stands for Fluid Catalytic Cracking process.
Therefore, the invention comprises the selection, preparation, modification and adsorptive properties of the abovementioned porous materials, which are based on porous silicates with metal species intercalated and/or impregnated, such as Ti(O,OH), Mg(O,OH)—, Zr(O,OH)—, Fe(O,OH), Al(O,OH). Also, additional options were considered, for example those comprising metals from the 1 st and 2 nd transition series, such as Cu + , Ni 2+ , Zn 2+ , Fe 2+ , Ag + , Co 2+ , Ti 4+ , V 2+,5+ , Cr 3+ and Mn 2+ .

First claim

Having described the present invention, this is considered as a novelty and therefore claimed as property the content of the following claims:

1. A process for obtaining porous silicate adsorbents for reducing the sulfur and nitrogen contents in petroleum fractions and products derived therefrom, comprising the following steps:
dissolving an amount of an EO/PO tri-block polymer in water, adding a 1-5 molar solution containing hydrochloric and citric acid to form a first mixture;
heating the first mixture to about 40-50° C. for about 1 h;
adding to said mixture about 20 to 40 mmol TEOS, under constant stirring for about 3 h to obtain a first reaction product,
adding to the first reaction product 70 to 75 mmol of 30% H 2 O 2 solution containing a nitrate of a metal cation selected from the group consisting of Cu + , Ni 2+ , Zn 2+ , Fe 2+ , Co 2+ , Ti 4+ , V 2+ , V 5+ , Cr 3+ and Mn 2+ or an inorganic compound containing a metal selected from the group consisting of Ti, Mg, Zn, Fe and Al under stirring at 40° C. for a period between 3 and 20 h,
aging the resulting solution in an autoclave with stirring while raising the temperature to 100° C. or less, keeping these conditions for a period of 24 h; then,
filtering and drying the resulting material, removing non-reacted compounds by rinsing with ethanol for a period of 24 hr;
filtering and washing the resulting material with ethanol, drying the material in an oven at 60° C.; and
calcining the dried material in air or nitrogen atmosphere for 6 h at 500° C. to obtain the porous silicate adsorbents, wherein integrated materials are formed by a metal-silicate complex, and wherein said porous silicate adsorbents have an average pore diameter of 3-30 nm and a wall thickness between pores of 1.5-2.5 nm.

2. A process for obtaining porous silicate adsorbents in accordance with claim 1 , wherein the porous silicate adsorbents have surface areas greater than 500 m 2 /g.

3. A process of obtaining porous silicate absorbents in accordance with claim 1 , wherein the porous silicate absorbents have a porous network with an average pore diameter of about 3 to 30 nm.

4. A process for obtaining porous silicate adsorbents in accordance with claim 1 , further comprising the step of impregnating said calcined silicate with an aqueous solution of a nitrate (NO 3− ) containing a metal cation selected from the group consisting of Cu + , Ni 2+ , Zn 2+ , Fe 2+ , Ag + , Co 2+ , Ti 4+ , V 2+,5+ , Cr 3+ and Mn 2+ .

5. The process of claim 1 , wherein said porous silicate adsorbents have a surface area of 500-1000 m 2 /g.

6. The process of claim 1 , wherein said porous silicate adsorbents have a surface area of greater than 1000 m 2 /g.

7. The process of claim 1 , wherein said H 2 O 2 solution contains TiO 4 4− , TiOH 4 4− , MgO − , MgOH − , ZrO 4 4− , ZrOH 4 4− , FeO 2 2− , FeOH 2 2− , AlO 3 3− , AlOH 3 3− and mixtures thereof, where said porous silicate adsorbents are intercalated with at least one metal selected from the group consisting of Ti, Mg, Zr, Fe and Al.

8. The process of claim 7 , wherein said porous silicate adsorbents include a metal compound selected from the group consisting of mixtures of TiO 4 4− and Ti(OH) 4 4− , mixtures of MgO − and MgOH − , mixtures of ZrO 4 4− and Zr(OH) 4 4− , mixtures of FeO 2 2− and Fe(OH) 2 2− , and mixtures of AlO 3 3− and Al(OH) 3 3− .

9. The process of claim 1 , wherein said porous silicate adsorbents have a specific surface area greater than 800 m 2 /g.

10. The process of claim 1 , wherein said citric acid solution is added to said EO/PO tri-block polymer.

11. A process for producing porous silicate adsorbents for reducing the sulfur and nitrogen contents in petroleum fractions and products derived of, said process comprising the steps of:
dissolving an amount of an EO/PO tri-block polymer in water, adding a 1-5 molar citric acid solution to form a first mixture and heating the resulting first mixture;
adding about 20 to 40 mmol TEOS to said mixture to obtain a first reaction product, under constant stirring,
adding to said first reaction product a H 2 O 2 solution containing a nitrate of a metal cation selected from the group consisting of Cu + , Ni 2+ , Zn 2+ , Fe 2+ , Co 2+ , Ti 4+ , V 2+ , V 5+ , Cr 3+ and Mn 2+ or an inorganic compound containing a metal selected from the group consisting of Ti, Mg, Zn, Fe and Al under stirring for between 3 and 20 h, aging the resulting solution in an autoclave with stirring while raising the temperature to 100° C. or less;
filtering and drying the resulting material,
removing non-reacted compounds by rinsing with ethanol;
filtering and washing the resulting material with ethanol, drying the material in an oven; and
calcining the material in air or nitrogen atmosphere to obtain the porous silicate adsorbents having a surface area of 500-1000 m 2 /g, an average pore diameter of 3-30 nm, and a wall thickness between pores of 1.5-2.5 nm, wherein integrated materials are formed by a metal-silicate complex.

12. The process of claim 11 , wherein
said mixture of said EO/PO tri-block polymer and citric acid is heated at a temperature of about 40-50° C.

13. The process of claim 11 , wherein
said H 2 O 2 solution is a 30% H 2 O 2 solution and is added in an amount of about 70 to 75 mmol.

14. The process of claim 11 , wherein
said material is dried at a temperature of about 60° C. and calcined at a temperature of about 500° C. for about 6 hours.

15. The process of claim 1 , wherein said first mixture consists essentially of said acid solution and said EO/PO tri-block polymer.

16. The process of claim 11 , wherein said first mixture consists essentially of said acid solution and said EO/PO tri-block polymer.

Assignees

• Mexicano Inst Petrol

Inventors

• Flores Sanchez Patricia
• Dominguez Esquivel Jose Manuel
• Aburto Anell Jorge Arturo

Classifications

• B01J20/3204

  Inorganic carriers, supports or substrates · CPC title

• B01J20/3078

  Thermal treatment, e.g. calcining or pyrolizing · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• B01J20/3433

  of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425 · CPC title

• B01J20/28064

  being in the range 500-1000 m2/g · CPC title