US 12,269,996 B2
Method for producing renewable C3 hydrocarbons and renewable aromatic hydrocarbons
Eveliina Mäkelä, Porvoo (FI); Marja Tiitta, Porvoo (FI); and Marja-Liisa Kärkkäinen, Porvoo (FI)
Assigned to NESTE OYJ, Espoo (FI)
Appl. No. 18/724,153
Filed by Neste Oyj, Espoo (FI)
PCT Filed Nov. 21, 2022, PCT No. PCT/FI2022/050765
§ 371(c)(1), (2) Date Jun. 25, 2024,
PCT Pub. No. WO2023/126561, PCT Pub. Date Jul. 6, 2023.
Claims priority of application No. 20216355 (FI), filed on Dec. 27, 2021.
Prior Publication US 2025/0011658 A1, Jan. 9, 2025
Int. Cl. C10G 11/05 (2006.01); B01J 29/06 (2006.01); B01J 35/61 (2024.01); C10G 3/00 (2006.01); C10G 11/20 (2006.01); C10G 65/12 (2006.01)
CPC C10G 3/44 (2013.01) [B01J 29/06 (2013.01); B01J 35/615 (2024.01); C10G 3/50 (2013.01); C10G 11/05 (2013.01); C10G 11/20 (2013.01); C10G 65/12 (2013.01); C10G 2300/1007 (2013.01); C10G 2300/1011 (2013.01); C10G 2300/4006 (2013.01); C10G 2300/4012 (2013.01); C10G 2400/28 (2013.01); C10G 2400/30 (2013.01)] 21 Claims
OG exemplary drawing
 
1. A method for producing renewable C3 hydrocarbons and renewable aromatic hydrocarbons from a renewable feedstock selected from animal oils, animal fats, plant oils, vegetable oils, microbial oils, and mixtures thereof, the method comprising the following steps:
a) pre-treating the renewable feedstock by reducing the amount of impurities therein not to include: more than 10 w-ppm alkali metal and alkaline earth metal impurities, calculated as elemental alkali metals and alkaline earth metals; more than 10 w-ppm other metals, calculated as elemental metals; more than 1000 w-ppm nitrogen containing impurities, calculated as elemental nitrogen; more than 30 w-ppm phosphorus containing impurities, calculated as elemental phosphorus; more than 5 w-ppm silicon containing impurities, calculated as elemental silicon; to produce a pre-treated feedstock,
b) subjecting the pre-treated feedstock to hydrodeoxygenation reaction to produce a hydrodeoxygenated stream, wherein the hydrodeoxygenation reaction comprise one or more of:
a. a temperature in the range from 250° C. to 400° C.,
b. a pressure in the range from 10 bar to 200 bar,
c. a WHSV in the range from 0.25 h−1 to 3 h−1,
d. a H2 flow of 350 to 1500 N-L H2/L feed, and
e. a hydrodeoxygenation catalyst selected from Pd, Pt, Ni, Co, Mo, Ru, Rh, and W or any combination thereof, on a support,
c) subjecting the hydrodeoxygenated stream to a gas-liquid separation to produce a gaseous stream and a hydrodeoxygenated liquid stream,
d) subjecting the hydrodeoxygenated liquid stream to catalytic cracking conditions comprising
i. a temperature in a range from 300° C. to 700° C.,
ii. a residence time from 0.2 s to 7200 s, and
iii. a catalyst comprising a zeolite and a support, wherein the zeolite is ZSM-12 with a pore size below 0.7 nm and at least one property selected from the group consisting of:
an aluminum content from 0.1 wt-% to 1.5 wt;
a BET surface area from 200 m2/g to 380 m2/g, determined by nitrogen physisorption;
the ratio of the Brønsted acid sites to the Lewis acid sites is 1.7-4 determined by pyridine FT-IR;
acidity from 180 umol/g to 500 umol/g, determined by NH3-TPD method wherein acidity is calculated from the amount of NH3 absorbed at 200° C. and desorbed between 100° C. and 500° C.,
to produce a catalytically cracked stream, and subsequently
e) separating the catalytically cracked stream at least to
i) a fraction comprising the renewable C3 hydrocarbons, and
ii) a fraction comprising the renewable aromatic hydrocarbons.