Adsorbent for desulfurization of gasoline and method for desulfurization of gasoline

Patent metadata

Field	Value
Publication number	US-10011779-B2
Application number	US-201514931690-A
Country	US
Kind code	B2
Filing date	Nov 3, 2015
Priority date	Feb 4, 2015
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

The present invention provides an adsorbent and a method for desulfurization of gasoline. The adsorbent is obtained by loading active metal component on a composite carrier comprising zeolite and active carbon subjected to alkali treatment respectively, the active metal is selected from one or more elements of IA, IIA, VIII, IB, IIB and VIB groups in the periodic table. This method uses the adsorbent to conduct gasoline adsorption desulfurization, which especially cuts the gasoline into a light and a heavy gasoline fraction firstly, then the light fraction is subjected to adsorption desulfurization using the adsorbent, and the heavy fraction is subjected to selective hydrodesulfurization, a cutting temperature of the light and the heavy gasoline fraction is 70-110° C. The adsorbent has a large sulfur adsorption, a long service life, and simply to be regenerated; the method can realize deep desulfurization of gasoline, and has a less octane number loss.

First claim

What is claimed is:

1. An adsorbent for desulfurization of gasoline, wherein the absorbent is obtained by loading an active metal component on a composite carrier, the composite carrier comprises a zeolite and an active carbon, wherein the zeolite and the active carbon are treated with alkali respectively before they are mixed to prepare the composite carrier, wherein the zeolite and the active carbon being treated with alkali respectively comprises treating the zeolite and the active carbon, respectively, as follows: blending at a mass ratio of the zeolite or the active carbon to alkali to water: (0.1-2):(0.05-2):(4-15), and stirring the mixture for 0.1-24 h at a temperature of 0-120° C., and then drying, the active metal is selected from one or more of elements of IA, VIII, IB, IIB and VIB groups in the periodic table.

2. The adsorbent for desulfurization of gasoline according to claim 1 , wherein a mass ratio of the zeolite to the active carbon in the composite carrier is (20-80): (80-20).

3. The adsorbent for desulfurization of gasoline according to claim 1 , wherein the zeolite is an X type, a Y type or a ZSM-5 type zeolite.

4. The adsorbent for desulfurization of gasoline according to claim 1 , wherein the active metal is selected from at least two of Ni, Fe, Ag, Co, Mo, Zn and K.

5. The adsorbent for desulfurization of gasoline according to claim 1 , wherein the active metal has a loading of 2-30% on the composite carrier.

6. A method for preparing the adsorbent for desulfurization of gasoline according to claim 1 , comprising steps of:
blending the zeolite and the active carbon subjected to alkali treatment, respectively, in proportion to prepare the composite carrier;
impregnating the composite carrier with a soluble salt solution of the active metal, drying the composite carrier impregnated with soluble salt solution and, then, calcinating to obtain the adsorbent for desulfurization of gasoline.

7. The method according to claim 6 , wherein the alkali treatment comprises treating the zeolite and the active carbon, respectively, as follows: blending at a mass ratio of the zeolite or the active carbon to alkali to water: (0.1-2):(0.05-2):(4-15), and stirring the mixture for 0.1-24 h at a temperature of 0-120° C., and then drying, the above alkali treatment is conducted at least one time.

8. The method according to claim 6 , wherein calcinating the composite carrier impregnated with the soluble salt solution after being dried is conducted for 4-6 h at a temperature of between 450-640° C.

9. The method according to claim 6 , wherein calcinating the composite carrier comprises cooling the composite carrier impregnated with the soluble salt solution after being dried down to a room temperature, elevating the temperature to 400° C. at a speed of 6° C./min firstly, and then elevating the temperature to 450-640° C. at a speed of 3° C./min.

10. A method for desulfurization of gasoline, comprising: conducting adsorption desulfurization to gasoline using the adsorbent according to claim 1 .

11. The method for desulfurization of gasoline according to claim 10 , comprising firstly cutting the gasoline into a light gasoline fraction and a heavy gasoline fraction, and then conducting adsorption desulfurization to the light gasoline fraction using the adsorbent to obtain a desulfurized light gasoline fraction, and conducting selective hydrodesulfurization to the heavy gasoline fraction to obtain a desulfurized heavy gasoline fraction; wherein, a cutting temperature of the light gasoline fraction and the heavy gasoline fraction is 70-110° C.

12. The method for desulfurization of gasoline according to claim 10 , wherein the adsorption desulfurization is conducted using a fixed-bed at atmospheric pressure, and a temperature of the adsorption desulfurization is controlled between 20-100° C., a flow rate of the gasoline is 0.3-1 mL/min.

13. The method for desulfurization of gasoline according to claim 11 , further comprising:
washing the adsorbent which is subjected to the adsorption desulfurization with steam to collect a sulfur-rich component;
mixing the sulfur-rich component with the heavy gasoline fraction to conduct the selective hydrodesulfurization.

14. The method for desulfurization of gasoline according to claim 11 , further comprising:
washing the desulfurization adsorbent which is subjected to the adsorption desulfurization with steam, drying the washed adsorbent with nitrogen at a temperature of 200-400° C., and cooling the dried adsorbent with nitrogen to realize regeneration of the adsorbent.

15. The method for desulfurization of gasoline according to claim 11 , wherein the heavy gasoline fraction and hydrogen are subjected to the selective hydrodesulfurization in the presence of a selective hydrodesulfurization catalyst to obtain the desulfurized heavy gasoline fraction, wherein, a temperature of the selective hydrodesulfurization is 200-300° C., a pressure is 1.5-2.5 MPa, a liquid hourly space velocity is 1-5 h-1, a volume ratio of hydrogen to oil is 400-600.

16. The method for desulfurization of gasoline according to claim 15 , wherein the hydrodesulfurization catalyst is obtained by loading a carrier with an active metal component, wherein the carrier is a zeolite or a metal oxide, and the active metal comprises Co and Mo.

17. The method for desulfurization of gasoline according to claim 16 , wherein Co and Mo have an overall loading of 5-20% on the carrier.

18. The method for desulfurization of gasoline according to claim 11 , wherein the light gasoline fraction is subjected to the adsorption desulfurization after being subjected to demercaptan treatment.

19. The method for desulfurization of gasoline according to claim 11 , wherein the gasoline is cut into the light gasoline fraction and the heavy gasoline fraction after being subjected to demercaptan treatment.

Assignees

• China Univ Of Petroelum Beijing
• Univ China Petroleum Beijing

Inventors

• Zhao Liang
• Gao Jinsen
• Xu Chunming
• Hao Tianzhen
• Han Xiaona

Classifications

• C10G53/12

  including at least one alkaline treatment step · CPC title

• C10G67/00

  Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only · CPC title

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• C10G53/08

  including at least one sorption step · CPC title

• C10G67/16

  plural parallel stages only · CPC title