Process for the production of renewable base oil, diesel and naphtha
Hydrotreatment of biological oil is disclosed for producing renewable base oil and a diesel oil from low value biological oils. Low value biological oils containing free fatty acids and fatty acid esters can be processed into a renewable base oil and a renewable diesel oil in an efficient manner by first separating at least part of the free fatty acids from the feedstock and then processing separately this free acid feed in a ketonisation reaction followed by hydrodeoxygenation and hydroisomerisation reactions to yield a renewable base oil stream. The remaining free fatty acid depleted feed is processed in a separate hydrodeoxygenation and hydroisomerisation step to yield a renewable diesel stream.
1. A method for producing a renewable base oil and a diesel fuel from a feedstock of biological origin, the method comprising:
a) providing a feedstock, the feedstock containing 2-95 wt % of a mixture of free fatty acids; 5-98 wt % fatty acid glycerols selected from mono-glycerides, di-glycerides and tri-glycerides of fatty acids; and 0-50 wt % of one or more compounds selected from a list consisting of: fatty acid esters of the non-glycerol compound, fatty amides, and fatty alcohols; wherein at least 50 wt % of the feedstock is made up of the mixture of free fatty acids and fatty acid glycerols;
b) separating the feedstock into at least:
a free fatty acid feed having a higher concentration of free fatty acids than the feedstock, the free fatty acids containing C 10 -C 24 fatty acids; and
one or more free fatty acid depleted feed(s) having higher concentration of the compounds selected from mono-glycerides, di-glycerides and tri-glycerides of fatty acids, and having a higher boiling point than the free fatty acid feed;
c) subjecting the free fatty acid feed to ketonisation reaction conditions where two fatty acids react to yield a ketone stream, the ketone stream containing as a major part saturated ketones;
d) subjecting the ketone stream to both hydrodeoxygenation reaction conditions and to hydroisomerisation reaction conditions, simultaneously or in sequence, to yield a deoxygenated and isomerised base oil stream containing the renewable base oil; and
e) transforming the one or more free fatty acid depleted feed(s) into a diesel fuel.
2. The method according to claim 1 , comprising:
prior to step a), pre-treating an initial feedstock containing fatty acid esters in at least a hydrolysis step thereby producing the feedstock, where a ratio of free fatty acids to fatty acid esters has been increased compared to the initial feedstock.
3. The method according to claim 1 , wherein the free fatty acid feed contains C 14 -C 22 fatty acids.
4. The method according to claim 1 , comprising:
distilling the deoxygenated and isomerised base oil stream of step d) to obtain a distilled renewable base oil.
5. The method according to claim 1 , comprising:
f) where the one or more free fatty acid depleted feed(s) is transformed into a diesel product by subjecting the one or more free fatty acid depleted feed(s) to both hydrodeoxygenation reaction conditions and to hydroisomerisation reaction conditions, simultaneously or in sequence, to yield a deoxygenated and isomerised diesel stream containing the diesel fuel; and
distilling the deoxygenated and isomerised diesel stream obtained from step f) to obtain a distilled diesel fuel.
6. The method according to claim 4 , comprising:
f) where the one or more free fatty acid depleted feed(s) is transformed into a diesel product by subjecting the one or more free fatty acid depleted feed(s) to both hydrodeoxygenation reaction conditions and to hydroisomerisation reaction conditions, simultaneously or in sequence, to yield a deoxygenated and isomerised diesel stream containing the diesel fuel; and
g) distilling the deoxygenated and isomerised diesel stream obtained from step f) to obtain a distilled diesel fuel.
7. The method according to claim 6 , additionally for producing a naphtha fuel, where the naphtha fuel is obtained from distillation of both the deoxygenated and isomerised base oil stream of step d) and from the distillation of a deoxygenated and isomerised diesel fuel of step e).
8. The method according to claim 6 , wherein no pre-treatment by hydrogenation or by hydrolysis is made in or in-between steps a)-c).
9. The method according to claim 6 , where the hydrodeoxygenation and hydroisomerisation of step d) take place in sequence, and where in-between the hydrodeoxygenation and hydroisomerisation there is a stripping step, where gasses are separated from liquids in a high temperature and high pressure separation step at a temperature between 300-330° C. and pressure between 40-50 barg.
10. The method according claim 6 , wherein between steps d) and e) there is a stripping step, where gasses are separated from liquids, at a temperature between 320-350° C. and pressure between 3-6 barg.
11. The method according to claim 6 , wherein the free fatty acid feed contains more than 90 wt % saturated fatty acid or C 16 fatty acids.
12. The method according to claim 6 , wherein the feedstock is palm oil fatty acid distillate (PFAD).
13. The method according to claim 6 , wherein the ketonisation reaction conditions include a temperature in a range from 300 to 400° C., a pressure in a range from 5 to 30 barg and a WHSV in a range from 0.25-3 h −1 , in a presence of a ketonisation catalyst, the ketonisation catalyst containing a metal oxide catalyst, in a presence of a gas in a range from 0.1-1.5 gas/feed ratio (w/w), the gas being selected from one or more of: CO 2 , H 2 , N 2 , CH 4 , and H 2 O.
14. The method according to claim 6 , wherein the ketonisation reaction conditions ensure liquid phase ketonisation;
wherein the ketonisation catalyst is a metal oxide catalyst selected from a list to contain metal consisting of one or more of: Ti, Mn, Mg, Ca, and Zr.
15. The method according to claim 6 , wherein the ketonisation catalyst is TiO 2 in anatase form having an average pore diameter of 80-160 Å, and/or a BET area of 40-140 m 2 /g, and/or porosity of 0.1-0.3 cm 3 /g.
16. The method according to claim 14 , wherein the ketonisation catalyst is TiO 2 , on a support, wherein a content of elements manganese, magnesium, calcium and potassium, are 0.05 wt % or less compared to a total catalyst weight as measured using X-ray diffraction.
17. The method according to claim 14 , wherein the ketonisation catalyst is TiO 2 on a support, wherein a content of the element potassium, is 0.05 wt % or less compared to a total catalyst weight as measured using X-ray diffraction.
18. The method according to claim 14 , wherein the hydrodeoxygenation reaction conditions of step d) and/or step f) include a temperature in a range from 250 to 400° C., a pressure in a range from 20 to 80 barg, a WHSV in a range from 0.5-3 h −1 , and a H 2 flow of 350-900 nl H 2 /l feed, in a presence of a hydrodeoxygenation catalyst NiMo on an alumina support.
19. The method according to claim 6 , wherein the hydroisomerization reaction conditions of step d) and/or step f) include a temperature in a range from 250 to 400° C., a pressure in a range from 10 to 60 barg, a WHSV in a range from 0.5-3 h −1 , and a H 2 flow of 100-800 nl H 2 /l feed, in a presence of an isomerisation catalyst including a Group VIII metal and a molecular sieve, on an alumina and/or silica support.
20. The method according to claim 6 , wherein the hydrodeoxygenation catalyst and isomerisation catalyst are the same; and
wherein more than 50 wt % of the feedstock is the mixture of free fatty acids and fatty acid glycerols.
21. The method according to claim 6 , wherein the feedstock comprises:
at least 10 wt % and below 90 wt % free fatty acids.
22. The method according to claim 6 , wherein the feedstock comprises:
at least 10 wt % and below 90 wt % fatty acid esters.
23. The method according to claim 6 , wherein the feedstock comprises:
at least 10 wt % and below 90 wt % free fatty acids and at least 10 wt % and below 90 wt % fatty acid esters, and wherein more than 70 wt % of the feedstock is said mixture of free fatty acids and fatty acid glycerols.
24. The method according to claim 6 , wherein said fatty acid esters are fatty acid glycerols.