Procedure for preparation of improved solid hydrogen transfer agents for processing heavy and extra-heavy crude oils and residues, and resulting product

Patent metadata

Field	Value
Publication number	US-10793784-B2
Application number	US-201816031725-A
Country	US
Kind code	B2
Filing date	Jul 10, 2018
Priority date	Jul 10, 2017
Publication date	Oct 6, 2020
Grant date	Oct 6, 2020

Abstract

The present invention relates to the process for preparing improved solid hydrogen transfer agents obtained from a polymer with units containing the structure of naphthalene, phenanthrene or anthracene, which exhibit activity as hydrogen transfer agents in any chemical reduction reaction involving the breaking of double bonds and in treatment, hydrotreatment and hydrodisintegration reactions of heavy and extra-heavy crude oils and of cuts and currents derived therefrom. These improved solid hydrogen transfer agents can be supported and not supported on metal oxides such as boehmite, alumina, silica, titania, kaolin and/or mixture thereof, in the presence of reducing agents such as hydrogen, methane, or natural gas. In addition, the application of these improved solid hydrogen transfer agents obtained from a polymer with units containing the structure of naphthalene, phenanthrene or anthracene, it allows to improve properties of the crudes such as viscosity, decrease in the formation of coke, increase in the yield of distillates and in API gravity. These hydrogen transfer agents, being solid, can be reused and recovered from the reaction medium; they also have a thermal stability such that it can carry out reactions at temperatures up to 450° C.

First claim

The invention claimed is:

1. A process for preparing improved solid hydrogen transfer agents for the processing of heavy or extra-heavy crudes or residues, comprising:
a) preparing raw materials by grinding one of AlO (OH) (“Boehmite”), SiO 2 , Al 2 O 3 , and kaolin, or a mixture thereof, with an organic macromolecule featuring fused aromatic rings, said organic macromolecule having a melting or decomposition point above 450° C. when supported or extruded, while sieving the raw materials through a 165 mesh (0.089 mm), resulting in a physical mixture;
b) adding distilled water to the physical mixture and mixing until the mixed distilled water and physical mixture forms a paste, and subsequently peptizing the paste by adding an aqueous solution of nitric acid of 5% by volume to form a gel;
c) mixing the gel with a naphthalene polymer that may be supported on a metal oxide, resulting in a resin material with adequate properties for extruding;
d) extruding the resin by a mechanical extrusion system at a constant speed, and receiving the extrudates in metal trays;
e) drying the extrudates for a time period of about 12 hours to about 24 hours at room temperature, resulting in solid hydrogen transfer agents;
f) preparing the solid hydrogen transfer agents for activation by cutting the transfer agents to a length in a range of about 0.5 cm to about 1.2 cm and leaving the transfer agents in an oven at a temperature of about 90° C. to about 120° C. for a time period of about 12 hours to about 24 hours; and
g) loading the material obtained in part f) into a continuous flow reactor where a hydrogen flow of about 100 ml/min to about 150 ml/min, a pressure of about 40 kg/cm2 to about 70 kg/cm2, and a temperature between about 100° C. and about 500° C. is passed for a time of about 10 hours to about 24 hours.

2. The process according to claim 1 , further comprising:
h) contacting the solid hydrogen transfer agent with a heavy, extra-heavy crude or residue of about 9° API to about 12° API and viscosity of about 5968 cSt, measured at 37.8° C., at a temperature of about 350° C. to about 450° C., at a pressure of about 50 kg/cm 2 to about 100 kg/cm 2 in hydrogen transfer reactions, where the hydrogen transfer reactions are carried out in the presence of a reducing agent selected from a group consisting of hydrogen, methane, and natural gas; and
i) obtaining heavy or extra-heavy crudes or residues with an increase in API gravity from 3 to 6 units, a decrease in viscosity up to about 100 cSt determined at 37.8° C. and an increase in the yield of distillates, naptha and intermediate distillates, determined by TBP (True Boiling Point),
wherein the solid hydrogen transfer agent has a specific area between about 100 m 2 /g to about 300 m 2 /g, a pore volume between about 0.15 cm 3 /g and about 0.20 cm 3 /g and a pore diameter of about 15 Å to about 19 Å, and an average molecular weight between about 300 g/mol and about 1000 g/mol with a thermal stability at about 800° C. between about 60% and about 90% by weight of the original material and chemical stability at a temperature up to about 450° C.

3. The process according to claim 1 , wherein the raw materials comprise Boehmite mixed with a polymer with units containing the structure of naphthalene.

4. An improved solid hydrogen transfer agent, obtained by a process comprising:
a) preparing raw materials by grinding one of AlO (OH) (“Boehmite”), SiO 2 , Al 2 O 3 , and kaolin, or a mixture thereof, with an organic macromolecule featuring fused aromatic rings, said organic macromolecule having a melting or decomposition point about 450° C. when supported or extruded, while sieving the raw materials through a 165 mesh (0.089 mm), resulting in a physical mixture;
b) adding distilled water to the physical mixture and mixing until the mixed distilled water and physical mixture forms a paste, and subsequently peptizing the paste by adding an aqueous solution of nitric acid of 5% by volume to form a gel;
c) mixing the gel with a naphthalene polymer that may be supported on a metal oxide, resulting in a resin material with adequate properties for extruding;
d) extruding the resin by a mechanical extrusion system at a constant speed, and receiving the extrudates in metal trays;
e) drying the extrudates for a time period of about 12 hours to about 24 hours at room temperature, resulting in solid hydrogen transfer agents;
f) preparing the solid hydrogen transfer agents for activation by cutting the transfer agents to a length in a range of about 0.5 cm to about 1.2 cm and leaving the transfer agents in an oven at a temperature of about 90° C. to about 120° C. for a time period of about 12 hours to about 24 hours; and
g) loading the material obtained in part f) into a continuous flow reactor where a hydrogen flow of about 100 ml/min to about 150 ml/min, a pressure of about 40 kg/cm2 to about 70 kg/cm2, and a temperature between about 100° C. and about 500° C. is passed for a time of about 10 hours to about 24 hours,
wherein the solid hydrogen transfer agent has a specific area between about 100 m 2 /g to about 300 m 2 /g, a pore volume between about 0.15 cm 3 /g and about 0.20 cm 3 /g and a pore diameter of about 15 Å to about 19 Å, and an average molecular weight between about 300 g/mol and about 1000 g/mol with a thermal stability at about 800° C. between about 60% and about 90% by weight of the original material and chemical stability at a temperature up to about 450° C.

5. The improved solid hydrogen transfer agent of claim 4 , wherein the raw materials comprise Boehmite mixed with a polymer with units containing the structure of naphthalene.

6. A method for preparing an improved solid hydrogen transfer agent and upgrading of heavy or extra-heavy crudes or residua, comprising:
obtaining the solid hydrogen transfer agent from a combination comprising one organic polymer and an inorganic compound,
wherein the organic polymer contains structural units based on the structure of one of naphthalene, phenanthrene, or anthracene, and has a melting or decomposition point above 450° C. when supported or extruded;
wherein the inorganic compound is a metal oxide; and
wherein the upgrading of heavy or extra-heavy crude oil or residua is carried out by hydrotreatment.

7. The method of claim 6 , wherein the organic polymer is physically mixed with the inorganic compound.

8. The method of claim 6 , wherein the inorganic compound is selected from a group consisting of AlO(OH) (“Boehmite”), SiO 2 , Al 2 O 3 , and kaolin.

9. The method of claim 6 , wherein the organic polymer has a molecular weight average between about 600 g/mol and about 1200 g/mol.

10. The method of claim 6 , wherein the improved solid hydrogen transfer agent has a specific area between about 100 m 2 /g to about 300 m 2 / g, a pore volume between about 0.1 cm 3 /g and about 0.60 cm 3 /g and a pore diameter of about 15 Å to about 20 Å, with a thermal stability and a chemical stability at temperatures up to about 450° C.

11. The method of claim 6 , wherein the solid hydrogen transfer agent is activated in a continuous flow reactor featuring a hydrogen flow of about 100 ml/min to about 500 ml/min, a pressure of about 40 kg/cm 2 to about 70 kg/cm 2 , and a temperature between about 100° C. and about 500° C. is passed for a time of about 10 hours to about 24 hours.

12. The method of claim 6 , wherein the upgrading is carried out by hydrotreatment in a fixed bed reactor under operating conditions comprising a temperature of about 350° C. to about 450° C., and a pressure of about 50 kg/cm 2 to about 100 kg/cm 2 .

13. The method of claim 6 , wherein an upgrading of heavy or extra-

Assignees

• Mexicano Inst Petrol

Inventors

• Alemán Vázquez Laura Olivia
• Torres Mancera León Pablo
• Ancheyta Juárez Jorge

Classifications

• C10G2300/302

  Viscosity · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• C08G61/10

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C10G2300/1077

  Vacuum residues · CPC title

• C10G2300/107

  Atmospheric residues having a boiling point of at least about 538 °C · CPC title