Ketones and alcohols to hydrocarbons

1. This research describes the production of alcohols from
ketones and the production of hydrocarbons from alcohols, being the
last two stages of the MixAlco process. The ketones ranged from C3
to C13. These ketones were hydrogenated to produce alcohols. The
catalyst used was Raney-Nickel in a stirred batch reactor. The
optimum temperature, pressure and residence time for
hydrogenation was 150˚C 1000 psi and 24 h. The maximum
conversion reached was 98%. The alcohols were oligomerized to
produce hydrocarbons. The oligomerization was in a plug flow
reactor packed with a zeolite type catalyst HZSM-5 silica alumina
ratio (Si/Al) 80 mol silica/mol alumina. A product similar to
commercial gasoline was obtained at T = 320˚C and WHSV= 1.3 to
2.7 h–1. Also, at these conditions, the amount of light hydrocarbons
(C1–C4) is low. The type of hydrocarbons obtained were
isoparaffins, olefins and aromatics. The olefins were saturated trough
hydrogenation using Raney-Nickel catalyst in a batch reactor.
 Dr. Mark Holtzapple for the opportunity to work in one of his projects.
 Sebastian Taco Vasquez, the graduate student who prepared the
training, the project guidelines and answered all my questions.
 Undergraduates Summer Research Grant (USRG) program for placing
the students in each different project.
The world is going through difficult times with the depletion of
fossil fuels and the environmental impact of these fuels have. For
that reason, biofuels are a good answer to solve the lack of energy
sources in the world. Biofuels are environmental friendly and
accessible in most of the world. The MixAlco process transforms
biomass into fuels. I worked with the hydrogenation of ketones to
transform them to alcohols and transform the alcohols to fuels such
as gasoline and jet fuel.
Abstract
Objective
Methods
Conclusion
Acknowledgments
Hydrogenation of Ketones and Alcohols Conversion to
Hydrocarbons Using HZSM-5 Catalyst
Emanuel Nieves, Dr. Mark Holtzapple, Sebastian Taco Vasquez
Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77843-
3122, USA
 For the hydrogenation, the conversion for the mixAlcohol was 98% using Raney-Nickel
catalyst.
 The best conditions were T = 150 ˚C, P = 1000 psi (absolute) and a
residence time of 24 hours.
 For the oligomerization, the conversion was 100 %.
 Using a packed bed reactor was the most suitable reactor for this
reaction.
The products obtained from the oligomerization were similar to a
commercial gasoline.
Results and Discussion
Alcohol Distribution after hydrogenation. Catalyst
Raney Nickel, P = 1000 psi (absolute), T = 150˚C,
residence time = 24 hrs.
Graph # 2 Liquid type product distribution of
mixAlcohol reaction.
Graph # 3 Carbon distribution of commercial
plus gasoline from a Shell gas
station taken in July 2010.
Liquid type product distribution of mixalcohol
reaction over HZSM-5 (280), WHSV = 1.31 h–1,
P = 1 atm (absolute), T = 370 ˚C .
Analysis Alcohol Reaction Path
 For hydrogenation, the ketones are fed into a batch reactor using
Raney Nickel as a Catalyst.
 The reaction temperature was 150 ˚C and pressure 1000 psi.
 The residence time was 24 h and the conversion reached 100%.
 The reactants are fed into a packed bed reactor with HZSM-5 as
catalyst.
For oligomerization, the reaction temperature range was from
300 ˚C to 410 ˚C.
 The reaction products are in three phases: gaseous hydrocarbons
from C1 - C4 , liquid hydrocarbons C5 - C13 and water. There are
more than 100 components in the hydrocarbon liquid phase.
 The type of product hydrocarbons are isomers, olefins, naphtenes
and aromatics.
MixAlco Process Oligomerization Process
Table # 1 Alcohol Distribution Graph # 1 Alcohol Distribution
Carbon
Number Alcohol Weight (%)
3 isopropanol 13.47
4 2-butanol 2.66
5 2-pentanol 9.15
6 3-hexanol 0.88
2-hexanol 2.72
7 4-heptanol 1.60
2-heptanol 19.15
8 4-octanol 1.17
3-octanol 2.46
2-octanol 4.28
9 4-nonanol 9.58
2-nonanol 3.46
10 5-decanol 5.23
11 6-undecanol 14.05
12 6-decanol 4.67
13 6-tridecanol 2.91
0.00
5.00
10.00
15.00
20.00
25.00
isopropanol
2-butanol
2-pentanol
3-hexanol
2-hexanol
4-heptanol
2-heptanol
4-octanol
3-octanol
2-octanol
4-nonanol
2-nonanol
5-decanol
6-undecanol
6-decanol
6-tridecanol
3 4 5 6 7 8 9 10 11 12 13
Concentration(wt%)
Carbon Number
Alcohol Distribution
Olefins and Naphtenes Olefinics
(g C Species i /100 g C liquid )
Naphtenes
(g C Species i /100 g C liquid )
1-propene 1.4–1.5 cyclohexane 1.0–2.3
2-butene 3.3–7.7 methyl-cyclopentane 2.3–2.9
2-methyl-1-butene 4.7–5.3 cyclopentane, 1,2-dimethyl-3-methylene 1.7–1.9
2-butene, 2,3-dimethy 1.6–6.6 Aromatics
(g C Species i /100 g C liquid )
2-pentene, 2-methyl 2.6–4.2 toluene 1.6–3.4
2-pentene, 3-methyl 2.4–8.5 ethyl benzene 1.3–2.1
3-methyl-2-pentene 2.0–5.8 xylene 1.7–7.8
2-hexene, 2,3-dimethyl 1.9–5.1 mesitylene 1.8–2.6
1,5-dimethyl-cyclopentene 1.3–2.8
1,3-dimethyl-cyclohexene 2.0–3.7
Table 2
Most abundant
compounds for the
mixalcohol reaction over
HZSM-5 (280), T = 300–
415˚C, WHSV = 1.31 h–1,
P = 1 atm (absolute).