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-10265685-B2
Application number	US-201615548928-A
Country	US
Kind code	B2
Filing date	Feb 3, 2016
Priority date	Feb 4, 2015
Publication date	Apr 23, 2019
Grant date	Apr 23, 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 CO 2 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 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 siliceous micro and/or meso porous structure.

2. The porous metallo-silicate composition as in claim 1 , wherein the porous structure is a MFI, MEL, MTW, FER, MEI, MTT, MWW, STT, SGT or RTE structure as defined by the International Union for Pure and Applied Chemistry (IUPAC) and the International Zeolite Association (IZA).

3. The porous metallo-silicate composition as in claim 1 , wherein the porous structure is any one of or a combination of a) any ordered siliceous meso-porous structure (OMS) having pore sizes between about 2 and about 50 nm as defined by the International Union for Pure and Applied Chemistry (IUPAC) b) is a SBA-15, SBA-1, SBA-2, SBA-3, HMS, MCM-41, MCM-48, MCM-50, MSU, TLCT, or CMK structure as defined by the International Union for Pure and Applied Chemistry (IUPAC) and c) is a disordered siliceous meso-porous structure (DMS).

4. The porous metallo-silicate composition of claim 1 , wherein any one of or a combination of the cerium and X is incorporated within the framework and/or porous channels of the porous structure.

5. The porous metallo-silicate composition of claim 1 , wherein the composition is a powder and further comprises at least one additive admixed with the composition to enhance any one of the catalytic behavior, morphological properties and/or mechanical strength of the composition or combinations thereof.

6. The porous metallo-silicate composition as in claim 5 , wherein the additive is a metal carbide in a concentration of greater than about 0.001 wt % and less than about 40 wt % of the composition.

7. The porous metallo-silicate composition as in claim 6 , wherein the metal carbide is any one of a molybdenum and/or tungsten carbide or combinations thereof.

8. The porous metallo-silicate composition as in claim 5 , wherein the additive is a clay, alumina, silica, hydrotalcite, metal-doped-hydrotalcite, other metal hydroxides, carbon or combinations thereof.

9. The porous metallo-silicate composition as in claim 1 , further comprising a carrier selected from any one of a hydrotalcite, metal-doped hydrotalcite, pyroxene, metal-doped pyroxene, clay, metal-doped clay, zeolite, metal-doped zeolite, silica, metal-doped silica, alumina, metal-doped alumina, silica-alumina, metal-doped silica-alumina, metal oxides carbons and combinations thereof.

10. The porous metallo-silicate composition as in claim 9 , wherein the carrier is about 5 to about 95 wt % of the composition.

11. The porous metallo-silicate composition of claim 1 , wherein the porous structure is effective as a catalyst for steam and/or CO 2 catalytic total acid number (TAN) reduction of hydrocarbon feedstock of produced hydrocarbons.

12. The porous metallo-silicate composition of claim 1 , further comprising nano-crystalline molybdenum carbide and/or tungsten carbide materials and a carrier and/or binder admixed to the MSC.

13. The porous metallo-silicate composition of claim 12 , wherein the carrier is a hydrotalcite, metal-doped hydrotalcite, pyroxene, metal-doped pyroxene, clay, metal-doped clay, zeolite, metal-doped zeolite, silica, metal-doped silica, alumina, metal-doped alumina, silica-alumina, metal-doped silica-alumina, metal oxide and mixtures thereof.

14. The porous metallo-silicate composition of claim 13 , wherein the metal-doped elements consist of Ce, V, Ni, Cu, Zn in proportions from about 0 to about 30 wt % by weight of each of them in the carrier.

15. A method of preparing a composition as defined in claim 1 , comprising the steps of:
a. preparing an acidic gel media containing cerium, divalent elements and silicon wherein the cerium, divalent elements and silicon have a molar relationship SiO 2 : mCeO 2 : nXO wherein X is a divalent element selected from nickel, copper, zinc and combinations thereof, m is from about 0.001 to about 0.5 and n is from about 0.001 to about 0.5.
b. increasing the pH of the acidic media to a pH effective to cause anchoring of the metal elements of step a within a silicate framework, and
c. forming the MSC by hydrothermal treatment.

16. The method of claim 15 , wherein a temperature of reaction to produce the MSC is between room temperature and about 250° C.

17. The method of claim 15 , wherein a time of reaction of step b. to produce the MSC is between about 1 hour and about 30 days.

18. The method as in claim 15 , further comprising the step of after step c. admixing nano-crystalline molybdenum carbide and/or tungsten carbide materials to the MSC together with a carrier and/or binder.

19. The method as in claim 18 , wherein the step of admixing includes preparing an amorphous carbide precursor with a metal molybdenum and/or tungsten to carbon ratio (M/C) between about 1 to about 10; allowing the amorphous prepared carbide precursor to undergo a suitable thermal reaction transformation to generate nano-crystalline molybdenum and/or tungsten carbides in the nanometer range (about 1 to 100 nm).

20. The use of the composition of claim 1 for reduction of the total acid number (TAN) of a hydrocarbon feedstock of the produced hydrocarbons by contacting the hydrocarbon feedstock with a porous metallo-silicate composition together with steam and/or CO 2 under reaction conditions to reduce the original TAN number of the hydrocarbon feedstock to a desired value.

21. The use as in claim 20 , wherein the original viscosity, density, sulfur content, or any combination thereof of the hydrocarbon feedstock is reduced.

22. The use as in claim 20 , wherein the siliceous micro and/or meso porous structure has a pore size enabling the catalytic removal of acidic moieties from heavy hydrocarbons under hydroprocessing conditions.

23. A porous metallo-silicate composition (MSC) prepared from a mixture having a molar composition:
aM 2 O:b R:SiO 2 :mCeO 2 :nXO:yH 2 O:zAC

wherein M is an inorganic cation selected from sodium, potassium, lithium, cesium, rubidium or a mixture thereof, R is an organic moiety having structure directing properties for porosity, a is from 0 to 10 and b is from 0.01 to 0.2, m is between 0.001 and about 0.5; n is between 0.001 and about 0.5; y is from 1 to 300; z is from 0.1 to 3; X is nickel, copper or zinc or a combination thereof; AC is an acid source; and wherein after a hydrothermal treatment the composition has a silicate framework having a micro and/or meso porous structure.

24. The porous metallo-silicate composition as in claim 23 , wherein M is sodium.

25. The porous metallo-silicate composition as in claim 23 , wherein R is a tetraalkylammonium salt and/or a hydroxide of the tetraalkylammonium.

26. The porous metallo-silicate composition as in claim 23 , wherein the cerium source is selected from a soluble salt, hydroxide and/or oxide of cerium.

27. The porous metallo-silicate composition as in claim 23 , wherein X is a soluble salt, hydroxide and/or oxide of nickel, copper and/or zinc.

28. The porous metallo-silicate composition as in claim 23 , wherein M is a salt, oxide and/or hydroxide of sodium, potassium, lithium, cesium and/or rubidium.

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

• B01J23/007

  Mixed salts · CPC title

• B01J37/082

  Decomposition and pyrolysis · CPC title

• B01J2523/22

  Magnesium · CPC title

• B01J2229/183

  in framework positions · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title