Metallo-silicate catalyst (MSC) compositions, methods of preparation and methods of use in partial upgrading of hydrocarbon feedstocks

Patent metadata

Field	Value
Publication number	US-10272417-B2
Application number	US-201715669405-A
Country	US
Kind code	B2
Filing date	Aug 4, 2017
Priority date	Feb 4, 2015
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

The invention relates to the preparation of novel bi- or tri metallic silicate micro-porous and/or meso-porous materials based on cerium, nickel, copper and/or zinc on a porous silicate framework matrix to use its molecular sieve effect to target preferentially the acidic organic molecules present in hydrocarbon feedstocks like crude oil, bitumen, VGO and the like. The chosen metals are selected based on their ability to activate steam and transfer oxygen for completing the oxidation of carboxylic compounds or decarboxylating them. These composite materials can be prepared under hydrothermal synthesis conditions in order to produce suitable porous solids where the metals are well dispersed and preferentially distributed inside the channels of the silicate framework where they can interact only with the molecules that can go inside the channels. According to the invention, the metallo-silicate materials are prepared under hydrothermal synthesis conditions Modification of the physical-chemical properties of the porous silicate materials can be accomplished by partial replacement of the silicon atoms by cerium, nickel, copper and/or zinc atoms in the material by isomorphous substitutions of these elements in a synthesis gel or by post-synthesis modifications like ion-exchange or impregnation/deposition. The materials can be used as prepared catalysts for the steam catalytic reduction of the total acid number (TAN) in acidic crude oil feedstocks and in the presence of steam and/or CO2 as oxidizing agent to complete decarboxylation and to keep the metal oxide active sites from reducing and deactivating as well as other partial upgrading reactions.

First claim

The invention claimed is:

1. A method for partially upgrading a feedstock of produced hydrocarbons, the method comprising the step of:
exposing the produced hydrocarbons to a catalyst having a catalyst material embedded within a catalyst support, the catalyst material having a molar composition:
mCeO 2 : nXO

wherein X is a divalent element selected from the group consisting of nickel, copper, zinc and combinations thereof; m is between about 0.001 and 0.5; n is between about 0.001 and 0.5; and the catalyst support has a micro and/or meso porous structure under conditions to promote partial upgrading so as to produce partially upgraded hydrocarbons.

2. The method as in claim 1 , wherein the catalyst material is a combination of transition metals with rare earth elements and/or earth alkali and/or alkaline earth metals doped inside the micro-porous or meso-porous structure and having a pore size reducing exposure of the catalytic material to produced hydrocarbon molecules.

3. The method as in claim 2 , wherein the pore size excludes molecules having an effective molecular diameter greater than 50 nm.

4. The method as in claim 1 , wherein the, catalyst material is a metallo-silicate material, a bi- or tri-metallic silicate material, nickel, copper or cerium based or an oxide thereof or metal oxide-based catalyst.

5. The method as in claim 1 , wherein the catalyst support comprises a porous support network enabling contact with some acid molecules while preventing contact with at least some other components of produced hydrocarbons.

6. The method as in claim 1 , wherein the catalyst catalyzes decarboxylation of a carboxylic acid present in the produced hydrocarbons.

7. The method as in any claim 1 , wherein the catalyst catalyzes decarboxylation of a carboxylic acid, and generates oxygen vacancies in the catalyst.

8. The method as in claim 1 , further comprising the step of exposing the catalyst to an oxygen source to regenerate the oxygen vacancies in order to regenerate the catalyst.

9. The method as in claim 1 , wherein the catalyst support comprises any one of or a combination of micro-porous and/or meso-porous zeolite frameworks, silicate-based frameworks, mordenite framework inverted (MFI) structures, aluminosilicate zeolite materials comprising Zeolite Socony Mobil-5 (ZSM-5), or non-acidic silicate framework structures.

10. The method as in claim 9 , wherein the catalyst support is selected from any one of or a combination of siliceous micro-porous materials including siliceous MFI, MTW, FER, MEI, MTT or MWW structures, ordered siliceous meso-porous material comprising SBA-15, MCM-41 or MCM-48 materials, disordered siliceous meso-porous material, or a combination thereof.

11. The method as in claim 1 , further comprising the step of integrating the catalyst into a fixed bed reactor.

12. The method according to claim 1 , wherein the partial upgrading of the produced hydrocarbons results in a reduction in TAN, viscosity, density, sulfur content, or any combination thereof.

13. The method according to claim 1 , wherein the partial upgrading is TAN reduction by acid decarboxylation.

14. The method as in claim 1 , wherein the feedstock is produced hydrocarbons having a high TAN and the method further comprises the step of exposing the produced hydrocarbons to the catalyst structure under conditions sufficient to lower TAN to less than 1mg KOH/g by enabling TAN molecules to contact the catalyst material.

15. The method as in claim 1 , wherein the feedstock is produced hydrocarbons having a high TAN and the method further comprises the step of exposing the produced hydrocarbons to the catalyst under conditions sufficient to lower TAN to less than 0.7 KOH/g by enabling TAN molecules to contact the catalyst.

16. The method of claim 1 , further comprising the step of exposing the catalyst to an oxygen donor under conditions to regenerate the catalyst.

17. The method as in claim 16 , wherein the step of exposing the catalyst to an oxygen donor includes the step of exposing the catalyst to any one of or a combination of steam, carbon dioxide, water and peroxide.

18. A method of partially upgrading a produced hydrocarbon, the method comprising the step of:
adjacent a production well, exposing the produced hydrocarbon to a catalyst in a reactor under conditions to promote partial upgrading the catalyst having a catalyst material embedded within a catalyst support, the catalyst material having a molar composition:
mCeO 2 : nXO

wherein X is a divalent element selected from the group consisting of nickel, copper, zinc and combinations thereof; m is between about 0.001 and 0.5; n is between about 0.001 and 0.5; and the catalyst support has a micro and/or meso porous structure.

19. The method of claim 18 , wherein the reactor is a fixed bed reactor and the step of exposing includes maintaining the reactor at about 280 ° C. to about 420 ° C. and about 50 to about 500 psi and a residence time between about 0.1 h −1 and about 3 h −1 , or between about 0.1 h −1 and about 2 h −1 , or between about 0.2 h −1 and about 1 h −1 .

20. A system for partial upgrading of a produced hydrocarbon comprising:
a fixed bed catalytic reactor (FBCR) supporting a catalyst defined as a porous metallo-silicate composition (MSC) having a molar composition:
SiO 2 : mCeO 2 : nXO

wherein X is a divalent element selected from the group consisting of nickel, copper, zinc and combinations thereof; m is between about 0.001 and 0.5; n is between about 0.001 and 0.5; and wherein the composition has a sileceous micro and/or meso porous structure. the FBCR enabling catalytic partial upgrading of the produced hydrocarbons under reaction conditions.

21. The system as in claim 20 further comprising a heater operatively connected to the FBCR for pre-heating the produced hydrocarbon stream prior to introduction into the FBCR.

22. The system as in claim 20 further comprising an oxygen regeneration system operatively connected to the FBCR for introducing an oxygen source to the FBCR.

Assignees

• Pc Cups Ltd
• Cenovus Energy Inc

Inventors

• Pereira Almao Pedro
• Vitale-Rojas Gerardo
• Perez Zurita Maria Josefina
• Carbognani Lante Antonio
• Smith Ronald Scott
• Sosa Clementina

Classifications

• C01B33/185

  of crystalline silica-polymorphs having molecular sieve properties, e.g. silicalites · CPC title

• B01J2523/3712

  Cerium · CPC title

• B01J37/10

  in the presence of water, e.g. steam · CPC title

• C10G29/04

  Metals, or metals deposited on a carrier · CPC title

• C10G2300/302

  Viscosity · CPC title