Demetalation of heavy hydrocarbon oils

Claim 2

A process for heavy hydrocarbon oil demetalation which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. for a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours; and (3) recovering the second stage visbroken effluent and fractionating it to provide liquid and solid products.

Claim 3

A process in accordance with claim 1 wherein the heavy hydrocarbon oil feedstock is a distillation residuum of crude oil.

Claim 4

A process in accordance with claim 1 wherein the particulate coal is finely divided bituminous coal.

Claim 5

A process in accordance with claim 1 wherein a light end fraction is removed from the first stage visbroken effluent before it is admixed with particulate coal in step (2).

Claim 6

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. for a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours; (3) subjecting the visbroken admixture to solvent deasphalting to provide an oil fraction and a precipitated asphaltic solids fraction; and (4) distilling the said oil fraction to remove the deasphalting solvent and yield a demetalized liquid hydrocarbon product.

Claim 7

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. for a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours; (3) subjecting the visbroken admixture to solvent deasphalting to provide an oil fraction and a precipitated asphaltic solids fraction; and (4) distilling the said oil fraction to remove the deasphalting solvent and yield a demetalized liquid hydrocarbon product.

Claim 8

A process in accordance with claim 5 wherein the weight ratio of heavy hydrocarbon oil to coal in the step (2) admixture is in the range between about 1.5-10:1.

Claim 9

A process in accordance with claim 5 wherein the first and second stage visbreaking heat treatments are conducted under a hydrogen pressure between about 50-1500 psi, and at a weight hourly space velocity between about 1-100.

Claim 10

A process in accordance with claim 5 wherein the weight ratio of deasphalting solvent to visbroken admixture in step (3) is in the range between about 0.5-5:1.

Claim 11

A process in accordance with claim 5 wherein the deasphalting solvent in step (3) is liquid hydrocarbon containing between about 3-12 carbon atoms.

Claim 12

A process in accordance with claim 5 wherein the deasphalting treatment in step (3) is conducted at a temperature between about 100°-500° F. and at a sufficient pressure to maintain the deasphalting solvent in liquid form, and for a period between about 0.1-1.5 hours.

Claim 13

A process in accordance with claim 5 wherein the liquid hydrocarbon product recovered in step (3) has a metals content of less than about 50 ppm.

Claim 14

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. for a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours; (3) removing a light end fraction and then subjecting the second stage visbroken effluent to solvent deasphalting to provide an oil fraction and a precipitated asphaltic solids fraction; (4) distilling the said oil fraction to remove the deasphalting solvent and yield a demetalized liquid hydrocarbon product, and (5) treating the said asphaltic solids fraction under flotation conditions in an aqueous medium to separate a float phase of organic solids product from a sink phase of inorganic ash.

Claim 15

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. for a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours; (3) removing a light end fraction and then subjecting the second stage visbroken effluent to solvent deasphalting to provide an oil fraction and a precipitated asphaltic solids fraction; (4) distilling the said oil fraction to remove the deasphalting solvent and yield a demetalized liquid hydrocarbon product, and (5) treating the said asphaltic solids fraction under flotation conditions in an aqueous medium to separate a float phase of organic solids product from a sink phase of inorganic ash.

Claim 16

A process in accordance with claim 12 wherein air-frothing is employed in the separation of the float and sink phases.

Claim 17

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heat-treating a heavy hydrocarbon oil in a first stage visbreaking zone at the highest Severity that yields not more than about 1.0 weight percent coke formation; (2) admixing the first stage visbroken effluent with particulate coal and heat-treating the admixture in a second stage visbreaking zone at the highest Severity that yields not more than about 10.0 weight percent coke formation; and (3) recovering the second stage visbroken effluent and fractionating it to provide liquid and solid products.

Claim 18

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heat-treating a heavy hydrocarbon oil in a first stage visbreaking zone at the highest Severity that yields not more than about 1.0 weight percent coke formation; (2) admixing the first stage visbroken effluent with particulate coal and heat-treating the admixture in a second stage visbreaking zone at the highest Severity that yields not more than about 10.0 weight percent coke formation; and (3) recovering the second stage visbroken effluent and fractionating it to provide liquid and solid products.

Claim 19

A process in accordance with claim 14 wherein particulate coal in a quantity up to about 5 weight percent, based on the weight of heavy hydrocarbon oil feedstock, is included in the first stage visbreaking zone.

Claim 20

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. and a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and a quantity of anti-solvent, and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours to provide a visbroken admixture consisting of an oil fraction and a precipitated ash solids fraction; and (3) recovering and distilling the said oil fraction to remove the deashing anti-solvent and yield a demetalized liquid hydrocarbon product.

Claim 21

A process for heavy hydrocarbon oil demetalation and coal liquefaction which comprises (1) heating a heavy hydrocarbon oil in a first stage visbreaking zone at a temperature between about 800°-1000° F. and a residence time between about 0.1-2 hours; (2) admixing the first stage visbroken effluent with particulate coal and a quantity of anti-solvent, and heating the admixture in a second stage visbreaking zone at a temperature between about 700°-850° F. for a residence time between about 0.1-2 hours to provide a visbroken admixture consisting of an oil fraction and a precipitated ash solids fraction; and (3) recovering and distilling the said oil fraction to remove the deashing anti-solvent and yield a demetalized liquid hydrocarbon product.

Claim 22

A process in accordance with claim 16 wherein the quantity of anti-solvent employed in step (2) is in the range between about 0.1-0.5 weight percent, based on the weight of the oil phase.