Conversion of triacylglycerides-containing oils

Patent metadata

Field	Value
Publication number	US-9675956-B2
Application number	US-201514685781-A
Country	US
Kind code	B2
Filing date	Apr 14, 2015
Priority date	Dec 11, 2012
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

A process for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels is disclosed. The process may include reacting a triacylglycerides-containing oil-carbon dioxide mixture at a temperature in the range from about 250° C. to about 525° C. and a pressure greater than about 75 bar to convert at least a portion of the triacylglycerides to a hydrocarbon or mixture of hydrocarbons comprising one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, and aromatics.

First claim

What is claimed:

1. A system for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels, the system comprising:
a mixing device for mixing a triacylglycerides-containing oil feed with carbon dioxide to form an oil-CO2 mixture;
a thermal reforming reactor for reacting the oil-CO2 mixture at a temperature in the range of 250° C. to about 525° C. and a pressure greater than about 75 bar to produce a reaction effluent;
a separator for separating the reaction effluent into a first separation product comprising carbon dioxide and a second separation product comprising hydrocarbon compounds including one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, and aromatics; and
a hydrotreater to hydrotreat at least a portion on of the second separation product.

2. The system of claim 1 , further comprising one or more fluid conduits for recycling the first separation product to at least one of the mixing device to form the oil-CO2 mixture and the thermal reforming reactor to control temperature within the thermal reforming reactor.

3. The system of claim 1 , further comprising a fractionator for fractionating hydrocarbons in the second separation product to form one or more hydrocarbon fractions boiling in the naphtha, jet or diesel range.

4. The system of claim 1 , further comprising a fractionator for fractionating hydrocarbons in the hydrotreated product to form one or more hydrocarbon fractions boiling in the naphtha, jet or diesel range.

5. The system of claim 1 , wherein the hydrotreater comprises at least two catalyst beds, and wherein:
a first catalyst bed comprises a catalyst having hydrogenation activity;
a second catalyst bed comprises a catalyst having hydrocracking activity.

6. The system of claim 5 , wherein the catalyst bed proximate an inlet of the hydrotreater comprises a catalyst useful for at least one of:
decarboxylation;
hydrodeoxygenation of unsaturated free fatty acids to produce C5-C24 paraffins;
saturation of mono-, di- and tri-olefins contained in the alkyl backbone of the free fatty acids;
hydrodenitrogenation of trace organic nitrogen compounds; and
catalyst tolerance for water coming in with the hydrocarbonaceous feed.

7. The system of claim 1 , further comprising at least one of:
one or more fluid conduits for co-processing a non-renewable hydrocarbon feedstock with the reaction effluent in the hydrotreater; and
one or more fluid conduits for introducing at least one of water and hydrogen to the triacylglycerides-containing oil feed, the carbon dioxide, or the oil-CO2 mixture upstream of the thermal reforming reactor.

8. A thermal reforming system for converting triacylglycerides-containing oils into hydrocarbons, the thermal reforming system comprising:
a flow conduit for providing a triacylglycerides-containing oil-carbon dioxide mixture;
a thermal reforming reactor configured for reforming, in the absence of an added catalyst, the triacylglycerides-containing oil-carbon dioxide mixture at a temperature in the range from about 250° C. to about 525° C. and a pressure greater than about 75 bar to convert at least a portion of the triacylglycerides to a mixture of hydrocarbons;
a flow conduit for recovering an effluent from the thermal reforming reactor;
a separator for separating the effluent recovered from the thermal reforming reactor into a first separation product comprising carbon dioxide and light reaction byproducts and a second separation product comprising the hydrocarons: and
a gas separation device for separating the carbon dioxide from the light reaction byproducts in the first separation product.

9. The thermal reforming system of claim 8 , further comprising a heat exchanger for heating the triacylglycerides-containing oil-carbon dioxide mixture via indirect heat exchange with the effluent recovered from the thermal reforming reactor.

10. The thermal reforming system of claim 8 , further comprising a flow conduit for introducing additional carbon dioxide to the thermal reforming reactor.

11. The thermal reforming system of claim 8 , further comprising one or more feed lines for mixing water or hydrogen with the triacylglyeerides-containing oil-carbon dioxide mixture upstream of the thermal reforming reactor.

12. The thermal reforming system of claim 8 , wherein the separator is a drum.

13. The thermal reforming system of claim 8 , further comprising:
a hydrotreater for hydrotreating at least a portion of the second separation product; and
a fractionator for fractionating hydrocarbons in the second separation product to form one or more hydrocarbon fractions boiling in the naphtha, jet or diesel range.

14. A thermal reforming system for converting triacylglycerides-containing oils into hydrocarbons, the thermal reforming system comprising:
a mixer for mixing a triacylglycerides-containing oil with carbon dioxide;
a thermal reforming reactor configured for reforming, in the absence of an added catalyst, the triacylglycerides-containing oil-carbon dioxide mixture to convert at least a portion of the triacylgiycerides to a mixture of hydrocarbons;
a flow conduit for recovering an effluent from the thermal reforming reactor;
a feed-effluent exchanger for indirectly heating the triacylglycerides-containing oil-carbon dioxide mixture with the effluent recovered from the thermal reforming reactor;
a drum for separating the effluent into a first separation product comprising carbon dioxide and light reaction byproducts and a second separation product comprising the mixture of hydrocarbons;
a gas separation device for separating the carbon dioxide from the light reaction byproducts in the first separation product;
a recycle system for compressing and recycling the carbon dioxide recovered from the gas separation device;
one or more flow conduits for mixing hydrogen, a non-renewable hydrocarbon feedstock, or a mixture thereof with the second separation product;
a hydrotreater for hydrotreating at least a portion of the second separation product;
a second drum for separating an effluent from the hydrotreater to recover a hydrogen recycle stream and a hydrocarbon stream; and
a fractionation system for fractionating hydrocarbons in the hydrocarbon stream to produce two or more hydrocarbon fractions.

15. The thermal reforming system of claim 14 , further comprising a flow conduit for injecting liquid carbon dioxide into the thermal reforming reactor to maintain a temperature or a temperature profile within the thermal reforming reactor.

16. The thermal reforming system of claim 14 , wherein the hydrotreater comprises at least two catalyst beds, and wherein:
a first catalyst bed comprises a catalyst having hydrogenation activity;
a second catalyst bed comprises a catalyst having hydrocracking activity.

17. The thermal reforming system of claim 16 , wherein the catalyst bed proximate an inlet of the hydrotreater comprises a catalyst useful for at least one of:
decarboxylation;
hydrodeoxygenation of unsaturated free fatty acids to produce C5-C24 paraffins;
saturation of mono-, di- and tri-olefins contained in the alkyl backbone of the free fatty acids;
hydrodenitrogenation of trace organic nitrogen compounds; and
catalyst tolerance for water coming in with the hydrocarbonaceous feed.

Assignees

• Lummus Technology Inc

Inventors

• Greene Marvin I

Classifications

• C10G69/06

  including at least one step of thermal cracking in the absence of hydrogen · CPC title

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• C10G2300/1011

  Biomass · CPC title

• C10G45/00

  Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds · CPC title

• C10G2400/08

  Jet fuel · CPC title