Beruflich Dokumente
Kultur Dokumente
INTRODUCTION
2-EH (2-Ethyl-1-hexanol).
2-Ethylhexanol ranks after the lighter alcohols (methanol to butanol) as the most
2-EH is used in the production dioctyl phthalate (DOP) other plasticizers, coatings,
adhesives and specialty. In these end use areas, it contributes significantly to may
high performance characteristics such as flexibility, good adhesion, lower
emissions and fuel performance improvement.
The production of 2-ethylhexanol has recorded a growth of 2.5% per year from
1986 to 2000.
The future of 2-EH is tied to the strength in phthalates, DOP, the largest volume
phthalate ester, is expected to remain flat or decline slightly due to competition
from other phthalates and environmental pressures. Substitutions by non-
phthalates in niche markets and the challenge of metallocene plastomers are
viewed as possible future threats. Modest growth is projected for 2-Ethylhexanol
based intermediates for acrylic surface coatings, dieisel fuel & lube additives.
CHAPTER-2
PROPERTIES AND USES
Physical properties:
(2.) it forms a transparent mixture with other alcohols, ethers and most organic
liquids. Chemical propertis:
Property Value
Molecular weight 130.23
2-Ethylhexanol ≥99.5 wt%
Color, Pt- Co scale Max.5
Distillation range (95vol%) at 101.3kPa 184-185°C
Viscosity at 20℃ 9.8 mPa.s
Vapor pressure at 20℃ ca.0.03 kPa
heat of vaporization at 184.8℃ 50.66 kJ/mol
Solubility in water at 20℃ 0.07 wt%
Solubility of water in 2-ethylhexanol at
20℃ 2.7 wt%
Surface tension at 20℃ 0.25 ×10-3 N/.cm
Dielectric constant at 20℃ 7.7
bp at 101.3kPa 184.6°C
Critical temperature 339.8℃
Critical pressure 2.67 Mpa
Critical density 0.2636 g/cm3
Critical compressibility 0.2670
Specific flow resistance at 20℃ 5.8 × 103 MΩ.cm
Azeotrope with water at 101.3kPa, 20%
2-ethylhexanol/ 80% water, bp 183.5℃
2-Ethylhexanol
15 0.8359
20 0.8323
25 0.8286
30 0.8247
50 0.8100
refractive index, 10 1.4356
15 1.4337
20 1.4317
25 1.4298
30 1.4278
50 1.4199
The acetaldehyde route starts from ethylene and operates near at atmosphere
pressure. Ethylene is first oxidized to acetaldehyde, which is then converted to
crotonaldehyde via aldol reaction & hydrogenated to n-butyraldehyde. route
(a)→(f)
The most important synthetic route accounting for over 95% of 2-EH production is
based on propylene which after initial hydroformylation is converted into an oxo
crude product. (routes (b)→ (g)). The crude oxo product is a mixture of valuable
products of propylene hydroformylation (n- and iso – butyraldehyde) along with
the byproducts (n- and iso- butanol) and the heavy ends. The individual
components of the mixture can be obtained after distillation.
n- Butyraldehyde is converted into butyraldehyde via an alkali catalyzed reaction
and then crotonized to 2-Ethylhexanol (Route (n)). Thereafter, 2-Ethylhexanol is
ether partially hydrogenated to 2-ethylhexanol or undergoes total hydrogenation
to 2-EH.
Aldox process is a case in which co-catalyst are added to the Oxo catalyst enabling
aldolization to occur in the same phase. Consequently, after hydrogenation a
mixture results consisting of2-EH, isomeric C8 alcohols & isobutanol (Route (m)).
Basically similar reservations pertaining to the quality of the resulting 2-EH also
apply to the process of the heavy ends of the Oxo synthesis (Route (j)). Which also
yields 2-EH after additional hydrogenation. However one drawback is that in molar
terms only 2/3 of the butanol feedstock is converted into 2-EH, the remaining third
resulting as sodium butanoate.
The reaction of 2-EH with 2-Ethylhexanol in which the very reactive unsaturated
aldehyde can be removed from the reaction mixture via reduction to the saturated
aldehyde (Route (o)) belongs to the more specialized but not industrially operated
methods: Removal of
2-Ethylhexanol prevents its conversion into higher boiling compounds.
COMPARISION OF COAL BASED ROUTE &
PETROCHEMICAL ROUTE.
The figure clearly indicates that the transition from the Coal based route to the
petrochemical route led to a reduction in the number of processing steps.
Therefore over 95% of the current 2-EH production is based on propylene.
PROCESS DISCRIPTION
The synthesis gas may contain several percent methane, which acts as an inert in
the reactor. Traces of water introduced with the synthesis gas are not harmful.
Impurities such as hydrogen sulfide and triethylamine should be carefully excluded,
however the prevent reaction with the active cobalt complex to form catalytically
inactive complexes.
Oxygen should be excluded from the system, during the start up phase when the
active catalyst concentration is being stablished. Oxygen has been shown to inhibit
cobalt Hydrocarbonyl formation, but once the system is operating, concentration
up to 2% can be tolerated carbondioxide acts in the same manner as oxygen, with
concentration up to 4% permissible.
Polymer grade (99+%) pure propylene may be fed. Propylene feed should be
vaporized & fed in to reactor as a gas. Designing for propylene conversion
grater then 95% per pass will minimize propylene losses in the blown vent stream.
The main reaction products are n-and iso butyraldehyde in the ratio of 4:1. The
former being the required product for the subsequent conversion to 2-EH. Within
the reactor, however 6% of n-butyraldehyde product is reduced to n-butanol, 4%
of iso-butyraldehyde product is reduced to iso-butanol & other reactions occur to
a small extent yielding molecular weight compounds.
(heavy ends) to the extent of 1% by weight of the butyraldehyde/ butanol mixture
as the reactor exit.
Separator:
In the separator, which follows the Oxo reactor, the catalyst solution is separated
from the oxo-raw product & recycled to the Oxo reactor.
Stripper:
In the stripper, the unconverted propylene is removed from the Oxo product suing
fresh synthesis gas. This synthesis gas is recycled to the Oxo reactor.
Aldolization:
The n-butyraldehyde stream passes on into an Aldolization reactor. In the
aldolization reactor n-butyraldehyde reacts very quickly to give 2-Ethylhexanol.
2% w/w aqueous NaOH is employed as the standard industrial catalyst. The
conversion efficiency is 90% the temperature is 80-130℃ & pressure 3-10 atm.
Local overheating in the reaction mixture must be avoided since this may cause
secondary reactions & thus decrease yields. Through mixing of the 2-phases in the
system is necessary. The aldolization reactor may be a mixing pump, a packed
column or a stirring vessel.
Separator:
The product from the aldolization reactor passes on to a separator where 2-
Ethylhexanol is separated and then sent to a hydrogenation unit.
Hydrogenerator:
The 2-Ethylhexanol is reduced to 2-Ethylhexanol by hydrogen in the presence of
Raney nickel catalyst with a 99% conversion rate. The selectivity attained is greater
then 99%.
2% NaOH
80-130c
2CH3-CH2-CH2-CHO CH3-CH2-CH2-CH=C-CHO +H2O
(3-10) atm
CH2-CH3
(n-butyraldehyde)
(2-Ethyl hexenal)
Nickel
CH3-CH2-CH2-CH-CH=C-CHO+2H2 CH3-CH2-CH2-CH2-CH-CH2OH
CH2-CH3 CH2-CH3
(2-Ethyl hexenal) (2-Ethyl hexanol)
CHAPTER-4
MATERIAL BALANCE
100(R) (1-x)
∴ ––––––––––– = 2 ………………… (1)
100 (1+ Rx)
R (1-x)
––––––– = 2
1+ Rx
R-Rx = 2+2Rx
3Rx = R-2
(R-2)
x = ––––
3R
2 (1+Rx)
x = ––––––––––––––––– ………………… (2)
2(1+Rx) +100 R(1-x)
x + 49Rx – 49 Rx2 = 1
(R – 2) (98R + 101) = 9R
+(
104)
± (−104)2− 4()(
9 8 − 202)
104 ±
2 ()98) 90000
R= = 2 ()98
0
∴ R= 2.061
Assume: all Aldehydes (both n & iso-butyraldehydes leave as the top product) and
all alcohols (both n and iso-butanol leave as bottom product).
19.198
ZF = ––––––– = 0.203; XD = 0.987 XW = 0.012
94.39
Over balance:
F= D+W
D= F-W= 94.39-W
Component balance:
F zF = DxD + wxw.
94.39(0.203) = (94.39-W) (0.987) + W (0.012)
19.161 = 93.163 - 0.987W + 0.012W
0.957W = 93.163 - 19.161 = 74.002
74.002
W = –––––– = 75.9 K-moles
0.975
50000×1000
∴Production (K-moles/hr) = –––––––––––– = 47.99 K-moles
8000×130.23
47.99×102.03
∴K-moles of Propylene required = –––––––––––––– = 146.564 K-moles
33.048
Distillation column:
Feed:
n- butyraldehyde = 114.91-6.89 = 108.02 K-moles
iso-butyraldehyde = 28.723-1.149 = 27.574 K- moles
F = 108.02+27.574 = 135.594 K-moles
27.574
ZF = = 0.203
135.594
Overall balance:
F=D+W
D= F-W = 135.594-W
Component balance:
FzF = DxD + Wxw
135.594 (0.203) = (135.594-W) (0.987) + W (0.012)
27.526 =133.831-0.975 W
W= 109.03 K-moles
n-butyraldehyde in W = 0.988×109.03 = 107.72 K- moles
iso-butyraldehyde in W = 109.03-107.72 = 1.31 K- moles
K-moles of 2-Ethylhexanol = 0.90×107.72/2 = 48.474 K- moles
m =146.564 K-moles/hr
= 146.564 ÷ 3600 K-moles/s
Q=m Cp ∆t
m = 293.13 K-moles/hr
= 293.13÷3600 K-moles/s
Cp=30×103 J/K-mole(K)
∆t =100-30 = 70°C
Q = (293.13÷3600)30×103 × (100-30) =170.99 KW
Let the reference temperature (TR) be equal to the feed temperature (Tf)
i.e TR = Tf
= 100℃
∴ heat in term → vanishes
Consider, steady state i.e heat accumulation → vanishes
Cp=120×103 J/K-moles/K
∆t = 130℃-72.55℃
= 57.45℃
Overhead condenser:
Q= mλ
m = 26.564 K-moles/s
3600
λ = 3.2×107 J/K-moles
Reboiler:
Q= m λ
λ=3.2×107 J/K-mole
m= 109.033÷3600 K-moles
Q= (109.03÷3600)×3.2×107 = 969.16 KW
i.e, 969.16 KW of heat has to be supplied.