Vacuum resid upgradation and graphite production

Patent metadata

Field	Value
Publication number	US-10201810-B2
Application number	US-201615232695-A
Country	US
Kind code	B2
Filing date	Aug 9, 2016
Priority date	Nov 9, 2015
Publication date	Feb 12, 2019
Grant date	Feb 12, 2019

Abstract

The present invention discloses a catalyst and process for hydrocracking of heavy hydrocarbon oils having majority portion boiling above 525° C. in the presence of hydrogen. A process comprising first step of converting heavy oil into lighter products in the presence of catalyst and hydrogen in slurry phase is disclosed. The process further comprises recycling of part of liquid products (HVGO) along with fresh heavy oil for improving the product selectivity. This recycled HVGO is having high concentrations of aromatics compounds. The separation of particles generated during the reaction at reactor exit also avoids the chances of choking of downstream sections.

First claim

We claim:

1. A method of producing in situ catalyst in a hydrocracking process, comprising:
(a) providing a mixture of hydrogen, heavy hydrocarbon oil, and an oil soluble catalyst, and
(b) decomposing the oil soluble catalyst by preheating the mixture at a predetermined fast enough velocity to predetermined temperature and passing through a confined hydrocracking zone maintained at a temperature between about 250° C. and 550° C., pressure between 40 to 250 bar and a space velocity of 0.5 h−1 up to 4 h−1, to obtain a finely dispersed nano sized metallic iron particles in hydrocarbon oil, wherein, the nano sized metallic iron particles act as hydrogenating catalyst.

2. The method of claim 1 , wherein the oil soluble catalyst is used in the range of about 0.01-2% by weight of heavy hydrocarbon oil.

3. The method of claim 2 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

4. The method of claim 1 , wherein the oil soluble catalyst is ferrocene.

5. The method of claim 4 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

6. The method of claim 1 , wherein the nano sized iron particles is composed of iron atoms in the range of 10 to 100.

7. The method of claim 6 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

8. The method of claim 1 , wherein the decomposition starts from 400° C. and gets completed before the feed and the catalyst reaches the slurry reactor.

9. The method of claim 8 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

10. The method of claim 1 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

11. A method of producing graphite, comprising:
(a) providing a mixture of hydrogen, heavy hydrocarbon oil, and an oil soluble catalyst,
(b) decomposing the oil soluble catalyst by preheating the mixture at a predetermined fast enough velocity to predetermined temperature and passing through a confined hydrocracking zone maintained at a temperature between about 250° C. and 550° C., pressure between 40 to 250 bar and a space velocity of 0.5 h −1 up to 4 h −1 , to obtain a finely dispersed nano sized metallic iron particles in hydrocarbon oil,
(c) hydrocracking the resultant of step (b) in a slurry reactor at elevated temperatures in the range of 400° C. to 510° C.,
(d) fractionating the effluent of step (c) to obtain a fraction boiling above 500° C. containing solid catalyst and coke particles,
(e) further fractionating/separating the fraction obtained in step (d) to obtain a fraction boiling above 525° C. termed as pitch,
(f) de-oiling the pitch to obtain graphite.

12. The method of claim 11 , wherein de-oiling of the pitch is processed using a solvent selected from propane, butane, pentane, hexane, heptanes, benzene, toluene, LPG, or a mixture thereof.

13. The method of claim 12 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

14. The method of claim 11 , wherein the volumetric ratio of solvent to pitch is from 0.5 to 10 vol/vol, and the temperature of extraction is in the range of 100 to 250° C.

15. The method of claim 14 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

16. The method of claim 11 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

17. A method for the hydrocracking conversion of heavy hydrocarbon oils into premium quality lighter hydrocarbon products, the method comprising:
(a) providing a mixture of hydrogen, heavy hydrocarbon oil, and oil soluble catalyst, decomposing the oil soluble catalyst by preheating the mixture at predetermined fast enough velocity to predetermined temperature and passed through a confined hydrocracking zone in upflow mode being maintained at temperature between 250° C. and 550° C., pressure between 40 to 250 bar and a space velocity of 0.5 h −1 up to 4 h −1 to obtain a finely dispersed nano sized metallic iron particles in hydrocarbon oil,
(b) passing the resultant of step (a) into a slurry reactor for hydrocracking,
(c) separating the effluent of step (b) into a first portion comprising hydrocarbons boiling upto 500° C. and free of solid catalyst particles and second portion boiling above 500° C. containing solid catalyst and coke particles,
(d) hydrotreating the first portion in a conventional hydrotreating reactor under conventional hydroprocessing conditions using conventional hydrotreating catalysts and fractionating to obtain premium quality lighter hydrocarbon products boiling upto 370° C. and hydrotreated Vaccum Gas Oil (VGO),
(e) optionally recycling the VGO to conventional hydrotreating reactor,
(f)separating the second portion of step (c) into a first part boiling between 500 and 525° C. termed as Heavy Vacuum Gas Oil (HVGO) and a second part boiling above 525° C. termed as pitch,
(g) optionally recycling the HVGO into the slurry reactor,
(h) deoiling the first part of step (f) using a solvent to obtain an extracted oil portion and graphite,
(i)optionally recycling the extracted oil portion to the slurry reactor.

18. The method of claim 17 , wherein the HVGO is aromatic rich stream.

19. The method of claim 17 , wherein the heavy hydrocarbon oil is selected from the group comprising of atmospheric tower bottoms products, vacuum tower bottoms products, crude oil residuum, heavy vacuum gas oils, tar sand bitumen or mixture thereof.

Assignees

• Indian Oil Corp Ltd

Inventors

• Kumar Brijesh
• Kumar Pravesh
• Kumar Kamal
• Butley Ganesh Vitthalrao
• Sau Madhusudan
• Das Biswapriya

Classifications

• C10G2300/205

  Metal content · CPC title

• B01J23/883

  and nickel · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title

• C10G65/12

  including cracking steps and other hydrotreatment steps · CPC title

• C10G2300/703

  Activation · CPC title