Integrated hydrolysis/hydroprocessing process for converting feedstocks containing renewable glycerides to paraffins and polyols
An integrated process for producing paraffins and polyols from renewable feedstocks has been developed in which a hydrolysis process is integrated with the hydroprocessing step, producing products suitable for use as transportation fuels. Integration allows the use of common equipment which minimizes cost, raw material consumption, and energy requirements.
1. An integrated process for producing paraffins and polyols from a glyceride containing renewable feedstock comprising:
reacting the glyceride containing renewable feedstock with water in a first reaction zone to produce an effluent stream comprising free fatty acids, glycerol, and water;
separating the free fatty acids from the glycerol and water to produce a free fatty acid stream substantially free of glycerol, water, and metals, and a glycerol stream substantially free of free fatty acids;
reacting the free fatty acid stream substantially free of glycerol, water, and metals with hydrogen from a hydrogen source in a second reaction zone in the presence of a hydroprocessing catalyst under hydroprocessing conditions thereby hydrodeoxygenating the free fatty acid stream substantially free of glycerol, water, and metals to produce a reaction product comprising n-paraffins and water;
recovering the n-paraffin reaction product;
reacting the glycerol stream substantially free of free fatty acids with hydrogen from the hydrogen source in a third reaction zone under selective hydrogenation conditions to produce a reaction product comprising polyols;
recovering the polyol reaction product.
2. The integrated process of claim 1 further comprising contacting at least a portion of the n-paraffin reaction product with an isomerization catalyst under isomerization conditions to isomerize at least a portion of the n-paraffins to isoparaffins.
3. The process of claim 1 wherein separating the free fatty acids from the glycerol and water comprises at least one of hot depressurization, cyclonic vapor liquid separation, liquid-liquid separation, multi-effect evaporation, steam distillation, vacuum distillation, reactive distillation, liquid extraction, adsorption, filtration, membrane separation, absorption, or ion exchange.
4. The integrated process of claim 1 wherein separating the free fatty acids from the glycerol and water comprises:
separating the effluent stream into a free fatty acid enriched stream and a glycerol containing stream;
purifying the free fatty acid enriched stream to form the free fatty acid stream substantially free of glycerol, water, and metals.
5. The integrated process of claim 4 further comprising purifying the glycerol containing stream to form the glycerol stream substantially free of free fatty acids.
6. The process of claim 1 wherein the free fatty acid stream substantially free of glycerol, water, and metals has less than about 5 wt % glycerol, less than about 5 wt % water, and less than about 20 ppm (wt) metals.
7. The process of claim 1 wherein reacting the glyceride containing renewable feedstock with water takes place in the presence of a hydrolysis catalyst.
8. The process of claim 1 wherein reacting the glyceride containing renewable feedstock with water is performed at sub-critical conditions.
9. The process of claim 1 wherein reacting the glyceride containing renewable feedstock with water takes place at a pressure of less than about 5516 kPa(g) and a temperature of less than about 300° C.
10. The process of claim 1 wherein the glyceride containing renewable feedstock comprises algae or a stream derived from algae.
11. The process of claim 1 further comprising contacting the glyceride containing renewable feedstock with one or more of an acid, a base, an extractive material, or an adsorptive material to remove contaminants from the glyceride containing renewable feedstock before reacting the glyceride containing renewable feedstock with the water.
12. The process of claim 1 wherein the hydroprocessing conditions include a temperature of less than about 400° C., a hydrogen partial pressure of greater than about 3450 kPa, an H 2 to organic oxygen ratio greater than about 5, and in the presence of a base metal catalyst.
13. The process of claim 1 wherein at least about 80 wt % of the total lipids in the glyceride containing renewable feedstock are converted to free fatty acids in the reaction with water.
14. The process of claim 1 wherein when reacting the glyceride containing renewable feedstock with water, a ratio of water to total lipids in the first reaction zone is greater than a stoichiometric minimum required for complete hydrolysis.
15. The process of claim 1 wherein at least about 80 wt % of oxygen in the free fatty acid stream substantially free of glycerol, water, and metals is converted to water and less than 10% of carbon in the free fatty acid stream substantially free of glycerol, water, and metals is reacted to form CO or CO 2 in the second reaction zone.
16. The process of claim 1 wherein at least about 80% of the n-paraffins in the reaction product have an even number of carbon atoms.
17. The process of claim 1 wherein reacting the free fatty acid stream substantially free of glycerol, water, and metals with hydrogen comprises selective catalytic hydrodeoxygenation.
18. An integrated process for producing paraffins and propylene glycol from a glyceride containing renewable feedstock comprising:
reacting the glyceride containing renewable feedstock with water in a first reaction zone to produce an effluent stream comprising free fatty acids, glycerol, and water;
separating the effluent stream into a free fatty enriched stream and a glycerol containing stream;
purifying the free fatty acid enriched stream to form a free fatty acid stream substantially free from glycerol, water, and metals;
purifying the glycerol enriched stream to form a glycerol stream substantially free of free fatty acids;
reacting the free fatty acid stream substantially free of glycerol, water, and metals with hydrogen from a hydrogen source in a second reaction zone in the presence of a hydroprocessing catalyst under hydroprocessing conditions thereby hydrodeoxygenating the free fatty acid stream substantially free of glycerol, water, and metals to produce a reaction product comprising n-paraffins and water;
recovering the n-paraffin reaction product;
reacting the glycerol stream substantially free of free fatty acids with hydrogen from the hydrogen source in a third reaction zone under selective hydrogenation conditions to produce a reaction product comprising propylene glycol;
recovering the propylene glycol reaction product.
19. The process of claim 18 wherein the free fatty acid stream substantially free of glycerol, water, and metals has less than about 5 wt % glycerol, less than about 5 wt % water, and less than about 20 ppm (wt) metals.
20. The process of claim 18 wherein at least about 80% of the total lipids in the triglyceride-rich renewable feedstock are converted to free fatty acids in the reaction with water and wherein less than 10% of carbon in the free fatty acid stream substantially free of glycerol, water, and metals is reacted to form CO or CO 2 in the second reaction zone.