Process for hydroconverting of a heavy hydrocarbonaceous feedstock

• US 7,585,406 B2
• Filed: 08/16/2006
• Issued: 09/08/2009
• Est. Priority Date: 08/16/2005
• Status: Expired due to Fees

• Current Assignee: NTI Corporation, Research Institute Of Petroleum Industry (Ripi)
• Original Assignee: NTI Corporation, Research Institute Of Petroleum Industry (Ripi)
• Inventors: Hashemi, Reza, Mezhidov, Vahid Khumaidovich, Khadzhiev, Salambek Naibovich, Kadiev, Khusain Magamedovich, Masoudian Targhi, Seyed Kamal, Zarkesh, Jamshid
• Primary Examiner(s): Griffin; Walter D
• Assistant Examiner(s): Marten; Jerrod B
• Application Number:
  US11/505,769
• Publication Number:
  US 20070045156A1
• Time in Patent Office: 1,119 Days
• Field of Search: 208/107, 208/108, 208/111.3, 208/112, 208/143, 208/144, 208/145, 208/192, 585/6.6, 585/13, 585/257, 585/25
• US Class Current: 208/112
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 27/051 Molybdenum
• CPC Class Codes: C10G 47/02 characterised by the catalyst used
• CPC Class Codes: C10G 47/26 suspended in the oil, e.g. slurries

Abstract

A Process for hydroconverting of a heavy hydrocarbonaceous feedstock comprising a catalyst to produce lower boiling hydrocarbon products. The method can be used for the high- boiling point residues of oil refining (asphaltene, the residues of vacuum and under pressure distillation of oil, and the useless and heavy materials of thermo catalytic processes), heavy oil, natural bitumen, and bitumen-containing sands. It can also be used in oil refinery industries for the production of gas, gasoline fractions, distillation gas oil, concentrate of ash containing metals and chemical fertilizers.

Claims

1. A process for hydroconverting a heavy hydrocarbonaceous feedstock comprising a catalyst to produce lower boiling hydrocarbon products, which process comprises the following steps:

(a) Activation of the feedstock by adding modifiers and stabilizers;

(b) Preparation of a catalyst complex comprising an emulsion of the pre-activated heavy hydrocarbons of step a), water and catalytic compounds;

(c) Hydrogenation of the remaining activated heavy hydrocarbons in the presence of hydrogen gas and the emulsion of catalytic complex of step (b);

(d) Fractionation of the products of step (c) as liquid-gas streams by means of atmospheric and/or vacuum distillation;

(e) Returning the residues of the distillation process to the process of step (a) after separating the solid particle content;

(f) Separation of catalyst elements from the solid particles, wherein said catalyst elements are recycled to a preliminary catalyst complex preparation unit.

2. The process according to claim 1, wherein the gases evolving from the catalyst regeneration step are purified by reducing NOx gases to molecular nitrogen as a result of ozone injection and converting SOx gases to ammonium sulfate chemical fertilizer by injecting ammonia.

3. The process according to claim 1, wherein the majority of the lower boiling hydrocarbon products comprise hydrocarbons with a boiling point of lower than 520°

C.

4. The process according to claim 1, wherein the products of step (c) are fractionized as liquid-gas streams by means of atmospheric and vacuum distillation towers.

5. The process according to claim 1, wherein the remaining solid particles in the recycled residues of distillation process are about 0.2% by weight.

6. The process according to claim 1, wherein the catalyst elements are separated from the solid particles by oxidation and ammoniacarbonate methods.

7. The process according to claim 1, wherein a physicochemical effect is used to increase the dispersion extent for activating heavy hydrocarbons.

8. The process according to claim 1, wherein the dispersed phase species are degraded and converted to groups each of which contains a number of molecules and activating hydrocarbons, which form the dispersed phase, and stabilizers are added.

9. The process according to claim 1, wherein the modifier comprises an oil fraction of at least 60% by mass of heat stable cyclic hydrocarbons.

10. The process according to claim 9, wherein the heat stable cyclic hydrocarbons are selected from cracking gas oils, pyrolysis resins or oil refinery extracts.

11. The process according to claim 9, wherein the amount of the modifier is 0.5 to 3.5 percent by mass of the initial feedstock.

12. The process according to claim 1, wherein surface active detergents are used as stabilizers.

13. The process according to claim 1, wherein a compound selected from acetone, diethyl ketone and/or nitrobenzene is used as stabilizer in an amount of 0.001-0.01 percent of the feedstock are added.

14. The process according to claim 1, wherein the catalyst comprises compounds which are water soluble and include transition metals.

15. The process according to claim 14, wherein the compounds of the catalyst are convertible to catalytically active sulfides.

16. The process according to claims 14, wherein the transition metal is Mo.

17. The process according to claim 14, wherein compound which is water soluble and includes a transition metal comprises ammonium paramolybdate.

19. The process according to claim 1, wherein for the preparation of catalyst complex emulsion an aqueous solution of catalyst is initially mixed with the activated oil fraction of step a) at a homogenization temperature lower than the boiling points of constituents of the catalyst complex.

20. The process according to claim 19 wherein the homogenizeation temperature is in the range of 60-98°

C.

21. The process according to claim 1, wherein, in order to improve the process, one fragment of the catalytic complex emulsion is added to the activated heavy hydrocarbon entering the heater before the reactor, together with hydrogen containing gas, and 2-4 fragments are sprayed to the reaction mixture within the reactor, together with hydrogen gas.

22. The process according to claim 21, wherein 3 fragments are sprayed.

23. The process according to claim 1, wherein the catalyst elements are separated from solid particles remaining from the filtration of the mid-emulsion of the atmospheric distillation and residue of vacuum distillation are recycled to the preliminary catalyst complex preparation unit.

24. The process according to claim 19, wherein in the preparation of said catalyst complex emulsion the mass ratio of said activated feedstock to water to ammonium paramolybdate can be 1 to (0.005-0.05) to (5×

10<sup>−

5</sup>-8×

10<sup>−

3</sup>).

25. The process according to claim 19, wherein in the preparation of said catalyst complex emulsion the drop diameters of stabilized emulsion are 100 to 7000 nm.

26. The process according to claim 14, wherein the Mo compound concentration in the reaction zone is 0.005 to 0.05% by mass.

27. The process according to claim 25, wherein in the preparation of said catalyst complex emulsion the drop diameters of stabilized emulsion are 200 to 600 nm.

18. The process according to claime 14, wherein the transition metals is Mo or Ni.