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

• US 20140110629A1
• Filed: 10/24/2013
• Published: 04/24/2014
• Est. Priority Date: 10/24/2012
• Status: Active Grant

• Current Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Original Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Inventors: Dominguez Esquivel, Jose Manuel, Flores Sanchez, Patricia, Aburto Anell, Jorge Arturo
• Granted Patent: US 10,010,864 B2
• Time in Patent Office: Days
• US Class Current: 252/189
• CPC Class Codes: B01J 20/10 comprising silica or silicate
• CPC Class Codes: B01J 20/28064 being in the range 500-1000 m2/g
• CPC Class Codes: B01J 20/305 Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
• CPC Class Codes: B01J 20/3071 Washing or leaching
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 55/06 including at least one catalytic cracking step

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⁺, Ni²⁺, Zn²⁺, Fe²⁺, Ag⁺, Co²⁺, Ti⁴⁺, V^2+,5+, Cr³⁺ and Mn²⁺.

Claims

1. A process for obtaining porous silicates that can be used as adsorbents for reducing the sulfur and nitrogen contents in petroleum fractions and products derived of, comprising the following steps:

dissolving an amount of Pluronic 123 (1.6×

10<sup>−

4</sup> M) in water, while simultaneously making an hydrochloric or citric acid solution with a concentration between 1 and 5 molar;

then, the mixture is heated up to about 40-50°

C., while keeping this temperature for about 1 h;

then, TEOS was added, i.e., 20 to 40 mmol, depending on the material to be processed;

ethanol is added too and this mixture is kept under constant stifling for about 3 h, then the next step is adding 70 to 75 mmol of 30% H₂O₂ solution and the main inorganic species abovementioned, this solution is maintained under stirring at 40°

C. for a period between 3 and 20 h, then it is aged in autoclave with stirring while rising the temperature up to 100°

C., then keeping these condition for a period of 24 h;

then, the material is filtered out and dried, before refluxing it for getting rid of non-reacted compounds, which procedure is performed using ethanol for a period of 24 hr.;

the next step consists of filtering and washing the material with ethanol, then drying in an oven at 60°

C.;

finally the material is calcined in air or nitrogen atmosphere for 6 h at 500°

C.

3. A process for obtaining adsorbent materials from porous silicates for reducing the proportion of sulfur and nitrogen compounds from petroleum fractions and products derived of, i.e., FCC gasoline, in accordance with claim 1, wherein the selective adsorption of nitrogen and sulfur-containing molecules takes place under low severity conditions, i.e., T<

100°

C., P=1 atm, while retaining unchanged the octane number of the FCC gasoline.

4. A process for obtaining adsorbent materials based upon porous silicates, which are used for reducing the amount of sulfur and nitrogen compounds in petroleum fractions and products derived of, in accordance with claim 1, wherein the porous materials have surface areas greater than 500 m²/g , sometimes reaching over 1,000 m²/g, depending on the preparation conditions as described herein.

5. A process for obtaining adsorbent materials based upon porous silicates for reducing sulfur and nitrogen compounds from petroleum fractions and products derived of, in accordance with claim 1, wherein the porous materials are constituted by a porous network with pore diameters of about 3 to 30 nm.(average);

this allows the design of new adsorbents and catalysts by formation of the porous networked materials, plus grafting or impregnating active phases and chemical species as described herein.

6. A process for obtaining adsorbent materials based upon porous silicates for reducing sulfur and nitrogen compounds in petroleum fractions ad products derived of, in accordance with claim 1, wherein there is a quality improvement of the FCC gasoline by reducing its content of thiophenic and benzothiophenic compounds from the liquid fraction.

7. A process for obtaining adsorbent materials based upon porous silicates for reducing sulfur and nitrogen compounds from petroleum fractions and derived of, in accordance with claim 1, wherein the materials obtained were impregnated with aqueous solutions of mineral salts (NO3-) containing metals from the 1^st and 2^nd transition series, such as Cu⁺, Ni²⁺, Zn²⁺, Fe²⁺, Ag⁺, Co²⁺, Ti⁴⁺, V^2+,5+, Cr³⁺ and Mn²⁺;

in particular Cu⁺, Ni²⁺, Ag⁺ and Zn²⁺ as specified in the present invention.

8. A process for obtaining adsorbent materials based upon porous silicates for reducing the amount of sulfur and nitrogen compounds from petroleum fractions and products derived of, i.e. FCC gasoline, in accordance with claim 1, wherein the adsorption process is carried out on such porous materials through their adsorbing properties, which are capable of reducing the sulfur content and total nitrogen in FCC product from 1,000 to 1,500 ppm to values allowed by environmental regulations (<

50 ppm), so that means a removal capacity greater than 96.6% wt, with respect to the calculation base (˜

1,500 ppm S).

2. A process for obtaining an adsorbent material consisting of a porous silicate that is used in reducing sulfur and nitrogen content in some petroleum fractions and products derived of, i.e., gasoline, in accordance with the first clause, wherein the typical sulfur content in the product is about 1,500 ppm sulfur and 300 ppm nitrogen or more, which are obtained usually by cracking and recombination processes in the FCC reactors.

9. The use of the porous silicates as adsorbents to reduce the amount of sulfur and nitrogen content in the petroleum fractions and products derived of, are characterized as described herein and it is used for effecting the adsorption of nitrogen and sulfur compounds from FCC in gasoline, where the gasoline is mixed with a certain amount of such adsorbent materials, as described in the abovementioned examples and then adsorption is carried out for a time between 15 to 30 min at room temperature;

after this the fuel is filtered and the effect is verified by chromatography analysis, in order to verify the amount of sulfur and nitrogen contained therein.