Hydrocarbon oil hydrotreating method

Patent metadata

Field	Value
Publication number	US-2016152902-A1
Application number	US-201314430499-A
Country	US
Kind code	A1
Filing date	Sep 18, 2013
Priority date	Sep 21, 2012
Publication date	Jun 2, 2016
Grant date	—

Abstract

Provided is a hydrocarbon oil hydrotreating method, comprising the following steps: (1) injecting hydrogen into the hydrocarbon oil via an opening having a nanoscale average diameter, so as to obtain hydrocarbon oil containing hydrogen; and (2) under a liquid phase hydrotreating condition, feeding into a reactor the hydrocarbon oil containing hydrogen to contact a catalyst having a hydrogenation catalysis effect. The method of the present invention can quickly and efficiently disperse and dissolve the hydrogen into the hydrocarbon oil even without the aid of a diluent or circulating oil, so as to obtain stable hydrogen-containing hydrocarbon oil with a high hydrogen content, and obtain an hydrotreating effect equivalent to or even better than the existing hydrotreating methods.

First claim

1 . A method for hydroprocessing hydrocarbon oil, comprising the following steps,
(1) injecting hydrogen gas into hydrocarbon oil through pores with an average pore diameter in nanometer size, to obtain a hydrogen-containing hydrocarbon oil; (2) feeding the hydrogen-containing hydrocarbon oil into a reactor, to contact with a catalyst having a hydrogenation catalytic action under a liquid-phase hydroprocessing condition.

2 . The method according to claim 1 , wherein the pores have an average pore diameter in a range of 1 nm to 1,000 nm.

3 . The method according to claim 2 , wherein percentage of the quantity of pores with a pore diameter in a range of 50 nm to 500 nm to total quantity of the pores is 95% or higher.

4 . The method according to claim 1 , wherein the hydrogen gas is injected into the hydrocarbon oil in a flowing state, the hydrogen gas is injected at a rate of v 1 by g·h −1 ·m −2 , the hydrocarbon oil has a flow rate of v 2 by kg·h −1 ·m −2 , ratio of v 1 /v 2 is in a range of 0.000625 to 0.09.

5 . The method according to claim 1 , wherein the hydrogen gas is injected into the hydrocarbon oil by means of a mixing device, to obtain the hydrogen-containing hydrocarbon oil, the mixing device comprises at least one liquid passage for accommodating the hydrocarbon oil and at least one gas passage for accommodating the hydrogen gas, the liquid passage is adjacent to the gas passage through a component, at least part of the component is a porous area having the pores with an average pore diameter in a nanometer size, the hydrogen gas is injected into the hydrocarbon oil through the pores with an average pore diameter in nanometer size.

6 . The method according to claim 5 , wherein the porous area has a porosity in a range of 5-28%.

7 . The method according to claim 1 , wherein the reactor is a fixed-bed reactor, volume space velocity of the hydrocarbon oil is in a range of 0.5 h −1 to 20 h −1 ; the liquid-phase hydroprocessing condition comprises a temperature in a range of 120° C. to 500° C. and a pressure in a range of 1 MPa to 20 MPa by gage pressure.

8 . The method according to claim 1 , wherein the reactor is a tubular reactor.

9 . The method according to claim 7 , wherein the tubular reactor has a ratio of length to inner diameter in a range of 5-50:1.

10 . The method according to claim 9 , wherein the tubular reactor has an inner diameter in a range of 20 nm to 1,000 mm.

11 . The method according to claim 1 , wherein the hydroprocessing is one or more selected from the group consisting of hydrodeolefin, hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, and hydrodemetalization.

12 . The method according to claim 1 , wherein the hydrocarbon oil is one or more selected from the group consisting of gasoline, reformate, aviation fuel, and diesel oil.

13 . The method according to claim 12 , wherein the hydrogen gas is injected in an amount for 0.1 to 4 times of the saturated solubility of the hydrogen gas in the hydrocarbon oil, the saturated solubility is a saturated solubility measured under the liquid-phase hydroprocessing condition.

14 . The method according to claim 1 , further comprising contacting the hydrogen-containing hydrocarbon oil with the catalyst without presence of diluent and/or circulating oil.

15 . The method according to claim 4 , further comprising contacting the hydrogen-containing hydrocarbon oil with the catalyst without presence of diluent and/or circulating oil.

16 . The method according to claim 7 , further comprising contacting the hydrogen-containing hydrocarbon oil with the catalyst without presence of diluent and/or circulating oil.

17 . The method according to claim 11 , further comprising contacting the hydrogen-containing hydrocarbon oil with the catalyst without presence of diluent and/or circulating oil.

18 . An apparatus for hydroprocessing hydrocarbon oil, comprising mixing device ( 5 ), for injecting hydrogen gas ( 7 ) into hydrocarbon oil ( 8 ), to obtain a hydrogen-containing hydrocarbon oil, the mixing device ( 5 ) comprises at least one liquid passage ( 1 ) for accommodating the hydrocarbon oil and at least one gas passage ( 2 ) for accommodating the hydrogen gas, the liquid passage ( 1 ) is adjacent to the gas passage ( 2 ) through a component ( 3 ), at least part of the component ( 3 ) is a porous area having pores with an average pore diameter in nanometer size;
and hydrogenation reactor ( 6 ), for contacting the hydrogen-containing hydrocarbon oil with a catalyst having a hydrogenation catalytic action under a liquid-phase hydroprocessing condition.

19 . The apparatus according to claim 18 , wherein the hydrogenation reactor ( 6 ) is a tubular reactor.

20 . The apparatus according to claim 19 , excluding the device for feeding diluent and/or circulating oil into the hydrogenation reactor ( 6 ).

Assignees

• China Petroleum & Chemical
• Hunan Changling Petrochemical Science And Technology Dev Co Ltd

Inventors

• Li Hua
• Liu Jianping
• She Xichun
• He Xiaojun
• Li Qinghua
• Chen Qingling
• Jiang Lei
• Zeng Zhiyu
• Liu Chengli
• Yang Qingpin

Classifications

• C10G45/22 Primary

  with hydrogen dissolved or suspended in the oil · CPC title

• C10G3/50

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• C10G3/42

  Catalytic treatment · CPC title

• C10G45/00

  Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds · CPC title

• B01J4/004

  Sparger-type elements · CPC title